METHOD STATUS TABLE
SW-846, THIRD EDITION, UPDATES I, II, AND IIA
                 September 1994
      Use this table as  a reference guide to identify the
      promulgation status of SW-846 methods.

      The methods in this table are listed sequentially by
      number.

      This table should not be used as a Table of Contents for
      SW-846. Refer to the Table of Contents found in Final
      Update II (dated September 1994} for the order in which
      the methods appear in SW-846.

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                            INSTRUCTIONS

 SW-846 is a "living" document that changes when new data and advances in
 analytical  techniques are incorporated into the manual as  new or revised
 methods.   Periodically, the Agency issues these methods  as  updates to  the
 manual. To date, the Agency has issued Final Updates I, II, and IIA. These
 instructions include directions on getting the basic manual  up-to-date and
 incorporating Final Updates II and IIA into your SW-846. The Agency will
 release additional proposed and final updates in the future. New instructions,
 to supersede these, will be included with each of those updates.  However, in
 general,  final  updates  should  always  be  incorporated into  SW-846  in
 chronological order (e.g. Update I should be incorporated before Update II).

 If you have any difficulty with these directions, you may telephone the Methods
 Information Communication Exchange (MICE) at 703-821-4789 for help.  If
 you have questions  concerning your SW-846 U.S. Government Printing Office
 (GPO) subscription, you should  telephone the GPO at 202-512-2303.  If you
 did not purchase your SW-846 from the GPO, the GPO will not be able to help
 you.
FINAL UPDATE IIA;  Final Update IIA contains only one method, Method
4010, dated August 1993.  This method was promulgated on January 4, 1994
(59 FR 458).  It should be inserted into the manual according to the location
specified in the Final Update II Table of Contents (dated September 1994).
FINAL UPDATE II:   Final  Update II has been  promulgated and is  now
officially part of SW-846. These instructions for insertion of Final Update II
are divided into two (2) sections: Section A • Instructions for New Subscribers
and Section B - Instructions for Previous Subscribers.

    New subscribers are defined as individuals who have recently (6-8 weeks) placed an
    order with the GPO and have received new copies of the 4 (four) volume set of the
    Third Edition, a copy of Final Update I, and a copy of Final Updates II and IIA.

    Previous subscribers are defined as individuals that have received  copies of the Third
    Edition and other SW-846 Updates (including proposed Updates) in the past and have
    just received their Final Update II and IIA package in the mail.
Update II and IIA               Instructions - 1                          Final

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Please  use  the  following  instructions for  new  subscribers  or  previous
subscribers in sequence to piece together your new SW-846 manual.
A. INSTRUCTIONS FOR NEW SUBSCRIBERS

  i. If you have not already done so, open the packages that contain the Third Edition of
    SW-846, The Third Edition should include 4 (four) volumes of material (i.e. Volumes
    IA, IB, 1C, and II) and will be dated "September 1986" in the lower right hand corner
    of each page.  Four 3-ring binders (one binder for each volume) and a set of tabs
    should  also be  included.   You  should  place  each  volume of  material  in  the
    appropriately labeled 3-ring binder and insert the tabs.  Check the Table of Contents
    (dated September 1986) if you have any questions about the order of the methods or
    about which volume the methods should be inserted into.

    You will be missing some methods from the Third Edition since any Third Edition
    September1986 material, that was superseded by Final Update I  July 1992 material.
    has already been removed from vour copy of the Third Edition.
 ii.  If you have not already done so, open the package that contains Final Update I.  Final
    Update I should be a single package printed on white paper with the date "July 1992"
    in the lower right hand corner of each page. This package contains new methods and
    revised methods. In order to have a complete SW-846 manual, you should insert the
    new and revised July 1992 material using the Table of Contents (dated July 1992) at
    the front of Final  Update I to identify the correct location for each chapter and
    method.

    Since you are a new subscriber to SW-846, you need  not be concerned about the
    removal or replacement of the previous version of Update I, as discussed in item (A)
    of the Final Update I instructions. Again, any Third Edition September 1986 material.
    that was superseded by Final Update I July 1992 material has already been removed
    from your copy of the Third Edition. For example, your copy of the Third Edition does
    not contain a copy of the September 1986 version of Chapter One because it was
    superseded by the July 1992 revision of Chapter One contained in your Final Update
    I package.

    Final Update I also includes copies of September 1986 "replacement methods" which
    are included with your copy of Final Update I and are discussed in item (E) in the
    Final Update I instructions.  You should not insert the replacement methods?  The
    replacement methods were sent to subscribers before final  Update II was released.
Update II and IIA                 Instructions - 2                             Final

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     The Disclaimer and Chapter One at the front of Update I should also be photocopied
     3 times and inserted at the front of volumes IB, 1C, and II in order to  complete the
     manual.

         Note:   Update I does not contain any changes to Volume II other than the
         insertion of the Disclaimer and Chapter One,  Also, some methods will have an
         "A" after the method number. The "A" methods have been revised once.
iii.   Finally, open the package labeled Final Updates II and HA. Final Updates II and IIA
     should be a single package printed on white paper. Update II has the date "September
     1994" in the lower right hand corner of each page. Update IIA (Method 4010) has the
     date "August 1993" in the lower right hand corner of each page.  This package contains
     new methods and revised methods.  In order to have a complete SW-846 manual, you
     should insert the new methods and use the revised September 1994 methods to  replace
     older Third Edition and Final Update I methods that  are out of date. Use the Table
     of Contents (September 1994) at the front of Final Update II  to identify the correct
     location for each chapter and  method.

     The Abstract and Table of Contents at the front of Final Update II should  also be
     photocopied 3 times  and inserted at the front of volumes IB,  1C, and II in order to
     complete the manual.

     Please Note:

       •  Update II does not contain any changes to Volume II other than the insertion of
         the Abstract and Table of Contents.

       •  Some methods will  have an "A" or a "B" after the method number.  The "A"
         methods have been revised once.  The "B" methods have been revised twice.

       •  Methods 5100, 5110,  and 9200A were included in the  Proposed Update II
         (November 1992) package but are not included in the Final Update II (September
         1994) package.  The final Federal Register Rule for Update II explains why these
         methods were not finalized (promulgated).
Update II and IIA                 Instructions - 3                             Final

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B.  INSTRUCTIONS FOR PREVIOUS SUBSCRIBERS

  i.  Background Information: A number of SW-846 update packages have been released
     to the public since the original Third Edition was released. The number and labels on
     these packages can be confusing.  The following table titled "A Brief History of the
     SW-846 Third Edition and Updates" has been provided as an aid. Currently finalized
     (promulgated) methods have been printed in bold. An individual or organization that
     has held an SW-846 GPO subscription for several years may have received copies of
     any or all of the  following documents:
A BRIEF HISTORY OF THE SW-846 THIRD EDITION AND UPDATES
Package
Third Edition
Proposed Update 1
Final Update I
(Accidently Released)
Proposed Update II
(Accidently Released)
Final Update I
Proposed Update II
Proposed Update IIA"
(Available by request only.)
Final Update IIA' (Included
wir ". il Update II.)
Final update II
Date Listed on Methods
September 1986
December 1987
November 1990
November 1990
July 1992
November 1992
October 1992
August 1993
September 1994
Color of Paper
White
Green
White
Blue
White
Yellow
White
White
White
Status of Package
Finalized (Promulgated)
Obsolete
Obsolete! Never formally
finalized.
Obsolete! Never formally
proposed.
Finalized (Promulgated)
Obsolete
Obsolete
Finalized (Promulgated)
Finalized (Promulgated)
    " Contains only Method 4010.

 ii.  In order to begin updating the manual it is important to establish exactly what is
    currently contained in the manual that you have.  If the manual has been properly
    updated, the ONLY white  pages in the document should be dat.v September 1986
    (Third Edition) and July 1992 (Final Update I).  Remove and discard (or archive) any
    white pages from your manual that have any date other than September 1986 and July
    1992.

    There may also be yellow pages dated September 1992 (Proposed Update II) inserted
    in the manual. Remove and discard  all yellow pages or other colored pages (green or
    blue) from the manual. Some individuals may have  chosen to keep their  copy of
    Proposed Update II in a separate binder and removal will not be necessary.
Update fl and IIA
Instructions - 4
Final

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iii.   Open the package labeled Final Updates II and IIA.  Final Updates II and IIA should
     be a single package printed on white paper. Update II has the date "September 1994"
     in the lower right hand corner of each page.  Update IIA (Method 4010) has the date
     "August 1993" in the lower right hand corner of each page. This package contains new
     methods and revised methods.  In order  to have a complete SW-846 manual, you
     should insert the new methods and use the revised September 1994 methods to replace
     older Third Edition and Final Update I methods that are out of date. Use the Table
     of Contents (September 1994) at  the front of Final Update II to identify  the correct
     location for each chapter and method.

     The Abstract and Table of Contents at the front of Final Update II should also be
     photocopied 3 times and inserted at the front of volumes IB, 1C, and II in order to
     complete the manual.

     Please Note:

       •  Update II does not contain any changes to Volume II other than the insertion of
         the Abstract and Table of Contents,

       •  Some  methods will have an "A" or a "B" after the method number.  The "A"
         methods have been revised once.  The "B" methods have been revised twice.

       •  Methods 5100, 5110,  and 9200A were  included in the Proposed  Update II
         (November 1992) package but are not included in the Final Update II (September
         1994) package. The final Federal Register Rule for Update II explains why these
         methods were not  finalized (promulgated).
Update II and IIA                 Instructions - 5                             Final

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                                   ABSTRACT

Test Methods  for Evaluating Solid Waste,  Physical/Chemical  Methods   (SW-846)
provides test procedures and guidance which are recommended for use in conducting
the evaluations and measurements needed to comply with the Resource Conservation
and Recovery  Act  (RCRA),  Public  Law 94-580, as  amended.    These  methods are
approved  by  the U.S.  Environmental  Protection  Agency  for  obtaining  data to
satisfy the requirements of 40 CFR Parts 122 through  270  promulgated  under RCRA,
as amended.   This  manual presents the  state-of-the-art in routine analytical
tested  adapted  for the  RCRA  program.    It contains procedures  for field and
laboratory quality control,  sampling,  determining   hazardous  constituents in
wastes,  determining  the  hazardous   characteristics  of  wastes  (toxicity,
ignitability,  reactivity,  and  corrosivity),   and   for determining  physical
properties of wastes.   It  also contains guidance on how to select  appropriate
methods.

      Several of the hazardous waste regulations  under Subtitle C of RCRA require
that  specific testing  methods  described  in SW-846  be employed for  certain
applications.  Refer to 40 Code of Federal  Regulations (CFR), Parts  260 through
270, for those specific requirements. Any reliable analytical method may be used
to meet other requirements under Subtitle C of RCRA.
                                 ABSTRACT - 1                       Revision 2
                                                                September 1994

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                           TABLE  OF  CONTENTS
                                     VOLUME ONE

                                      SECTION  A
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
ACKNOWLEDGEMENTS
                    PART I     HETHODS  FOR ANALYTES  AND  PROPERTIES

CHAPTER ONE - QUALITY CONTROL

      1.0   Introduction
      2.0   QA Project Plan
      3.0   Field Operations
      4.0   Laboratory Operations
      5.0   Definitions
      6.0   References

CHAPTER TWO -- CHOOSING THE CORRECT PROCEDURE

      2.1   Purpose
      2.2   Required Information
      2.3   Implementing the guidance
      2.4   Characteristics
      2.5   Ground Water
      2.6   References

CHAPTER THREE - METALLIC ANALYTES

      3.1   Sampling Considerations
      3.2   Sample Preparation Methods

            Method 3005A:     Acid  Digestion of  Waters  for  Total  Recoverable  or
                              Dissolved Metals for Analysis by Flame Atomic Absorption
                              (FLAA) or Inductively Coupled  Plasma (ICP) Spectroscopy
            Method 3010A;     Acid Digestion of Aqueous Samples and Extracts for Total
                              Metals for Analysis by Flame Atomic Absorption (FLAA) or
                              Inductively Coupled Plasma (ICP) Spectroscopy
            Method 3015:      Microwave Assisted Acid Digestion of Aqueous Samples ind
                              Extracts
                                    CONTENTS - 1                          Revision 2
                                                                      September 1994

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      Method 3020A:
      Method 3040:
      Method 3050A:
      Method 3051:
           Acid Digestion of Aqueous Samples and Extracts for Total
           Metals   for   Analysis  by   Graphite  Furnace  Atomic
           Absorption (6FAA) Spectroscopy
           Dissolution Procedure for Oils, Greases, or Waxes
           Acid Digestion of Sediments, Sludges, and Soils
           Microwave Assisted Acid Digestion of Sediments, Sludges,
           Soils, and Oils
3.3   Methods for Determination of Metals
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
6010A:
6020:
7000A:
7020:
7040:
7041:
7060A:
7061A:
7062:
7080A:
7081:
7090:
7091:
7130:
7131A:
7140:
7190:
7191:
7195:
7196A:
7197:
7198:
7200:
7201:
7210:
7211:
7380:
7381:
7420:
7421:
7430:
7450:
7460:
7461:
7470A:
7471A:
      Method 7480:
      Method 7481:
      Method 7520:
      Method 7550:
      '• ^thod 7610:
        Chod 7740:
Inductively Coupled PIasma-Atomic Emission Spectroscopy
Inductively Coupled Plasma - Mass Spectrometry
Atomic Absorption Methods
Aluminum (AA, Direct Aspiration)
Antimony (AA, Direct Aspiration)
Antimony (AA, Furnace Technique)
Arsenic (AA, Furnace Technique)
Arsenic (AA, Gaseous Hydride)
Antimony and Arsenic (AA, Borohydride Reduction)
Barium (AA, Direct Aspiration)
Barium (AA, Furnace Technique)
Beryl!iui (AA, Direct Aspiration)
Beryl!iui (AA, Furnace Technique)
Cadmium (AA, Direct Aspiration)
Cadmium (AA, Furnace Technique)
Calcium (AA, Direct Aspiration)
Chromium (AA, Direct Aspiration)
Chromium (AA, Furnace Technique)
Chromium, Hexavalent (Coprecipitation)
Chromium, Hexavalent (Colorimetric)
Chromium, Hexavalent (Che!at ion/Extract ion)
Chromium, Hexavalent (Differential Pulse Polarography)
Cobalt (AA, Direct Aspiration)
Cobalt (AA, Furnace Technique)
Copper (AA, Direct Aspiration)
Copper (AA, Furnace Technique)
Iron (AA, Direct Aspiration)
Iron (AA, Furnace Technique)
Lead (AA, Direct Aspiration)
Lead (AA, Furnace Technique)
Lithium (AA, Direct Aspiration)
Magnesium (AA, Direct Aspiration)
Manganese (AA, Direct Aspiration)
Manganese (AA, Furnace Technique)
Mercury in Liquid Waste (Manual Cold-Vapor Technique)
Mercury in Solid or Semisolid Waste  (Manual Cold-Vapor
Technique)
Molybdenum (AA, Direct Aspiration)
Molybdenum (AA, Furnace Technique)
Nickel (AA, Direct Aspiration)
Osmium (AA, Direct Aspiration)
Potassium (AA, Direct Aspiration)
Selenium (AA, Furnace Technique)
                              CONTENTS - 2
                                                       Revision 2
                                                   September  1994

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            Method 7741A:     Selenium (AA, Gaseous Hydride)
            Method 7742:      Selenium (AA, Borohydride Reduction)
            Method 7760A:     Silver (AA, Direct Aspiration)
            Method 7761:      Silver (AA, Furnace Technique)
            Method 7770:      Sodium (AA, Direct Aspiration)
            Method 7780;      Strontium (AA, Direct Aspiration)
            Method 7840:      Thallium (AA, Direct Aspiration)
            Method 7841:      Thallium (AA, Furnace Technique)
            Method 7870:      Tin (AA, Direct Aspiration)
            Method 7910:      Vanadium (AA, Direct Aspiration)
            Method 7911:      Vanadium (AA, Furnace Technique)
            Method 7950:      Zinc (AA, Direct Aspiration)
            Method 7951:      Zinc (AA, Furnace Technique)
APPENDIX -- COMPANY REFERENCES
        NOTE:  A  suffix  of "A* in the method number  indicates  revision  one
        (the method has  been  revised once).   A suffix of "B" in  the method
        number indicates revision two (the method has been revised twice). In
        order to properly  document the method used  for  analysis,  the entire
        method number including the suffix letter designation (e.g.,  A or B)
        must be identified by  the analyst.  A method  reference  found within
        the  RCRA  regulations   and the  text of  SW-846 methods  and  chapters
        refers to the latest promulgated revision of the method, even though
        the method number does not include the appropriate letter suffix.
                                    CONTENTS - 3
    Revision 2
September 1994

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                                     VOLUME ONE

                                     SECTION 8
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
HETHOD INDEX AND CONVERSION TABLE
PREFACE
ACKNOWLEDGEMENTS

CHAPTER ONE. REPRINTED -- QUALITY CONTROL

      1.0   Introduction
      2.0   QA Project Plan
      3.0   Field Operations
      4.0   Laboratory Operations
      5.0   Definitions
      6.0   References

CHAPTER FOUR -- ORGANIC ANALYTES

      4.1   Sampling Considerations
      4.2   Sample Preparation Methods

            4.2.1       Extractions and Preparations

            Method 3500A:     Organic Extraction and Sample Preparation
            Method 3510B:     Separatory Funnel  Liquid-Liquid Extraction
            Method 3520B:     Continuous Liquid-Liquid Extraction
            Method 3540B:     Soxhlet Extraction
            Method 3S41:      Automated Soxhlet  Extraction
            Method 3550A:     Ultrasonic Extraction
            Method 3580A;     Haste Dilution
            Method 5030A:     Purge-and-Trap
            Method 5040A:     Analysis of Sorbent  Cartridges from Volatile  Organic
                              Sampling  Train   (VOST):     Gas   Chromatography/Mass
                              Spectrometry Technique
            Method 5041:      Protocol  for  Analysis  of  Sorbent  Cartridges  from
                              Volatile  Organic  Sampling  Train   (VOST):    Wide-bore
                              Capillary Column Technique
            Method 5100:      Determination  of the  Volatile Organic Concentration of
                              Waste Samples
            Method 5110:      Determination  of Organic Phase Vapor Pressure in Waste
                              Samples

            4.2.2       Cleanup

            Method 3600B:     Cleanup
            Method 3610A:     Alumina Column Cleanup
                                    CONTENTS - 4                          Revision 2
                                                                      September 1994

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      Method 3611A:
      Method
      Method
      Method
      Method
      Method
      Method
3620A;
3630B;
3640A:
3650A:
3660A:
3665:
Alumina    Column
Petroleum Wastes
Florisil Column Cleanup
Silica Gel Cleanup
Gel-Permeation Cleanup
Acid-Base Partition Cleanup
Sulfur Cleanup
Sulfuric Acid/Permanganate Cleanup
                                Cleanup    and    Separation    of
4.3   Determination of Organic Analytes
      4.3.1
     Gas Chromatographic Methods
      Method 8000A:
      Method 801OB:
      Method 8011:

      Method 8015A:
      Method 8020A:
      Method 8021A:
      Method 8030A:
      Method 8031:
      Method 8032:
      Method 8040A:
      Method 8060:
      Method 8061:

      Method 8070:
      Method 8080A:

      Method 8081:

      Method 8090:
      Method 8100:
      Method 8110:
      Method 8120A:
      Method 8121:

      Method 8140:
      Method 8141A;

      Method 8150B:
      Method 8151:
           Gas Chromatography
           Halogenated Volatile Organics by Gas Chromatography
           1,2-Dibromoethane  and  l»2-Dibromo-3-chloropropane  by
           Microextraction and Gas Chromatography
           Nonhalogenated Volatile Organics by Gas Chromatography
           Aromatic Volatile Organics by Gas Chromatography
           Halogenated  Volatiles  by  Gas  Chromatography  Using
           Photoionization and Electrolytic Conductivity Detectors
           in Series: Capillary Column Technique
           Acrolein and Acrylonitrile by Gas Chromitography
           Acrylonitrile by Gas Chromatography
           Acrylamide by Gas Chromatography
           Phenols by Gas Chromatography
           Phthalate Esters
           Phthalate Esters by Capillary  Gas Chromatography with
           Electron Capture Detection (GC/ECD)
           Nitrosamines by Gas Chromatography
           Organochlorine Pesticides and Polychlorinated Biphenyls
           by Gas Chromatography
           Organochlorine Pesticides and  PCBs  as Aroclors by Gas
           Chromatography:  Capillary Column Technique
           Nitroaromatics and Cyclic Ketones
           Polynuclear Aromatic Hydrocirbons
           Haloethers by Gas Chromatography
           Chlorinated Hydrocarbons by Gas Chromatography
           Chlorinated   Hydrocarbons  by  Gas   Chromatography:
           Capillary Column Technique
           Organophosphorus Pesticides
           Organophosphorus  Compounds  by   Gas  Chromatography:
           Capillary Column Technique
           Chlorinated Herbicides by Gas Chromatography
           Chlorinated  Herbicides  by  GC Using Methylation  or
           PentafluorobenzylationDerivatization: Capillary Column
           Technique
                              CONTENTS - 5
                                                       Revision 2
                                                   September 1994

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4.3.2
            Gas Chromatographic/Mass Spectroscopic Methods
Method 8240B:

Method 8250A:

Method 8260A:

Method 8270B:


Method 8280:

      Appendix A:
      Appendix B:

Method 8290:



      Appendix A:
                                                                    Gas
Volatile Organic Compounds by  Gas  Chromatography/Mass
Spectrometry (GC/MS)
Semivolatile     Organic    Compounds    by
Chromatograph. 'Mass Spectroraetry (GC/MS)
Volatile Organic Compounds by  Gas  Chroraatography/Mass
Spectrometry (GC/MS):  Capillary Column  Technique
Semivolatile     Organic    Compounds    by    Gas
Chromatography/Mass  Spectrometry  (GC/MS):   Capillary
Column Technique
The Analysis of Polychlorinated  Dibenzo-p-Dioxins
Polychlorinated Dibenzofurans
      Signal-to-No1se Determination Methods
      Recommended  Safety  and Handling  Procedures
      PCDDs/PCDFs
Polychlorinated    Dibenzodioxins    (PCDDs)
Polychlorinated Dibenzofurans (PCDFs) by High-Resolution
Gas  Chromatography/High-Resolution  Mass  Spectroraetry
(HRGC/HRMS)
      Procedures   for   the    Collection,    Handling,
      Analysis,  and Reporting of Wipe  Tests  Performed
      within the Laboratory
                                                                     and
                                                                     for

                                                                     and
4.3.3

Method 8310:
Method 8315:
      Appendix A:

Method 8316:

Method 8318:

Method 8321:


Method 8330:

Method 8331:
            High Performance Liquid Chromatographic Methods
                  Polynuclear Aromatic Hydrocarbons
                  Determination of Carbonyl Compounds by High Performance
                  Liquid Chromatography (HPLC)
                        Recrystallization  of  2,4-Dinitrophenylhydrazine
                        (DNPH)
                  Acrylamide,   Acrylonitrile   and  Acrolein   by   High
                  Performance Liquid  Chromatography  (HPLC)
                  N-Methylcarbamates    by   High    Performance    Liquid
                  Chromatography (HPLC)
                  Solvent  Extractable Non-Volatile  Compounds  by  High
                  Performance   Liquid   Chromatography/Thermospray/Mass
                  Spectrometry (HPLC/TSP/MS) or Ultraviolet (UV) Detection
                  Nitroaromatics and Nitramines by High Performance Liquid
                  Chromatography (HPLC)
                  Tetrazene  by Reverse  Phase High  Performance  Liquid
                  Chromatography (HPLC)
4.3.4

Method 8410:
            Fourier Transform Infrared Methods

                  Gas Chromatography/Fourier Transform Infrared (GC/FT-IR)
                  Spectrometry  for  Semi volatile  Organics:    Capillary
                  Column
                        CONTENTS - 6
                                                              Revision  2
                                                          September  1994

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      4.4   Miscellaneous Screening Methods

            Method 3810:      Headspace
            Method 3820:      Hexadecane  Extraction  and  Screening   of  Purgeable
                              Organics
            Method 4010:      Screening for Pentachlorophenol  by Immunoassay
            Method 8275:      Thermal  Chromatography/Mass  Spectrometry  (TC/MS)  for
                              Screening Semi volatile Organic  Compounds

APPENDIX -- COMPANY REFERENCES
        NOTE;  A  suffix of "A" in the method number indicates  revision  one
        (the method has been  revised  once).   A suffix of "B" in the  method
        number indicates revision two  (the method has been revised twice). In
        order to properly  document the method used for analysis, the  entire
        method number including the suffixletterdesignation  (e.g., A or B)
        must be identified by  the analyst.  A method reference  found  within
        the  RCRA  regulations  and the text of  SW-846  methods  and chapters
        refers to the latest promulgated revision of  the  method, even  though
        the method number does not include the appropriate letter suffix.
                                    CONTENTS -  7                           Revision 2
                                                                      September 1994

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                         VOLUME ONE

                          SECTION C
                                                                     UV)
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE

CHAPTER ONE. REPRINTED — QUALITY CONTROL

      1.0   Introduction
      2.0   QA Project Plan
      3,0   Field Operations
      4,0   Laboratory Operations
      5,0   Definitions
      6.0   References

CHAPTER FIVE — MISCELLANEOUS TEST METHODS

            Method SOSO:      Bomb Preparation Method for Solid Waste
            Method 9010A:     Total and Amenable Cyanide (Colorimetric, Manual)
            Method 9012:      Total and Amenable Cyanide  (Colorimetric, Automated
            Method 9013:      Cyanide Extraction Procedure for Solids and Oils
            Method 9020B:     Total Organic Hal ides (TOX)
            Method 9021:      Purgeable Organic Hal ides  (POX)
            Method 9022:      Total  Organic  Hal ides   (TOX)  by  Neutron  Activation
                              Analysis
                              Acid-Soluble and Acid-Insoluble Sulfides
                              Extractable Sulfides
                              Sulfate (Colorimetric, Automated,
                              Sulfate (Colorimetric, Automated,
                              II)
            Method 9038:      Sulfate (Turbidimetric)
            Method 90S6:      Determination of Inorganic  Anions by Ion Chromatography
            Method 9060:      Total Organic Carbon
            Method 906S:      Phenolics   (Spectrophotometric,
                              Distillation)
                              Phenolics    (Col orimetric,   Automated
                              Distillation)
            Method 9067:      Phenolics (Spectrophotometric,  MBTH with Distillation)
            Method 9070:      Total Recoverable Oil & Grease  (Gravimetric, Separatory
                              Funnel Extraction)
            Method 9071A:     Oil and firease Extraction Method for Sludge and Sediment
                              Samples
            Method 9075:      Test Method for Total Chlorine in New and Used Petroleum
                              Products by X-Ray Fluore-cence Spectrometry (XRF)
            Method 9076:      Test Method for Total Ch   -ine in New and Used Petroleum
                              Products by Oxidative Combustion and Microcoulometry
Method 9030A:
Method 9031:
Method 903S:
Method 9036:
Method 9066:
 Chioranilate)
Methylthymol Blue, AA
                                                    Manual   4-AAP  with
        4-AAP    with
                        CONTENTS - 8
                                                                          Revision 2
                                                                      September 1994

-------
            Method 9077:

                  Method A:
                  Method B:

                  Method C:
            Method 9131;
            Method 9132:
            Method 9200;
            Method 9250:
            Method 9251:
            Method 9252A:
            Method 9253:
            Method 9320:

CHAPTER SIX -- PROPERTIES

            Method 1312:
            Method 1320:
            Method 1330A:
            Method 9040A:
            Method 9041A:
            Method 90451:
            Method 9050:
            Method 9080:
            Method 9081:
            Method 9090A:
            Method 9095:
            Method 9096:
                  Appendix A:
            Method 9100:

            Method 9310:
            Method 9315:
                              Test  Methods  for  Total  Chlorine  in  New  and  Used
                              Petroleum  Products  (Field Test  Kit Methods)
                                    Fixed  End  Point Test Kit  Method
                                    Reverse Titration Quantitative End Point Test Kit
                                    Method
                              Direct Titration Quantitative End Point Test Kit Method
                              Total Coliform:  Multiple Tube  Fermentation  Technique
                              Total Coliform:  Membrane Filter  Technique
                              Nitrate
                              Chloride (Colorimetric, Automated Ferricyanide  AAI)
                              Chloride (Colorimetric, Automated Ferricyanide  AAII)
                              Chloride (Titrimetric, Mercuric Nitrate)
                              Chloride (Titrimetric, Silver Nitrate)
                              Radium-228
                              Synthetic Precipitation Leaching Procedure
                              Multiple Extraction Procedure
                              Extraction Procedure for Oily Wastes
                              pH Electrometric Measurement
                              pH Paper Method
                              Soil and Waste pH
                              Specific Conductance
                              Cation-Exchange Capacity of Soils  (Ammonium Acetate)
                              Cation-Exchange Capacity of Soils  (Sodium Acetate)
                              Compatibility Test for Wastes and  Herabrane Liners
                              Paint Filter Liquids Test
                              Liquid Release Test (LRT) Procedure
                                    LRT Pre-Test
                              Saturated  Hydraulic  Conductivity,  Saturated Leachate
                              Conductivity, and Intrinsic Permeability
                              Gross Alpha and Gross Beta
                              Alpha-Emitting Radium Isotopes
                              PART II    CHARACTERISTICS

CHAPTER SEVEN -- INTRODUCTION AND REGULATORY DEFINITIONS

      7.1   Ignitability
      7.2   Corrosivity
      7.3   Reactivity

            Test Method to Determine Hydrogen Cyanide Released from Wastes
            Test Method to Determine Hydrogen Sulfide Released from Wastes

      7.4   Toxicity Characteristic Leaching Procedure
                                    CONTENTS - 9
                                                                          Revision 2
                                                                      September 1994

-------
CHAPTER EIGHT -- METHODS FOR DETERMININGCHARACTERISTICS

      8.1   Ignitability

            Method 1010:

            Method 1020A;

      8.2   Corrosivity

            Method 1110:
      8.3
      8.4
                  Pensky-Martens   Closed-Cup   Method   for  Determining
                  Ignilability
                  Setaflash Closed-Cup Method for Determining Ignitability
                  Corrosivity Toward Steel
Reactivity
Toxicity
            Method 1310A:

            Method 1311:

APPENDIX — COMPANY REFERENCES
                  Extraction  Procedure  (EP)  Toxicity  Test  Method  and
                  Structural Integrity Test
                  Toxicity Characteristic Leaching Procedure
        NOTE;  A  suffix  of "A* in the method number  indicates  revision  one
        (the method has  been  revised once).   A suffix of  "B" in the  method
        number indicates revision two (the method has been revised twice). In
        order to properly  document the method used  for  analysis, the  entire
        method number including the suffix letter designation (e.g., A or B)
        must be identified by the analyst.  A method  reference  found  within
        the  RCRA  regulations  and the text of  SW-846 methods  and  chapters
        refers to the latest promulgated revision of the method, even  though
        the method number does not include the appropriate letter suffix.
                                    CONTENTS  -  10
                                                              Revision 2
                                                          September 1994

-------
                                     VOLUME  TWO
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
CHAPTER ONE. REPRINTED - QUALITY CONTROL

      1.0   Introduction
      2.0   QA Project Plan
      3.0   Field Operations
      4.0   Laboratory Operations
      5.0   Definitions
      6.0   References
                                 PART III    SAMPLING

CHAPTER NINE -- SAMPLING PLAN

      9.1   Design and Development
      9.2   Implementation

CHAPTER TEN - SAMPLING HETHODS

            Method 0010:      Modified Method 5 Sampling Train
                  Appendix A:       Preparation of XAD-2 Sorbent Resin
                  Appendix B;       Total  Chromatographable Organic Material Analysis
            Method 0020;      Source Assessment Sampling System (SASS)
            Method 0030:      Volatile Organic Sampling Train
                                PART IV   MONITORING

CHAPTER ELEVEN -- GROUND MATER MONITORING

      11.1  Background and Objectives
      11.2  Relationship to the Regulations and to Other Documents
      11.3  Revisions and Additions
      11.4  Acceptable Designs and Practices
      11.5  Unacceptable Designs and Practices


CHAPTER TWELVE -- LAND TREATMENT MONITORING

      12.1  Background
      12.2  Treatment Zone
      12.3  Regulatory Definition
                                    CONTENTS  -  11                          Revision 2
                                                                      September 1994

-------
      12.4  Monitoring and Sampling Strategy
      12.5  Analysis
      12.6  References and Bibliography

CHAPTER THIRTEEN - INCINERATION

      13.1  Introduction
      13.2  Regulatory Definition
      13.3  Waste Characterization Strategy
      13.4  Stack-Gas Effluent Characterization Strategy
      13.5  Additional Effluent Characterization Strategy
      13.6  Selection of Specific Sampling and Analysis Methods
      13.7  References

APPENDIX — COMPANY REFERENCES
        NOTE;  A  suffix of "A" in the method  number  indicates  revision  one
        (the method has been  revised once).   A suffix of  "B"  in  the  method
        number indicates revision two (the method has been revised twice). In
        order to properly  document the method  used  for  analysis,  the  entire
        method number including the suffix 1 etter designation (e.g.f A or B)
        must be Identified by the analyst.   A  method  reference found  within
        the  RCRA  regulations  and the text  of SW-846 methods  and  chapters
        refers to the latest promulgated revision of the method, even  though
        the method number  does not include the appropriate letter suffix.
                                    CONTENTS  -  12                          Revision 2
                                                                      September 1994

-------

-------
SH-846 METHOD STATUS TABLE
      September 1994
NETH NO.
THIRD ED
DATED
9/86
0010
0020
0030
1010
1020
1110
1310
"

NETH NO.
FINAL
UPDATE I
DATED
7/92
"
** *"•

"** ™"
1020A
"
1310A
1311

NETH NO.
FINAL
UPDT. II
DATED
9/94
"


*•> mt
* "
"

"
1312
METHOD TITLE
Modified Method 5
Sampling Train
Source Assessment
Sampling System
(SASS)
Volatile Organic
Sampling Train
Pensky-Mirtens
Closed-Cup Method
for Determining
Ignitability
Setaflash Closed-Cup
Method for
Determining
Igni lability
Corrosivity Toward
Steel
Extraction Procedure
(EP) Toxicity Test
Method and
Structural Integrity
Test
Toxicity
Characteristic
Leaching Procedure
Synthetic
Precipitation
Leaching Procedure
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol I!
Chap 10
Vol II
Chap 10
Vol II
Chap 10
Vol 1C
Chap 8
Sec 8.1
Vol 1C
Chap 8
Sec 8.1
Vol 1C
Chap 8
Sec 8.2
Vol 1C
Chap 8
Sec 8.4
Vol 1C
Chap 8
Sec 8.4
Vol 1C
Chap 6
CURRENT
PROMUL-
GATED
METHOD
0010
Rev 0
9/86
0020
Rev 0
9/86
0030
Rev 0
9/86
1010
Rev 0
9/86
1020A
Rev 1
7/92
1110
Rev 0
9/86
1310A
Rev 1
7/92
1311
Rev 0
7/92
1312
Rev 0
9/94

-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
HETH MO.
THIRD ED
DATED
9/86
1320
1330
3005
3010
"" ""
3020
3040
3050
HETH NO.
FINAL
UPDATE I
DATED
7/92
"
1330A
3005A
3010A
4* -m
3020A
"" ""
3050A
METH NO.
FINAL
UPDT. II
DATED
9/94
"
"


3015

""" """

METHOD TITLE
Multiple Extraction
Procedure
Extraction Procedure
for Oily Wastes
Acid Digestion of
Waters for Total
Recoverable or
Dissolved Metals for
Analysis by FLAA or
ICP Spectroscopy
Acid Digestion of
Aqueous Samples and
Extracts for Total
Metals for Analysis
by FLAA or ICP
Spectroscopy
Microwave Assisted
Acid Digestion of
Aqueous Samples and
Extracts
Acid Digestion of
Aqueous Samples and
Extracts for Total
Metals for Analysis
by GFAA Spectroscopy
Dissolution
Procedure for Oils,
Greases, or Waxes
Acid Digestion of
Sediments, Sludges,
and Soils
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
CURRENT
PROMUL-
GATED
METHOD
1320
Rev 0
9/86
1330A
Rev 1
7/92
3005A
Rev 1
7/92
3010A
Rev 1
7/92
3015
Rev 0
9/94
3020A
Rev 1
7/92
3040
Rev 0
9/86
3050A
Rev 1
7/92

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
NETH NO.
THIRD ED
DATED
9/86
«K -m
3500
3510
3520
3540
** «
3550
3580
3600
METH NO.
FINAL
UPDATE I
DATED
7/92
** mm
3500A
3510A
3520A
3540A
*~ """
"
3580A
3600A
NETH NO.
FINAL
UPDT. II
DATED
9/94
3051
— »
3510B
3520B
3540B
3541
3550A

3600B
METHOD TITLE
Microwave Assisted
Acid Digestion of
Sediments, Sludges,
Soils, and Oils
Organic Extraction
and Sample
Preparation
Separatory Funnel
Liquid-Liquid
Extraction
Continuous Liquid-
Liquid Extraction
Soxhlet Extraction
Automated Soxhlet
Extraction
Ultrasonic Extrac-
tion
Waste Dilution
Cleanup
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.2
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.2
CURRENT
PROMUL-
GATED
METHOD
3051
Rev 0
9/94
3500A
Rev 1
J7/92
3510B
Rev 2
9/94
3520B
Rev 2
9/94
3540B
Rev 2
9/94
3541
Rev 0
9/94
3550A
Rev 1
9/94
3580A
Rev 1
7/92
3600B
Rev 2
9/94

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
3610
3611
3620
3630
3640
3650
3660
«* *»
3810
METH NO.
FINAL
UPDATE I
DATED
7/92
3610A
361 1A
3620A
3630A
'"" '"*
3650A
3660A


METH NO.
FINAL
UPDT. II
DATED
9/94
«* «•>,
"" "™
•H *•>
3630B
3640A
™* ""
*. *.
3665

METHOD TITLE
Alumina Column
Cleanup
Alumina Column
Cleanup and
Separation of
Petrol eui Wastes
Florisil Column
Cleanup
Silica Gel Cleanup
Gel -Permeation
Cleanup
Acid-Base Partition
Cleanup
Sulfur Cleanup
Sulfuric
Acid/Permanganate
Cleanup
Headspace
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec 4.4
CURRENT
PROMUL-
GATED
METHOD
3610A
Rev 1
7/92
3611A
Rev 1
7/92
3620A
Rev 1
7/92
3630B
Rev 2
9/94
3640A
Rev 1
9/94
3650A
Rev 1
7/92
3660A
Rev 1
7/92
3665
Rev 0
9/94
3810
Rev 0
9/86

-------
SW-846 METHOD STATUS TABLE (9/94),  CONTINUED
NETH NO.
THIRD ED
DATED
9/86
3820

5030
5040

«. i.
6010
NETH NO.
FINAL
UPDATI I
DATED
7/9Z
"

5030A


™" ™
601 OA
NETH NO.
FINAL
UPDT. II
DATED
9/94
"
4010
(Update
IIA,
dated
8/93)
*• **
5040A
5041
5050
"
NETHOD TITLE
Hexadecane
Extraction and
Screening of
Purgeable Organics
Screening for
Pentachl orophenol
by Immunoassay
Purge-and-Trap
Analysis of Sorbent
Cartridges from
Volatile Organic
Sampling Train
(VOST): Gas
Ch romat ography/Has s
Spectrometry
Technique
Protocol for
Analysis of Sorbent
Cartridges from
Volatile Organic
Sampling Train
(VOST) : Wide -bore
Capillary Column
Technique
Bomb Preparation
Hethod for Solid
Waste
Inductively Coupled
Plasma-Atomic
Emission
Spectroscopy
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec 4.4
Vol IB
Chap 4
Sec 4.4
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4,2.1
Vol IB
Chap 4
Sec
4.2.1
Vol 1C
Chap 5
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
3820
Rev 0
9/86
4010
Rev 0
8/93
503 OA
Rev 1
7/92
5040A
Rev 1
9/94
5041
Rev 0
9/94
5050
Rev 0
9/94
6010A
Rev 1
7/92

-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
"
7000
7020
7040
7041
7060
7061
<•* «•
7080
METH NO.
FINAL
UPDATE I
DATED
7/92
"
7000A
•H w.
W —
"™ ~"
"
7061A
«. «~

HETH NO.
FINAL
UPDT. II
DATED
9/94
6020
"
mm mm
— ~
"" ""
7060A
"
7062
7080A
METHOD TITLE
Inductively Coupled
Plasma - Mass
Spectrometry
Atomic Absorption
Methods
Aluminum (Atomic
Absorption, Direct
Aspiration)
Antimony (Atomic
Absorption, Direct
Aspiration)
Antimony (Atomic
Absorption, Furnace
Technique)
Arsenic (Atomic
Absorption, Furnace
Technique)
Arsenic (Atomic
Absorption, Gaseous
Hydride)
Antimony and Arsenic
(Atomic Absorption,
Borohydride
Reduction)
Barium (Atomic
Absorption, Direct
Aspiration)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
6020
Rev 0
9/94
7000A
Rev 1
7/92
7020
Rev 0
9/86
7040
Rev 0
9/86
7041
Rev 0
9/86
7060A
Rev 1
9/94
7061A
Rev 1
7/92
7062
Rev 0
9/94
7080A
Rev 1
9/94

-------
SH-846 METHOD STATUS TABLE (9/94),  COKTINUED
KETH NO.
THIRD ED
DATED
9/86
"
7090
7091
7130
7131
7140
7190
7191
7195
HETH NO.
FINAL
UPDATE I
DATED
7/92
7081
"M "*
*" — •
*" *"
*"" """
**. _
™" ""
"™ ""*
"
HETH NO.
FINAL
UPDT. II
DATED
9/94
•m mm
•mm —
<** «••
"* ""
7131A
**• """
_ «
*"" ™*

METHOD TITLE
Barium (Atomic
Absorption, Furnace
Technique)
Beryllium {Atomic
Absorption, Direct
Aspiration)
Beryllium {Atomic
Absorption, Furnace
Technique)
Cadmium (Atomic
Absorption, Direct
Aspiration)
Cadmium (Atomic
Absorption, Furnace
Technique)
Calcium (Atomic
Absorption, Direct
Aspiration)
Chromium (Atomic
Absorption, Direct
Aspiration)
Chromium (Atomic
Absorption, Furnace
Technique)
Chromium, Hexavalent
(Coprecipitation)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3,3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3,3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7081
Rev 0
7/92
7090
Rev 0
9/86
7091
Rev 0
9/86
7130
Rev 0
9/86
7131A
Rev 1
9/94
7140
Rev 0
9/86
7190
Rev 0
9/86
7191
Rev 0
9/86
7195
Rev 0
9/86

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
7196
7197
7198
7200
7201
7210
""" *"
7380

METH NO.
FINAL
UPDATE I
DATED
7/92
7196A
** ""
"
"


7211
mm «•
7381
HETH NO.
FINAL
UPDT, II
DATED
S/94
-— -»
*" *"
"
"
•* w
** *"
"
"*° "™"
"
METHOD TITLE
Chromium, Hexavalent
(Colorimetric)
Chromium, Hexavalent
(Chel at ion/Extrac-
tion)
Chromium, Hexavalent
(Differential Pulse
Polarography)
Cobalt (Atonic
Absorption, Direct
Aspiration)
Cobalt (Atonic
Absorption, Furnace
Technique)
Copper (Atomic
Absorption, Direct
Aspiration)
Copper (Atonic
Absorption, Furnace
Technique)
Iron (Atomic
Absorption, Direct
Aspiration)
Iron (Atomic
Absorption, Furnace
Technique)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7196A
Rev 1
7/92
7197
Rev 0
9/86
7198
Rev 0
9/86
7200
Rev 0
9/86
7201
Rev 0
9/86
7210
Rev 0
9/86
7211
Rev 0
7/92
7380
Rev 0
9/86
7381
Rev 0
7/92

-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
HETH NO.
THIRD ED
DATED
9/86
7420
7421
™" "~
7450
7460

7470
7471
7480
HETH NO.
FINAL
UPDATE I
DATED
7/92
_ _•
•" **
7430
*" "**
»_ «
7461
™" ™"
""" "°*
"
METH NO.
FINAL
UPDT. II
DATED
9/94
** ™"
"" **
*"" **

_ _.
"
7470A
7471A
"
NETHOD TITLE
Lead {Atomic
Absorption, Direct
Aspiration)
Lead (Atomic
Absorption, Furnace
Technique)
Lithium (Atomic
Absorption, Direct
Aspiration)
Magnesium (Atomic
Absorption, Direct
Aspiration)
Manganese (Atomic
Absorption, Direct
Aspiration)
Manganese (Atomic
Absorption, Furnace
Technique)
Mercury in Liquid
Waste (Manual Cold-
Vapor Technique)
Mercury in Solid or
Semi sol id Waste
(Manual Cold- Vapor
Technique)
Molybdenum (Atomic
Absorption, Direct
Aspiration)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3,3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7420
Rev 0
9/86
7421
Rev 0
9/86
7430
Rev 0
7/92
7450
Rev 0
9/86
7460
Rev 0
9/86
7461
Rev 0
7/92
7470A
Rev 1
9/94
7471A
Rev 1
9/94
7480
Rev 0
9/86

-------
SM-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO*
THIRD ED
DATED
9/86
7481
7520
7550
7610
7740
7741
«. —
7760
™ "
METH NO.
FINAL
UPDATE I
DATED
7/92

m* HP
"" "~
_ —
*" "
~ "•
H* «*•
7760A
7761
METH NO.
FINAL
UPDT. II
DATED
9/94
"
~" *"
™* "°*
*** "*"
<•» <•»
7741A
7742
"
^ ^
METHOD TITLE
Molybdenum {Atomic
Absorption, Furnace
Technique)
Nickel (Atomic
Absorption, Direct
Aspiration)
Osmium (Atomic
Absorption, Direct
Aspiration)
Potassium (Atomic
Absorption, Direct
Aspiration)
Selenium (Atomic
Absorption, Furnace
Technique)
Selenium (Atomic
Absorption, Gaseous
Hydride)
Selenium (Atomic
Absorption,
Borohydride
Reduction)
Silver (Atomic
Absorption, Direct
Aspiration)
Silver (Atomic
Absorption, Furnace
Technique)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol 1A
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7481
Rev 0
9/86
7520
Rev 0
9/86
7550
Rev 0
9/86
7610
Rev 0
9/86
7740
Rev 0
9/86
7741A
Rev 1
9/94
7742
Rev 0
9/94
7760A
Rev 1
7/92
7761
Rev 0
7/92
                                      10

-------
SW-846 METHOD STATUS TABLE (9/94)t CONTINUED
HETH NO.
THIRD ED
DATED
9/86
7770
*** ***
7840
7841
7870
7910
7911
7950
"
HETH NO.
FINAL
UPDATE I
DATED
7/92
"
7780
** **•

"
"" ""

** *"*
7951
HETH NO.
FINAL
UPDT. II
DATED
9/94
™ —
™" ""*
** **•

"
*"* *"


"
METHOD TITLE
Sodium (Atomic
Absorption, Direct
Aspiration)
Strontium (Atomic
Absorption, Direct
Aspiration)
Thallium (Atomic
Absorption, Direct
Aspiration)
Thallium (Atomic
Absorption, Furnace
Technique)
Tin (Atomic
Absorption, Direct
Aspiration)
Vanadium (Atomic
Absorption, Direct
Aspiration)
Vanadium (Atomic
Absorption, Furnace
Technique)
Zinc (Atomic
Absorption, Direct
Aspiration)
Zinc (Atomic
Absorption, Furnace
Technique)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3,3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7770
Rev 0
9/86
7780
Rev 0
7/92
7840
Rev 0
9/86
7841
Rev 0
9/86
7870
Rev 0
9/86
7910
Rev 0
9/86
7911
Rev 0
9/86
7950
Rev 0
9/86
7951
Rev 0
7/92
                                      11

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
8000
8010

8015
8020

8030

METH NO.
FINAL
UPDATE I
DATED
7/92
8000A
8010A
8011
801 5A
mm, mm.
8021
8030A

METH NO.
FINAL
UPDT. II
DATED
9/94
** "*
8010B


8020A
8021A
"
8031
METHOD TITLE
Gas Chromatography
Halogenated Volatile
Organics by Gas
Chromatography
1 , 2-Di bromoethane
and l,2-Dibr0mo-3-
chloropropane by
Microextraction and
Gas Chroraatography
Nonhal ogenated
Volatile Organics by
Gas Chromatography
Aromatic Volatile
Organics by Gas
Chromatography
Halogenated
Volatiles by Gas
Chromatography Using
Photoionization and
Electrolytic
Conductivity
Detectors in Series:
Capillary Column
Technique
Acrolein and
Acrylonitrile by Gas
Chromatography
Acrylonitrile by Gas
Chromatography
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3,1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
CURRENT
PROMUL-
GATED
METHOD
8000A
Rev 1
7/92
8010B
Rev 2
9/94
8011
Rev 0
7/92
8015A
Rev 1
7/92
8020A
Rev 1
9/94
8021A
Rev 1
9/94
8030A
Rev 1
7/92
8031
Rev 0
9/94
                                      12

-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
~ ™
8040
8060

» •*
8080

8090
METH NO.
FINAL
UPDATE I
DATED
7/92
~ —
8040A
«* «*

8070


~ ~
HETH NO.
FINAL
UPDT. II
DATED
9/94
8032
"
"
8061
"
8080A
8081

METHOD TITLE
Acryl amide by Gas
Chromatography
Phenols by Gas
Chromatography
Phthalate Esters
Phthalate Esters by
Capillary Gas
Chromatography with
Electron Capture
Detection (6C/ECD)
Nitros amines by Gas
Chromatography
Organochlorine Pes-
ticides and
Polychlorinated
Biphenyls by Gas
Chromatography
Organochlorine
Pesticides and PCBs
as Aroclors by Gas
Chromatography:
Capillary Column
Technique
Nitroaromatics and
Cyclic Ketones
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3,1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4,3.1
Vol IB
Chap 4
Sec
4.3.1
CURRENT
PROMUL-
GATED
METHOD
8032
Rev 0
9/94
8040A
Rev 1
7/92
8060
Rev 0
9/86
8061
Rev 0
9/94
8070
Rev 0
7/92
8080A
Rev 1
9/94
8081
Rev 0
9/94
8090
Rev 0
9/86
                                      13

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
8100
"" ""
8120

8140

8150

NETH NO.
FINAL
UPDATE I
DATED
7/92
*"* *"*
8110
w <«*

™ ™
8141
81 BOA

HETH NO.
FINAL
UPDT. II
DATED
9/94
"* """
"
8120A
8121
~* ™
8141A
81506
8151
METHOD TITLE
Polynuclear Aromatic
Hydrocarbons
Haloethers by Gas
Chroiatography
Chlorinated
Hydrocarbons by Gas
Chromatography
Chlorinated
Hydrocarbons by Gas
Chromatography:
Capillary Column
Technique
Organophosphorus
Pesticides
Organophosphorus
Compounds by Gas
Chromatography:
Capillary Column
Technique
Chlorinated
Herbicides by Gas
Chromatography
Chlorinated
Herbicides by GC
Using Methyl at ion or
Ptntaf 1 uorobenzyl -
atlon Derivati-
zation: Capillary
Column Technique
SN-S46
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4,3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
CURRENT
PROMUL-
GATED
METHOD
8100
Rev 0
9/86
8110
Rev 0
7/92
8120A
Rev 1
9/94
8121
Rev 0
9/94
8140
Rev 0
9/86
8141A
Rev 1
9/94
8150B
Rev 2
9/94
8151
Rev 0
9/94
                                      14

-------
SH-646 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
8240
8250

8270

8280
HETH NO.
FINAL
UPDATE I
DATED
7/92
8240A

8260
8270A


METH NO.
FINAL
UPDT. II
DATED
9/94
8240B
8250A
8260A
8270B
8275

METHOD TITLE
Volatile Organic
Compounds by Gas
Chromatography/Mass
Spectrometry {GC/MS)
Semi volatile Organic
Compounds
by Gas
Chromatography/Mass
Spectroraetry { GC/MS }
Volatile Organic
Compounds by Gas
Chromatography/Mass
Spectroraetry
(GC/MS): Capillary
Column Technique
Serai volatile Organic
Compounds by Gas
Chroraatography/Mass
Spectroraetry
(GC/MS): Capillary
Column Technique
Thermal
Chromatography/Mass
Spectrometry (TC/MS)
for Screening
Serai volatile Organic
Compounds
The Analysis of
Polychlorinated
Dibenzo-p-Dioxins
and Polychlorinated
Dibenzofurans
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec 4.4
Vol IB
Chap 4
Sec
4.3.2
CURRENT
PROMUL-
GATED
METHOD
8240B
Rev 2
9/94
8250A
Rev 1
9/94
8260A
Rev 1
9/94
8270B
Rev 2
9/94
8275
Rev 0
9/94
8280
Rev 0
9/86
                                      15

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
NETHNO.
THIRD ED
DATED
9/86

8310


"
METH NO.
FINAL
UPDATE I
DATED
7/92

«* «*



METH NO.
FINAL
UPDT, II
DATED
9/94
8290
 mm
8315
8316
8318
METHOD TITLE
Polychlorinated
Dibenzod toxins
(PCDDs) and
Polyehlorinated
Dibenzofurans
(PCDFs) by High-
Resolution Gas
Chromatography/HI gh-
Resolution Mass
Spectrometry
(HRGC/HRMS)
Polynuclear Aromatic
Hydrocarbons
Determination of
Carbonyl Compounds
by High Performance
Liquid
Chromatography
(HPLC)
Acryl amide,
Acrylonitrile and
Acrolein by High
Performance Liquid
Chrotnatography
(HPLC)
N-Methyl carbamates
by High Performance
Liquid Chroma-
tography (HPLC)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
CURRENT
PROMUL-
GATED
METHOD
8290
Rev 0
9/94
8310
Rev 0
9/86
8315
Rev 0
9/94
8316
Rev 0
9/94
8318
Rev 0
9/94
                                      16

-------
SH-846 METHOD STATUS TABLE (9/94)f CONTINUED
HETH NO.
THIRD ED
DATED
9/86




9010
9012
METH NO.
FINAL
UPDATE I
DATED
7/92




9010A

HETH NO.
FINAL
UPDT. II
DATED
9/94
8321
8330
8331
8410
"

METHOD TITLE
Solvent Extractable
Non-Volatile
Compounds by High
Performance Liquid
Chromatography/Ther-
mo spray/Mass
Spectrometry
(HPLC/TSP/MS) or
Ultraviolet (UV)
Detection
Nitroaromatics and
Nitramines by High
Performance Liquid
Chroraatography
(HPLC)
Tetrazene by Reverse
Phase High
Performance Liquid
Chromatography
(HPLC)
Gas Chroroa-
tography/Fouri er
Transform Infrared
(EC/FT- IR) Spec-
trometry for
Semi volatile
Organ ics: Capillary
Column
Total and Amenable
Cyanide
(Colorimetric,
Manual)
Total and Amenable
Cyanide
(Colorimetric,
Automated UV)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.4
Vol 1C
Chap 5
Vol 1C
Chap 5
CURRENT
PROMUL-
GATED
METHOD
8321
Rev 0
9/94
8330
Rev 0
9/94
8331
Rev 0
9/94
8410
Rev 0
9/94
9010A
Rev 1
7/92
9012
Rev 0
9/86
                                      17

-------
SW-846 METHOD STATUS TABLE (9/94),  CONTINUED
METH NO.
THIRD ED
DATED
9/86
«H *»
9020
mm w
9022
9030
"* ™*
9035
9036
9038
METH NO.
FINAL
UPDATE I
DATED
7/92
9013
9020A
9021

9030A
9031
•V K


METH NO.
FINAL
UPDT. II
DATED
9/94
*"" *"
9020B
•» *»
"
_ _
~ ~
« »


METHOD TITLE
Cyanide Extraction
Procedure for Solids
and Oils
Total Organic
Hal ides (TOX)
Purgeable Organic
Hal ides (POX)
Total Organic
Hal ides (TOX) by
Neutron Activation
Analysis
Acid-Soluble and
Acid- Insoluble
Sul fides
Extractable Syl fides
Sul fate
{Colorimetric,
Automated ,
Chi orani late)
Sul fate
(Colorimetric,
Automated,
Methyl thymol Blue,
AA II)
Sul fate
(Turbidimetric)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
CURRENT
PROMUL-
GATED
METHOD
9013
Rev 0
7/92
9020B
Rev 2
9/94
9021
Rev 0
7/92
9022
Rev 0
9/86
9030A
Rev 1
7/92
9031
Rev 0
7/92
9035
Rev 0
9/86
9036
Rev 0
9/86
9038
Rev 0
9/86
                                     18

-------
SH-846 METHOD STATUS TABLE (9/94),  CONTINUED
METH NO.
THIRD ED
DATED
9/86
9040
9041
9045
9050
_ „. ,
9060
9065
9066
9067
METH NO.
FINAL
UPDATE I
DATED
7/92
"
9041A
9045A
"
un *

-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
METH HO.
THIRD ED
DATED
9/86
9070
9071



9080
9081
METH NO.
FINAL
UPDATE I
DATED
7/§2





"
"
METH NO.
FINAL
UPDT. II
DATED
9/§4

9071A
9075
9076
9077
"
"
METHOD TITLE
Total Recoverable
Oil & Grease
(Gravimetric,
Separatory Funnel
Extraction)
Oil and Grease
Extraction Method
for Sludge and
Sediment
Sampl es
Test Method for
Total Chlorine in
New and Used
Petroleum Products
by X-Ray
Fluorescence
Spectrometry (XRF)
Test Method for
Total Chlorine in
New and Used
Petroleum Products
by Oxi dative
Combustion and
MicrocouTometry
Test Methods for
Total Chlorine in
New and Used
Petroleum Products
(Field Test Kit
Methods)
Cit ion -Exchange
Capacity of Soils
(tenon i urn Acetate)
Cat ion -Exchange
Capacity of Soils
(Sodium Acetate)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 6
Vol 1C
Chap 6
CURRENT
PROMUL-
GATED
METHOD
9070
t
Rev 0
9/86
9071A
Rev 1
9/94
9075
Rev 0
9/94
9076
Rev 0
9/94
9077
Rev 0
9/94
9080
Rev 0
9/86
9081
Rev 0
9/86
                                     20

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
9090
9095
~ ™
9100
9131
9132
9200
9250
9251
METH NO.
FINAL
UPDATE I
DATED
7/92
9090A
— —
mm —

_ <•
™* "™*
"" "
* *°

METH NO.
FINAL
UPDT. II
DATED
9/94
"
"* "™
9096

~ ~
"
_ — .
*** """

METHOD TITLE
Compatibility Test
for Wastes and
Membrane Liners
Paint Filter Liquids
Test
Liquid Release Test
(LRT) Procedure
Saturated Hydraulic
Conductivity,
Saturated Leachate
Conductivity, and
Intrinsic
Permeability
Total Col i form:
Multiple Tube
Fermentation
Technique
Total Col i form:
Membrane Filter
Technique
Nitrate
Chloride
(Colorimetric,
Automated
Ferri cyanide AAI)
Chloride
(Coloriraetrie,
Automated
Ferri cyanide AAI I)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 5
Vol 1C
Chap 5
.Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
CURRENT
PROMUL-
GATED
METHOD
9090A
Rev 1
7/92
9095
Rev 0
9/86
9096
Rev 0
9/94
9100
Rev 0
9/86
9131
Rev 0
9/86
9132
Rev 0
9/86
9200
Rev 0
9/86
9250
Rev 0
9/86
9251
Rev 0
9/86
                                      21

-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
9252
™" "*
9310
9315
9320
HCN Test
Method
H2S Test
Method
KETH NO.
FINAL
UPDATE I
DATED
7/92
_ M
*" ""
*** **
** —
_ ^,
HCN Test
Method
H2S Test
Method
HETH NO.
FINAL
UPDT. II
DATED
9/94
9252A
9253
*"* **"
mm «•
*"" ""
HCN Test
Method
H2S Test
Method
METHOD TITLE
Chloride
(Titrimetric,
Mercuric Nitrate)
Chloride
(Titrimetric, Silver
Nitrate)
Gross Alpha and
Gross Beta
Alpha- Emitting
Radium Isotopes
Radium- 2 28
Test Method to
Determine Hydrogen
Cyanide Released
from Wastes
Test Method to
Determine Hydrogen
Sulfide Released
from Wastes
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 5
Vol 1C
Chap 7
Sec 7.3
Vol 1C
Chap 7
Sec 7.3
CURRENT
PROMUL-
GATED
METHOD
9252A
Rev 1
9/94
9213
Rev 0
9/94
9310
Rev 0
9/86
9315
Rev 0
9/86
9320
Rev 0
9/86
Guidance
Method
Only
Guidance
Method
Only
                                      22
       \

-------
                            PREFACE AND OVERVIEW
PURPOSE OF THE MANUAL

     Test Methods for Evaluating Solid Waste (SW-846)  1s Intended to provide a
unified, up-to-date source of Information  on sampling and analysis related to
compliance with RCRA regulations.   It  brings together Into one reference all
sampling and testing methodology approved by the Office of Solid Waste for use
1n Implementing the RCRA regulatory  program.  The manual  provides methodology
for collecting and testing representative samples of waste and other materials
to be monitored.  Aspects  of  sampling  and testing covered 1n SW-846 include
quality control, sampling  plan  development  and  Implementation, analysis of
Inorganic and  organic  constituents,  the  estimation  of  Intrinsic physical
properties, and the appraisal of waste characteristics.

     The procedures described 1n this manual are meant to be comprehensive and
detailed, coupled  with  the  realization  that  the  problems  encountered 1n
sampling and analytical situations  require  a  certain amount of flexibility.
The solutions to these problems will  depend, in part, on the skill, training,
and experience of the analyst.    For  some  situations, it 1s possible to use
this manual  1n  rote  fashion.    In  other  situations,  1t  will  require a
combination of technical abilities, using  the  manual as guidance rather than
in a step-by-step, word-by-word fashion.    Although this puts an extra burden
on the  user,  1t  1s  unavoidable  because  of  the  variety  of sampling and
analytical conditions found with hazardous wastes.
ORGANIZATION AND FORMAT


     This manual 1s divided into two  volumes.  Volume I focuses on laboratory
activities and 1s divided  for  convenience  Into  three  sections.  Volume IA
deals  with  quality  control,  selection  of  appropriate  test  methods, and
analytical methods for metallic species.    Volume  IB consists of methods for
organic  analytes.    Volume  1C  includes  a  variety  of  test  methods  for
miscellaneous  analytes  and  properties  for  use  1n  evaluating  the  waste
characteristics.  Volume II deals with sample acquisition and includes quality
control, sampling plan design and  implementation, and field sampling methods.
Included for the convenience  of  sampling  personnel  are discusssions of the
ground water, land treatment, and Incineration monitoring regulations.

     Volume I begins with an overview  of the quality control precedures to be
imposed upon the sampling and  analytical methods. The quality control chapter
(Chapter One) and the  methods  chapters  are  Interdependent.  The analytical
procedures cannot be  used  without  a  thorough  understanding of the quality
control requirements and the means to  implement them.  This understanding can
be achieved only be reviewing Chapter One and the analytical methods together.
It is expected that  Individual  laboratories,  using  SW-846 as the reference
                                 PREFACE - 1
                                                         Revision
                                                         Date  September 1986

-------
source, will  select  appropriate  methods  and  develop  a standard operating'
procedure (SOP) to be followed by  the laboratory.   The SOP should Incorporate
the pertinent Information from this  manual   adopted to the specific needs and
circumstances of the Individual laboratory as  well   as to the materials to be
evaluated.

     The method  selection  chapter  (Chapter  Two)   presents  a comprehensive
discussion of the application  of  these  methods  to  various matrices in the
determination of groups of analytes or specific analytes.  It aids the chemist
1n constructing the correct  analytical  method  from  the array of procedures
which may  cover  the  matrix/analyte/concentration  combination of interests.
The  section  discusses  the  objective   of   the  testing  program  and  Its
relationship to the choice of an analytical method.  Flow charts are presented
along with  tables  to  guide  in  the  selection  of  the  correct analytical
procedures to form the appropriate method.

     The analytical methods are  separated Into distinct procedures describing
specific,   independent  analytical  operations.    These   Include  extraction,
digestion,  cleanup, and  determination.    This  format  allows Unking of the
various steps  1n  the analysis  according   to:   the type of  sample  (e.g., water,
soil,  sludge,  still bottom),' analytes(s)  of interest; needed  sensitivity; and
available analytical instrumentation.     The chapters describing  Miscellaneous
Test Methods and   Properties,  however,   give  complete  methods  which  are not
amenable  to such  segmentation  to form  discrete procedures.

     The  Introductory material  at  the   beginning  of each  section containing
analytical   procedures    presents    information   on    sample   handling  and
preservation,  safety, and  sample preparation.

     Part   II   of  Volume    I    (Chapters   Seven  and   Eight)  describes  the
characteristics of a waste.    Sections   following the  regulatory descriptions
contain  the methods  used to  determine  if   the  waste  1s  hazardous because  it
exhibits  a  particular characteristic.

     Volume II gives background   Information on  statistical  and nonstatistical
aspects   of sampling.     It   also   presents  practical   sampling techniques
appropriate for situations presenting  a  variety  of physical  conditions.

     A discussion  of   the  regulatory  requirements  with  respect to  several
monitoring  categories is also  given   1n   this  volume.    These include ground
water  monitoring,  land   treatment,  and   incineration.     The  purpose  of  this
guidance  1s to orient the  user to  the  objective  of the  analysis,  and  to assist
In developing  data quality objectives, sampling  plans,  and laboratory SOP's.

     Significant  interferences,  or other  problems,  may   be encountered  with
certain  samples.   In these situations,  the  analyst  1s  advised to contact the
Chief,  Methods Section  (WH-562B)  Technical   Assessment  Branch, Office of  Solid
Waste,  US EPA,  Washington,   DC     20460  (202-382-4761)   for assistance.  The
manual  1s Intended to serve   all   those   with  a need to evaluate solid waste.
Your comments,  corrections,  suggestions,  and questions  concerning any material
contained in,  or  omitted  from,   this  manual  will  be  gratefully appreciated.
 Please direct  your comments  to the above address.


                                  PREFACE - 2
                                                          Revision      0
                                                          Date  September  1986

-------
                      METHOD INDEX AND CONVERSION TABLE
Method Number,
Third Edition
    0010
    0020
    0030
    1010
    1020

    1110
    1310
    1320
    1330
    3005

    3010
    3020
    3040
    3050
    3500

    3510
    3520
    3540
    3550
    3580

    3600
    3610
    3611
    3620
    3630

    3640
    3650
    3660
    3810
    3820

    5030
    5040
    6010
    7000
    7020
Chapter Number,
Third Edition
   Ten
   Ten
   Ten
   Eight (8.1)
   Eight (8.1)

   Eight (8.2)
   Eight (8.4)
   Six
   Six
   Three

   Three
   Three
   Three
   Three
   Four (4.2.1)
        Method  Number,
Current Revision
        (4.2.1)
          .2.1)

   Four (4.2.2)
   Four (4.2.2
   Four (4.2.2
   Four (4.2.2
   Four (4.2.2)
   Four  (4.2.2)
   Four  (4.2.2)
   Four  (4.2.2)
   Four  (4.4)
   Four  (4.4)
   Four  (4,
   Four  (4,
   Three
   Three
   Three
*ll
.1)
Second Edition
0010
0020
0030
1010
1020
1110
1310
1320
1330
3005
3010
3020
3040
3050
None (new method)
3510
3520
3540
3550
None (new method)
None (new method)
None (new method)
3570
None (new method)
None (new method)
None (new method)
None (new method)
None (new method)
5020
None (new method)
5030
3720
6010
7000
7020
Number
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
                               METHOD  INDEX - 1
                                                          Revision      0
                                                          Date  September 1986

-------
                      METHOD INDEX AND CONVERSION TABLE
                                 (Continued)
Method Number,
Third Edition
Chapter Number,
Third Edition
Method Number,
Second Edition
Current Revision
    Number
    7040
    7041
    7060
    7061
    7080

    7090
    7091
    7130
    7131
    7140

    7190
    7191
    7195
    7196
    7197

    7198
    7200
    7201
    7210
    7380

    7420
    7421
    7450
    7460
    7470

    7471
    7480
    7481
    7520
    7550

    7610
    7740
    7741
    7760
    7770
   Three
   Three
   Three
   Three
   Three

   Three
   Three
   Three
   Three
   Three

   Three
   Three
   Three
   Three
   Three

   Three
   Three
   Three
   Three
   Three

   Three
   Three
   Three
   Three
   Three

   Three
   Three
   Three
   Three
   Three

   Three
   Three
   Three
   Three
   Three
  7040
  7041
  7060
  7061
  7080

  7090
  7091
  7130
  7131
  7140

  7190
  7191
  7195
  7196
  7197

  7198
  7200
  7201
  7210
  7380

  7420
  7421
  7450
  7460
  7470

  7471
  7480
  7481
  7520
  7550

  7610
  7740
  7741
  7760
  7770
     0
     0
     0
     0
     0

     0
     0
     0
     0
     0

     0
     0
     0
     0
     0

     0
     0
     0
     0
     0

     0
     0
     0
     0
     0

     0
     0
     0
     0
     0

     0
     0
     0
     0
     0
                               METHOD  INDEX  - 2
                                                          Revision   	  p
                                                          Date   September 1986

-------
                      METHOD INDEX AND CONVERSION TABLE
                                 (Continued)
Method Number,
Third Edition
    7840
    7841
    7870
    7910
    7911

    7950
    8000
    8010
    8015
    8020

    8030
    8040
    8060
    8080
    8090

    8100
    8120
    8140
    8150
    8240

    8250
    8270
    8280
    8310
    9010

    9020
    9022
    9030
    9035
    9036

    9038
    9040
    9041
    9045
    9050
ChapterNumber,
Third Edition
   Three
   Three
   Three
   Three
   Three

   Three
   Four (4.3.1)
   Four (4.3.1)
   Four (4.3.1)
   Four (4.3.1)

   Four (4.3.1)
   Four (4.3.1)
   Four (4.3.1)
   Four (4.3.1)
   Four (4.3.1)
            Method Number,
                            Current Revision
    Four
    Four
    Four
(4.3
 4.3
 4.3
.1)
.1)
   Four  (4.3.1
   Four  (4.3.2)
Four (4
Four (4
Four (4
Four (4
Five
Five
Five
Five
Five
Five
Five
Six
Six
Six
Six
.3.2)
.3.2)
.3.2)
.3.3)










Second Edition
7840
7841
7870
7910
7911
7950
None (new method)
8010
8015
8020
8030
8040
8060
8080
8090
8100
8120
8140
8150
8240
8250
8270
None (new method)
8310
9010
9020
9022
9030
9035
9036
9038
9040
9041
9045
9050
Number
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
                               METHOD  INDEX - 3
                                                          Revision       0
                                                          Date  September 1986

-------
                      METHOD INDEX AND CONVERSION TABLE
                                 (Continued)
Method Number,
Third Edition
Chapter Number,
Third Edition
Method Number,
Second Edition
Current Revision
    9060               Five
    ,9065               Five
    -9066               Five
    9067               Five
    9070               Five

    9071               Five
    9080               Six
    9081               Six
    9090               Six
    9095               Six

    9100               Six
    9131               Five
    9132               Five
    9200               Five
    9250               Five

    9251               Five
    9252               Five
    9310               Six
    9315               Six
    9320               Five

    HCN Test Method    Seven
    H2S Test Method    Seven
                       9060
                       9065
                       9066
                       9067
                       9070

                       9071
                       9080
                       9081
                       9090
                       9095

                       9100
                       9131
                       9132
                       9200
                       9250

                       9251
                       9252
                       9310
                       9315
                       9320

                       HCN Test Method
                       H2S Test Method
                         0
                         0
                         0
                         0
                         0

                         0
                         0
                         0
                         0
                         0

                         0
                         0
                         0
                         0
                         0

                         0
                         0
                         0
                         0
                         0

                         0
                         0
                              METHOD   INDEX - 4
                                                         Revision  	0_
                                                         Date  September
                                                     1986

-------
   CHAPTER ONE
TABLE OF CONTENTS
Section
1.0
2.0















3.0






















INTRODUCTION 	 	
QA PROJECT PLAN 	
2.1 DATA QUALITY OBJECTIVES 	
2.2 PROJECT OBJECTIVES . . 	
2.3 SAMPLE COLLECTION 	 , . . . .
2.4 ANALYSIS AND TESTING 	 	 	
2.5 QUALITY CONTROL 	 	 . . .
2.6 PROJECT DOCUMENTATION ......... 	
2.7 ORGANIZATION PERFORMING FIELD OR LABORATORY
OPERATIONS 	 	 . .
2.7.1 Performance Evaluation 	
2.7.2 Internal Assessment by QA Function 	
2.7.3 External Assessment 	 . 	
2.7.4 On-Site Evaluation 	
2.7.4.1 Field Activities 	
2.7.4.2 Laboratory Activities 	
2.7.5 QA Reports ....... 	
FIELD OPERATIONS 	
3.1 FIELD LOGISTICS 	
3.2 EQUIPMENT/INSTRUMENTATION 	
3.3 OPERATING PROCEDURES 	
3.3.1 Sample Management ........ 	
3.3.2 Reagent/Standard Preparation . . 	
3.3.3 Decontamination 	 	 	
3.3.4 Sample Collection 	
3.3.5 Field Measurements 	 . 	
3.3.6 Equipment Calibration And Maintenance . . . .
3.3.7 Corrective Action 	 .
3.3.8 Data Reduction and Validation ........
3.3.9 Reporting 	 	 	
3.3.10 Records Management ... 	
3.3.11 Waste Disposal 	 .
3.4 FIELD QA AND QC REQUIREMENTS 	
3.4.1 Control Samples 	
3.4.2 Acceptance Criteria 	
3.4.3 Deviations . . 	
3.4.4 Corrective Action 	 	 . .
3.4.5 Data Handling .... 	
3.5 QUALITY ASSURANCE REVIEW 	
3.6 FIELD RECORDS 	
Paae
.... 1
.... 1
.... 2
.... 2
.... 3
.... 3
.... 3
.... 3

.... 4
.... 5
.... 5
.... 5
.... 5
.... 5
.... 6
.... 7
.... 8
.... 8
.... 9
.... 9
.... 9
.... 9
.... 9
.... 10
.... 10
.... 10
.... 10
.... 11
.... 11
.... 11
.... 11
.... 11
.... 11
.... 12
.... 12
.... 12
.... 12
.... 13
.... 13
     ONE -  I                          Revision 1
                                      July 1992

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                               TABLE OF  CONTENTS
                                  (continued)


Section                                                                   Page

4.0  LABORATORY OPERATIONS  	   14
      4.1  FACILITIES	   14
      4.2  EQUIPMENT/INSTRUMENTATION  ..................   15
      4.3  OPERATING PROCEDURES 	   15
            4.3.1  Sample Management	   16
            4.3.2  Reagent/Standard Preparation 	   16
            4.3.3  General Laboratory Techniques  	   16
            4.3.4  Test Methods	   16
            4.3.1  Equipment Calibration and Maintenance  	   17
            4.3.6  QC	   17
            4.3.7  Corrective Action  	   17
            4.3.8  Data Reduction and Validation	   18
            4.3.9  Reporting  .	   18
            4.3.10 Records Management 	   18
            4.3.11 Waste Disposal	   18
      4.4  LABORATORY QA AND QC PROCEDURES  .	   18
            4.4.1  Method Proficiency	   18
            4.4.2  Control Limits	   19
            4.4.3  Laboratory Control  Procedures  	 .  .   19
            4.4.4  Deviations   	   20
            4.4.5  Corrective Action	     20
            4.4.6  Data Handling	   20
      4.5  QUALITY ASSURANCE REVIEW 	  .   21
      4.6  LABORATORY RECORDS	   21

5.0  DEFINITIONS	   23

6.0  REFERENCES 	  .  	 .........   29

INDEX	   30
                                   ONE - ii                         Revision 1
                                                                     July 1992

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                                  CHAPTER ONE
                                QUALITY CONTROL
1.0  INTRODUCTION
      It  is  the goal  of the  U.S.  Environmental Protection  Agency's (EPA's)
quality assurance (QA) program to ensure that  all data be scientifically valid,
defensible,  and of  known  precision  and  accuracy.    The data  should be  of
sufficient known quality to  withstand scientific and legal  challenge relative to
the use for which the data are obtained.  The QA program is  management's tool for
achieving this goal.

      For RCRA analyses, the recommended minimum requirements for a QA program
and the associated  quality control (QC) procedures are provided in this chapter.

      The data acquired from QC procedures are used to estimate the quality of
analytical data, to determine the  need for corrective action  in  response to
identified deficiencies,  and  to  interpret  results  after corrective  action
procedures are implemented.  Method-specific QC procedures are incorporated in
the individual methods since they are not applied universally.

      A total program to generate data of acceptable quality should include both
a QA component, which encompasses the management procedures and controls, as well
as  an  operational  day-to-day QC component.   This  chapter defines fundamental
elements of such a data collection program.  Data collection efforts involve:

      1.    design  of a project plan to achieve the data quality objectives
            (DQOs);

      2.    implementation  of the project plan; and

      3.    assessment of the data to determine if the DQOs are met.

The project plan may be a  sampling and analysis plan or a waste analysis plan if
it  covers  the QA/QC  goals  of  the Chapter, or  it  may be  a  Quality Assurance
Project Plan as described later in this chapter.

      This chapter identifies the minimal QC components that should be used in
the performance  of sampling and analyses, including  the  QC  information  which
should be documented.  Guidance is provided to construct QA programs for field
and laboratory work conducted in support of the RCRA program.


2.0  QA PROJECT PLAN

      It is recommended that all  projects which generate environment-related data
in  support of RCRA  have  a QA  Project  Plan  (QAPjP)  or  equivalent.   In  some
instances, a sampling  and  analysis  plan  or a waste  analysis  plan may  be
equivalent if it covers all of the QA/QC goals outlined  in this  chapter.   In
addition,  a   separate QAPjP  need  not  be  prepared  for  routine  analyses  or
activities where  the  procedures  to be  followed are described in  a  Standard

                                    ONE  -  1                          Revision 1
                                                                     July 1992

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Operating Procedures manual or  similar  document  and include the elements of a
QAPjP.  These documents should be  available  and referenced  in the documentation
and/or records for the  analysis activities.   The term "QAPjP" in this chapter
refers to any of these QA/QC documents.

      The QAPjP should detail  the  QA/QC  goals  and protocols for a specific data
collection activity.   The QAPjP  sets  forth a plan for  sampling  and analysis
activities that will generate  data of a quality commensurate with their intended
use.   QAPjP  elements  should  include  a  description  of  the  project and  its
objectives; a statement of the DQOs  of the project;  identification of those in-
volved  in  the data  collection  and their  responsibilities  and  authorities;
reference  to  (or inclusion  of) the specific sample collection  and analysis
procedures that will  be followed for all  aspects  of  the project; enumeration of
QC procedures  to  be  followed; and  descriptions  of  all  project documentation.
Additional elements should  be included  in the QAPjP  if  needed to address  all
quality related  aspects of the data  collection  project.   Elements  should be
omitted only when  they are inappropriate for  the project or when absence of those
elements will  not affect the quality  of data obtained  for  the  project (see
reference 1).

      The role and importance of  DQOs  and project documentation are discussed
below in Sections 2.1  through 2,6.  Management and organization play a critical
role In determining the effectiveness of a QA/QC program and ensuring that all
required procedures are  followed.   Section 2.7  discusses  the  elements  of an
organization's QA program that have been found to ensure an effective program.
Field operations  and laboratory  operations (along  with applicable QC procedures)
are discussed in Sections 3 and 4,  respectively.


2.1  DATA QUALITY OBJECTIVES

      Data quality objectives (DQOs) for the data collection activity describe
the overall level of uncertainty that a decision-maker is  willing to accept in
results derived from environmental data.  This  uncertainty is used to specify the
quality of  the measurement  data required,  usually  in terms of objectives  for
precision, bias,  representativeness, comparability  and completeness.  The DQOs
should be defined prior to the initiation of the field and laboratory work.  The
field and laboratory organizations  performing the work  should be aware  of the
DQOs so that their personnel may make informed  decisions during the course of the
project to attain those  DQOs.  Hore detailed  information on DQOs is available
from the U.S.  EPA Quality Assurance Management  Staff  (QAMS)  (see references 2 and
4).


2.2  PROJECT OBJECTIVES

      A statement of  the project  objectives  and  how  the  objectives  are  to be
attained should be concisely  stated and sufficiently detailed to permit clear
understanding  by  all   parties involved  in  the data collection effort.   This
includes a statement of what problem is  to be solved and the information required


                                    ONE - 2                          Revision 1
                                                                     July 1992

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                                         41
in the process.   It also includes  appropriate statements of the DQOs (i.e., the
acceptable level of uncertainty in the information).


2.3  SAMPLE COLLECTION

      Sampling procedures,  locations,  equipment,  and sample  preservation and
handling requirements  should  be specified  in  the  QAPjP.   Further  details on
quality assurance procedures for field  operations are described in Section 3 of
this chapter.  The OSW is developing policies and procedures for sampling In a
planned revision  of Chapter  Nine of  this manual.   Specific procedures for
groundwater sampling are provided in Chapter Eleven of this manual.


2.4  ANALYSIS AND TESTING

      Analytes and properties of concern, analytical and testing procedures to
be employed,  required detection  limits, and  requirements for precision and bias
should be specified.  All applicable regulatory requirements and the project DQOs
should be considered when developing the specifications.  Further details on the
procedures for analytical operations are described in Section 4 of this chapter.


2.5  QUALITY CONTROL

      The  quality  assurance  program  should address both  field  and  laboratory
activities.  Quality control procedures should  be specified for estimating the
precision  and bias of the data.  Recommended minimum requirements for QC samples
have been  established by EPA and should be met  in order to satisfy recommended
minimum criteria for acceptable data quality. Further details on procedures for
field and laboratory operations are described in Sections 3 and 4, respectively,
of this chapter.


2.6  PROJECT DOCUMENTATION

      Documents  should be prepared and maintained in conjunction with  the data
collection effort.  Project documentation should be sufficient to allow review
of all aspects of the work being performed.  The QAPjP discussed in  Sections 3
and 4 is one important document that should be  maintained.

      The   length   of storage  time  for  project  records  should  comply  with
regulatory  requirements,  organizational  policy,   or  project   requirements,
whichever  is  more  stringent.  It is recommended  that  documentation be stored for
three years from submission of the project final report.

      Documentation  should   be  secured   in   a  facility   that   adequately
addresses/minimizes  its deterioration for the  length of time  that it  is  to be
retained.   A system allowing for the expedient  retrieval  of information should
exist.


                                   ONE -  3                          Revision 1
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      Access  to  archived  information should  be controlled  to maintain  the
integrity  of the  data.    Procedures should  be developed  to  identify  those
individuals with access to the data.
2.7  ORGANIZATION PERFORMING FIELD OR LABORATORY OPERATIONS

      Proper design and structure of  the organization facilitates effective and
efficient transfer of information and helps to prevent important procedures from
being overlooked.

      The  organizational  structure,  functional  responsibilities,  levels  of
authority,  job  descriptions,  and  lines  of  communication for  all  project
activities should be established  and documented.  One person may cover more than
one  organizational  function.   Each  project  participant  should  have  a  clear
understanding of his or her  duties and responsibilities and the relationship of
those responsibilities to the overall data collection effort.

      The management of each organization participating in a project involving
data collection activities should establish  that organization's operational and
QA policies. This information should be documented in the QAPjP.  The management
should ensure that (1) the appropriate methodologies are followed as documented
in   the   QAPjPs;   (2)   personnel   clearly   understand   their   duties   and
responsibilities;  (3) each  staff member  has access  to  appropriate  project
documents;  (4)  any  deviations  from the QAPjP  are communicated to  the project
management  and  documented;   and  (5)  communication  occurs between  the field,
laboratory, and project management, as specified in the QAPjP. In addition, each
organization should  ensure  that  their activities do not  increase  the  risk to
humans or the environment  at or about  the project location.  Certain projects may
require specific policies  or a Health and Safety Plan to provide this assurance.

      The management of the participating field or laboratory organization should
establish personnel qualifications and training requirements for the project.
Each person  participating in the project  should  have the education, training,
technical knowledge,  and  experience, or a  combination  thereof, to  enable that
individual to perform assigned functions.   Training  should be provided for each
staff  member as  necessary   to  perform  their  functions  properly.    Personnel
qualifications  should be documented  in terms  of education, experience,  and
training,   and   periodically   reviewed   to  ensure   adequacy   to   current
responsibilities.

      Each  participating  field  organization or laboratory organization should
have a designated QA  function  (i.e., a team or individual  trained  in QA) to
monitor  operations  to  ensure  that the   equipment,  personnel,  activities,
procedures,  and documentation conform with the QAPjP.  To the extent possible,
the QA monitoring function should be entirely separate from, and independent of,
personnel  engaged in  the work  being monitored.    The  QA  function  should be
responsible  for the QA review.
                                    ONE - 4                         Revision 1
                                                                     July 1992

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      2.7.1  Performance Eva!nation

      Performance evaluation studies are used  to measure the  performance of the
laboratory on  unknown samples.   Performance  evaluation  samples are typically
submitted to the laboratory as blind samples by an independent outside source.
The  results  are  compared to  predetermined  acceptance  limits.   Performance
evaluation samples  can  also  be  submitted to the laboratory  as  part of the QA
function during internal assessment of laboratory performance.  Records of all
performance evaluation studies should be maintained by the  laboratory.  Problems
identified through  participation  in performance evaluation  studies  should be
immediately investigated and corrected.

      2.7.2  Internal Assessment by QA Function

      Personnel performing field and laboratory activities are responsible for
continually monitoring  Individual compliance  with  the QAPjP.  The QA function
should review procedures, results  and calculations  to  determine compliance with
the  QAPjP.   The  results of this  internal  assessment  should be  reported to
management with requirements for a plan to correct observed deficiencies.

      2.7.3  External Assessment

      The field and laboratory activities may  be reviewed by personnel external
to the organization.   Such an  assessment is  an extremely valuable method for
identifying overlooked problems.   The results  of the external assessment should
be submitted  to management with requirements  for  a  plan  to correct observed
deficiencies.

      2.7.4  On-Site Evaluation

      On-site evaluations may be conducted as part  of both  internal  and external
assessments.   The focus  of an on-site  evaluation  is  to evaluate the degree of
conformance of project activities with the applicable QAPjP. On-site evaluations
may  include, but  are not limited  to,  a  complete review of facilities,  staff,
training, instrumentation, procedures,  methods, sample collection,  analyses, QA
policies and  procedures related to  the generation of environmental data.  Records
of each evaluation should include the date of the evaluation, location, the areas
reviewed, the  person performing  the  evaluation,   findings and problems,  and
actions recommended and  taken to resolve problems.   Any problems identified that
are  likely  to  affect data  integrity  should  be   brought  immediately to  the
attention of management.

            2.7.4.1  Field Activities

      The review of field activities should be conducted by one or more persons
knowledgeable  in  the activities being  reviewed and  include evaluating,  at  a
minimum,  the following subjects:

      Completeness  ofField Reports  --  This review determines   whether  all
      requirements for field activities in the QAPjP have been fulfilled, that
      complete  records exist for each  field activity, and that  the procedures

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      specified  in  the  QAPjP  have  been  implemented.    Emphasis  on  field
      documentation  will  help assure sample integrity and sufficient technical
      information to   recreate  each  field  event.     The  results  of  this
      completeness check  should be documented,  and environmental  data affected
      by incomplete  records  should be identified.

      Identification of Valid Samples -- This review involves interpretation and
      evaluation of  the field records  to  detect problems  affecting  the repre-
      sentativeness  of environmental  samples.   Examples  of  items  that  might
      indicate potentially invalid  samples  include improper  well  development,
      improperly screened wells,  instability of pH or conductivity, and collec-
      tion of volatiles  near  internal  combustion  engines.   The  field records
      should be evaluated against the QAPjP and  SOPs.  The reviewer should docu-
      ment the sample validity and  identify the environmental  data  associated
      with any poor  or incorrect field work.

      Correlation of  Field  Test  Data  --  This review  involves comparing  any
      available results of field  measurements obtained by more than one method.
      For example,  surface  geophysical methods should  correlate with  direct
      methods  of site  geologic  characterization  such  as   lithologic  logs
      constructed during  drilling operations.

      Identification ofAnomalous Field Test Data -- This review identifies any
      anomalous field  test data.   For example, a water temperature for one well
      that is  5 degrees  higher  than  any  other well  temperature in  the  same
      aquifer should  be  noted.   The reviewer should evaluate the  impact  of
      anomalous field  measurement results  on the associated environmental  data.

      Validationof  Field Analyses  --  This  review validates  and  documents all
      data from  field analysis that  are  generated  in situ  or from  a  mobile
      laboratory as  specified in  Section 2.7.4.2.  The reviewer should document
      whether the QC checks meet the acceptance criteria, and whether corrective
      actions were taken for any analysis  performed when  acceptance criteria
      were exceeded.

            2.7.4.2   Laboratory Activities

      The review of  laboratory data should be  conducted  by one or more persons
knowledgeable in laboratory activities and include  evaluating,  at a minimum, the
following subjects:

      Completeness of  Laboratory  Records --  This review determines whether: (1)
      all samples and analyses required by  the QAPjP have  been processed,  (2)
      complete records exist for each  analysis and the associated QC samples,
      and that (3) the procedures  specified  in the QAPjP have  been implemented.
      The  results  of  the   completeness   check   should   be   documented,   and
      environmental  data  affected by incomplete records  should be identified.

      Evaluation of  Data with Respect  to  Detection and Quantitation Limits  --
      This review compares  analytical results  to required quantitation limits.
      Reviewers should document instances where  detection or quantitation limits

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      exceed  regulatory  limits,  action  levels,  or  target  concentrations
      specified in the QAPjP.

      Evaluation of Data withRespect to  Control  Limits  -- This review compares
      the   results of QC and  calibration check samples  to control criteria.
      Corrective  action  should  be  implemented  for data  not within  control
      limits. The reviewer should check that corrective  action reports, and the
      results  of  reanalysis,  are  available.    The  review should determine
      whether samples associated with out-of-control QC data are identified in
      a written  record  of the data  review,  and whether an  assessment  of the
      utility of such analytical results is recorded.

      Review of Holding Time Data -- This review compares sample holding times
      to those required by the QAPjP, and notes all deviations.

      Review of Performance Evaluation (PE) Results -- PE study results can be
      helpful in evaluating the impact of out-of-control  conditions.  This review
      documents  any  recurring trends  or problems  evident  in  PE  studies and
      evaluates their effect on environmental  data.

      Correlation  of  Laboratory Data  -- This  review  determines  whether the
      results of data obtained  from  related  laboratory  tests,  e.g., Purgeable
      Organic Hal ides (POX)  and Volatile Organics,  are documented,  and whether
      the significance of any differences is discussed in the reports.

      2.7.5  QA Reports

      There should be periodic reporting of pertinent QA/QC information to the
project management to allow assessment of  the  overall effectiveness of the QA
program.  There are three major types of QA reports to project management:

      Periodic Report on  Key QA Activities -- Provides summary of key QA activi-
      ties during the  period, stressing measures that are being taken to improve
      data  quality;   describes  significant  quality  problems  observed  and
      corrective actions taken;  reports  information regarding any changes in
      certification/accreditation status; describes involvement  in resolution of
      quality issues  with clients  or agencies; reports any  QA  organizational
      changes; and provides  notice of the distribution of  revised documents
      controlled by the QA organization (i.e.,  procedures).

      Report on Measurement Quality Indicators  -- Includes the assessment of QC
      data gathered over the period,  the frequency of analyses  repeated due to
      unacceptable QC performance, and,  if possible, the  reason  for the unac-
      ceptable performance and corrective action taken.

      Reports on QA Assessments -- Includes the results  of the  assessments and
      the plan  for correcting identified deficiencies; submitted  immediately
      following any internal  or external  on-site evaluation  or  upon receipt of
      the results of  any performance evaluation studies.
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3.0  FIELD OPERATIONS

      The field  operations should be  conducted In such  a way  as  to provide
reliable Information  that meets the DQOs.   To achieve this,  certain minimal
policies and procedures should be implemented.  The OSW is considering revisions
of Chapter Nine and Eleven of this manual.  Supplemental information and guidance
is available 1n  the RCRA Ground-Water Honltoring Technical Enforcement Guidance
Document (TEGD)  (Reference 3).   The project documentation  should contain the
information specified below.


3.1  FIELD LOGISTICS

      The QAPjP should describe the type(s)  of  field operations to be performed
and the  appropriate  area(s) in which  to  perform  the work.   The QAPjP should
address ventilation,  protection  from extreme weather and temperatures, access to
stable power, and provision for water and gases of required purity.

      Whenever practical, the sampling  site  facilities should be  examined prior
to the start of work to ensure that  all  required items are available.  The actual
area of sampling should be examined to ensure that trucks, drilling equipment,
and personnel have adequate access to the site.

      The determination as to whether sample  shipping is necessary should be made
during planning  for  the project.   This need is established by evaluating the
analyses to be performed,  sample holding times,  and location of the site and the
laboratory.   Shipping or transporting of  samples to a  laboratory  should be done
within a timeframe such that recommended holding times are met.

      Samples should be packaged, labelled, preserved (e.g.,  preservative added,
iced,  etc.),  and documented  in an area  which is  free  of  contamination  and
provides for secure storage. The level  of  custody and  whether sample storage is
needed should be addressed in the QAPjP.

      Storage areas for solvents, reagents,  standards, and reference materials
should  be  adequate  to preserve  their identity,  concentration, purity,  and
stability prior to use.

      Decontamination  of  sampling  equipment may be performed  at the location
where sampling occurs,  prior to going  to the  sampling site,  or in designated
areas near the sampling site.  Project documentation should specify where and how
this work is accomplished.  If decontamination  is to be done at the site, water
and  solvents of appropriate  purity  should  be  available.    The  method  of
accomplishing decontamination,  including the required materials, solvents, and
water purity should be  specified.

      During the sampling process and during on-site or jm situ analyses, waste
materials are sometimes generated.  The method for  storage  and disposal of these
waste  materials  that  complies with  applicable  local,   state and  Federal
regulations should be specified. Adequate facilities should be provided for the
collection and storage of all wastes, and these  facilities  should be operated so

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as  to  minimize  environmental  contamination.    Waste  storage  and  disposal
facilities should comply with applicable federal,  state,  and  local regulations.

      The location of long-term and short-term storage for field records,  and the
measures to ensure the integrity of the data  should  be specified.


3.2  EQUIPMENT/INSTRUMENTATION

      The equipment,  instrumentation, and supplies at the sampling site should
be specified and should be appropriate to accomplish the activities planned.  The
equipment and  instrumentation  should  meet the requirements of  specifications,
methods, and procedures as specified  in the QAPjP.


3.3  OPERATING  PROCEDURES

      The QAPjP  should describe or make reference to all field  activities that
may affect data quality.  For routinely performed activities,  standard operating
procedures (SOPs) are often prepared to ensure consistency  and to  save time and
effort in preparing QAPjPs.  Any deviation from an established procedure during
a data  collection activity  should  be documented.   The procedures  should  be
available for the  indicated  activities,  and  should  include,  at  a minimum,  the
information described below.

      3.3.1  Sample Management

      The numbering and labeling system, chain-of-custody procedures, and  how the
samples  are  to  be  tracked  from collection  to  shipment  or  receipt  by  the
laboratory should be specified. Sample management procedures should also specify
the  holding  times,  volumes  of sample  required  by  the laboratory,  required
preservatives, and shipping requirements.

      3.3.2  Reagent/StandardPreparation

      The procedures describing how  to prepare standards  and  reagents should be
specified.  Information concerning specific grades of materials  used in reagent
and standard preparation, appropriate glassware and containers for preparation
and storage,  and labeling and record keeping for stocks and dilutions should be
included.

      3.3.3  Decontanii nation

      The procedures  describing decontamination of  field equipment before  and
during the  sample collection process  should  be specified.   These procedures
should include cleaning materials used, the order of washing  and rinsing with the
cleaning materials, requirements for protecting or covering cleaned equipment,
and procedures for disposing of cleaning materials.
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      3.3.4  Sample Collection

      The  procedures  describing  how  the  sampling  operations  are  actually
performed  in  the  field should be  specified.   A  simple  reference to standard
methods is not sufficient, unless  a  procedure  is performed  exactly as described
in the published method.   Methods  from source documents published by the EPA,
American Society  for Testing and Materials,  U.S.  Department of the Interior,
National  Water  Well  Association,   American   Petroleum Institute,  or  other
recognized organizations with appropriate expertise should be used, if possible.
The procedures for sample collection should include at least the  following:

   •  Applicability of the procedure,

   »  Equipment required,

   •  Detailed  description  of  procedures  to be  followed  in  collecting  the
      samples,

   •  Common problems encountered and corrective  actions to  be  followed, and

   *  Precautions to be taken.

      3.3.5  Field Measurements

      The  procedures  describing  all methods  used  in  the  field to determine a
chemical or physical  parameter  should  be  described in detail.  The procedures
should address criteria from  Section 4, as  appropriate.

      3-3.6  Equipment Callbration  And Maintenance

      The  procedures  describing  how  to  ensure  that  field  equipment  and
instrumentation  are in  working order  should be  specified.   These describe
calibration procedures and  schedules,  maintenance procedures  and  schedules,
maintenance logs,  and  service  arrangements  for  equipment.   Calibration  and
maintenance of field equipment and instrumentation should be in  accordance with
manufacturers'  specifications or  applicable test  specifications and should be
documented.

      3.3.7  Corrective Action

      The procedures describing how to identify and correct deficiencies in the
sample collection process should  be specified.  These should include specific
steps  to  take  in  correcting   deficiencies   such as  performing  additional
decontamination  of  equipment,  resampling,  or additional  training  of field
personnel.  The procedures should specify that each corrective  action should be
documented with a description of the deficiency and the corrective  action taken,
and should include  the person(s) responsible for implementing the corrective
action.
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      3.3.8  Data Reduction and Validation

      The procedures describing how to compute results from field measurements
and to review and validate these data  should  be specified.  They should Include
all formulas  used to calculate  results  and  procedures  used  to Independently
verify that field measurement results are correct.

      3.3.9  Reporting

      The procedures describing the process for reporting the results of field
activities should be specified.

      3.3.10 Records Management

      The  procedures  describing  the  means  for  generating,  controlling,  and
archiving  project-specific records  and  field  operations  records  should  be
specified.  These procedures should detail record  generation and control and the
requirements for record retention, including type, time, security, and retrieval
and disposal authorities.

      Project-specifI.e. recordj  relate  to field work performed  for a project.
      These records may  Include  correspondence, chain-of-custody records, field
      notes, all reports issued as a result of the work,  and procedures used.

      Fieldopjerat1ons records document overall field operations  and may include
      equipment performance and maintenance logs,  personnel  files, general field
      procedures, and corrective action reports.

      3.3.11 Waste Disposal

      The  procedures describing the methods  for disposal  of waste materials
resulting from field operations should be specified.


3.4  FIELD QA AND QC REQUIREMENTS

      The  QAPjP  should  describe how the  following   elements of the  field  QC
program will be implemented.

      3.4.1  Control Samples

      Control samples  are QC samples  that are  introduced  into a  process  to
monitor the performance of the system.  Control samples,  which may include blanks
(e.g.,  trip,  equipment,  and  laboratory),   duplicates,  spikes,   analytical
standards, and reference materials,  can be used in different phases of the data
collection process beginning with sampling and continuing through transportation,
storage, and analysis.

      Each  day  of sampling, at  least one field  duplicate and one equipment
rinsate should be collected for each matrix sampled.  If this frequency is not
appropriate for the sampling equipment and method, then the appropriate changes

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should be  clearly identified in  the  QAPjP.   When  samples are  collected  for
volatile organic  analysis, a trip blank  is  also  recommended  for each day that
samples are collected.   In addition, for  each sampling batch (20 samples of one
matrix type), enough  volume should be collected for at least one  sample so as to
allow the laboratory  to  prepare one matrix spike and  either  one matrix duplicate
or one matrix spike duplicate for each analytical method employed.   This means
that the following control samples are recommended:

      •Field duplicate (one per day per matrix type)
      •Equipment  rinsate (one per day per matrix type)
      •Trip blank (one per day,  volatile organics only)
      •Matrix spike (one per batch [20 samples of each matrix type])
      •Matrix duplicate or matrix spike duplicate (one per batch)

Additional control samples may be necessary in order to assure data quality to
meet the project-specific DQOs.   "

      3.4.2  Acceptance Criteria

      Procedures  should  be in  place for establishing  acceptance criteria  for
field activities described in the QAPjP.  Acceptance  criteria may be qualitative
or  quantitative.    Field  events  or  data  that  fall  outside  of  established
acceptance criteria may  indicate a problem with the sampling process that should
be investigated.

      3.4.3  Deviations

      All deviations from  plan  should be documented as to the  extent  of,  and
reason  for,  the  deviation.   Any  activity not  performed  in accordance  with
procedures or QAPjPs  is  considered a deviation  from  plan.  Deviations from plan
may or may not affect data quality.

      3.4.4  CorrectiveAction

      Errors, deficiencies, deviations, certain field events, or data that fall
outside  established  acceptance  criteria  should be  investigated.   In some  in-
stances,  corrective  action may be  needed  to  resolve the  problem  and  restore
proper  functioning to  the system.  The  investigation of  the problem  and  any
subsequent corrective action taken should be documented.

      3.4.5  Data Handling

      All  field  measurement  data  should  be   reduced  according to  protocols
described or referenced  in the QAPjP.  Computer programs used for data reduction
should be validated before use and verified on a regular basis.  All  information
used in the calculations should be recorded to enable reconstruction  of the final
result at a  later date.

      Data should be  reported in accordance with the requirements  of  the end-user
as described in the QAPjP.


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3.5  QUALITY ASSURANCE REVIEW

      The QA Review consists of Internal and external  assessments  to ensure that
QA/QC procedures  are  in use and to  ensure that field  staff  conform to these
procedures.  QA review should  be  conducted  as deemed  appropriate  and necessary.


3.6  FIELD RECORDS

      Records provide  the direct evidence and support for the necessary technical
interpretations, judgments, and discussions  concerning project activities. These
records, particularly those that  are anticipated to be used  as evidentiary data,
should directly support current or ongoing  technical  studies and  activities and
should provide the  historical evidence  needed  for  later reviews  and analyses.
Records should be legible, identifiable, and retrievable and protected against
damage, deterioration, or loss.   The discussion in this section  (3.6) outlines
recommended procedures for record keeping.  Organizations  which  conduct field
sampling  should  develop appropriate record  keeping procedures  which  satisfy
relevant technical and legal  requirements.

      Field records generally  consist of bound field  notebooks with prenumbered
pages,  sample  collection  forms,  personnel  qualification  and  training  forms,
sample  location  maps,  equipment  maintenance and calibration  forms,  chain-of-
custody forms, sample  analysis request  forms,  and  field change request forms.
All records should  be written in indelible ink.

      Procedures for reviewing, approving,  and revising  field records should be
clearly defined, with the lines  of authority included.  It is recommended that
all documentation errors should be corrected by drawing a single line through the
error  so  it  remains  legible and  should  be  initialed  by  the  responsible
individual, along with  the date  of  change.  The correction  should  be  written
adjacent to the error.

      Records should include (but are not limited to) the following:

      Calibration Records  & Traceability of  Standards/Reagents  --  Calibration is
      a reproducible  reference point to which all sample  measurements  can  be
      correlated.   A  sound  calibration program should  include provisions  for
      documentation of frequency, conditions, standards, and records reflecting
      the calibration  history of a  measurement  system.   The accuracy  of  the
      calibration standards  is important because all  data will be 1n  reference
      to  the  standards used.   A program  for  verifying  and documenting  the
      accuracy of all  working  standards against primary grade standards should
      be routinely followed.

      Sample Collection --To  ensure maximum utility  of the sampling effort  and
      resulting data,  documentation  of  the sampling  protocol,  as performed  in
      the field,  is  essential.  It is  recommended that sample collection records
      contain, at  a minimum,  the names of persons  conducting  the  activity,
      sample  number,  sample  location,  equipment  used,  climatic  conditions,
      documentation of  adherence to  protocol,  and unusual observations.   The

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      actual  sample collection  record  is usually one of the following:  a bound
      field notebook with prenumbered pages, a pre-printed  form,  or digitized
      information on a computer tape or  disc.

      Chain-of-Custody Records  -- The chain-of-custody involving the possession
      of samples from  the  time they are obtained  until  they are  disposed  or
      shipped off-site should be documented as  specified in the QAPjP and should
      include the following information:   (1)  the  project name;  (2) signatures
      of samplers;  (3)  the  sample number, date and time of collection, and grab
      or composite  sample designation; (4)  signatures of individuals Involved 1n
      sample  transfer; and  (5)  if  applicable,  the air bill or  other shipping
      number.

      Maps and Drawings --  Project planning documents and reports often contain
      maps.  The maps  are  used to  document the location of  sample collection
      points  and monitoring wells  and  as  a means of  presenting environmental
      data.  Information used to prepare maps and drawings is normally obtained
      through field  surveys,  property surveys, surveys  of monitoring  wells,
      aerial  photography or photogrammetric mapping.   The final, approved maps
      and/or  drawings should have a  revision number and date and should be sub-
      ject to the same controls as  other project records.

      QC Samples -- Documentation for generation of QC  samples, such as trip and
      equipment rinsate blanks, duplicate  samples,  and any field spikes should
      be maintained.

      Deviations --  All deviations  from  procedural   documents  and  the  QAPjP
      should  be recorded in the site logbook.

      Reports -- A copy of  any  report issued  and  any  supporting documentation
      should  be retained.
4.0  LABORATORY OPERATIONS

      The laboratory should conduct its operations in such a way as to provide
reliable information.   To  achieve this, certain minimal policies and procedures
should be implemented.


4.1  FACILITIES

      The QAPjP  should address  all  facility-related  issues  that may  impact
project  data  quality.    Each  laboratory  should  be of  suitable  size  and
construction to facilitate the proper conduct of the analyses.   Adequate bench
space or working  area per analyst should be provided.   The space requirement per
analyst depends on  the equipment or apparatus that is  being utilized, the number
of samples that the analyst is expected  to handle at any one time, and the number
of operations that  are  to  be  performed  concurrently by a single analyst.  Other
issues to be considered include,  but  are not limited to, ventilation,  lighting,


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control of dust and drafts, protection from extreme  temperatures,  and access to
a source of stable power.

      Laboratories should  be  designed so  that there is adequate  separation of
functions to  ensure  that no laboratory activity has  an  adverse effect on the
analyses. The laboratory may require specialized facilities such as a perchloric
acid hood or glovebox.

      Separate space for laboratory operations and appropriate ancillary support
should be provided,  as  needed,  for  the performance  of routine and specialized
procedures.

      As  necessary  to  ensure  secure  storage  and  prevent  contamination  or
misidentification, there should be adequate facilities for receipt and storage
of samples.   The level  of custody  required and any  special  requirements for
storage such as refrigeration should  be described in planning documents.

      Storage areas  for reagents, solvents, standards, and reference materials
should  be  adequate  to  preserve  their identity,  concentration,  purity,  and
stability.

      Adequate facilities  should be provided for the collection and storage of
all wastes,  and these facilities should be operated so as to minimize environ-
mental contamination.  Waste storage and disposal facilities  should comply with
applicable federal,  state, and local  regulations.

      The location of long-term and short-term storage of laboratory records and
the measures to ensure the integrity  of the data should be specified.


4.2  EQUIPMENT/INSTRUMENTATION

      Equipment and instrumentation  should meet the  requirements and specifica-
tions of  the  specific test methods  and other procedures as  specified in the
QAPjP.  The  laboratory should  maintain an  equipment/instrument description list
that includes the manufacturer, model  number, year of purchase, accessories, and
any modifications, updates, or upgrades that have been made.


4.3  OPERATING PROCEDURES

      The QAPjP should describe or make reference to all laboratory activities
that may affect data quality.  For routinely performed activities, SOPs are often
prepared to  ensure consistency and to save time and  effort in preparing QAPjPs.
Any deviation  from an  established procedure during  a data collection activity
should be documented.  It  is recommended that procedures  be available for the
indicated activities,  and  include,  at a minimum,   the  information  described
below.
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      4.3.1  Sample Management

      The procedures describing the receipt, handling, scheduling, and storage
of samples should be specified.

      Sample Receipt and Handling -- These procedures describe the precautions
      to be used in opening  sample  shipment  containers  and how to verify that
      chain-of-custody has been maintained,  examine  samples for damage,  check
      for  proper preservatives  and  temperature,  and  log  samples  into  the
      laboratory sample streams.

      Sample Scheduling --  These procedures describe the sample scheduling in
      the laboratory and  includes procedures  used  to ensure that holding time
      requirements are met.

      Sample Storage -- These procedures describe the  storage conditions for all
      samples, verification and documentation of daily storage temperature, and
      how to  ensure that  custody  of the samples  is maintained while  in the
      laboratory.

      4,3.2  Reagent/Standard Preparati on

      The procedures describing how to prepare standards and  reagents should be
specified.  Information concerning  specific  grades  of materials used in reagent
and standard preparation, appropriate glassware and containers for preparation
and storage, and labeling and recordkeeping for stocks and dilutions should be
included.

      4.3.3  General Laboratory Techniques

      The procedures describing all essentials of laboratory operations that are
not addressed elsewhere should be specified.  These techniques should include,
but are not limited to, glassware cleaning procedures, operation of analytical
balances, pipetting techniques, and use of volumetric glassware.

      4.3.4  Test Methods

      Procedures for  test methods  describing how the  analyses  are  actually
performed in the laboratory should be specified.   A  simple reference to standard
methods is not sufficient,  unless the analysis is  performed  exactly as described
in the  published method.  Whenever  methods from SW-846 are not appropriate,
recognized methods from source documents published by the EPA, American Public
Health Association  (APHA), American Society for Testing and Materials  (ASTM), the
National  Institute  for   Occupational  Safety  and  Health   (NIOSH),  or  other
recognized organizations  with appropriate expertise should be used, if possible.
The documentation of  the actual laboratory procedures  for analytical  methods
should include the following:

      Sample  Preparation  and Analysis Procedures  --  These include  applicable
      holding time, extraction, digestion, or preparation steps as appropriate
      to  the  method;  procedures for  determining the appropriate dilution  to

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      analyze;  and any  other information  required  to  perform  the analysis
      accurately and consistently.

      Instrument Standardization  -- This includes coneentration(s)  and frequency
      of analysis  of  calibration standards,  linear range of  the method,  and
      calibration acceptance criteria.

      Sample Data -- This includes recording  requirements and documentation in-
      cluding sample identification  number,  analyst,  data verification, date of
      analysis and verification,  and computational method(s).

      Precision and Bias -- This includes all analytes for which the method is
      applicable and the conditions for use of this  information.

      Detection  and Reporting Limits  -- This  includes  all  analytes  in  the
      method.

      Test-Specific QC  --  This  describes   QC  activities  applicable to  the
      specific test and references any applicable QC procedures.

      4.3.5  Equipment Calibration and Maintenance

      The procedures  describing  how to  ensure  that  laboratory  equipment  and
instrumentation  are in working order  should be specified.   These  procedures
include  calibration  procedures   and   schedules,  maintenance  procedures  and
schedules,  maintenance logs, service arrangements for all  equipment, and spare
parts available in-house.  Calibration and maintenance of laboratory equipment
and instrumentation should be in accordance with manufacturers' specifications
or applicable test specifications and should be documented.

      4.3.6  flC

      The type,  purpose, and frequency  of  QC  samples  to be  analyzed  in  the
laboratory and the acceptance criteria  should be  specified.  Information should
include  the  applicability  of  the QC  sample to  the analytical  process,  the
statistical  treatment  of  the data, and the responsibility of laboratory staff and
management in generating and using the  data.   Further details on development of
project-specific QC protocols are described in Section 4.4.

      4.3.7  Corrective Action

      The procedures describing how  to  identify  and correct deficiencies in the
analytical  process should be specified.   These should include specific steps to
take in  correcting the deficiencies such as  preparation of  new standards  and
reagents,  recalibration  and  restandardization  of  equipment,  reanalysis  of
samples,  or  additional   training  of  laboratory  personnel   in  methods  and
procedures.   The procedures  should specify that each corrective  action should be
documented with a description of the deficiency and the corrective  action taken,
and should  include the person(s) responsible for  implementing the corrective
action.


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      4.3.8  Data Reduction and Validation

      The procedures describing how  to  review and validate the data should be
specified.  They  should  include procedures  for computing and  interpreting the
results from QC samples, and independent  procedures to verify that the analytical
results are reported correctly.  In addition, routine procedures used to monitor
precision and bias,  including evaluations of  reagent, equipment rinsate, and trip
blanks,  calibration standards, control samples,  duplicate and  matrix spike
samples, and  surrogate  recovery,  should be detailed  in the procedures.  More
detailed validation procedures should be performed when required in the contract
or QAPjP.

      4.3.9  Reporting

      The procedures describing the process  for reporting the analytical results
should be specified.

      4.3.10 Records Management

      The  procedures describing  the means  for generating,  controlling,  and
archiving laboratory records should be specified.   The  procedures  should detail
record generation and control, and  the requirements  for record retention, includ-
ing type, time, security, and retrieval  and disposal authorities.

      Project-specific  records may  include  correspondence,   chain-of-custody
      records, request for analysis,  calibration data records,  raw and finished
      analytical  and QC data, data reports, and procedures  used.

      Laboratory operations records may  include laboratory notebooks, instrument
      performance logs and maintenance  logs  in bound  notebooks  with prenumbered
      pages;  laboratory  benchsheets; software  documentation;  control  charts;
      reference material certification;  personnel  files; laboratory procedures;
      and corrective action reports.
                          *
      4.3.11 Waste  Disposal

      The procedures describing the methods  for disposal of  chemicals including
standard and reagent solutions, process  waste, and samples should  be specified.


4.4  LABORATORY QA  AND QC PROCEDURES

      The  QAPjP should describe  how the  following  required  elements  of the
laboratory QC  program are to  be implemented.

      4.4.1  Method Profi ci ency

      Procedures  should  be in place for demonstrating proficiency with each
analytical  method  routinely  used in  the  laboratory.    These should  include
procedures for demonstrating  the  precision  and  bias of the  method as performed
by  the  laboratory  and  procedures for   determining the method  detection limit

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(MDL).  All terminology, procedures and frequency of determinations associated
with the laboratory's establishment of the HDL and the reporting limit  should be
well-defined  and  well-documented.    Documented  precision,  bias,  and  HDL
information should be maintained for  all methods performed in the laboratory.

      4.4.2  Control Limits

      Procedures should be  in place for establishing and updating control limits
for  analysis.   Control  limits should  be  established  to  evaluate laboratory
precision and bias based  on the analysis of control  samples.  Typically, control
limits for bias are  based on the  historical  mean recovery plus or minus three
standard deviation units, and control limits for precision range from zero (no
difference between duplicate control  samples)  to the historical mean relative
percent difference plus three standard deviation units.  Procedures  should be in
place for monitoring  historical performance and should include graphical (control
charts) and/or tabular presentations  of the data.

      4.4.3  Laboratory Control Procedures

      Procedures should be  in place for demonstrating  that the laboratory is in
control during each  data collection  activity.   Analytical  data generated with
laboratory control samples that fall  within prescribed limits are judged to be
generated while the  laboratory was in control.  Data generated with laboratory
control samples that fall outside the established control limits are judged to
be generated during  an "out-of-control"  situation.   These data are considered
suspect and should be repeated or reported with qualifiers.

      Laboratory  Control  Samples  --   Laboratory control  samples should  be
      analyzed for each  analytical method  when  appropriate for the method.   A
      laboratory control  sample consists of either a control matrix spiked with
      analytes representative of the  target  analytes  or a certified reference
      material.

      Laboratory control  sample(s)  should be analyzed with each batch of samples
      processed to verify that the  precision  and  bias of the analytical process
      are  within  control  limits.    The  results  of  the  laboratory  control
      sample(s) are  compared to control  limits  established for both precision
      and bias to determine  usability of the data.

      Method Blank -- When  appropriate for  the method,  a method blank should be
      analyzed with  each batch of  samples processed  to  assess  contamination
      levels in the laboratory.  Guidelines should be  in place for accepting or
      rejecting data based  on the level of contamination in the blank.

      Procedures should be  in place for documenting the effect of the matrix on
method performance.  When appropriate for the method,  there should be at least
one matrix spike and either  one matrix duplicate or one matrix spike duplicate
per analytical  batch. Additional control  samples may be necessary to assure data
quality to meet the  project-specific DQOs.
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      Matrix-Specific Bias -- Procedures should  be  in place for determining the
      bias of  the  method due to the matrix.  These  procedures should include
      preparation and analysis of matrix spikes,  selection and use of surrogates
      for organic  methods, and the  method  of  standard  additions for metal and
      inorganic methods.  When the concentration of the  analyte in the sample is
      greater than 0.1%, no  spike is necessary.

      Matrix-Specific Precision -- Procedures should be  in place for determining
      the precision  of  the  method  for a  specific matrix.   These  procedures
      should  include  analysis  of  matrix  duplicates  and/or  matrix  spike
      duplicates.  The frequency of use of these techniques should be based on
      the DQO for the data collection activity.

      Matrix-Specific  Detection Limit  --  Procedures should  be 1n  place for
      determining the HDL for a  specific matrix type (e.g., wastewater treatment
      sludge, contaminated soil, etc).

      4.4.4  Deviations

      Any activity  not performed in accordance with laboratory procedures or
QAPjPs is considered a deviation from plan.  All deviations from plan should be
documented as to the extent  of, and reason for,  the deviation.

      4.4.5  Corrective  Action

      Errors, deficiencies,  deviations, or laboratory events or data that fall
outside  of  established  acceptance  criteria should be  investigated.   In some
instances, corrective  action may be needed  to resolve  the problem and restore
proper functioning to the analytical system.  The  investigation of the problem
and any  subsequent corrective  action taken should be documented.

      4.4.6  Data Hand!ing

      Data resulting from the analyses of samples should be reduced according to
protocols described  in  the  laboratory  procedures.   Computer programs used for
data reduction should be validated before use and verified on a regular basis.
All information  used in the  calculations  (e.g., raw data,  calibration files,
tuning records, results  of standard additions, interference check results, and
blank- or background-correction protocols) should be recorded in order to enable
reconstruction  of the  final  result  at a  later  date.    Information on the
preparation of the  sample  (e.g., weight or  volume  of sample used,  percent dry
weight  for  solids,  extract  volume,  dilution  factor  used)   should  also  be
maintained in order to enable reconstruction of the  final result at a later date.

      All data should be reviewed by a second analyst or supervisor according to
laboratory  procedures  to ensure that  calculations are correct and  to detect
transcription errors.  Spot checks  should be performed on computer calculations
to verify program validity.   Errors detected in the review process should be
referred to the  analyst(s)  for corrective  action.   Data  should be reported in
accordance with  the  requirements of the end-user.   It  is recommended that the
supporting documentation include at a minimum:

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   *  Laboratory name and address.

   •  Sample  information  (including  unique  sample  Identification,  sample
      collection date and time, date of  sample  receipt,  and date(s) of sample
      preparation and analysis).

   *  Analytical results  reported  with  an  appropriate number  of significant
      figures.

   •  Detection limits that reflect dilutions, interferences, or correction for
      equivalent dry weight.

   •  Method reference,

   •  Appropriate QC results  (correlation with sample batch should be traceable
      and documented).

   «  Data qualifiers with appropriate references and narrative on the quality
      of the results.


4.5  QUALITY ASSURANCE REVIEW

      The QA review consists of internal and external  assessments to ensure that
QA/QC procedures are in use and to ensure that laboratory staff conform to these
procedures.  QA review should be conducted as deemed appropriate and necessary.


4.6  LABORATORY RECORDS

      Records provide the direct evidence  and support for the necessary technical
interpretations, judgements,  and discussions  concerning project  activities.
These records, particularly those that are anticipated to be used as evidentiary
data, should directly support technical studies and activities, and provide the
historical evidence needed for later reviews and  analyses.   Records should be
legible,   identifiable,   and   retrievable,   and  protected   against   damage,
deterioration,  or   loss.    The  discussion  in  this   section  (4.6)  outlines
recommended procedures for record keeping.   Organizations which  conduct field
sampling  should  develop  appropriate record  keeping  procedures which  satisfy
relevant technical  and legal  requirements.

      Laboratory records  generally  consist  of bound notebooks with prenumbered
pages,  personnel qualification  and  training forms, equipment maintenance  and
calibration forms,  chain-of-custody forms,  sample  analysis  request  forms,  and
analytical change request forms. All records should be written in indelible ink.

      Procedures for reviewing,  approving, and revising laboratory records should
be clearly defined,  with  the lines  of authority  included.   Any  documentation
errors should be corrected by drawing a single line through the error so that it
remains legible and should be initialed by the responsible individual, along with
the date of change.  The  correction  is  written  adjacent to the error.

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      Strip-chart recorder printouts should be signed by the person who performed
the instrumental analysis.  If corrections need to be made  in computerized data,
a system parallel to the corrections for handwritten data should be in place.

      Records of sample management should be available  to permit the re-creation
of an analytical event for review in the case  of  an audit  or investigation of a
dubious result.

      Laboratory records should include, at least, the following:

      Operating Procedures -- Procedures should be available to those performing
      the  task outlined.   Any  revisions  to  laboratory  procedures  should  be
      written,  dated,  and distributed to  all affected individuals  to ensure
      implementation  of changes.   Areas  covered by  operating  procedures are
      given in Sections 3.3 and 4.3.

      Quality Assurance Plans -- The QAPjP should be on file.

      Equipment Maintenance Documentation  -- A history of the maintenance record
      of each  system serves as  an  indication of the  adequacy  of maintenance
      schedules and parts inventory.  As appropriate, the maintenance guidelines
      of the  equipment manufacturer  should be followed.   When  maintenance is
      necessary,  it  should be  documented  in   either  standard  forms or  in
      logbooks.  Maintenance procedures should  be clearly defined and written
      for each measurement  system and required support equipment.

      Proficiency -- Proficiency information on all compounds  reported should be
      maintained and should include (1) precision; (2) bias;  (3) method detec-
      tion limits;  (4)  spike recovery, where applicable;  (5) surrogate recovery,
      where  applicable; (6) checks on  reagent  purity, where  applicable;  and
      (7) checks on glassware cleanliness, where applicable.

      Calibration Records & Traceability of Standards/Reagents --  Calibration is
      a reproducible  reference  point  to which all sample measurements can be
      correlated.   A sound calibration program  should  include  provisions for
      documenting frequency, conditions, standards, and records  reflecting the
      calibration  history  of   a  measurement  system.    The   accuracy  of  the
      calibration standards is  important because all  data will be in reference
      to  the  standards  used.   A  program for  verifying  and  documenting the
      accuracy  and  traceability of all working  standards against appropriate
      primary grade standards or the highest  quality standards available should
      be routinely  followed.

      Sample Management --All  required records pertaining to sample management
      should  be maintained  and updated  regularly.   These  include  chain-of-
      custody  forms, sample receipt forms, and sample disposition records.

      Original  Data -- The  raw data  and  calculated  results for  all  samples
      should be maintained in laboratory notebooks, logs,  benchsheets,  files or
      other sample tracking or data entry  forms.   Instrumental output should be
      stored  in  a computer  file or a hardcopy report.

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      QCData  -- The  raw data  and  calculated results  for all  QC  and field
      samples and standards should be maintained in  the manner  described in the
      preceding  paragraph.   Documentation should allow  correlation  of sample
      results with associated QC data.   Documentation should also include the
      source and lot  numbers of standards for traceability.  QC  samples include,
      but are not limited  to, control samples, method blanks, matrix spikes, and
      matrix spike duplicates.

      Correspondence -- Project correspondence can provide  evidence supporting
      technical interpretations.   Correspondence pertinent to the project should
      be kept and placed  in the project files.

      Deviations -- All deviations from procedural and planning  documents should
      be recorded  in laboratory  notebooks.  Deviations  from QAPjPs  should be
      reviewed  and  approved  by   the  authorized  personnel  who  performed  the
      original  technical  review or by their designees.

      Final Report -- A copy of any  report  issued  and  any  supporting documenta-
      tion should be retained.


5.0  DEFINITIONS

      The following  terms are defined for use in this document:

ACCURACY              The  closeness  of agreement between an observed value and
                      an  accepted reference  value.   When applied  to  a  set of
                      observed values,  accuracy will  be a combination of  a
                      random component  and of  a  common  systematic  error  (or
                      bias)  component.

BATCH:                A group  of  samples which behave  similarly with respect to
                      the  sampling or the testing  procedures being  employed and
                      which  are processed as a unit (see  Section 3.4.1 for field
                      samples  and Section 4.4.3 for laboratory samples).  For QC
                      purposes,  if the number of samples in a group is greater
                      than 20, then each group of 20 samples  or  less will all be
                      handled  as  a separate batch.

BIAS:                 The  deviation  due to  matrix  effects  of the measured value
                      (x,  - xj from a known spiked amount.  Bias can be assessed
                      by  comparing a  measured  value  to  an  accepted  reference
                      value  in a  sample of known concentration or by determining
                      the  recovery of a known amount of contaminant spiked into
                      a sample (matrix spike).  Thus, the bias (B) due to matrix
                      effects  based  on a  matrix spike is  calculated as:

                                    B - (x. -  xu  ) - K
                        where:
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BLANK:

CONTROL SAMPLE:
DATA QUALITY
OBJECTIVES {DQOs}
DATA VALIDATION:
DUPLICATE:


EQUIPMENT BLANK:

EQUIPMENT RINSATE:
ESTIMATED
QUANTITATION
LIMIT (EQL):
                                    x. - measured value for spiked sample,
                                    xu - measured value for unspiked sample, and
                                    K  * known value of the spike in the sample.

                      Using the following equation yields the percent recovery
                      (XR).
                                    %R
                    100  (x. - xu)/
see Equipment Rinsate, Method Blank, Trip Blank.

A  QC  sample  introduced  into a  process  to  monitor  the
performance of the system.

A  statement  of  the overall level  of uncertainty that  a
decision-maker  is  willing to accept  in results derived
from environmental data (see reference  2, EPA/QAMS, July
16, 1986).   This  is  qualitatively distinct from quality
measurements such  as precision, bias, and detection limit.
The process of evaluating the available data against the
project DQOs  to  make sure that  the  objectives are met.
Data  validation  may  be  very
depending on  project  DQOs.   The
will include analytical  results,
data, and may also include field
                                                       rigorous,  or  cursory,
                                                       available data reviewed
                                                       field QC  data and lab QC
                                                       records.
see  Matrix  Duplicate,
Duplicate.

see Equipment Rinsate.
Field  Duplicate,   Matrix  Spike
A  sample  of analyte-free  media  which has  been used to
rinse  the sampling  equipment.    It  is  collected after
completion of decontamination and prior to sampling.   This
blank is useful  in documenting adequate decontamination of
sampling equipment.

The  lowest  concentration that can  be reliably  achieved
within specified limits of precision  and accuracy during
routine  laboratory  operating  conditions.    The  EQL is
generally 5  to 10  times the MDL.    However,  it may be
nominally chosen within these guidelines  to  simplify  data
reporting.      For   many   analytes  the   EQL   analyte
concentration is selected as the  lowest non-zero standard
in the calibration curve.  Sample EQLs are highly matrix-
dependent.  The EQLs  in SW-846 are  provided  for guidance
and may not always be achievable.
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FIELD DUPLICATES:
LABORATORY CONTROL
SAMPLE:
MATRIX:


MATRIX DUPLICATE:


MATRIX SPIKE:
MATRIX SPIKE
DUPLICATES:
METHOD BLANK:
METHOD DETECTION
LIMIT (MDL):
Independent  samples  which are  collected  as  close  as
possible to the  same  point in space and time.  They are
two separate samples taken  from the same source,  stored  in
separate containers,  and  analyzed independently.   These
duplicates are useful  in documenting the precision of the
sampling process.

A known matrix spiked with compound(s)  representative  of
the target analytes.  This is  used to document laboratory
performance.

The component or substrate (e.g.,  surface water, drinking
water) which contains the analyte of interest.

An intralaboratory split sample which is used  to document
the precision of a method in a given sample matrix.

An aliquot of sample spiked with a known concentration  of
target analyte(s).   The spiking  occurs prior to sample
preparation  and  analysis.   A  matrix  spike  is  used  to
document the bias of a method in a given sample matrix.

Intralaboratory  split  samples   spiked  with   identical
concentrations of target analyte(s).  The  spiking occurs
prior to sample preparation and analysis.  They are  used
to document the precision and  bias of a  method in a given
sample matrix.

An analyte-free matrix to which all  reagents are added  1n
the  same  volumes  or  proportions  as   used   in  sample
processing.   The  method blank should be carried through
the complete sample preparation and analytical procedure.
The  method  blank  is  used  to  document  contamination
resulting from the analytical  process.

For  a method  blank to be  acceptable  for use  with the
accompanying  samples,  the  concentration in the blank  of
any  analyte of  concern should  not  be  higher  than the
highest of either:

(l)The method detection limit, or

(2)Five percent of the regulatory limit  for that analyte,
or

(3)Five  percent  of the  measured concentration  in the
sample.

The  minimum concentration  of  a  substance that  can  be
measured and reported  with  99% confidence that  the analyte
concentration is greater than  zero and  is determined  from
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analysis of a  sample  in  a given matrix type  containing
the analyte.

For  operational  purposes,  when  it  is  necessary  to
determine  the  MDL  in  the  matrix,  the  MDL  should  be
determined by multiplying the appropriate one-sided 99% t-
statistic  by  the  standard  deviation  obtained  from a
minimum of three analyses of a matrix spike containing  the
analyte of Interest  at a concentration three to five times
the estimated MDL, where the  t-statistic  is obtained from
standard references or the table below.
No. of samples;            t-statistic
      3                       6.96
      4                       4.54
      5                       3.75
      6                       3.36
      7                       3.14
      8                       3.00
      9                       2.90
     10                       2.82

Estimate the MDL as follows:
Obtain the concentration value that corresponds to:

a) an  instrument  signal/noise  ratio within the range of
2.5 to 5.0, or

b) the region  of  the standard  curve where  there is a
significant change  in sensitivity (i.e.,  a break  in  the
slope of the standard curve).

Determine the variance (S2) for each analyte as follows:
where xt  -  the  ith  measurement of the variable x
and x = the average value of x;
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ORGANIC-FREE
REAGENT WATER:
PRECISION:
                      Determine the standard deviation (s) for each analyte as
                      f ol1ows;

                                    s .  (S8)"2

                      Determine the MDL  for each  analyte as follows:
                                    MDL
                                           "Cn-1, a « .99)'
where t(nw1     w, is the one-sided t-statistic  appropriate
for the number" of samples used to determine (s)» at the 99
percent level.

For volatiles,  all  references  to water  in  the  methods
refer to water in which an  interferant is  not  observed at
the method detection limit of the compounds of interest.
Organic-free reagent water can be generated by  passing  tap
water through a  carbon  filter bed containing about 1 pound
of activated carbon.  A water purification system may be
used   to   generate   organic-free   deionized   water.
Organic-free reagent water may also be prepared by boiling
water for 15 minutes and, subsequently,  while  maintaining
the temperature  at 90*C» bubbling a contaminant-free inert
gas through the water for 1 hour.

For  semivolatiles  and  nonvolatiles,  all  references  to
water  in  the  methods  refer  to  water  in  which   an
interferant is not  observed at  the method  detection limit
of the compounds of interest.   Organic-free reagent water
can be  generated by passing tap  water through  a carbon
filter bed containing about 1 pound of  activated carbon.
A  water purification  system  may be  used to  generate
organic-free deionized water.

The  agreement  among   a  set of  replicate measurements
without  assumption of  knowledge of  the true value.
Precision  is  estimated by  means  of duplicate/replicate
analyses.  These samples should contain  concentrations of
analyte above the MDL, and may  involve  the use of matrix
spikes.  The most commonly used estimates of precision  are
the relative standard deviation (RSD) or  the  coefficient
of variation (CV),

              RSD  - CV - 100 S/x,
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PROJECT:
QUALITY ASSURANCE
PROJECT PLAN
(QAPjP):
RCRA:

REAGENT BLANK:

REAGENT GRADE:




REAGENT WATER:
REFERENCE MATERIAL:
SPLIT SAMPLES:
STANDARD ADDITION:
STANDARD CURVE:
where:
 x - the  arithmetic mean of  the  xf measurements, and S -
variance; and the relative percent difference  (RPD) when
only two  samples are available.

               RPD - 100 [(x,  - x2)/{(Xl + x2)/2}].

Single  or multiple data collection  activities that are
related through the same planning sequence.

An orderly assemblage of detailed procedures designed to
produce  data  of  sufficient  quality  to  meet  the data
quality   objectives   for   a  specific  data   collection
activity.

The Resource Conservation and Recovery Act.

See Method Blank.

Analytical  reagent  (AR) grade,  ACS  reagent  grade, and
reagent  grade  are  synonymous  terms  for  reagents  which
conform to the current specifications of the Committee on
Analytical Reagents of the American Chemical  Society.

Water  that  has  been generated by any method which  would
achieve  the  performance specifications for ASTM Type II
water.    For organic  analyses,   see  the  definition  of
organic-free reagent water.

A material containing known quantities of target analytes
in  solution  or in a homogeneous  matrix.   It  is used to
document  the bias of the analytical process.

Aliquots  of sample  taken  from  the  same  container and
analyzed  independently.    In  cases  where  aliquots  of
samples  are impossible to obtain, field duplicate samples
should  be taken for the matrix duplicate analysis.   These
are usually taken after mixing or compositing and are used
to document  intra- or interlaboratory precision.

The practice of adding  a known amount  of  an analyte to a
sample  immediately  prior to  analysis.   It is  typically
used to  evaluate  interferences.

A plot of concentrations of known analyte standards versus
the  instrument  response  to  the analyte.   Calibration
standards are prepared by successively diluting a standard
solution  to produce  working standards  which  cover the
working  range of  the  instrument.   Standards   should be
prepared  at the  frequency  specified in the appropriate
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                      section.   The  calibration  standards should  be prepared
                      using  the same type  of  acid  or solvent and  at the same
                      concentration  as  will  result  in  the  samples  following
                      sample preparation.  This  is applicable to  organic and
                      inorganic chemical  analyses.

SURROGATE:            An  organic  compound  which  is similar  to  the  target
                      analyte(s)  in chemical  composition  and behavior  in the
                      analytical  process, but which  is  not  normally found in
                      environmental  samples.

TRIP BLANK:           A sample  of  analyte-free media  taken from the laboratory
                      to  the  sampling  site  and  returned to  the  laboratory
                      unopened.  A trip  blank is used to  document contamination
                      attributable  to shipping and field  handling  procedures.
                      This type of blank  is useful in documenting contamination
                      of  volatile organics  samples.


6.0  REFERENCES

1.   Interim Guidelines  and Specifications  for  Preparing  Quality  Assurance
     Project Plans, QAMS-005/80, December 29,  1980,  Office  of Monitoring Systems
     and Quality Assurance,  ORD, U.S.  EPA,  Washington, DC  20460.

2.   Development of Data Quality Objectives, Description of Stages I  and II, July
     16, 1986, Quality Assurance Management Staff, ORD, U.S. EPA, Washington, DC
     20460.

3.   RCRA  Ground-Water  Monitoring  Technical  Enforcement Guidance  Document,
     September,  1986,  Office of Waste Programs Enforcement.  OSWER,  U.S.  EPA,
     Washington, DC,  20460.

4,   DQO Training  Software, Version  6.5,  December,  1988,  Quality  Assurance
     Management  Staff, ORD,  U.S. EPA,  Washington, DC  20460.

5.   Preparing   Perfect  Project Plans,   EPA/600/9-89/087,   October  1989,  Risk
     Reduction  Engineering Laboratory (Guy  Simes),  Cincinnati OH.

6.   ASTM Method D 1129-77,  Specification for  Reagent Water.   1991  Annual  Book
     of ASTM Standards.   Volume 11.01  Water and Environmental Technology.

7.   Generation  of Environmental Data  Related to Waste Management Activities
     (Draft).  February  1989.   ASTM.
                                   ONE - 29                         Revision 1
                                                                     July 1992

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                                     INDEX

Accuracy  1, 13, 22, 23", 24
Batch  12, 19, 21, 23"
Bias  2, 3, 17-20, 22, 23"-25, 28
Blank  11, 12, 14, 18-20, 23', 24, 25, 28, 29
   Equipment Rinsate  11, 12,  14,  18, 24*
   Method Blank  19, 24, 25", 28
   Reagent Blank  28"
   Trip Blank  12, 18, 24, 29"
Chain-of-Custody  9, 11, 13,  14,  18, 21,  22
Control Chart  18, 19
Control Sample  11, 12,  18,  19, 23, 24"
Data Quality Objectives  (DQO)  1-3, 8, 12, 19, 20, 24", 28
Decision-maker  2, 24
Duplicate  11, 12, 14, 18-20, 23,  24*, 25, 27, 28
   Field Duplicate  11,  12,  24, 25", 28
   Matrix Duplicate  12, 19,  20,  24, 25", 28
   Matrix Spike Duplicate  12, 19, 20, 23, 24, 25"
Equipment Blank  11, 24"
Equipment Rinsate  11, 12, 14, 18, 24*
Estimated Quantitation Limit  (EQL)  24"
Field Duplicate  12, 24, 25", 28
Laboratory Control Sample  19, 25"
Matrix  11, 12, 18-20, 23-25", 26-28
Matrix Duplicate  12, 19, 20, 24,  25*, 28
Matrix Spike  12, 18-20, 23,  25",  26,  27
Matrix Spike Duplicate   12,  19, 20, 23, 24, 25"
Method Blank  19, 24, 25",  28
Method Detection Limit (MDL)  18-20, 22, 24, 25"-27
Organic-Free Reagent Water   27",  28
Precision  1-3, 17-20, 22, 24, 25, 27", 28
Project  1-5, 7, 8, 11-14, 17-19,  21, 23, 24, 28"
Quality Assurance Project Plan (QAPjP)   1-9, 11,  12, 14, 15, 18, 20, 22, 23, 28*
RCRA  1, 8, 28"
Reagent Blank  28"
Reagent Grade  28'
Reagent Water  27, 28"
Reference Material  8, 11, 15, 18, 19, 28"
Split Samples  25, 28'
Standard Addition  20, 28"
Standard Curve  26, 28"
Surrogate  18, 20, 22, 29"
Trip Blank  12, 18, 24,  29*
   Definition of term.
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                                  CHAPTER TWO

                        CHOOSING THE CORRECT PROCEDURE
2.1  PURPOSE

      This chapter  aids the analyst  in choosing the  appropriate  methods for
samples, based upon sample matrix and the analytes to be determined.

      2.1.1  Trace Analysis vs. .MacrganaTy_s_1s

      The methods presented  in  SW-846  were  designed  through sample sizing and
concentration procedures to address the problem of "trace" analyses  (<1000 ppm),
and have been developed for an  optimized working range.  These methods are also
applicable to "minor"  (1000 ppm - 10,000 ppn) and "major" (>10,000 ppm) analyses,
as well as to  "trace"  analyses,  through use of appropriate sample preparation
techniques that result  in analyte concentration within that optimized range. Such
sample preparation techniques include:

      1) adjustment of size of sample prepared for analysis,
      2) adjustment of injection volumes,
      3) dilution or concentration of sample,
      4) elimination of concentration steps prescribed for "trace" analyses,
      5) direct injection (of samples to be analyzed for volatile constituents).

      The performance data presented in each  of these methods were generated from
"trace" analyses, and  may not  be applicable to "minor"  and "major" analyses.
Generally, extraction efficiency improves as concentration  increases.

CAUTION:    Care  should  be taken  when  analyzing  samples  for trace analyses
            subsequent  to  analysis  of concentrated   samples   due  to  the
            possibility of contamination.

      2.1.2   Choice  of  Apparatus  and  Preparation of Reagents

      Since  many types  and  sizes of  glassware and supplies  are  commercially
available, and since it  is  possible  to  prepare reagents  and standards in many
different ways, those specified in these methods may be replaced by any similar
types as long  as this  substitution does  not affect the  overall  quality of the
analyses.


2.2  REQUIRED  INFORMATION

      In  order to  choose  the  correct  combination  of  methods  to form  the
appropriate analytical  procedure, some basic information is required.
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      2.2.1  Physical Statefs)  of Sample

      The phase characteristics of the  sample must be known.  There are several
general categories of phases in which the sample may be categorized:

               Aqueous                  Oil  and Organic  Liquid
               Sludges                  Solids
               Multiphase  Samples       EP and TCLP Extracts
               Ground Water

      2.2.2  Analvtes

      Analytes are divided into classes based on  the determinative methods which
are used to identify and quantify them.  Table 2-1  lists the organic analytes of
SW-846 methods, Table 2-2 lists the analytes that may be prepared using Method
3650,  and Table  2-3 lists  the analytes  that  are collected  from stack  gas
effluents  using VOST methodology.   Tables 2-4 through  2-31  list  the target
analytes of each organic determinative method.  Some of the analytes appear on
wore  than  one  table, as  they may be determined using  any  of  several  methods.
Table 2-32 indicates which methods are  applicable to inorganic target analytes.

      2.2.3  Detection Limits Required

      Regulations may require a specific sensitivity or detection limit for an
analysis,  as in the  determination  of analytes for the Toxicity Characteristic
(TC)  or  for  delisting  petitions.   Drinking water detection limits,  for those
specific organic and metallic analytes covered by the National  Interim Primary
Drinking Water  Standards, are desired in the analysis of ground water.

      2.2.4  Analytical Objective

      Knowledge  of  the analytical  objective will  be  useful  in the  choice of
aliquoting procedures and in the selection of a determinative method.   This is
especially true when the sample  has more  than one  phase.   Knowledge  of  the
analytical objective may not be possible or desirable at all management levels,
but  that  information  should   be  transmitted  to the analytical  laboratory
management to  ensure  that  the correct  techniques  are  being  applied  to  the
analytical effort.

      2.2.5  Detection and Monitoring

      The strategy for detection of compounds in environmental or process samples
may be contrasted with the strategy for monitoring samples.  Detection samples
define initial  conditions. When there is little  information available about the
composition of the sample source,  e.g.,  a well or process stream, mass spectral
identification of organic  analytes  leads to fewer false positive results.  Thus,
the most practical form of detection  for organic analytes, given the analytical
requirements,  is mass  spectral identification.    The choice of  technique  for
metals  is  governed  by  the   detection   limit  requirements   and  potential
interferents.

      Monitoring samples,  on the other hand, are analyzed to confirm existing and
on-going conditions, tracking  the presence  or  absence of constituents  in an


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environmental  or  process  matrix.    In well  defined  and  stable  analytical
conditions and matrices less compound-specific detection modes may be used.

      2.2.6  Sample Containers, Preservations, and HoldingTimes

      Appropriate sample containers,  sample  preservation techniques, and sample
holding times for aqueous matrices are listed in Table 2-33, near the end of this
chapter.   Similar  information may  be found  in  Table 3-1  of  Chapter  Three
(inorganic analytes) and Table 4-1 of Chapter Four (organic analytes).  Samples
must be extracted/analyzed within  the specified holding times for the results to
be considered  reflective of total concentrations.  Analytical  data  generated
outside of the specified holding times must be considered to be minimum values
only.  Such data may be used to demonstrate that a waste is hazardous where it
shows the concentration  of a constituent to be above the regulatory threshold but
cannot be used to demonstrate that a waste is not hazardous.


2.3  IMPLEMENTING THE GUIDANCE

      The  choice  of the  appropriate  sequence  of  methods  depends  on  the
information required and on the experience of the analyst.  Figure 2-1 summarizes
the organic analysis options available.  Appropriate selection is confirmed by
the quality control  results.  The use of the recommended procedures, whether they
are approved or mandatory,  does not release the analyst from demonstrating the
correct execution of the method.

      2-3.1  Extraction andSample Preparation Procedures

      Methods for preparing organic  analytes  are  shown in Table 2-34.   Method
3500 and associated methods should be consulted for further details on preparing
the sample for analysis.

            2.3.1.1  AqueousSamples

            The choice of a preparative method depends on the sample.  Methods
      3510  and  3520 may be  used  for  extraction  of the  semivolatile  organic
      compounds.  Method 3510,  a  separatory funnel  extraction,  is appropriate
      for samples which will not form a persistent emulsion interphase between
      the sample and the extraction solvent.   The formation of an emulsion that
      cannot  be  broken up  by  mechanical   techniques  will  prevent  proper
      extraction  of the  sample.    Method  3520,  a liquid-liquid  continuous
      extraction, may be used for  any aqueous  sample; this method will minimize
      emulsion formation.

                  2.3.1.1.1  Basic or Neutral Extraction of Semivolatiles

                  The solvent extract obtained by performing either Method 3510
            or 3520 at  a neutral  or basic pH will  contain  the  compounds of
            interest.  Refer to Table 1 in the extraction methods (3510 and/or
            3120} for guidance  on  the  pH requirements  for extraction prior to
            analysis.
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            2-3.1.1.2  Acidic ExtractionofPhenolsandAcids

            The extract obtained by performing  either Method 3510 or 3520
      at a pH  less  than  or  equal  to 2 will  contain the phenols and acid
      extractables.

      2.3.1.2  Solid Samples

      Soxhlet  (Methods  3540  and  3541}  and   ultrasonic  (Method  3550}
extractions are used with solid samples.  Consolidated samples should be
ground  finely  enough  to  pass  through  a  1   mm  sieve.     In  limited
applications,  waste dilution  (Method  3580}  may  be  used  if  the  entire
sample is soluble in the specified solvent.

      Methods 35401 and 3541  and 3550  are neutral-pH extraction techniques
and therefore,  depending  on the analysis requirements, acid-base partition
cleanup (Method 3650} may be necessary.  Method 3650 will  only be needed
if chromatographic interferences are severe enough to prevent detection of
the analytes of interest. This  separation will  be most important if a GC
method is chosen for analysis of  the sample.   If GC/MS is used,  the ion
selectivity  of   the  technique  may   compensate   for  chromatographic
interferences.

      2.3.1.3  Oils and Organic Liquids

      Method 3580,  waste  dilution, may be  used  and the resultant  sample
analyzed directly by GC  or  GC/MS.   To avoid overloading  the  analytical
detection system, care must be exercised to ensure that proper dilutions
are made.  Method 3580 gives guidance on performing waste  dilutions.

      To remove  interferences,  Method 3611 may be performed on  an oil
sample directly, without prior sample preparation.

      Method 3650  is  the only other preparative procedure for  oils and
other organic  liquids.   This procedure  Is  a  back  extraction into  an
aqueous phase.   It is generally  introduced  as a cleanup  procedure for
extracts rather than as  a preparative  procedure.   Oils generally  have a
high concentration of semivolatile compounds and, therefore,  preparation
by Method 3650  should be done on a relatively small  aliquot of the sample.
Generally,  extraction  of 1 ml  of oil  will  be  sufficient  to obtain  a
saturated aqueous phase and avoid emulsions.

      2.3.1.4  Sludge Samples

      There 1s no set ratio of liquid to solid  which enables the anajyst
to determine which of the  three extraction methods  cited is the  most
appropriate.    If the  sludge  is an  organic  sludge (solid material  and
organic liquid, as  opposed  to an aqueous sludge}, the  sample should be
handled as  a multiphase sample.

      Determining  the  appropriate methods  for  analysis  of  sludges  is
complicated because of the  lack  of  precise  definition of sludges  with
respect to  the  relative percent  of liquid and solid components.  They may
be classified into three categories but with appreciable overlap.

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            2.3.1.4.1  Liquids

            Use of Method 3510 or Method 3520 may be applicable to sludges
      that  behave like  and  have  the consistency  of  aqueous  liquids.
      Ultrasonic  extraction  (Method  3550)  and  Soxhlet  (Method  3540)
      procedures  will,  most  likely,  be   ineffective   because  of  the
      overwhelming presence of the liquid aqueous phase.

            2.3.1.4.2  Solids

            Soxhlet  (Methods  3540 and 3541) and ultrasonic extraction
      (Method 3550) will  be more effective when applied to sludge samples
      that resemble solids.  Samples may be dried or centrifuged to form
      solid  materials  for  subsequent  determination  of  semi volatile
      compounds.

            Using Method  3650,  Acid-Base Partition Cleanup,  on the extract
      may be necessary, depending on whether chromatographic interferences
      prevent determination of the analytes of interest.

            2.3.1.4.3  Emulsions

            Attempts should be made to break up and separate the phases of
      an emulsion. Several techniques are effective in breaking emulsions
      or separating the phases of emulsions.

      1.  Freezing/thawing:  Certain emulsions will separate if exposed to
          temperatures below 0°C.

      2.  Salting out:  Addition of a salt to make the aqueous phase of an
          emulsion too  polar  to  support a less  polar phase  promotes
          separation.

      .3.  Centrifugation:     Centrifugal  force  may  separate  emulsion
          components  by density.

      4.  Addition of water  or  ethanol:     Emulsion  polymers  may  be
          destabilized when a preponderance  of the aqueous phase is added.

            If techniques for  breaking emulsions fail,  use Method 3520.
      If the emulsion  can be broken, the different phases  (aqueous, solid,
      or organic liquid)  may then be analyzed separately.

      2.3.1.5  Multiphase Samples

      Choice of  the procedure  for  aliquoting multiphase samples is very
dependent on the objective of the analysis.   With a sample in which some
of the phases tend to  separate rapidly,  the percent weight or volume of
each  phase  should be calculated and  each  phase  should  be individually
analyzed for the required analytes.

      An alternate approach is to obtain  a homogeneous sample and attempt
a single analysis on the combination of phases.  This  approach will give


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      no  information on  the  abundance  of the  analytes  in the  Individual  phases
      otr  r than what  can  be implied by solubility.

            A third alternative  is  to  select  phases of interest and to analyze
      only  those selected phases.   This  tactic must  be  consistent  with the
      sampling/analysis  objectives or it will yield insufficient information for
      the time and resources expended.   The phases selected should be compared
      with Figure 2-1  and  Tables 2-34  through 2-36 for further guidance.

      2.3.2  Cleanup Procedures

      Each  category  in  Table  2-35,   Cleanup  of  Organic Analyte  Extracts,
corresponds to one of the possible determinative  methods available in the manual,
Cleanups employed are determined by  the analytes of interest within the extract.
However, the necessity of performing cleanup may  also depend upon the matrix  from
which the  extract was  developed.  Cleanup of a sample may be done exactly as
listructed  in  the cleanup method for  some of  the analytes.    There  are  some
instances  when  cleanup  using  one of  the  methods  may  only proceed  after the
procedure  is  modified to  optimize  recovery and separation.   Several  cleanup
techniques may be possible for each analyte category.   The  information provided
is  not  meant  to imply that  any  or  all of these methods must be  used  for the
analysis  to be  acceptable.    Extracts  with  components which  interfere  with
spectral  or chromatographic  determinations  are expected  to  be  subjected to
cleanup procedures.

      The  analyst's  discretion  must  determine  the   necessity  for  cleanup
procedures, as there are no clear cut criteria for indicating their use.  Method
3600 and associated methods  should be  consulted for further details on extract
cleanup.

      2.3.3  Determinative Procedures

      The determinative methods for organic analytes have been divided into three
categories, shown in Table 2-36:   gas chromatography/mass spectrometry (GC/MS);
specific detection methods, i.e., gas  chromatography (GC);  and high performance
liquid chromatography  (HPLC).   This division  is intended to help an  analyst
choose which determinative method will  apply.  Under each analyte column, SH-846
method numbers have  been indicated, if appropriate,  for the  determination of the
analyte.  A blank has  been left  if no chromatographic determinative  method is
available.

      Generally, the MS procedures are more specific but less sensitive than the
appropriate gas chromatographic/specific detection method.

      Method  8000  gives  a   general   description  of   the technique  of  gas
chromatography.  This method  should be  consulted prior  to application of any of
the gas chromatographic  methods.

      Methods 8080 and 8081,  for  organochlorine pesticides and polychlorinated
biphenyls, Methods 8140  and 8141, for organophosphorus pesticides,  and Me'thods
8150 and 8151, for chlorinated herbicides, are preferred over GC/MS because of
the  combination of  selectivity  and   sensitivity  of  the  flame  photometric,
nitrogen-phosphorus, and electron capture detectors.


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      Methods 8240 and 8260 are both GC/HS methods for volatile analytes.  Method
8240 uses a packed column whereas Method 8260 employs a capillary column.  Better
chromatographic separation of  the  volatile compounds may be obtained by using
Method 8260 rather than 8240.  Performance criteria will be based on Method 8260.
Method 5030 has been combined with both Method 8240  and 8260, with which it was
used  exclusively.    A GC  with  a  selective detector is  also useful  for the
determination of volatile organic compounds in a monitoring scenario, described
in Sec. 2,2.5.

      Methods 8250  and 8270  are  both GC/MS methods  for semi volatile analytes.
Method 8250 uses a packed column whereas Method 8270  employs  a capillary column.
Better chromatographic separation of the semi volatile compounds may be obtained
by using Method 8270 rather  than 8250.   Performance criteria will be based on
Method 8270.
2.4  CHARACTERISTICS

      Figure 2-2 outlines a sequence for determining if a waste exhibits one or
more of the characteristics of a hazardous waste.

      2-4.1  EP and TCLP extracts

      The leachate obtained from using either the EP (Figure 2-3A) or the TCLP
(Figure 2-3B)  is  an aqueous  sample,  and therefore, requires  further solvent
extraction prior to the analysis of semi volatile compounds.

      The TCLP leachate is solvent extracted with methylene chloride at  a pH > 11
and at a pH <2 by either Method 3510 or 3520.   Method 3510 should be used unless
the formation  of emulsions between the sample and  the solvent prevent proper
extraction.  If this problem is encountered,  Method 3520 should be employed.

      The solvent extract obtained by performing either Method 3510 or 3520 at
a basic or neutral pH will  contain the base/neutral compounds of interest.  Refer
to the  specific determinative  method for guidance  on  the  pH requirements for
extraction prior to analysis.

      Due to  the  high  concentration of  acetate  in the  TCLP extract,  it  is
recommended that purge-and-trap be used to Introduce the volatile sample into the
gas chromatograph.


2.5  GROUND WATER

      Appropriate analysis schemes for the determination of analytes in ground
water are presented in Figures 2-4A, 2-4B,  and 2-4C.  Quantitation limits for the
metallic  analytes  should correspond  to the drinking  water limits which are
available.
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      2.5,1 Special Techniques for Hetal Analvtes

      All  atomic  absorption  analyses  should  employ appropriate  background
correction systems whenever  spectral  interferences  could be present.  Several
background  correction  techniques  are  employed in  modern  atomic  absorption
spectrometers.  Matrix modification can complement background correction in some
cases.  Since no approach to  interference  correction  is completely effective in
all cases, the analyst should attempt to verify the adequacy of correction.   If
the interferant is known (e.g. high concentrations of iron  in the determination
of selenium), accurate analyses of synthetic solutions of the interferant (with
and without analyte)  could establish the efficacy of  the  background correction.
If the nature of the interferant is not established, good agreement of analytical
results  using two substantially different  wavelengths could substantiate the
adequacy of the background correction.

      To  reduce matrix interferences,  all.  graphite  furnace  atomic  absorption
(GFAA) analyses should be performed using techniques which  maximize an isothermal
environment within the furnace cell.  Data  indicate  that two such  techniques,
L'vov platform and the Delayed Atomization Cuvette (DAC),  are  equivalent in this
respect, and  produce  high quality results.

      All furnace atomic absorption analysis should be carried out using the best
matrix modifier for the analysis.  Some  examples of modifiers are listed below.
(See also the appropriate methods.)

            ElementIs)           Hodifier|s)

            As and Se         Nickel  nitrate, palladium
            Pb                Phosphoric acid, ammonium phosphate,  palladium
            Cd                Ammonium phosphate, palladium
            Sb                Ammonium nitrate, palladium
            Tl                Platinum,  palladium

      The ICP calibration standards must match the acid composition and strength
of the acids  contained in the samples.  Acid strengths  in the ICP  calibration
standards should be stated in the raw data.

      2.5.2  Special  Techniques for Indicated Analvtes and Anions

      If  an  Auto-Analyzer   is  used  to  read  the   cyanide  distillates,  the
spectrophotometer must  be used with a 50  mm path length cell.  If a  sample is
found to  contain cyanioa, the  sample  must  be  redistilled a  second time and
analyzed to confirm the  presence of the cyanide.  The second distillation must
fall  within the 14-day holding time.

2.6  REFERENCES

1.   Barcelona, M.J.   "TOC Determinations  in Ground Water"; Ground Mater  1984,
     22(1).  18-24,
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2.   Riggin, R.;  et al.  Development and Evaluation of Methods for Total Organic
     Halide and  Purqeable  Organic  Halidein  Wastewater; U.S.  Environmental
     Protection  Agency,  Office  of  Research  and  Development.  Environmental
     Monitoring and Support Laboratory. ORD  Publication  Offices  of Center for
     Environmental  Research  Information: Cincinnati, OH, 1984; EPA-600/4-84-008.

3.   McKee, 6.;  et  al.  Determination of Inorganic  Anions  in  Water by  Ion
     Chromatography; (Technical addition  to Methods  for  Chemical  Analysis of
     Water  and  Wastewater,  EPA 600/4-79-020),  U.S.   Environmental  Protection
     Agency. Environmental Monitoring and Support Laboratory.  ORD Publication
     Offices of Center for Environmental  Research Information:  Cincinnati, OH,
     1984; EPA-600/4-84-017.
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                                   TABLE 2-1
             DETERMINATIVE  ANALYTICAL METHODS  FOR ORGANIC  COMPOUNDS
 Compound
Applicable Method(s)
Acenaphthene
Acenaphthylene
Acetaldehyde
Acetone
Acetonitrile
Acetophenone
2-Acetylami nof 1uorene
1-Acetyl-2-thiourea
Acifluorfen
Acrolein  (Propenal)

Acrylamide
Acrylonitrile
Alachlor
Aldicarb  (Temik)
Aldicarb  Sulfone
Aldrin
Ally! alcohol
Ally! chloride
2-Aminoanthraquinone
Aminoazobenzene
4-Aminobiphenyl
2-Amino-4,6-dinitrotoluene (2-Ara-DNT)
4-Amino-2,6-dinitrotoluene (4-Ara-DNT)
3-Amino-9-ethylcarbazole
Anilazine
Aniline
o-Anisidine
Anthracene
Araraite
Aroclor-1016 (PCB-1016)
Aroclor-1221 (PCB-1221)
Aroclor-1232 (PCB-1232)
Aroclor-1242 (PCB-1242)
Aroclor-1248 (PCB-1248)
Aroclor-1254 (PCB-1254)
Aroclor-1260 (PCB-1260)
Aspon
Asulam
Atrazine
Azinphos-ethyl
Azinphos-methyl
Barban
Bentazon
8100, 8250/8270, 8310, 8410
8100, 8250/8270, 8310, 8410
8315
8240/8260, 8315
8240/8260
8250/8270
8270
8270
8151
8030/8031, 8240/8260, 8315,
8316
8032, 8316
8030/8031, 8240/8260, 8316
8081
8318
8318
8080/8081, 8250/8270, 8275
8240/8260
8010, 8240/8260
8270
8270
8250/8270
8330
8330
8270
8270
8250/8270
8270
8100, 8250/8270, 8310, 8410
8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8253/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8141
8321
8141
8141
8140/8141, 8270
8270
8151
                                   TWO - 10
                   Revision 2
               September  1994
                                   \

-------
                                  TABLE  2-1.
                                  (Continued)
 Compound
Applicable  Method(s)
 Benzal chloride
 Benzaldehyde
 Benz(a)anthracene
 Benzene
 Benzidine
 Benzo(b)fluoranthene
 Benzo(j)f1uoranthene
 Benzo(k)fluoranthene
 Benzoic acid
 Benzo(g,h,i)perylene
 Benzo(a)pyrene

 p-Benzoquinone
 Benzotrichloride
 Benzyl alcohol
 Benzyl benzoate
 Benzyl chloride
 BHC  (Hexachlorocyclohexane)
 a-BHC  (alpha-Hexachlorocyclohexane)
 p-BHC (beta-Hexachlorocyclohexane)
 5-BHC  (delta-Hexachlorocyclohexane}
 7-BHC (Lindane, gamma-Hexachlorocyclohexane)
 Bi s(2-Chloroethoxy)methane
 Bis(2-Chloroethyl)ether
 Bi s(2-Chloroethyl)sul fide
 Bis (2-Chloroisopropyl) ether
 Bis(2-Ethylhexyl) phthalate
 Bo!star (Sulprofos)
 Broriiqacetone
 Broraobenzene
 Bromochloromethane
 Bromod i ch1orometh ane
4-Bromof1uorobenzene
Bromoform
Bromomethane
4-Bromophenyl  phenyl ether
Bromoxynil
Butanal
n-Butanol
2-Butanone (Methyl  ethyl ketone, MEK)
n-Butyl benzene
sec-Butyl benzene
tert-Butylbenzene
Butyl benzyl  phthalate
8121
8315
8100, 8250/8270, 8310,  8410
8020, 8021,  8240/8260
8250/8270
8100, 8250/8270, 8310
8100
8100, 8250/8270, 8275,  8310
8250/8270, 8410
8100, 8250/8270, 8310
8100, 8250/8270, 8275,  8310,
8410
8270
8121
8250/8270
8061
8010, 8121,  8240/8260
8120
8080/8081, 8121, 8250/8270
8080/8081, 8121, 8250/8270
8080/8081, 8121, 8250/8270
8080/8081, 8121, 8250/8270
8010, 8110,  8250/8270,  8410
8110, 8250/8270, 8410
8240/8260
8010, 8110,  8250/8270,  8410
8060/8061, 8250/8270, 8410
8140/8141
8010, 8240/8260
8010, 8021,  8260
8021, 8240/8260
8010, 8021,  8240/8260
8240/8260
8010, 8021,  8240/8260
8010, 8021,  8240/8260
8110, 8250/8270, 8410
8270
8315
8260
8015, 8240/8260
8021, 8260
8021, 8260
8021, 8260
8060/8061, 8250/8270, 8410
                                   TWO - 11
                    Revision  2
               September  1994

-------
                                  TABLE 2-1.
                                  (Continued)
Compound
Applicable Method(s)
2-sec-Butyl-4,6-dinitrophenol (ONBP, Dinoseb)
Captafol
Captan
Carbaryl  (Sevin)
Carbazole
Carbofuran  (Furaden)
Carbon disulfide
Carbon tetrachlon'de
Carbophenothion (Carbofenthion)
Chloral hydrate
Chloramben
Chlordane (technical)
a-Chlordane
7-Chlordane
Chlorfenvinphos
Chloroacetonitrile
4-Chloroaniline
Chlorobenzene
Chlorobenzilate
2-Chloro-l,3-butadiene
1-Chlorobutane
Chiorodibromomethane (Dibromochloromethane)
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane
Chloromethane
5-Chloro-2-raethylaniline
Chloromethyl methyl ether
4-Chloro-3-methylphenol
Chloroneb
3-(Chloromethyl)pyridine hydrochloride
1-Chioronaphthalene
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenol
4-Chloro-l,2-phenylenediamine
4-Chloro-l,3-phenylenediamine
4-Chlorophenyl phenyl ether
Chloroprene
3-Chloropropene
3-Chloropropionitrile
ChloropropyTate
8040, 8150/8151, 8270, 8321
8081, 8270
8081, 8270
8270, 8318
8275
8270, 8318
8240/8260
8010, 8021, 8240/8250
8141, 8270
8240/8260
8151
8080, 8250/8270
8081
8081
8141, 8270
8260
8250/8270, 8410
8010, 8020, 8021, 8240/8260
8081, 8270
8260
8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8240/8260
8010, 8240/8260
8010, 8021, 8240/8260
8010, 8260
8010, 8021, 8240/8260
8270
8010
8040, 8250/8270, 8275, 8410
8081
8270
8250/8270, 8275
8120/8121, 8250/8270, 8410
8040, 8250/8270, 8271, 8410
8410
8270
8270
8110, 8250/8270, 8410
8010, 8240/8260
8260
8240/8260
8081
                                   TWO - 12
                   Revision 2
               September 1994

-------
                                   TABLE 2-1.
                                   (Continued)
 Compound
Applicable  Method(s)
Chlorothalonil
2-Chlorotoluene
4-Chlorotoluene
Chlorpyrifos
Chlorpyrifos methyl
Chrysene
Coumaphos
Coumarin Dyes
p-Cres1dine
o-Cresol (2-Methylphenol)
m-Cresol (3-Methylphenol)
p-Cresol (4-Methylphenol)
Cresols (Methylphenols, Cresylic acids)
Crotonaldehyde
Crotoxyphos
Cyclohexanone
2-Cyclohexyl-4,6-di nitrophenol
2,4-D
Dalapon
2,4-DB
DBCP
2,4-D, butoxyethanol ester
DCPA
DCPA diacid
4,4'-DDD
4,4'-DDE
4,4'-DDT
Decanal
Deraeton-0, and -S
2,4-D,ethylhexyl ester
Dial late
2,4-Diaminotoluene
Diazinon
Dibenz{a,h)acridine
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
7H-Dibenzo(c,g)carbazole
Di benzofuran
Di benzo(a,e)pyrene
Dibenzo(a,h)pyrene
Dibenzo{a,i)pyrene
Dibenzothiophene
Dibromochloromethane (Chlorodibromomethane)
1,2-Dibrorao-3-chloropropane
8081
8021,  8260
8010,  8021, 8260
8140/8141
8141
8100,  8250/8270, 8310, 8410
8140/8141, 8270
8321
8270
8250/8270, 8410
8270
8250/8270, 8275, 8410
8040
8260,  8315
8141,  8270
8315
8040,  8270
8150/8151, 8321
8150/8151, 8321
8150/8151, 8321
8081
8321
8081
8151
8080/8081, 8250/8270
8080/8081, 8270
8080/8081, 8250/8270
8315
8140/8141, 8270
8321
8081,  8270
8270
8140/8141
8100
8100,  8250/8270
8100,  8250/8270, 8310
8100
8250/8270, 8410
8100,  8270
8100
8100
8275
8010,  8021, 8240/8260
8010,  8011, 8240/8260, 8270
                                   TWO - 13
                   Revision 2
               September  1994

-------
                                   TABLE 2-1.
                                  (Continued)
 Cofpound
Applicable Method(s)
 1,2-Dibroraoethane  (Ethylene  dibromide)
 Di bromof1uoromethane
 D   "omomethane
 C   5-butyl  phthalate
 Dicamba
 Dichlone
 1,2-Dichlorobenzene

 1,3-Dichlorobenzene

  4-Di chlorobenzene

  J'-Dichlorobenzidine
 -,5-Dichlorobenzoic acid
 l,4-Dich1oro-2-butene
 ci s-1,4-Dichloro-2-butene
 •' ins-l,4-Dichloro-2-butene
   .hiorodi fl uororaethane
 j., 1 -Di chl oroethane
 1,2-Dichloroethane
 1,1-Dichloroethene (Vinylidene chloride)
 cis-l»2-Dichloroethene
 trans-1,2-Dichloroethene
 Dichlorofenthion
 Dichloromethane (Methylene chloride)
 2,4-Dichlorophenol
 2,6-Dichlorophenol
 Dichlorprop
 1,2-Dichloropropane
 1,3-Dichloropropane
 2,2-Dichloropropane
 l,3-Dichloro-2-propanol
 1,1-Dichloropropene
 cis-l,3-Dichloropropene
 trans-l,3-Dichloropropene
Dichlorvos  (Dichlorovos)
Dichrotophos
Dicofol
Dieldrin
 1,2,3,4-Diepoxybutane
Diethyl  ether
Diethyl  phthalate
Diethylstilbestrol
Diethyl  sulfate
8010, 8011, 8021, 8240/8260
8260
8010, 8021, 8240/8260
8060/8061, 8250/8270, 8410
8150/8151, 8321
8081, 8270
8010, 8020, 8021, 8120/8121,
8250/8270, 8260, 8410
8010, 8020, 8021, 8120/8121,
8250/8270, 8260, 8410
8010, 8020, 8021, 8120/8121,
8250/8270, 8260, 8410
8250/8270
8151
8010, 8240
8260
8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8021, 8260
8010, 8021, 8240/8260
8141
8010, 8021, 8240/8260
8040, 8250/8270, 8275, 8410
8040, 8250/8270
8150/8151, 8321
8010, 8021, 8240/8260
8021, 8260
8021, 8260
8010, 8240/8260
8021, 8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8140/8141, 8270, 8321
8141, 8270
8081
8080/8081, 8250/8270
8240/8260
8015, 8260
8060/8061, 8250/8270, 8410
8270
8270
                                   TWO - 14
                   Revision  2
               September  1994

-------
                                   TABLE 2-1.
                                   (Continued)
 Compound
 Applicable  Method(s)
 1,4-Di f1uorobenzene
 Dihydrosaffrole
 Dimethoate
 3,3'-Dimethoxybenzidine
 Dimethyl aminoazobenzene
 2,5-Dimethylbenzaldehyde
 7,12-Dimethylbenz(a)anthracene
 3,3'-Dimethylbenzidine
 a,a-Dimethylphenethylamine
 2,4-Dimethylphenol
 Dimethyl phthalate
 Dinitrobenzene
 1,2-Di n i trobenzene
 1,3-Dinitrobenzene (1,3-DNB)
 1,4-Di n'1 trobenzene
 4,6-Dinitro-2-methylphenol
 2,4-Dinitrophenol
 2,4-Dinitrotoluene (2,4-DNT)

 2,6-Dinitrotoluene (2,6-DNT)
 Dinocap
 Dinoseb {2-sec-Butyl-4,6-dinitrophenol, DNBP)
 Di-n-octyl phthalate
 Di-n-propyl phthalate
 Dioxacarb
 1,4-Dioxane
 Dioxathion
 Diphenylamine
 5,5-Di phenylhydantoi n
 1,2-Di phenylhydrazi ne
 Disperse Blue 3
 Disperse Blue 14
 Disperse Brown 1
 Disperse Orange 3
 Disperse Orange 30
Disperse Red 1
 Disperse Red 5
Disperse Red 13
Disperse Red 60
Disperse Yellow 5
Disulfoton
 Endosulfan I
 Endosulfan II
 Endosulfan sulfate
8240/8260
8270
8141, 8270,  8321
8270
8250/8270
8315
8250/8270
8270
8250/8270
8040, 8250/8270
8060/8061, 8250/8270,  8410
8090
8270
8270, 8330
8270
8250/8270, 8410
8040, 8250/8270, 8410
8090, 8250/8270, 8275, 8330,
8410
8090, 8250/8270, 8330, 8410
8270
8040, 8150/8151, 8270, 8321
8060/8061, 8250/8270,  8410
8410
8318
8240/8260
8141, 8270
8250/8270, 8275
8270
8250/8270
8321
8321
8321
8321
8321
8321
8321
8321
8321
8321
8140/8141, 8270, 8321
8080/8081, 8250/8270
8080/8081, 8210/8270
8080/8081, 8210/8270
                                   TWO - 15
                    Revision  2
                September  1994

-------
                                   TABLE 2-1.
                                   (Continued)
 Compound
Applicable Method(s)
 Endrin
 Endrin  aldehyde
 Endrin  ketone
 Epichlorohydrin
 EPN
 Ethanol  (Ethyl  alcohol)
 Ethion
 Ethoprop
 Ethyl acetate
 Ethyl benzene
 Ethyl carbamate
 Ethylene dibromide
 Ethylene oxide
 Ethyl methacrylate
 Ethyl methanesulfonate
 Ethyl parathion
 Etridiazole
 Famphur
 Fenitrothion
 Fensulfothion
 Fenthion
 Fluchloralin
 Fluoranthene
 Fluorene

 Fluorescent Brightener 61
 Fluorescent Brightener 236
 Fluorobenzene
 2-Fluorobiphenyl
 2-Fluorophenol
 Fonophos
 Formaldehyde
 Halowax-1000
 Halowax-1001
 Halowax-1013
 Halowax-1014
 Halowax-1051
Halowax-1099
Heptachlor
Heptachlor epoxide
Heptanal
Hexach1orobenzene
8080/8081, 8250/8270
8080/8081, 8250/8270
8081, 8210/8270
8010, 8240/8260
8141, 8270
8015, 8240/8260
8141, 8270
8140/8141
8260
8020, 8021, 8240/8260
8270
8010, 8011, 8021, 8240/8260
8240/8260
8240/8260
8250/8270
8270
8081
8141, 8270, 8321
8141
8140/8141, 8270, 8321
8140/8141, 8270
8270
8100, 8250/8270, 8310, 8410
8100, 8250/8270, 8275, 8310,
8410
8321
8321
8260
8250/8270
8250/8270
8141
8315
8081
8081
8081
8081
8081
8081
8080/8081, 8250/8270
8080/8081, 8250/8270
8315
8081, 8120/8121, 8250/8270,
8275, 8410
                                   TWO - 16
                   Revision 2
               September 1994

-------
                                  TABLE 2-1.
                                  (Continued)
Compound
Applicable Method(s)
Hexachlorobutadiene  (1,3-Hexachlorobutadiene)

Hexachlorocyclohexane
a-Hexachlorocyclohexane  (a-BHC)

/3-Hexachl orocyclohexane  {/3-BHC)

5-Hexachlorocyclohexane  (5-BHC)

•y-Hexachl orocycl ohexane  (-y-BHC)

Hexachlorocyclopentadiene

Hexachl oroethane

Hexachlorophene
Hexachloropropene
Hexahydro-l,3,5-trinitro-l,3,5-triazine  (RDX)
Hexamethylphosphoramide  (HMPA)
Hexanal
2-Hexanone
HMX
  2,3,4,6,7,8-HpCDD
  2,3,4,6,7,8-HpCDF
  2,3,4,7,8,9-HpCDF
  2,3,4,7,8-HxCDD
  2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
Hydroquinone
3-Hydroxycarbofuran
5-Hydroxydicamba
2-Hydroxypropionitrile
Indeno(l»2,3-cd)pyrene
lodoraethane
Isobutyl alcohol (2-Methyl-l-propanol}
Isodrin
Isophorone
Isopropylbenzene
p-Isopropyltoluene
Isosafrole
8021, 8120/8121, 8250/8270,
8260, 8410
8120
8080/8081, 8120/8121, 8250,
8270
8080/8081, 8120/8121, 8250,
8270
8080/8081, 8120/8121, 8250,
8270
8080/8081, 8120/8121, 8250,
8270
8081, 8120/8121, 8250/8270,
8410
8120/8121, 8250/8270, 8260,
8410
8270
8270
8330
8141, 8270
8315
8240/8260
8330
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8270
8318
8151
8240/8260
8100, 8250/8270, 8310
8240/8260
8240/8260
8081, 8270
8090, 8250/8270, 8410
8021, 8260
8021, 8260
8270
                                   TWO - 17
                    Revision  2
               September  1994

-------
                                   TABLE  2-1.
                                  (Continued)
 Compound
Applicable Method(s)
 Isovaleraldehyde
 Kepone
 Leptophos
 Malathion
 Maleic anhydride
 Halononitrile
 MCPA
 MCPP
 Merphos
 Mestranol
 Methacrylonitrile
 Methanol
 Methapyrilene
 Methiocarb  (Hesurol)
 Methomy! (Lannate)
 Methoxychlor (4,4'-Methoxychlor)
 Methyl acrylate
 Methyl-t-butyl ether
 3-Methylcholanthrene
 2-Methyl-4,6-dinitrophenol
 4,4'-Methylenebi s(2-chloroani1i ne)
 4,4'-Methylenebis(N,N-dimethy1aniline)
 Methyl ethyl ketone (MEK,  2-Butanone)
 Methylene chloride  (Dichloromethane)
 Methyl iodide
 Methyl isobutyl ketone (4-Methyl-2-pentanone)
 Methyl methacrylate
 Methyl tnethanesulfonate
 2-Methylnaphtha!ene
 2-Methyl-5-nitroani1ine
 Methyl parathion
 4-Methyl-2-pentanone  (Methyl isobutyl ketone)
 2-Methylphenol  (o-Cresol)
 3-Methylphenol  (m-Cresol)
 4-Methylphenol  (p-Cresol)
 2-Methylpyridine
Methyl-2,4,6-trinitrophenylnitramine (Tetryl)
Mevinpho'
 Mexacarbcte
Mi rex
Monochrotophos
Naled
Naphthalene
8315
8081, 8270
8141, 8270
8141, 8270
8270
8240/8260
8150/8151, 8321
8150/8151, 8321
8140/8141, 8321
8270
8240/8260
8260
8270
8318
8318, 8321
8080/8081, 8250/8270
8260
8260
8100, 8250/8270
8040
8270
8270
8015, 8240/8260
8010, 8021, 8240/8260
8010, 8240/8260
8015, 8240/8260
8240/8260
8250/8270
8250/8270, 8410
8270
8270, 8321
8015, 8240/8260
8250/8270, 8410
8270
8250/8270, 8275, 8410
8270
8330
8140/8141, 8270
8270
8081, 8270
8141, 8270, 8321
8140/8141, 8270, 8321
8021, 8100, 8250/8270, 8260,
8275, 8310, 8410
                                   TWO - 18
                   Revision  2
               September  1994

-------
                                  TABLE 2-1.
                                  (Continued)
Compound
Applicable Method(s)
Naphthoquinone
1,4-Naphthoquinone
1-Naphthylaraine
2-Naphthylamine
Nicotine
5-Nitroacenaphthene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
S-Nitro-o-anisidine
Nitrobenzene (NB)

4-Nitrobiphenyl
Nitrofen
2-Nitrophenol
4-Nitrophenol
2-Nitropropane
Nitroquinoline-1-oxide
N-Ni trosodi butyl ami ne
N-Nitrosodiethyl amine
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylami ne
N-Ni trosomethylethyl ami ne
N-Nitrosomorpholine
N-Nitrosopi peridi ne
N-Nitrosopyrrolidine
o-Nitrotoluene (2-NT)
m-Nitrotoluene (3-NT)
p-Nitrotoluene (4-NT)
5-Nitro-o-toluidine
trans-Nonachlor
Nonanal
OCDD
OCDF
Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine
                           (HMX)
Octamethyl pyrophosphoramide
Octanal
4,4'-Oxydianiline
Parathion
Parathion, ethyl
Parathion, methyl
PCB-1016 (Aroclor-1016)
8090
8270
8250/8270
8250/8270
8270
8270
8250/8270, 8410
8250/8270, 8410
8250/8270, 8410
8270
8090, 8250/8270, 8260, 8330,
8410
8270
8081, 8270
8040, 8250/8270, 8410
8040, 8151, 8250/8270, 8410
8260
8270
8250/8270
8270
8070, 8250/8270, 8410
8070, 8250/8270, 8410
8070, 8250/8270, 8410
8270
8270
8250/8270
8270
8330
8330
8330
8270
8081
8315
8280/8290
8280/8290

8330
8270
8315
8270
8270
8141
8140/8141
8080/8081, 8250/8270
                                   TWO - 19
                   Revision  2
               September  1994

-------
                                  TABLE 2-1.
                                  (Continued)
Compound
Applicable Method(s)
PCB-1221 (Aroclor-1221)
PCB-1232 (Aroclor-1232)
PCB-1242 (Aroclor-1242)
PCB-1248 (Aroclor-1248)
PCB-1254 (Aroclor-1254)
RCB-1260 (Aroclor-1260)
PCNB
1,2,3,4,7-PeCDD
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
"antaehlorobenzene
 entachloroethane
 ;entachlorohexane
Pentachloroni trobenzene
Pentachlorophenol
Pentaf1uorobenzene
Pentanal
trans-Permethrin
Perthane
Phenacetin
Phenanthrene

Phenobarbltal
Phenol
1,4-Phenylened1 ami ne
Phorate
Phosalone
Phosmet
Phosphamidion
Phthalic anhydride
Pi cloram
2-Picoline
Piperonyl sulfoxide
Promecarb
Pronaroide
Propachlor
Propanal
Propargyl alcohol
8-Propiolactone
Propionitrile
Propoxur (Baygon)
n-Propylamine
n-Propylbenzene
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8081
8280/8290
8280/8290
8280/8290
8280/8290
8121, 8250/8270
8240/8260
8120
8250/8270
8040, 8151, 8250/8270, 8410
8260, 4010
8315
8081
8081
8250/8270
8100, 8250/8270, 8275, 8310,
8410
8270
8040, 8250/8270, 8410
8270
8140/8141, 8270, 8321
8270
8141, 8270
8141, 8270
8270
8151
8240/8260, 8250/8270
8270
8318
8250/8270
8081
8315
8240/8260
8240/8260
8240/8260
8318
8240/8260
8021, 8260
                                   TWO - 20
                   Revision 2
               September  1994

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                                  TABLE  2-1.
                                  (Continued)
Compound
Applicable Method(s)
Propylthiouracil
Pyrene

Pyridine
RDX
Resorcinol
Ronnel
Safrole
Simazine
Solvent Red 3
Solvent Red 23
Stirophos  (Tetrachlorvinphos)
Strobane
Strychnine
Styrene
Sulfall ate
Sulfotepp
2,4,5-T
2,4,5-T, butoxyethanol ester
2,4,5-T» butyl ester
1,2,3,4-TCDD
1,2,7,8-TCDD
1,2,8,9-TCDD
1,3,6,8-TCDD
1,3,7,8-TCDD
1,3,7,9-TCDD
2,3,7,8-TCDD
1,2,7,8-TCDF
2,3,7,8-TCDF
TEPP
Terbuphos  (Terbufos)
Terphenyl
1,2,3,4-Tetrachl orobenzene
1,2,3,5-Tetrachlorobenzene
1,2,4,5-Tetrachlorobenzene
Tetrachlorobenzenes
1,1,1,2-Tetrachl oroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
2,3,4,6-Tetrachl orophenol
Tetrachlorophenol s
Tetrachlorvinphos {Stirophos}
Tetraethyl dithiopyrophosphate
Tetraethyl pyrophosphate
8270
8100, 8250/8270, 8275, 8310,
8410
8240/8260, 8270
8330
8270
8140/8141
8270
8141
8321
8321
8140/8141, 8270
8081
8270, 8321
8021, 8240/8260
8270
8141
8150/8151, 8321
8321
8321
8280
8280
8280
8280
8280
8280
8280/8290
8280
8280/8290
8141
8141, 8270
8250/8270
8121
8121
8121, 8250/8270
8120
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8250/8270
8040
8140/8141, 8270
8270
8270
                                   TWO - 21
                   Revision 2
               September 1994

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                                  TABLE 2-1.
                                  (Continued)
 Compound
Applicable Method(s)
Tetrazene
Thiofanox
Thlonazine
Thlophenol  (Benzenethiol)
TOCP  (Tri-o-cresylphosphate)
Tokuthion (Prothiofos)
m-Tolualdehyde
o-Tolualdehyde
p-Tolualdehyde
Toluene
Toluene diisocyanate
o-Toluidine
Toxaphene
2,4,5-TP (SHvex)
2,4,6-Tribromophenol
1,2,3-Tr1chlorobenzene
1,2,4-Trichlorobenzene

1,3,5-Trichlorobenzene
1,1,1-Trichloroethane
1»1,2-Tri chloroethane
Trichloroethene
Trlchlorof1uoromethane
Trichlorfon
Trichloronate
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Trichlorophenols
1,2,3-Trichloropropane
0,0,0-Triethyl phosphorothioate
Tn'fluralin
2,4,5-Trimethylaniline
1,2,4-Trimethylbenzene
1,3,5-Trimethylbenzene
Trimethyl phosphate
1,3,5-Trinitrobenzene (1,3,5-TNB)
2,4,6-Trlnltrotoluene (2,4,6-TNT)
Tri-o-cresyl phosphate (TOCP)
Tri-p-tolyl  phosphate
Tris(2,3-Dibroraopropyl) phosphate (Tris-BP)
Vinyl  acetate
Vinyl  chloride
8331
8321
8141, 8270
8270
8141
8140/8141
8315
8315
8315
8020, 8021, 8240/8260
8270
8270
8080/8081, 8250/8270
8150/8151, 8321
8250/8270
8021, 8121, 8260
8021, 8120/8121, 8250/8270,
8260, 8410
8121
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8141, 8321
8140/8141
8250/8270, 8410
8040, 8250/8270, 8410
8040
8010, 8021, 8240/8260
8270
8081, 8270
8270
8021, 8260
8021, 8260
8270
8270, 8330
8330
8141
8270
8270, 8321
8240/8260
8010, 8021, 8240/8260
                                   TWO - 22
                   Revision 2
               September 1994

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                                  TABLE  2-1.
                                  (Continued)
Compound                                         Applicable Method(s)
o-Xylene                                         8021, 8260
m-Xylene                                         8021, 8260
p-Xylene                                         8021, 8260
Xylene  (Total)                                   8020, 8240
                                  TABLE 2-2A.
                      HETHOD 3650 - BASE/NEUTRAL FRACTION


Benz(a)anthracene                               Hexachlorobenzene
Benzo(a)pyrene                                  Hexachlorobutadi ene
Benzo(b)fluoranthene                            Hexachloroethane
Chiordane                                       Hexac hiorocyclopentad i ene
Chlorinated dibenzodioxins                      Naphthalene
Chrysene                                        Nitrobenzene
Creosote                                        Phorate
Dichlorobenzene(s)                              2-Picoline
Dinitrobenzene                                  Pyridine
2,4-Di ni trotoluene                              Tetrachlorobenzene(s)
Heptachlor                                      Toxaphene
                                  TABLE 2-2B.
                          METHOD 3650  - ACID FRACTION

2-Chlorophenol                                  4-Nitrophenol
Cresol(s)                                       Pentachlorophenol
Creosote                                        Phenol
Dichlorophenoxyacetic acid                      Tetrachlorophenol(s)
2,4-Dimethylphenol                              Trichlorophenol(s)
4,6-Dinitro-o-cresol                            2,4,5-TP (Silvex)
                                   TWO - 23                         Revision 2
                                                                September 1994

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                                  TABLE 2-3.
                    METHOD 5041 - SORBENT CARTRIDGES FROM
                    VOLATILE ORGANIC SAMPLING TRAIN (VOST)

Acetone                                         1,2-Dichloropropane
Acrylonitrile                                   cis-l»3-Dichloropropene
Benzene                                         trans-l,3-Dichloropropene
Bromodichloromethane                            Ethyl benzene3
Bromoform8                                      lodomethane
Bromomethane                                    Methylene chloride
Carbon disulfide                                Styrene3
Carbon tetrachloride                            1,1,2,2-Tetrachloroethane*
Chi orobenzene                                   Tetrachloroethene
Chi orodlbrompmethane                            To!uene
Chioroethane                                    1,1,1-Trlchloroethane
Chloroform                                      1,1,2-Trichloroethane
Chloromethane                                   Trichloroethene
Dibromomethane                                  Trichlorofluoromethane
1,1-DIchloroethane                              1,2,3-Trichlorppropane8
1,2-Dichloroethane                              Vinyl chloride
1,1-Dichloroethene                              Xylenes3
trans-1,2-Dichloroethene


3  Boiling point of this compound  is above 132DC,  Method 0030  is  not
appropriate for quantitative sampling of this analyte.

b  Boiling point of this compound  is below 30°C.  Special precautions must  be
taken when sampling for this analyte by Method 0030.  Refer to Sec. 1.3 of
Method 5041 for discussion.
                                   TWO - 24                         Revision 2
                                                                September 1994

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                                  TABLE 2-4.
                      METHOD  8010 -  HALOGENATED VOLATILES
Ally! chloridi
Benzyl chloride
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl) ether
Bromoacetone
Bromobenzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane
Chioromethane
Chioromethyl methyl ether
Chioroprene
4-Chlorotoluene
Dibromochloromethane
l,2-D1bromo-3-chloropropane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Di chlorobenzene
l,4-Dichloro-2-butene
Dichlorodifluoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene (Vinylidene chloride)
trans-1,2-Dichloroethene
Dichloromethane (Methylene Chloride)
1,2-Dichloropropane
1,3-Di chloro-2-propanol
cis-l,3-Dichloropropene
trans-1,3-Dichloropropene
Epichlorhydrin
Ethylene dibromide
Methyl iodide
1,1,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
Tetrachloroethene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chlorof1uoromethane
1,2,3-Trichloropropane
Vinyl chloride
                    For Method 8011,  see Table 2-7
            TABLE 2-5.
METHOD 8015 - NONHALOGENATED VOLATILES
                   TABLE 2-6.
           METHOD 8020 - AROMATIC VOLATILES
Diethyl ether
Ethanol
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
           Benzene
           Chlorobenzene
           1,2-Di chlorobenzene
           1,3-Dichlorobenzene
           1,4-Di chlorobenzene
           Ethyl benzene
           Toluene
           Xylenes
                                   TWO - 25
                                  Revision 2
                              September 1994

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                                        TABLE 2-7.
             METHOD 8021  (METHOD 8011*)  -  HALOGENATED AND AROMATIC VOLATILES

Benzene                                         1,3-Dichloropropane
Bromobenzene                                    2,2-Dichloropropane
Bromochloromethane                              1,1-Di chloropropene
Bromodichloromethane                            cis-l,3-Dichloropropene
Bromoform                                       trans-l,3-Dichloropropene
Bromomethane                                    Ethyl benzene
n-Butyl benzene                                  Hexachlorobutadiene
sec-Butyl benzene                                Isopropyl benzene
tert-Butylbenzene                               p-Isopropyltoluene
Carbon tetrachloride                            Methylene chloride (DCM)
Chlorobenzene                                   Naphthalene
Chlorodibromomethane                            n-Propylbenzene
Chloroethane                                    Styrene
Chloroform                                      1,1,1,2-Tetrachloroethane
Chloromethane                                   1,1,2,2-Tetrachloroethane
2-Chlorotoluene                                 Tetrachloroethene
4-Chlorotoluene                                 Toluene
l,2-Dibromo-3-chloropropane*                    1,2,3-Trichlorobenzene
1,2-Di bromoethane*                              1,2,4-Tri chlorobenzen e
Di bromomethane                                  1,1,1-Tri chloroethane
1,2-Dichlorobenzene                             1,1,2-Trichloroethane
1,3-Dichi  obenzene                             Trichloroethene
1,4-Dichlorobenzene                             Trichlorofluoromethane
Dichlorodifluoromethane                         1,2,3-Trichloropropane
1,1-Di chloroethane                              1,2,4-Trlmethylbenzene
1,2-Dlchloroethane                              1,3,5-Trimethyl benzene
1,1-Dichloroethene (Vinylidene chloride)        Vinyl chloride
cis-l,2-Dichloroethene                          o-Xylene
trans-l,2-Dichloroethene                        ra-Xylene
1,2-Dichloropropane                             p-Xylene

      *  Indicates the only two target analytes of Method 8011.  These constituents are
                                 also target analytes of Method 8021.
           TABLE 2-8.                                            TABLE 2-9
      METHODS 8030/8031  -                                     METHOD 8032 -
      ACROLEIN,  ACRYLONITRILE                                   ACRYLAMIDE

      Acrolein (Propenal)*                                  Acrylamide
      Acrylonitrile

     Target analyte  of Method 8030 only.
                                         TWO - 26                         Revision 2
                                                                      September 1994

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                                        TABLE Z-10.
                                  METHOD 8040  -  PHENOLS
2-sec-Butyl-4,6-dinitrophenol  (DNBP, Dinoseb)
4-Chloro-3-methylphenol
2-Chlorophenol
Cresols (Methylphenols)
2-Cyclohexyl-4,6-dinitrophenol
2,4-Dichlorophenol
2,6-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
    2-Hethyl -4,6-dinitrophenol
    2-Nitrophenol
    4-Nitrophenol
    Pentachlorophenol
    Phenol
    Tetrachlorophenols
    2,4,6-Trichlorophenol
    TrichlorophenolIs
            TABLE 2-11.
   METHODS 8060/8061 - PHTHALATE ESTERS

Benzyl benzoate*
Butyl benzyl phthalate
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-oetyl phthalate

*  Target analyte of Method 8061 only.
       TABLE 2-12.
METHOD 8070 - NITROSAMINES

    N-Nitrosodinethylaiine
    N-Nitrosodiphenylamine
    N-Ni trosodi-n-propylami ne
                                         TWO - 27
                    Revision 2
                September 1994

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                                  TABLE 2-13.
            METHODS  8080/8081 - ORGANOCHLORINE PESTICIDES AND PCBs
Aroelor-1016  (PCB-1016)
Aroclor-1221  (PCB-1221)
Aroclor-1232  (PCB-1232)
Aroclor-1242  (PCB-1242)
Aroclor-1248  (PCB-1248)
Aroclor-1254  (PCB-1254)
Aroclor-1260  (PCB-1260)
Alachlor*
 Odrin
a-BHC
0-BHC
5-BHC
-BHC (Lindane)
  rtafol*
 .iptan*
Cnlorobenzilate*
Chlordane (technical)**
a-Chlordane*
y-Chlordane*
Chloroneb*
Chloropropylate*
Chlorothalonil*
DBCP*
DCPA*
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dial!ate*
Dichlone*
Dicofol*
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone*
Etridiazole*
Halowax-1000*
Halowax-1001*
Halowax-1013*
*  Target analyte of Method 8081 only.
** Target analyte of Method 8080 only.
Halowax-1014*
Halowax-lOSl*
Halowax-1099*
Heptachlor
Heptachlor epoxide
Hexachlorobenzene*
Hexachlorocyclo-
  pentadiene*
Isodrin*
Kepone*
Hethoxychlor
Hi rex*
Nitrofen*
trans-Nonachlor*
PCNB*
trans-Permethrin*
Perthane*
Propachlor*
Strobane*
Toxaphene
Trifluralin*
                               TABLE 2-14.
                        METHOD 8090 - NITROAROMATICS AND
                              CYCLIC KETONES

                              Dinitrobenzene
                              2,4-Dinitrotoluene
                              2,6-Dinitrotoluene
                              Isophorone
                              Naphthoquinone
                              Nitrobenzene
                                   TWO - 28
                                          Revision 2
                                      September 1994


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                                      TABLE 2-15,
                   METHODS 8100  -  POLYNUCLEAR AROMATIC  HYDROCARBONS
    Acenaphthene
    Acenaphthylene
    Anthracene
    Benzo(a)anthracene
    Benzo(b)fluoranthene
    Benzo(j)f1uoranthene
    Benzo(k)fluoranthene
    Benzo (g»h»i)perylene
    Benzo(a)pyrene
    Chrysene
    Dibenz(a»h)acridine
    D1benz(a,j)acr1dine
    Dibenzo(a,h)anthracene
        7H-Dibenzo(c»i)carbazole
        Dibenzo(a,e)pyrene
        Dibenzo(a,h)pyrene
        Dibenzo(a,i)pyrene
        Fluoranthene
        Fl uorene
        Indeno(l,2,3-cd)pyrene
        3-Methylcholanthrene
        Naphthalene
        Phenanthrene
        Pyrene
                                     TABLE 2-16
                               METHOD 8110 -  HALOETHERS
          Bis{2-Chloroethoxy)methane
          Bis(Z-Chloroethyl) ether
          Bis(Z-Chloroisopropyl) ether
        4-Bromophenyl phenyl ether
        4-Chlorophenyl phenyl ether
                                      TABLE 2-17.
                     METHODS 8120/8121 - CHLORINATED HYDROCARBONS
Benzal chloride*
Benzotrichloride*
Benzyl chloride*
2-Chloronaphthalene
1,2-Di chlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadi ene
Hexachlorocyclohexane**
o-Hexachlorocyclohexane  (a-BHC)*
p-Hexachlorocyclohexane  (
5-Hexachlorocyclohexane (5-BHC)*
y-Hexachlorocyclohexane (y-BHC}*
Hexachlorocyclopentad i ene
Hexachloroethane
Pentachlorobenzene*
Pentachlorohexane**
Tetrac h1orobenzene s**
1,2,3,4-Tetrachl orobenzene*
1,2,3,5-Tetrachl orobenzene*
1,2(4,5-Tetrachl orobenzene*
1,2,3-Trichlorobenzene*
1,2,4-Trichlorobenzene
l»3»S-Trichlorobenzene*
*  Target analyte of Method 8121 only.
** Target analyte of Method 8120 only.
                                       TWO - 29
                            Revision 2
                        September 1994

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                                  TABLE 2-18.
                METHODS 8140/8141  - ORGANOPHOSPHORUS COMPOUNDS
                         (PACKED AND CAPILLARY COLUMNS)


 Aspon*                              Fenthion
 Atrazine*                           Fonophos*
 Azinphos ethyl*                     Hexamethylphosphoramide* (HMPA)
 Azinphos methyl                     Leptophos*
 Bolstar (Sulprofos)                 Malathion*
 Carbophenothion*                    Merphos
 Chlorofenvinphos*                   Mevinphos
 Chlorpyrifos                        Monochrotophos*
 Chlorpyrifos methyl*                Naled
 Coumaphos                           Parathlon,  ethyl*
 Crotoxypos*                         Parathlon,  methyl
 Demeton-0, and -S                   Phorate
 Dlazinon                            Phosmet*
 Dichlorofenthion*                   Phosphamidon*
 Dichlorvos (DDVP)                   Ronnel
 Dichrotophos*                       Simazine*
 Dimethoate*                         Stirophos (Tetrachlorvinphos)
 Dioxathion*                         Sulfotep*
 Disulfoton                          TEPP*
 EPN*                                Terbufos*
 Ethion*                             Thionazin*
 Ethoprop                            Tokuthion (Prothiofos)
 Famphur*                            Trichlorfon*
 Fen1 trothion*                       Trichloronate
 Fensulfothlon                       Trl-o-cresylphosphate (TOCP)*
      *  Target analyte of Method 8141 only.
                                  TABLE 2-19.
                  METHODS 8150/8151 - CHLORINATED HERBICIDES


Acifluorfen*             Dicamba                      MCPA
Bentdzon*                3,5-Dichlorobenzoic acid*    MCPP
Chloramben*              'Dichlorprop                  4-Nitrophenol*
2,4-D                    Dinoseb  (DNBP)               Pentachlorophenol*
Dalapon                  5-Hydroxydicamba*            Piclorara*
2,4-DB                                                2,4,5-TP (Silvex)
DCPA diacid*                                          2,4,5-T

   *  Target analyte of Method 8151 only.
                                   TWO - 30                         Revision 2
                                                                September 1994

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                                        TABLE 2-20,
                               METHODS 8240/8260 - VOLATILES
Acetone
Acetonitrlle
Acrole i n (Propenal)
Acrylonltrile
Allyl alcohol
Allyl chloride
Benzene
Benzyl chloride
Bis(2-chloroethyl) sulflde
Bromoacetone
Bromobenzene*
Bromochloromethane
Bromodichloromethane
4-Bromof1uorobenzene
Bromoform
Bromomethane
n-Butanol*
2-Butanone (Methyl ethyl
ketone)
n-Butylbenzene*
sec-Butyl benzene*
tert-Butylbenzene*
Carbon disulfide
Carbon tetrachlorlde
Chloral hydrate
Chioroacetoni trl1e*
Chlorobenzene
2-Chloro-l,3-butadiene*
1-Chlorobutane*
Chiorod1bromomethane
Chioroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane*
Chloromethane
Chloroprene
3-Chloropropene*
3-Chl oropropi oni tri1e
2-Chlorotoluene*
4-Chlorotoluene*
Crotonaldehyde*
l,2-Dibromo-3-
 chloropropane
1,2-Dibromoethane
Dibromomethane
Di bromofluoromethane*
1,2-Di chlorobenzene*
1,3-Dichlorobenzene*
1,4-Dichlorobenzene*
l,4-Dichloro-2-butene**
cis-l,4-Diehloro-
 2-butene*
trans-l»4-Dichloro-2-
  butene*
l,4-Dichloro-2-butene**
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
ci s-1,2-Di chloroethene*
trans -1,2-Dichloroethene
1,2-Dichloropropane
1,3-Di chloropropane*
2,2-Di chloropropane*
l,3-Dichloro-2-propanol
1,1-Di chloropropene*
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
1,2,3,4-Diepoxybutane
Diethyl ether*
1,4-Difluorobenzene
1,4-Qioxane
Epichlorohydrln
Ethanol
Ethyl acetate*
Ethyl benzene
Ethylene oxide
Ethyl ntethacrylate
Fluorobenzene*
Hexachlorobutadi ene*
Hexachloroethane*
2-Hexanone
2-Hydroxypropionitrile
lodomethane
Isobutyl alcohol
Isopropylbenzene*
p-Isopropyltoluene*
Malononitrile
Methacrylonitrile
Methanol*
Methyl acrylate*
Methyl-t-butyl ether*
Methylene chloride (DCM)
Methyl iodide
Methyl methacrylate
4-Methyl-2-pentanone
  (MIBK)
Naphthalene*
Nitrobenzene*
2-Nitropropane*
Pentachloroethane
Pentafluorobenzene*
2-Picoline
Propargyl alcohol
6-Propiolactone
Propionitrile
n-Propylamine
n-Propylbenzene*
Pyridine
Styrene
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene*
1,2,4-Trichlorobenzene*
1,1,1-Tri chloroethane
1,1,2-Tri chloroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane
1,2,4-Trimethylbenzene*
1,3,5-Trimethylbenzene*
Vinyl acetate
Vinyl chloride
Xylene (Total)**
o-Xylene*
m-Xylene*
p-Xylene*
* Target analyte of Method 8260 only.
** Target analyte of Method 8240 only.
                                         TWO - 31
                                          Revision 2
                                      September 1994

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                                        TABLE 2-21.
                             METHODS 8250/8270 - SEMIVOLATILES
Acenaphthene
Acenaphthyl ene
Acetophenone
2 -Acetyl ami nof 1 uorene*
1 -Acetyl -2-th iourea*
Aldrin
2 - Ami noanthraqu i none*
Ami noazobenzene*
4-Aminobiphenyl
3-Amino-9-ethylcarbazole*
Anilazine*
Aniline
o-Anisidine*
Anthracene
Aramite*
Aroclor-1016 (PCB-10I6)
Aroclor-1221 (PCB-1221)
Aroclor-1232 (PCB-1232)
Ar-"? or- 1242 (PCB-I242)
Ar   or-1248 (PCB-1248)
Ar   ;or-1254 (PCB-1254)
Arcclor-1260 (PCB-1268)
Azinphos-methyl*
Barban*
Benz{a)anthracene
Benzidine
Benz f b) f 1 uoranthene
Benzo{ k) f 1 uoranthene
Benzole acid
Benzofgjhjijperylene
Benzo|a)pyrene
p-Benzoquinone*
Benzyl alcohol
a-BHC
5-BHC
7-BHC (Lindane)
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
Bromoxynil*
Butyl benzyl phthalate
2-sec-Butyl-4,6-dinitrophenol (Dinoseb)
Captafol*
Captan*
Carbaryl*
Carbofuran*
Carbophenothion*
Chlordane (technical)
Chlorfenvinphos*
4-Chloroaniline
Chi orobenz Hate*
5-Chloro-2-methylani1ine*
4-Chloro-3-methylphenol
3-(Ch1oromethy1)pyridine hydrochloride*
1-Chioronaphthalene
2-Chloronaphthalene
2-Chlorophenol
4-Chloro-1,2-phenylenedi ami ne*
4-Chloro-l,3-phenylenediamine*
4-Chlorophenyl phenyl ether
Chrysene
Coumaphos*
p-Cresidine*
Crotoxyphos*
2-Cyclohexyl-4,6-dinitrophenol*
4,4'-ODD
4,4'-DDE*
4,4'-DDT
Demeton-0*
Demeton-S*
Diallate (cis or trans)*
2,4-Diaminotoluene*
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
Dibenzofuran
Dibenzo(a,e)pyrene*
l,2-Dibromo-3-chloropropane*
Di-n-butyl phthalate
Dichlone*
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos*
Dicrotophos*
Dieldrin
Diethyl phthalate
D1ethylstilbestrol*
Diethyl sulfate*
Dihydrosaffrole*
Dimethoate*
3,3'-Dimethoxybenzidine*
Dimethyl aminoazobenzene
                                         TWO - 32
                          Revision 2
                      September 1994

-------
                                        TABLE 2-21.
                       METHODS 8250/8270 - SEMIVOLATILES (CONTINUED)
7,12-Dimethylbenz(a)anthracene
3,3'-Dimethylbenzidine*
a»Q!-Dimethylphenethylainine
2,4-Dimethylphenol
Dimethyl phthalatt
1,2-Dinitrobenzene*
1,3-Dinitrobenzene*
1,4-Dinitrobenzene*
4,6-Dinitro-2-methylphenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap*
Dioxathion*
Diphenylaraine
5,5-Diphenylhydantoi n*
1,2-Diphenylhydrazine
Di-n-octyl phthalate
Disulfoton*
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
EPN*
Ethion*
Ethyl  carbamate*
Ethyl  methanesulfonate
Ethyl  parathion*
Famphur*
Fensulfothion*
Fenthion*
Fluchloralin*
Fluoranthene
Fluorene
2-Fluorobiphenyl
2-Fluorophenol
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutad i ene
Hexachlorocyclopentadiene
Hexachloroethane
Hexachlorophene*
Hexachloropropene*
Hexamethylphosphoramide*
Hydroquinone*
Indeno(l,2,3-cd)pyrene
Isodrin*
Isophorone
Isosafrole*
Kepone*
Leptophos*
Malathion*
Maleic anhydride*
Mestranol*
Methapyrilene*
Methoxychlor
3-Methylcholanthrene
4,4'-Methylenebis(2-chloroaniline)*
4,4'-Methylenebis(N,N-dimethyl aniline)*
Methyl methanesulfonate
2-Hethylnaphthalene
2-Methyl-5-nitroaniline*
Methyl parathion*
2-Methylphenol (o-Cresol)
3-Methylphenol (m-Cresol)*
4-Methylphenol (p-Cresol)
2-Methylpyridine*
Mevinphos*
Mexacarbate*
Mi rex*
Monocrotophos*
Nal ed*
Naphthalene
1,4-Naphthoquinone*
1-Naphthylamine
2-Naphthylamine
Nicotine*
5-Nitroaeenaphthene*
2-Nitroaniline
3-Nitroaniline
4-Nitroanil ine
5-Nitro-o-anisidine*
Nitrobenzene
4-Nitrobiphenyl*
Nitrofen*
2-Nitrophenol
4-Nitrophenol
Nitroquino!ine-1-oxide*
N-Nitrosodibutyl amine
N-Nitrosodiethylamine*
N-Nitrosodimethylamine
N-N i trosodi phenylami ne
N-Nitrosodi-n-propylamine
                                         TWO - 33
                          Revision  2
                      September  1994

-------
                                        TABLE 2-21.
                       METHODS 8250/8270 - SEMIVOLATILES (CONTINUED)
N-Nitrosomethyl ethyl ami m*
N-Nitrosomorphol ine*
N-Nitrosopfperidine
N-Nitrosopyrrolidine*
5-Nitro-o-toluid1ne*
Octamethyl pyrophosphoramide*
4,4'-Qxydianiline*
Parathion*
Pentachlorobenzene
Pentachloronitrobenzene
Pentachlorophenol
Phenacetin
Phenanthrene
Phenobarbital*
Phenol
1,4-Phenylenediamine*
Phorate*
Phosalone*
Phos«ji=t*
Phospnamidion*
Phthas vc anhydride*
2-Picoline
Piperonyl sulfoxide*
Pronamide
Propylthiouracil*
'yrene
Jyr1d1ne*
Resorcinol*
Safrole*
Strychnine*
Sulfall ate*

*  Target analyte of Method 8270 only.
                  Terbuphos*
                  Terphenyl
                  1,2,4,5-Tetrachlorobenzene
                  2,3,4,6-Tetrachlorophenol
                  Tetrachlorvinphos (Stlrophos)*
                  Tetraethyl dlthiopyrophosphate*
                  Tetraethyl pyrophosphate*
                  Thionazine*
                  Thiophenol (Benzenethiol)*
                  Toluene dilsocyanate*
                  o-Toluidine*
                  Toxaphene
                  2,4,6-Tri broroophenol
                  1,2,4-Tri chlorobenzene
                  2,4»5-Trichlorophenol
                  2,4,6-Trichlorophenol
                  0,0,0-Triethyl phosphorothioate*
                  Trifluralin*
                  2,4,5-Trimethylaniline*
                  Trimethyl phosphate*
                  1,3,5-Tr1nitrobenzene*
                  Tris(2,3-dibromopropyl} phosphate*
                  Trl-p-tolyl  phosphate*
                                        TABLE  2-22.
                          METHOD 8275 -  SEMIVOLATILES (SCREENING)
Aldrin
Benzo(k)fl uoranthene
Benzo(a)pyrene
Carbazole
4-Chloro-3-methylphenol
1-Chloronaphthalene
2-Chlorophenol
Dibenzothlophene
2,4-Dichlorophenol
2,4-Dinltrotoluene
Diphenylamine
Fluorene
Hexachlorobenzene
4-Methylphenol
Naphthalene
Phenanthrene
Pyrene
                                         TWO - 34
                                            Revision 2
                                        September 1994
                                                                           \.
                                                                             \

-------
2,3,7,8-TCDD
1,2,3,4-TCDD*
1,3,6,8-TCDD*
1,3,7,9-TCDD*
1,3,7,8-TCDD*
1,2,7,8-TCDD*
1,2,8,9-TCDD*
                                TABLE  2-23.
              METHODS 8280/8290 -  DIOXINS AND DIBENZOFURANS
1,2,3,4,7-PeCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
      Target analyte of 8280 only
1,2,7,8-
2,3,7,8-
1,2,3,7,
2,3,4,7,
1,2,3,4,
1,2,3,6,
1,2,3,7,
2,3,4,6,
1,2,3,4,
1,2,3,4,
OCDF
TCDF
TCDF
8-PeCDF
8-PeCDF
7,8-HxCOF
7,8-HxCOF
8,9-HxCDF
7,8-HxCDF
6,7,8-HpCDF
7,8,9-HpCDF
                               TABLE 2-24.
             METHOD 8310  - POLYNUCLEAR AROMATIC HYDROCARBONS
              Acenaphthene
              Acenaphthylene
              Anthracene
              Benzo(a)anthracene
              Benzo(a)pyrene
              Benzo(b)f1uoranthene
              Benzo(g,h,1)perylene
              Benzo(k)f1uoranthene
                     Chrysene
                     Dibenzo(a,h)anthracene
                     Fluoranthene
                     Fluorene
                     Indeno(l,2,3-cd)pyrene
                     Naphthalene
                     Phenanthrene
                     Pyrene
                                 TWO -  35
                                         Revision 2
                                     September 1994
                                                             \
                                                               \

-------
                           TABLE 2-25.
                 METHOD 8315  -  CARBONYL COMPOUNDS

   Acetaldehyde                  Heptanal
   Acetone                       Hexanal (Hexaldehyde)
   Acrolein (Propanol)           Isovaleraldehyde
   Benzaldehyde                  Nonanal
   Butanal (Butyraldehyde)       Octanal
   Crotonaldehyde                Pentanal (Valeraldehyde)
   Cyclohexanone                 Propanal (Propionaldehyde)
   Decanal                       m-Tolualdehyde
   2,5-Dimethylbenzaldehyde      o-Tolualdehyde
   Formaldehyde                  p-Tolualdehyde
       TABLE 2-26.                                 TABLE  2-27.
METHOD 8316 - ACRYLAMIDE,                METHOD 8318  - N-HETHYLCARBAHATES
ACRYLONITRILE AND ACROLEIN
                                                Aldicarb (Temlk)
       Acrolein {Propanol)                      Aldicarb Sulfone
       Acrylamide                               Carbaryl  (Sevin)
       Acrylonitrile                            Carbofuran (Furadan)
                                                Dioxacarb
                                                3-Hydroxycarbofuran
                                                Methiocarb (Mesurol)
                                                Methomyl  (Lannate)
                                                Promecarb
                                                Propoxur (Baygon)
                            TWO -  36                         Revision 2
                                                         September 1994

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                                        TABLE 2-28.
                                METHOD 8321  - NONVOLATILES
    Azo Dv.es..
Disperse Red 1
Disperse Red 5
Disperse Red 13
Disperse Yellow 5
Disperse Orange 3
Disperse Orange 30
Disperse Brown 1
Solvent Red 3
Solvent Red 23

Anthraquinone Dves
Disperse Blue 3
Disperse Blue 14
Disperse Red 60
Coumarin Dyes

(Fluorescent Brighteners)
Fluorescent Brightener 61
Fluorescent Brightener 236

Chlorinated Phenoxvacid Compounds
2,4-D
2,4-D, butoxyethanol ester
2,4-D, ethylhexyl ester
2,4-OB
Dalapon
Dicamba
Dichlorprop
Dinoseb
MCPA
MCPP
Silvex (2,4,S-TP)
2,4,5-T
2,4,5-T,  butyl  ester
2,4,5-T,  butoxyethanol ester
Alkaloids
Strychnine
Qrganophpsphorus Compounds
Asulam
Dichlorvos
Dimethoate
Disulfoton
Famphur
Fensulfothion
Merphos
Methomyl
Methyl parathion
Monocrotophos
Naled
Phorate
Trichlorfon
Thiofanox
Tris-(2,3-dibromopropyl) phosphate,
  (Tris-BP)
                                         TWO - 37
                    Revision 2
                September 1994

-------
                           TABLE 2-29.
           METHOD 8330 - NITROAROHATICS AND NITRAMINES

4-Amino-2»6-dinitrotoluene (4-Am-DNT)
2-Amino-4,6-dinitrotoluene (2-Am-DNT)
1,3-Dinitrobenzene (1,3-DNBJ
2,4-Dinitrotoluene (2,4-DNT)
2,6-Dinitrotoluene (2,6-DNT)
Hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX)
Methyl-2,4,6-trin1trophenylnitramine  (Tetryl)
Nitrobenzene (NB)
2-Nitrotoluene (2-NT)
3-Nitrotoluene (3-NT)
4-Nitrotoluene (4-NT)
Octahydro-MjSJ-tetnnitro-M^S^-tetrazocine (HMX)
1,3,5-THnitrobenzene  (1,3,5-TNB)
2,4,6-THnitrotoluene  (2,4,6-TNT)
                           TABLE 2-30.
                     METHOD 8331 - TETRAZENE

                             Tetrazene
                            TWO -  38                        Revision 2
                                                        September 1994

-------
                              TABLE  2-31
                      METHOD 8410 - SEHIVOLATILES
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)pyrene
Benzole acid
Bi s(2-chloroethoxyjmethane
Bis(2-chloroethyl)ether
Bis(2-chloroisopropyljether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
4-Chloroaniline
4-Chl oro-3-methyl phenol
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Dibenzofuran
Di-n-butyl  phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
2,4-Dichlorophenol
Diethyl phthalate
Dimethyl phthalate
4»6-Dinitro-2-methylphenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Di ni trotoluene
Di-n-octyl phthalate
Di-n-propyl phthalate
Fluoranthene
Fluorene
Hexachlorobenzene
1,3-Hexachlorobutadi ene
Hexachlorocyclopentadiene
Hexachloroethane
Isophorone
2-Methylnaphthalene
2-Methylphenol
4-Hethylphenol
Naphthalene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
2-N1trophenol
4-N1trophenol
N-Ni trosodi methyl ami ne
N-Nitrosodiphenylamine
N-Nitroso-di-n-propylamine
Pentachlorophenol
Phenanthrene
Phenol
Pyrene
1,2,4-Tri chlorobenzene
2,4,5-Trichlorophenol
2,4,6-Tri chlorophenol
                               TWO - 39
                              Revision 2
                          September 1994

-------
               TABLE  2-32.
ANALYSIS METHODS FOR INORGANIC COMPOUNDS
Compound
Aluminum
Antimony
Arsenic
Barium
Beryl 1 i urn
Bromide
Cadmium
Calcium
Chloride
Chromium
Chromium, hexavalent
Cobalt
Copper
Cyanide
Fluoride
Iron
Lead
Lithium
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Nitrate
Nitrite
Osmi urn
Phosphate
Phosphorus
Potassium
Selenium
Silver
Sodium
Strontium
Sulfate
Sulfide
Thallium
Tin
Vanadium
Zinc
Applicable Hethod(s)
6010,
6010,
6010,
6010,
6010,
9056
6010,
6010,
9056,
6010,
7195,
6010,
6010,
9010,
9056
6010,
6010,
6010,
6010,
6010,
7470,
6010,
6010,
9056,
9056
7550
9056
6010
6010,
6010,
6010,
6010,
6010,
9035,
9030,
6010,
7870
6010,
6010,
6020,
6020,
6020,
6020,
6020,

6020,
7140
9250,
6020,
7196,
6020,
6020,
9012,

7380,
6020,
7430
7450
6020,
7471
7480,
6020,
9200




7610
7740,
6020,
7770
7780
9036,
9031
6020,

7310,
6020,
7020
7040,
7060,
7080,
7090,

7130,

9251,
7190,
7197,
7200,
7210,
9013

7381
7420,


7460,

7481
7520






7741,
7760,


9038,

7840,

7911
7950,

7041,
7061,
7081
7091

7131

9252,
7191
7198
7201
7211



7421


7461









7742
7761


9056

7841


7951

7062
7062





9253






























               TWO  - 40
    Revision 2
September 1994


-------
                                                        TABLE 2-33,
                        CONTAINERS,  PRESERVATION TECHNIQUES, AND HOLDING TINES FOR AQUEOUS MATRICES*
Name
Bacterial Tests:
Col i form, total
Inorganic Tests:
Chloride
Cyanide, total and amenable
to ch lor (nation
Container
P, C
P, C
P, G
Preservation
Cool, 4*C. 0.008% Ma,S,0,
None required
Cool, 4t; if oxidizing
agents present add 5 ml
Maximum holding
6 hours
28 days
14 days
time

                                                        0.1N NaAsO., per L or 0.06 g
                                                        of ascorbic ecid per  L;
                                                        adjust pH>12 with SOX NaOH.
                                                        See Method 9010 for other
                                                        interferences.
Hydrogen ion 

0.

008% Na2S,0,
dark

0.
008% Ka,S,0, ,
dark
,e»«C
4°C
4°C

4°C

4°C

4"C

4'C
in
4°C

4"C

4"C


£


7 days until extraction,
after extraction



7 days until extraction,
after extraction

7 days until extraction,
after extraction

7 days until extraction.
after extraction

7 days until extraction.
after extraction

7 days until extraction,
after extraction
28 days
28 days



7 days until extraction,



after extraction

7 days until extraction,

i


0.


008% Na,S,033

after extraction

7 days until extraction,
after extraction

7 days until extraction.

,

0.

008% Na.S.0,3
dark


i

2


0.

0.




008% Ma,SA '

008% NatSA3




to pH<2
after extraction

7 days until extraction,
after extraction
14 days

14 days

28 days


6 months









40


40

40

40

40

40



40

40

40

40

40









days


days

days

days

days

days



days

days

days

days

days









1
Table excerpted,  in part, from Table II, 49 FR 209,  October  26,  1984, p 28.
Polyethylene (P)  or Glass 
-------
                   TABLE 2-34.   PREPARATION  METHODS  FOR ORGANIC ANALYTES

Acids
Acrolein
Acrylonitrile
Acetonitrile
Aromatic Volatile*
Base/Neutral
Chlorinated
Herbicides
Chlorinated
Hydrocarbons
Halogenated
Volatiles
Nitroaromatic and
Cyclic Ketones
Non-halogenated
VolatHes
Organochlorine
Pesticides and PCBs
Organophosphorus
Pesticides
Phenol s
Phthalate Esters
Polynuclear
Aromatic
Hydrocarbons
Volatile Organics
Aqueous (pH)3
3510
3520
(PH <2)
5030
S030
3510
3S20
(pH >11)
8150
8151
(PH <2)
3510
3520
(pH 7)
5030
3510
3520
(pH 5-9)
5030
3510
3520
3665
(pH 5-9)
3510
3520
{pH 6-8)
3510
3520
(pH <2)
3510
3520
(pH 7)
3510
3520
(PH 7)
5030
Solids
3540, 3541
3550
35802
5030
5030
3540
3541
3550
35802
8150
8151
35802
3540
3541
3550
35802
5030
3540
3541
3550
35802
5030
3540
3541
35802
3665
3540
3541
35802
3540
3541
3550
35802
3540
3541
3550
35802
3540, 3541
3550
35802
5030
Sludges
Emulsions1 (pH)3
3520
(PH <2)
5030
5030
3520
(pH >11)
8150
8151
(pH <2)
3520
(pH 7)
5030
3520
(pH 5-9)
5030
3520
(pH 5-9)
3520
(pH 6-8)
3520
(pH <2)
3520
(pH 7)
3520
(PH 7)
5030
Oils
3650,
35802
5030
5030
3650
35802
35802
35802
5030
35802
5030
35802
35802
3650
35802
35802
3560
35802
5030
1  If attempts  to  break up emulsions are unsuccessful,
2  Method 3580  is  only appropriate if the sample is  sol
3  pH at which  extraction should be performed.
these methods may be used.
uble in the specified solvent,
                                         TWO - 42
                    Revision 2
                September 1994

-------
            TABLE 2-3i,
CLEANUP OF ORGANIC ANALYTE EXTRACTS
Analyte Type
Acids
Base/Neutral
Chlorinated
Herbicides
Chlorinated
Hydrocarbons
Nitroaromatics &
Cyclic Ketones
Organophosphorus
Pesticides
Organochlorine
Pesticides &
PCBs
Phenol s
Phthalate
Esters
Polynuclear
Aromatic
Hydrocarbons
Method(s)
3610
3650
8150
8151
3620
3640
3620
3640
3620
3620
3630
3640
3660
3665
3630
3640
3650
3610
3611
3620
3640
3610
3611
3630
3640
             TWO - 43
    Revision 2
September 1994

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                                      TABLE  2-36.
                          DETERMINATION OF  ORGANIC  ANALYTES

SC/MS Determination
Methods
Specific SC Detection
Methods
1
HPIC
SOttVOlATILES
Acids
Base/Neutral
Carbamates
Chlorinated Herbicides
Chlorinated Hydrocarbons
Oves
Explosives
Haloethers
Nitroaromatics and Cyclic
Ketones
Nitrcsoamines
Qrganochlorine Pesticides and
PCBs
Organophosphorous Pesticides
Phenols
Phthalate Esters
Polynuelear Aromatic
Hydrocarbons
8270
8250
8270
8250

8270*
8270
8250


8270
8250
8270
8250
827D
8250
8270*
8270*
8270
8250
8270
8250
8270
8250



8150
8151
8120
8121


8110
8090
8070
8080
8081
8140
8141
8040
8060
8061
8100


8318


83Z1
8330
8331




8321


8310
WEATIIES
Acrolein, Acrylonitrile,
Ac*1" wilt rile
Acr> : amide
Aromatic Volatile:
Formaldehyde
Halogenated Volatiles
Non-haloejenated Volatiles
Volatile Organies
8240
8260

8240
8260

8240
8260
8240
8240
8260
8030
8031
8032
8020
8021

8010
8011
8021
8015
8010
8011
8020
8021
8030
8031
8316
8315
8316

8315


8315
8316
*This method is an alternative confirmation method.  It is not the method of choice.
                                       TWO - 44
     Revision  2
September 1994

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                                                                           FIGURE  2-1.
                                                                ORGANIC  ANALYSIS OPTIONS
                                                        Sample
                                                    lo be Analyzed
                                                    lor Exlractables
                                                       Volaliles
                                                   GC/MS Analysis
                                                   Procedure:
                                                   Packed Column: 6240
                                                  Capillary Column: 8260
          GC Analysis Procedure
          Halogenated Volatile Organics:        8010
          EDBandDBCP:                    8011
          Nonhalogenated Volatile Organics      8015
          Aromatic Volatile Organics:           8020
          Halogenated Volatile Compounds:      6021
          Acrolein, Acrylonittile:               6030
          Acrylamlde	6032
                     Cleanup Procedure:
                      Alumina Column:
                      Alumina Column lor Petroleum Wastes:
                       Ftorisil Column:
                      Silica Gel Column:
                     Gel Permeation:
                      Acid Base Partitioning:
                      Sullur:
3610
3611
3620
3630
3640
36SO
3660
HPLC Analysis Procedures:
8310.6318,8321.6330.6331
HPLC Analysis Procedures:
Acrolein, Acrylonitrile, Acrylamide:  8316
Formaldehyde:                 8315
                                                                                                            :/MS
                                 GC/MS Procedures:
                                 Packed Column:   8250
                                 Capillary Column:  B270
  GC Analysis Procedures:
  Phenols:                          8040
  Phthalate Esters:                   B060
  NKrosamines:                      8070
  Organochlorine Pesticides and PCBs:   80BO
  Nitroaromatics and Cyclic Ketones:     8090
  Polynuclear Aromatic Hydrocarbons:    8100
  Haloelhers:                       8110
  Chlorinated Hydrocarbons:           8120, 8121
  Organophosphorus Pesticides:        6140, 6141
  Chlorinated Herbicides:              6150.8151
                                                                        TWO  -   45
                                                                                          Revision  2
                                                                                    September  1994

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                                 FIGURE 2-2,
                  SCHEMATIC  OF  SEQUENCE  TO  DETERMINE
              IF A  WASTE  IS HAZARDOUS BY  CHARACTERISTIC
                                               DOT(49CFR173.3QO)
                                        Is waste
                                       ignttable?
        is
      waste
     reactive to
     strand/or
      water1?
                             Nonhazardous by
                                reason of
                                ignrtabiltty
                               characteristic
      Is waste
     explosive?
                                               Generator Knowledge
                                               DOT (49 CFH 173.151)
       What is
     physical state
      of waste?
Is waste
tanitabte?
    Perform Paint
      FtterTest
    (Method 9095)
            Methods iroand9040

                    Yes
f   Nonhazardous  X
(    for corrosivlty    )
               Methods 1010 or 1020
                    Yas
                                  TWO  -  46
                                     Revision 2
                                September  1994

-------
        FIGURE  2-2.
        (Continued)
    Nonhazardous
    for ignitabilily
    characteristic
             Reactive CN
             and Sulfide Tests
   Nonhazardous
tor toxic gas generation
(reactivity) characteristic
    istotai
   concert, of TC
   constituents-^ 20 <
   TC regutaBJiy
      limit?
 Nonhazardous
  (ortoxicity
 characteristic
     is waste
   teachaWe and
      toxic?
  (Method 1311)
Nonhazardous
  for toxicity
charactarisSc
           TWO -  47
                      Revision  2
                 September  1994
                            \

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                                FIGURE 2-3A.
                                     EP
    3010
  (7760 Aq)
    6010
                              I    Sample    I


                              i     1310
              7470
               Hg
   3510
 Neutral
 Ba-




Cr --


Ag -
-- As




-- Cd


-- Pb


- Se
   8080
   8081
Pesticides
   8150
   8151
Herbicides
                                  TWO -  48
                                                            Revision 2
                                                        September 1994

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                      FIGURE 2-3B.
RECOMMENDED SH-846 METHODS OF ANALYSIS FOR TCLP•LEACHATES





3010





6010



Ba -

Cr -

Ag -









- As

- Cd

- Pb

- Se








7470
Hg

























Sampl e


. 	
TCLP















3S10
Neutral






8240 3510
8260 (Acidic
Volatile and
Orqanics Basic)

8080
8081
Pestic-
ides








8270
Semivol -
atile
Organ ics

















81SO
8151
Herbic-
ides











                        TWO - 49
    Revision 2
September 1994

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                                 FIGURE 2-4A.
                           GROUND WATER ANALYSIS
1

r
VOA
1

8240 or
8260






r
Sam ivola tiles
1
i
3510 or
3520
!

8270 or
8250


Organic
Sample




1

' if \ i
Pesticides
Herbicides Dioxins
1 1 1
3510 or
3520
Neutral
1

1 3620, 3640
and/or 3660
I
8080
S1SO 8280

1 -Optional: Cleanup required only u    a anees prevent analysis
                                   TWO  - 50
     Revision  2
September 1994

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   FIGURE  2-4B.
INDICATOR ANALYTE
1
POC
                 1 - Barcelona, 19B4, (See Reference 1)
                 2 • Riggin. 1984. (See Reference 2}
     TWO - 51
    Revision 2
September  1994

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                                    FIGURE 2-4C.
                                    GROUND WATER
             SAMPLE PREPARATION
                 3005 OR 3015
                                                               1
                                  SAMPLE PREPARATION
                                      3015 OR 3020
  i
  i
I
Ag, A). As, Ba. Be,
Cd, Co, Ct, Cu, Fe,
Mg, Mn, Mo, Ni, Pb,
Sb. Se, Tl, V, Zn

Ag, Al, As, Ba, Be,
Cd, Co, Cr, Cu, Mn,
Ni. Pb. Sb, Tl. Zn
AS- 7760
Ba-7080
Cd - 7130
Cr-7190
Fe-7380
Mn - 7460
Ni-7520
Sb-7040
Tl-7840
Zn-7950
AI-7020
Be-7090
Co- 7200
Cu - 7210
Mg - 7450
Mo- 7480
Pb-7420
5n- 7870
V-7910
Ag-7761"
Ba-7081*
Be -7091
Cd-7131
Co -7201
Cf-7191
Cu- 7211*
F»-7381*
Mn-7461'
Mo - 7481
Pb - 7421 '
Tl-7841
Sb-7041"
Toer
V-7911
Zn-7951'
*  Fallow the digestion procedures as detailed in the individual
  determinative methods.

1  Whan analyzing tor total dissolved metals, digestion is not'
  necessary if Vie samples are filtered at the time of
  collection, and then acidified to the same concentration as the standards
                                       TWO  -  52
                                                             Revision  2
                                                        September  1994

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                                 CHAPTER THREE

                               METALLIC ANALYTES
 3,1   SAMPLING CONSIDERATIONS

 3.1.1   Introduction

      This manual contains procedures for the analysis of metals in a variety of
 matrices.  These methods are written  as  specific steps in the overall  analysis
 scheme  -- sample handling and preservation, sample digestion or preparation,  and
 sample  analysis for specific metal  components.   From these methods,  the analyst
 must assemble a total  analytical  protocol which is appropriate for the sample to
 be analyzed and for the information required.  This  introduction discusses  the
 options  available  in  general  terms, provides  background   information on  the
 analytical techniques, and highlights  some of the considerations to be made when
 selecting a total analysis protocol.


 3.1.2   Definition of Terms

      Optimum concentration  range:    A  range,  defined by  limits  expressed in
 concentration, below which scale expansion must  be used  and above which  curve
 correction should be considered.  This range will vary with the sensitivity of
 the instrument and the operating conditions employed.

      Sensitivity:  a) Atomic  Absorption:  The  concentration in milligrams of
 metal per liter  that produces an absorption of 1%; b)  Inductively Coupled Plasma
 (ICP):   The  slope  of the analytical  curve,  i.e.,  the functional  relationship
 between emission intensity and concentration.

      Method detection limit (HDL):   The minimum concentration  of a  substance
 that  can be  measured  and  reported  with  99%  confidence  that  the  analyte
 concentration is greater than  zero.   The MDL  is  determined from analysis of a
 sample in a given matrix containing analyte which has been processed  through the
 preparative procedure.

      Total  recoverable metals:  The  concentration of metals in an unfiltered
 sample following treatment with hot dilute mineral acid (Method 3005).

      Dissolved metals: The concentration of metals determined in a sample  after
the sample is filtered through a 0.45-um filter (Method 3005).

      Suspended metals:  The concentration of metals determined in the
portion of a sample that is retained by a 0.45-um filter (Method 3005).

      Total metals:  The concentration of metals determined in a sample following
digestion by Methods 3010,  3015, 3020, 3050 or 3051.
                                  THREE  -  1                       Revision 2
                                                                  September 1994
                                    \

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       Instrument detection limit (IDL):  The concentration equivalent to a signal
 due  to the analyte which is equal to  three times the standard deviation of  a
 series  of 7  replicate  measurements  of  a  reagent blank's  signal  at the same
 wavelength.

       Interference check sample  (ICS):   A  solution containing  both interfering
 and analyte elements of  known concentration that can be used to verify  background
 and  interelement correction factors.

       Initial  calibration  verification   standard   (ICV):     A  certified  or
 independently  prepared  solution  used  to  verify  the accuracy of  the  initial
 calibration.   For  ICP analysis,  it must be run at each wavelength used  in the
 analysis.

      Continuing calibration  verification   (CCV):  Used  to assure calibration
 accuracy during each analysis  run.  It must  be run for each  analyte as described
 in the particular analytical method.  At a minimum, it should be analyzed at the
 beginning  of  the run and  after the  last analytical  sample.  Its concentration
 should be  at or near the mid-range levels  of the  calibration curve.

      Calibration standards:  A series of  known standard solutions used  by the
 analyst for calibration of the instrument  (i.e.,  preparation of the analytical
 curve).

      Lineardynamic range:  The concentration range over which the analytical
 curve remains  linear.

      Method blank:  A  volume of reagent  water  processed  through each  sample
 preparation procedure.

      CalIbration bl ank:   A volume  of  reagent water acidified with the same
 amounts of acids as were the standards and  samples.

      Laboptpry control standard: A volume of reagent water spiked with known
 concentrations of  analytes  and  carried  through  the  preparation  and analysis
 procedure as a sample.   It is used to monitor loss/recovery values.

      Method  of  standard  addition   (MSA):   The standard-addition  technique
 involves the  "se of  the unknown  and  the unknown plus several  known amounts of
 standard.  St  Method 7000,  Section  8.7 for detailed instructions.

      Sample holding time:   The storage time allowed between sample collection
 and sample analysis  when the designated  preservation  and  storage techniques are
employed.
                                  THREE  -  2                       Revision 2
                                                                  September 1994

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      3.1.3  Sample Handling and Preservation

      Sample holding times, digestion procedures and suggested collection volumes
are  listed  in  Table 1.   The  sample volumes required depend upon the number of
different digestion procedures necessary for analysis.  This may be determined
by the  application  of graphite-furnace atomic absorption spectrometry (GFAA),
flame atomic absorption  spectrometry (FLAA),  inductively coupled argon plasma
emission spectrometry (ICP), hydride-generation atomic absorption spectrometry
(HGAA),  inductively  coupled plasma  mass  spectrometry  (ICP-MS)  or cold-vapor
atomic  absorption  spectrometry (CVAA)  techniques,  each of  which  may require
different digestion procedures.  The indicated volumes in Table 3-1 refer to that
required  for  the  individual   digestion   procedures and  recommended  sample
collection volumes.

      In the  determination of  trace metals,  containers can  introduce either
positive  or  negative errors   in  the  measurement  of  trace  metals  by  (a)
contributing  contaminants through  leaching  or  surface  desorption,   and  (b)
depleting concentrations through adsorption.   Thus  the collection and treatment
of the  sample  prior to analysis require particular  attention.   The following
cleaning treatment  sequence has  been determined  to be adequate  to  minimize
contamination  in  the  sample  bottle,  whether  borosilicate  glass,  linear
polyethylene, polypropylene,  or Teflon;  detergent, tap water, 1:1 nitric acid,
tap water,  1:1 hydrochloric acid, tap water, and reagent water.

            NOTE: Chromic acid  should not be used  to clean glassware, especially
            if chromium is to be included in the analytical scheme.  Commercial,
            non-chromate  products  (e.g.,  Nochromix)  may  be  used  in  place  of
            chromic acid  if  adequate cleaning is documented by  an analytical
            quality control program.   (Chromic acid should also  not be used with
            plastic bottles.)

      3.1.4

      The toxicity or  carcinogenicity of each  reagent used in these methods has
not been precisely defined.  However, each chemical compound should be treated
as a potential  health  hazard.   From this viewpoint, exposure to these chemicals
must be reduced to the lowest possible level by whatever means available.  The
laboratory  is  responsible for  maintaining a  current awareness  file  of OSHA
regulations regarding the safe handling of  the  chemicals specified  in  these
methods. A reference  file of material data-handling  sheets should also be made
available to  all personnel  involved  in  the  chemical  analysis.   Additional
references  to laboratory safety are available.  They are:

1.    "Carcinogens -  Working  with Carcinogens," Department  of Health,
Education,  and Welfare,  Public Health Service, Center  for  Disease
Control, National  Institute  for Occupational  Safety and Health,
Publication No. 77-206,  August 1977.
                                  THREE - 3                       Revision 2
                                                                  September 1994

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                                  TABLE 3-1.

  SAMPLE HOLDING TIMES, REQUIRED DIGESTION VOLUMES AND  RECOMMENDED  COLLECTION
         VOLUMES FOR METAL DETERMINATIONS IN AQUEOUS AND SOLID SAMPLES
Measurement
Digestion
Vol. Reci."
 (mL)
Collection
Volume (mL)a
Treatment/
Preservative
Holding Timec
 tetals  (except hexavalent  chromium  and  mercury):
Aqueous
      Total
      Dissolved



      Suspended

Solid
      Total

Chromium VI:b

      Aqueous

      Solid

Mercury:

Aqueous
      Total


      Dissolved
    100
    100
    100
   2g
    100
Solid
      Total
   100


   100



   0.2g
  600


  600



  600


  200g



  400

  200g




  400


  400



  ZOOg
HN03 to pH <2
6 months

Filter on site;
HN03 to pH <2
6 months

Filter on site
6 months

6 months
24 hr
HN03 to pH <2
28 days

Filter;
HN03 to pH <2
28 days

28 days
"Unless  stated otherwise.
bThe  holding  time for the analysis of hexavalent chromium  in  solid  samples  has
not yet  been determined,  A holding time  of "as soon as possible" is recommended.
CA11  non-aqueous samples  and  all  aqueous samples that  are to be analyzed  for
mercury and  hexavalent chromium  must  be stored at  4"" ± 2°C until  analyzed,
either glass or plastic containers may  be used.
                                   THREE - 4
                                      Revision 2
                                      September 1994

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 2,        "OSHA Safety and Health Standards, General Industry"  (29 CFR  1910),
 Occupational  Safety and Health  Administration,  OSHA 2206,  revised
 January  1976.

 3,        "Proposed OSHA Safety and Health Standards, Laboratories," Occupational
 Safety and  Health  Administration, Federal  Register,  July 24, 1986, p. 26660.

 4.        "Safety in Academic Chemistry Laboratories," American  Chemical  Society
 Publication, Committee  on Chemical  Safety,  3rd edition, 1979.
3.2  SAMPLE  PREPARATION METHODS

          The methods  in SW-846  for sample digestion  or preparation  are as
follows1:

          Method 3005 prepares ground water and  surface water samples for total
recoverable  and dissolved metals determination by FLAA, ICP-AES, or ICP-HS.  The
unfiltered or filtered sample is heated with dilute HC1  and HN03 prior to metal
determination.

          Method3010 prepares waste samples for  total  metal  determination by
FLAA, ICP-AES, or ICP-MS.  The samples are vigorously  digested with nitric acid
followed by dilution with  hydrochloric acid. The method is applicable to aqueous
samples, EP  and mobility-procedure extracts.

          Method 3015 prepares aqueous samples, mobility-procedure  extracts, and
wastes that contain  suspended solids for total metal determination by FLAA, GFAA,
ICP-AES, or  ICP-MS.  Nitric  acid is  added to  the  sample in  a Teflori digestion
vessel and heated in a microwave unit prior to metals determination.

          Method 3020 prepares waste samples for total metals determination by
furnace GFAA or  ICP-MS.   The  samples are vigorously digested with nitric acid
followed by  dilution with nitric add.   The  method  is  applicable to aqueous
samples, EP  and mobility-procedure extracts.

          Hethod 3040 prepares oily waste samples  for determination of soluble
metals by FLAA, GFAA, and  ICP-AES methods. The samples are dissolved and diluted
in organic solvent prior  to analysis.  The method is applicable to the organic
extract in the oily  waste  EP procedure and other  samples  high  in oil, grease, or
wax content.

          Hethod 3050 prepares waste samples for total metals determination by
FLAA and ICP-AES,  or ICP-HS.  The samples are vigorously  digested in nitric acid
and hydrogen peroxide followed  by dilution with either  nitric or hydrochloric
acid.  The method is applicable to soils, sludges, and solid waste samples.

          Method 3051 prepares  sludges,  sediments,  soils  and oils  for  total
metals determination by FLAA,  GFAA,  ICP-AES or ICP-MS.  Nitric acid is added to


                                  THREE - 5                      Revision 2
                                                                  September 1994

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the representative sample in a Teflon digestion vessel  and heated  in  a microwave
unit prior to metals determination,

1  Please note that chlorine  is  an interferent in  ICP-MS  analyses  and its use
should be discouraged except when absolutely necessary.
                                  THREE - 6                       Revision 2
                                                                  September 1994

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3.3  METHODS  FOR DETERMINATION  OF  METALS

          This section  of  the manual  contains seven analytical techniques  for
trace  metal  determinations:  inductively  coupled  argon  plasma atomic emission
spectrometry  (ICP-AES),  inductively coupled  plasma mass spectrometry  (ICP-MS),
direct-aspiration or flame  atomic absorption  spectrometry  (FLAA),  graphite-
furnace   atomic   absorption   spectrometry  (GFAA),  hydride-generation  atomic
absorption spectrometry (HGAA),  cold-vapor atomic absorption spectrometry  (CVAA),
and  several  procedures  for hexavalent chromium  analysis.   Each  of  these  is
briefly discussed below  in terms of advantages,  disadvantages,  and  cautions  for
analysis  of wastes.

          ICP's  primary advantage  is that  it allows  simultaneous  or rapid
sequential  determination  of many  elements  in a  short  time.    The  primary
disadvantage  of  ICP  is  background  radiation  from other elements and the plasma
gases.  Although all  ICP instruments  utilize high-resolution optics  and back-
ground correction to minimize these interferences, analysis for traces  of metals
in the presence of a large  excess of a single metal  is difficult. Examples would
be traces of  metals  in  an  alloy or traces of metals in  a limed (high calcium)
waste.  ICP and Flame AA have comparable detection limits (within a  factor of 4)
except that  ICP  exhibits greater sensitivity for refractories (Al, Ba,  etc.).
Furnace AA, in general,  will  exhibit  lower detection limits than either ICP  or
FLAA.  Detection limits  are drastically improved when ICP-MS is used. In general
ICP-MS exhibits greater  sensitivity than either GFAA of  FLAA for most  elements.
The greatest disadvantage of ICP-MS is isobaric  elemental  interferences.  These
are caused by different  elements forming atomic ions with the same nominal mass-
to-charge ratio.  Mathematical correction for interfering ions can minimize these
interferences.

          Flame AAS (FLAA)  direct aspiration  determinations, as opposed to ICP,
are normally  completed  as  single element analyses and  are  relatively free  of
interelement  spectral  interferences.    Either  a nitrous-oxide/acetylene   or
air/acetylene flame is used  as  an energy  source for dissociating the  aispirated
sample into the free atomic state making  analyte atoms available for absorption
of light.   In  the  analysis of some elements the temperature or type of flame used
is critical.    If the proper  flame   and  analytical  conditions are not used,
chemical  and ionization  interferences can occur.

          Graphite Furnace AAS  (GFAA)  replaces  the  flame  with an  electrically
heated graphite furnace.  The furnace allows for gradual heating of the sample
aliquot  in   several   stages.    Thus,  the processes of  desolvation,  drying,
decomposition of  organic and inorganic molecules and salts,  and  formation of
atoms which must occur in a  flame or ICP in a few milliseconds may be allowed to
occur over  a much  longer  time period and  at controlled temperatures  in  the
furnace.  This allows an experienced analyst to remove unwanted matrix components
by using temperature programming and/or matrix modifiers.   The major  advantage
of this technique is that it affords extremely low detection limits.   It is the
easiest to perform on relatively clean  samples.   Because  this technique is so
sensitive, interferences can be a real problem;  finding the optimum combination
of digestion,  heating times  and temperatures,  and  matrix modifiers  can  be a

                                   THREE  - 7                       Revision 2
                                                                  September  1994

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challenge for complex matrices.

          Hydride AA utilizes a chemical reduction to reduce and separate arsenic
or selenium selectively from a sample digestate.  The technique therefore has the
advantage of being  able to isolate these two elements from  complex samples which
may  cause   interferences  for   other   analytical   procedures.     Significant
interferences have  been reported when any of the following is present:  1) easily
reduced metals (Cu, Ag,  Hg);  2) high concentrations of transition metals (>200
mg/L); 3)  oxidizing agents  (oxides of  nitrogen)  remaining following  sample
digestion.

          Cold-Vapor AA uses a chemical  reduction to reduce mercury selectively.
The procedure is extremely sensitive but is subject to interferences from some
volatile organics,  chlorine,  and sulfur compounds.
                                  THREE - 8                       Revision 2
                                                                  Septenfcer 1994

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                                 CHAPTER  FOUR
                               ORGANIC ANALYTES
4.1   SAMPLING  CONSIDERATIONS

      4.1.1   Introduction

      Following the initial  and  critical  step  of designing  a  sampling plan
(Chapter  Nine)  is the implementation of  that  plan such that  a representative
sample of the solid waste is collected.   Once  the  sample has been collected it
must  be stored  and preserved  to maintain the chemical and physical properties
that  it possessed at the time of collection.   The sample type,  type of containers
and their preparation,  possible  forms of contamination, and preservation methods
are  all   items  which  must  be  thoroughly  examined in  order  to  maintain the
integrity of the samples.   This  section  highlights  considerations which must be
addressed in order to maintain a  sample's  integrity and representativeness. This
section is, however, applicable only to trace  analyses.

      Quality  Control  (QC)  requirements need  not be  met  for  all  compounds
presented in the Table of Analytes for the  method  in  use, rather, they must be
met  for  all  compounds reported.    A  report  of  non-detect   is considered  a
quantitative  report,  and must  meet  all  applicable QC requirements  for that
compound  and the method used.

      4.1.2  Sample Handlino. and Preservation

      This  section deals  separately  with volatile and semivolatile organics.
Refer to Chapter Two and Table 4-1 of this section for  sample containers,  sample
preservation, and  sample holding time information.

      Volatile  Organics

      Standard 40 ml glass screw-cap  VOA vials  with Teflon lined silicone septa
may be used for both liquid and solid matrices.  The  vials and septa should be
washed with soap  and  water and rinsed with distilled deionized  water.   After
thoroughly cleaning the vials and septa,  they  should  be placed in  an oven and
dried at  100°C for approximately one  hour.

NOTE: Do not heat  the  septa for extended  periods  of time  (i.e.,  more than one
      hour,  because the silicone begins to  slowly degrade at 105'C).

      When collecting  the  samples, liquids and  solids  should be introduced into
the vials gently to reduce agitation  which might drive off volatile compounds.
In general,  liquid  samples should be poured into the vial without introducing any
air bubbles within the vial as it is  being  filled.  Should bubbling occur as a
result of violent pouring,  the sample must be poured out and the vial refilled.
The vials should be completely filled at  the time of sampling,  so that when the
septum cap is  fitted and sealed,  and the vial inverted, no headspace is visible.
The sample should be hermetically sealed in the  vial  at the time  of sampling, and
must not be opened prior to analysis  to preserve their integrity.
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                                                                September 1994

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            due  to differing solubility  and  diffusion  properties of gases  in
            LIQUID matrices  at  different temperatures,  it is possible for the
            sample to  generate  some headspace during storage.  This headspace
            will appear in the form of micro bubbles, and  should not  invalidate
            a  sample for volatiles  analysis.

            The presence of a macro bubble in a sample vial generally indicates
            either improper  sampling technique  or a source  of  gas evolution
            within the sample.    The  latter case  is  usually  accompanied by a
            buildup  of pressure  within  the  vial,  (e.g.  carbonate-containing
            samples  preserved with acid).   Studies conducted  by  the  USEPA
            (EMSL-Ci, unpublished data) indicate that "pea-sized" bubbles  (i.e.,
            bubbles  not exceeding  1/4  inch  or  6  mm  in  diameter) did  not
            adversely  affect volatiles  data.   These bubbles were generally
            encountered in wastewater samples, which are more  susceptible to
            variations in gas solubility  than are groundwater samples.

 At the time of  analysis, the aliquot to be analyzed should  be taken from the
vial with a gas-tight syringe inserted directly through  the septum of the vial.
Only one analytical sample can be  taken from each vial.  If these guidelines are
not followed, the  validity of the data generated from the samples  is suspect.

      VOA vials  for  samples  with  solid or semi-solid matrices (e.g., sludges)
should be completely  filled  as  best as possible.   The  vials  should be tapped
slightly as  they  are  filled  to  try and  eliminate  as much free  air  space as
possible.  Two vials should also  be filled per sample location.

      At least two VOA vials should be filled  and  labeled  immediately  at the
point at which  the  sample is collected. They should NOT be  filled near a running
motor or any  type of  exhaust  system  because discharged fumes and  vapors  may
contaminate the samples.   The two vials from each sampling location should then
be  sealed  'in  separate plastic  bags  to  prevent  cross-contamination  between
samples, particularly if the sampled waste is suspected of containing high levels
of volatile organics.   {Activated carbon may also  be included in  the  bags to
prevent cross-contamination  from highly contaminated samples).  VOA samples may
also be contaminated by diffusion  of volatile organics through  the septum during
shipment and storage.   To monitor possible contamination, a trip blank prepared
from organic-free  reagent water  (as defined  in Chapter  One)  should be carried
throughout  the sampling,  storage, and shipping process.

      Semi volatile Organics  (including Pesticides,  PCBs and Herbicides.)

      Containers used to collect samples  for the determination of semivolatile
organic compounds  should  be  soap and water  washed followed by  methanol  (or
isopropanol) rinsing  (see  Sec.  4.1.4  for specific  instructions  on glassware
cleaning).   The sample containers should  be of glass  or Teflon, and have screw-
caps with Teflon  lined septa.   In  situations where Teflon is not  available,
solvent-rinsed aluminum foil  may be used  as a liner.  However, acidic or basic
samples may react with the aluminum  foil,  causing eventual  contamination of the
sample.   Plastic containers  or lids may NOT be used for the storage of samples
due to the  possibility of  sample contamination from  the  phthalate  esters and
other hydrocarbons within  the plastic.  Sample containers should be filled with
care so  as to prevent any portion of the collected sample coming in contact with

                                   FOUR - 2                         Revision 2
                                                                September 1994

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the  sampler's  gloves,  thus  causing contamination.    Samples  should  not be
collected or  stored  in  the presence of  exhaust fumes.   If the sample comes in
contact with the sampler {e.g. if an automatic sampler is used), run organic-free
reagent water through the  sampler  and use as a field blank.

      4.1.3  Safety

      Safety  should  always be the  primary  consideration  in  the collection of
samples.  A thorough understanding  of the waste production process, as well as
all of the potential hazards making up the waste, should be  investigated whenever
possible.   The  site  should be visually  evaluated  just prior  to  sampling to
determine additional safety measures.  Minimum protection of gloves and safety
glasses should  be worn to  prevent  sample  contact with the skin and  eyes.  A
respirator  should be worn  even  when working  outdoors if organic  vapors are
present.  More  hazardous sampling missions may require the use of supplied air
and special  clothing.

      4-1.4  Cleaning of Glassware

      In the analysis of samples  containing  components  in the parts per billion
range, the  preparation of scrupulously clean glassware is necessary.  Failure to
do  so  can  lead  to a myriad  of  problems in the  interpretation of  the final
chromatograms   due to  the  presence  of  extraneous   peaks  resulting  from
contamination.   Particular care  must be taken with  glassware such  as Soxhlet
extractors,  Kuderna-Danish  evaporative concentrators,  sampling-train components,
or any other glassware coming  in contact with an extract that will be evaporated
to a smaller volume.   The process  of concentrating the  compounds of interest in
this operation may similarly concentrate the contaminating substance(s), which
may seriously distort the results.

      The basic  cleaning steps are:

      1.  Removal  of surface residuals immediately after use;

      2.  Hot soak to loosen and float most particulate material;

      3.  Hot water rinse to flush away floated particulates;

      4.  Soak with an oxidizing agent to destroy traces of organic compounds;

      5.  Hot water rinse to flush away materials loosened  by the deep penetrant
          soak;

      6.  Distilled water rinse to remove metallic deposits from the tap water;

      7.  Alcohol, e.g., isopropanol or methanol,  rinse to flush off any final
          traces of organic materials and remove the water; and

      8.  Flushing the item immediately before use with some of the same solvent
          that will be used in the analysis.
                                   FOUR - 3                         Revision 2
                                                                September 1994

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      Each of these eight fundamental  steps are discussed here in the order in
which they appeared on the preceeding  page.

      1.   As soon possible after glassware  (i.e.,  beakers,  pi pets,  flasks, or
          bottles) has come in contact with sample or standards,  the glassware
          should  be  flushed  with   alcohol  before  it is  placed  in the  hot
          detergent soak.   If this is  not done,  the  soak  bath may  serve to
          contaminate all other glassware placed therein.

      2.   The hot soak consists of  a bath  of a  suitable  detergent  in water of
          50°C  or higher.   The detergent,  powder or liquid,  should  be entirely
          synthetic and not a  fatty  acid base.  There are very few areas of the
          country where  the water  hardness is  sufficiently low to  avoid  the
          formation of some hard-water scum resulting from the reaction between
          calcium and magnesium salts  with a fatty acid soap.  This hard-water
          scum or curd  would have an affinity particularly for many  chlorinated
          compounds and,  being almost  wholly water-insoluble, would deposit on
          all  glassware in the bath  in a thin  film.

          There are many suitable detergents on the wholesale  and retail market.
          Most of the common  liquid dishwashing detergents  sold  at  retail  are
          satisfactory but are more expensive  than other comparable products
          sold industrially.   Alconox,  in powder  or tablet form, is manufactured
          by Alconox,  Inc.,  New York, and is marketed by a number of laboratory
          supply firms.   Sparkleen,  another powdered product, is distributed by
          Fisher Scientific Company.

      3.   No comments required.

      4.   The most common and  highly effective oxidizing agent for  removal  of
          traces of organic compounds  is the traditional  chromic  acid solution
          made  up of  concentrated sulfuric acid and  potassium  or  sodium
          dichromate.   For maximum  efficiency, the soak solution  should be  hot
          (40-506C),    Safety   precautions  must  be  rigidly observed  in  the
          handling of this  solution.    Prescribed  safety gear should  include
          safety goggles,  rubber  gloves,  and apron.  The  bench  area where this
          operation is conducted should be covered with  fluorocarbon sheeting
          because spattering will disintegrate any unprotected  surfaces.

          The potential hazards of using  chromic-sulfuric  acid mixture are great
          and have been well publicized.   There  are now commercially available
          substitutes  that possess the advantage of safety  in handling.   These
          are biodegradable concentrates with a claimed cleaning strength equal
          to the chromic acid  solution.   They are  alkaline,  equivalent  to  ca.
          0.1  N  NaOH  upon dilution, and  are claimed  to remove dried  blood,
          silicone greases,  distillation residues,  insoluble organic residues,
          etc.   They  are  further  claimed to remove radioactive  traces and will
          not attack glass or exert a corrosive effect  on  skin or clothing.  One
          such  product is  "Chem  Solv  2157," manufactured by Mallinckrodt  and
          available through laboratory supply firms. Another comparable product
          is "Detex,"  a product of Borer-Chemie,  Solothurn,  Switzerland.
                                   FOUR -  4                          Revision 2
                                                                September 1994

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      5, 6, and 7.  No comments required,

      8.  There is always a possibility that between the time  of washing and the
          next use, the glassware could pick up some contamination from either
          the  air or  direct contact.   To  ensure  against  this,  it  is  good
          practice to  flush the item immediately before use with  some of the
          same solvent that will be used in the analysis.

      The drying and storage of the cleaned glassware is of critical importance
to  prevent the  beneficial  effects   of  the  scrupulous cleaning  from  being
nullified.    Pegboard  drying  is  not  recommended.    It is  recommended  that
laboratory glassware and  equipment be dried  at  100°C.   Under no  circumstances
should such small  items  be  left in the open  without protective covering.   The
dust  cloud  raised  by  the  daily  sweeping of  the  laboratory  floor can  most
effectively recontaminate the clean glassware.

      As  an  alternate  to  solvent  rinsing,  the glassware  can  be heated  to  a
minimum of 300°C  to  vaporize any  organics.   Do not use this  high  temperature
treatment  on  volumetric  glassware,  glassware  with ground  glass  joints,  or
sintered glassware.

      4.1.5  High Concentration Samples

            Cross contamination of trace concentration  samples may  occur  when
      prepared in the same laboratory with high concentration samples.  Ideally,
      if  both type  samples are  being  handled,  a  laboratory  and  glassware
      dedicated solely  to the preparation of high concentration samples would be
      available for this purpose.   If this is not feasible,  as a minimum  when
      preparing high concentration samples, disposable glassware should be  used
      or,  at  least,  glassware  dedicated entirely  to  the  high  concentration
      samples.    Avoid  cleaning  glassware  used  for  both  trace  and  high
      concentration samples in the same area.
                                   FOUR -  5                          Revision 2
                                                                September Iii4

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                                                     TABLE  4-1.
                           SAMPLE  CONTAINERS,  PRESERVATION,  TECHNIQUES, AND HOLDING TIMES
Analyte Class
Container
Preservative
Holding Time
Volatile Orqanics

   Concentrated Waste Samples



   Liquid Samples

     No Residual Chlorine
     Present

     Residual Chlorine Present
     Acrolein and
     Acrylonitrile

   Soil/Sediments and Sludges
125 mL widemouth glass
container with Teflon
lined lid
2 X 40 mL vials with
Teflon lined septum caps

2 X 40 mL vials with
Teflon lined septum caps
2 X 40 mL vials with
Teflon lined septum caps

125 mL widemouth glass
container sealed with a
septum
Cool, 4'C
Cool, 4'C1


Collect sample in a 125 mL
container which has been pre-
preserved with 4 drops of 10%
sodium thiosulfate solution.
Gently swirl to mix sample and
transfer to a 40 mL VGA vial.1
Cool, 4'C

Adjust to pH 4-5; cool, 4'C


Cool, 4'C
   14 days
   14 days


   14 days
   14 days


   14 days
          Adjust pH <2 with H2S04,  HC1  or  solid  NaHS04.
                                                      FOUR  -  6
                                                                          Revision  2
                                                                      September 1994

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                                                TABLE 4-1, Continued
Analyte  Class
Container
Preservative
   Holding Time
 Semivolatile  Organics/Orqanochlorine  Pesticides/PCBs  and  Herbicides

   Concentrated Waste Samples    125 ml  widemouth  glass       None
                                 with  Teflon  lined lid
   Water  Samples

     No Residual Chlorine
     Present
1-gal.  or 2 x 0.5-gal.,or
4 x 1-L, amber glass
container with Teflon
lined lid
Cool,  4°C
     Residual Chlorine  Present   1-gal.  or 2 x 0.5-gal.,  or  Add  3  ml  10% sodium thiosulfate
                                 4 x 1-U amber glass        solution  per gallon.2  Cool, 4°C
                                 container with Teflon
                                 lined lid
    Soil/Sediments  and  Sludges    250 ml widemouth glass      Cool,  4°C
                                 container with Teflon
                                 lined lid
                                                                Samples must be
                                                                extracted within 14
                                                                days and extracts
                                                                analyzed within 40
                                                                days following
                                                                extraction.
Samples must be
extracted within 7
days and extracts
analyzed within 40
days following
extraction.

Samples must be
extracted within 7
days and extracts
analyzed within 40
days following
extraction.

Samples must be
extracted within 14
days and extracts
analyzed within 40
days following
extraction.
2 Pre-preservation may be performed  in  the  laboratory  prior  to  field  use.

                                                      FOUR  - 7
                                                                          Revision 2
                                                                      September 1994

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4.2  SAMPLE PREPARATION METHODS

     4.2.1  EXTRACTIONS AND PREPARATIONS

         The following methods are included in this section:

         Method 3500A:     Organic Extraction and Sample Preparation
         Method 3510B:     Separatory Funnel Liquid-Liquid Extraction
         Method 3520B:     Continuous Liquid-Liquid Extraction
         Method 3540B:     Soxhlet Extraction
         Method 3541:      Automated Soxhlet Extraction
         Method 3550A:     Ultrasonic Extraction
         Method 3580A:     Waste Dilution
         Method 5030A;     Purge-and-Trap
         Method 5040A:     Analysis  of  Sorbent  Cartridges  from  Volatile
                           Organic    Sampling    Train    (VOST):       Gas
                           Chromatography/Mass Spectrometry Technique
         Method 5041:      Protocol for Analysis of Sorbent Cartridges from
                           Volatile Organic  Sampling  Train  (VOST):   Wide-
                           bore Capillary Column Technique
                                  FOUR - 8                        Revision 2
                                                             September 1994

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4.2  SAMPLE PREPARATION METHODS
     4.2.2  CLEANUP
         The following methods are included in this section;
         Method 3600B:
         Method 3610A:
         Method 3611A:

         Method 3620A:
         Method 3630B:
         Method 3640A:
         Method 3650A:
         Method 3660A:
         Method 3665:
Cleanup
Alumina Column Cleanup
Alumina   Column   Cleanup   and   Separation   of
Petroleum Wastes
Florisil Column Cleanup
Silica Gel Cleanup
Gel-Permeation Cleanup
Acid-Base Partition Cleanup
Sulfur Cleanup
Sulfuric Ac id/Permanganate Cleanup
                                  FOUR  -  9
                                      Revision 2
                                  September 1994

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4.3  DETERMINATION OF ORGANIC ANALYTES
     4.3.1 GAS CHROMATOGRAPHIC METHODS

         The following methods are included in this section:
         Method 8000A:
         Method 801OB:

         Method 8011:

         Method 80ISA:

         Method 8020A:
         Method 8021A:
         Method B030A:
         Method 8031:
         Method 8032:
         Method 8040A;
         Method 8060:
         Method 8061:

         Method 8070:
         Method B080A:

         Method 8081:

         Method 8090:
         Method 8100:
         Method 8110:
         Method 8120A:
         Method 8121:

         Method 8140:
         Method B141A:

         Method 81SOB:
         Method 8151:
Gas Chromatography
Halogenated    Volatile    Organics    by    Gas
Chromatography
1,2-Dibromoethane and l,2-Dibromo-3-chloropropane
by Microextraction and Gas Chromatography
Nonhalogenated    Volatile    Organics    by   Gas
Chromatography
Aromatic Volatile Organics by Gas Chromatography
Halogenated Volatiles  by Gas  Chromatography Using
Photoionization  and  Electrolytic  Conductivity
Detectors in Series: Capillary Column Technique
Acrolein and Acrylonitrile by Gas Chromatography
Acrylonitrile by Gas Chromatography
Acrylamide by Gas Chromatography
Phenols by Gas Chromatography
Phthalate Esters
Phthalate Esters by Capillary Gas Chromatography
with Electron Capture Detection (6C/ECD)
Nitrosamines by Gas Chromatography
Organochlorine  Pesticides  and  Polychlorinated
Biphenyls by Gas Chromatography
Organochlorine Pesticides  and PCBs as Aroclors by
Gas Chromatography:  Capillary Column Technique
Nitroaromatics and Cyclic  Ketones
Polynuclear Aromatic Hydrocarbons
Haloethers by Gas Chromatography
Chlorinated Hydrocarbons by Gas Chromatography
Chlorinated Hydrocarbons  by  Gas Chromatography:
Capillary Column Technique
Organophosphorus Pesticides
Organophosphorus Compounds by Gas Chromatography:
Capillary Column Technique
Chlorinated Herbicides by  Gas Chromatography
Chlorinated Herbicides by  GC  Using Methylation or
Pentafluorobenzylation Derivatization:  Capillary
Column Technique
                                 FOUR - 10
                                      Revision Z
                                  September 1994
                                    \

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4.3  DETERMINATION OF ORGANIC ANALYTES

     4.3,3  HIGH PERFORMANCE LIQUID CHRQMATQGRAPHIC METHODS

         The following methods are included  in  this section:
         Method 8310:
         Method 8315:

               Appendix A:

         Method 8316:

         Method 8318;

         Method 8321:



         Method 8330;

         Method 8331;
Polynuclear Aromatic Hydrocarbons
Determination  of  Carbonyl   Compounds  by  High
Performance Liquid Chromatography (HPLC)
      Recrystallization    of    2,4-
      Dinitrophenylhydrazine (DNPH)
Acrylamide, Acrylonitrile and  Acrolein by  High
Performance Liquid Chromatography (HPLC)
N-Methylcarbamates  by  High  Performance  Liquid
Chromatography (HPLC)
Solvent  Extractable Non-Volatile  Compounds  by
High    Performance     Liquid
Chromatography/Thermospray/Mass   Spectrometry
(HPLC/TSP/MS)  or Ultraviolet (UV)  Detection
Nitroaromatics and Nitramines by High Performance
Liquid Chromatography (HPLC)
Tetrazene  by  Reverse   Phase  High   Performance
Liquid Chromatography (HPLC)
                                 FOUR - 12
                                      Revision  2
                                  September  1994

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4.3  DETERMINATION OF ORGANIC ANALYTES
     4,3,4  FOURIER TRANSFORM INFRARED METHODS
         The following method is included in this section:
         Hethod 8410:      Gas  Chromatography/Fourier  Transform  Infrared
                           (GC/FT-IR)    Spectrometry    for    Semivolatile
                           Organics:  Capillary Column
                                 FOUR - 13                       Revision,2
                                                             September 1994

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4.4  MISCELLANEOUS SCREENING METHODS

         The following methods are included in this section:
         Method 3810:
         Method 3820:

         Method 4010:
         Method 8275:
Headspace
Hexadecane Extraction and Screening of Purgeable
Organics
Screening for Pentachlorophenol by Immunoassay
Thermal Chromatography/Mass Spectrometry (TC/MS)
for Screening Semi volatile Organic Compounds
                                 FOUR -  14
                                      Revision 2
                                  September 1994

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                           CHAPTER FIVE
                    MISCELLANEOUS TEST METHODS
The following methods are found in Chapter Five:
      Method
      Method
      Method

      Method
      Method
      Method
      Method

      Method
      Method
      Method
      Method

      Method
      Method

      Method
      Method

      Method

      Method

      Method

      Method

      Method
5050:
9010A:
9012:

9013:
9020B:
9021:
9022:

9030A:
9031:
903i:
9036:

9038:
9056:

9060:
9065:

9066:

9067:

9070:

9071A:

9075:
      Method 9076:


      Method 9077:

      Method 9131:

      Method 9132:
      Method 9200:
      Method 9250:
      Method 9251:
      Method 9252A:
      Method 9253:
      Method 9320:
Bomb Preparation Method for Solid Waste
Total and Amenable Cyanide  (Colorimetric, Manual)
Total   and   Amenable   Cyanide   (Colorimetric,
Automated UV)
Cyanide Extraction Procedure for Solids and Oils
Total Organic Hal ides (TOX)
Purgeable Organic Hal ides  (POX)
Total Organic Hal ides (TOX) by Neutron Activation
Analysis
Acid-Soluble and Acid-Insoluble Sulfides
Extractable Sulfides
Sulfate (Colorimetric,  Automated, Chloranilate)
Sulfate  (Colorimetric,  Automated,  Methylthymol
Blue, AA II)
Sulfate (Turbidimetric)
Determination   of   Inorganic
Chromatography Method
Total Organic Carbon
Phenolics (Spectrophotometric,
Distillation)
Phenolics  (Colorimetric,   Automated
Distillation)
Phenolics    (Spectrophotometric,
Distillation)
Total  Recoverable  Oil  &  Grease
Separatory Funnel Extraction)
Oil and Grease  Extraction  Method  for Sludge and
Sediment Samples
                       Chlorine in New  and Used
                       by   X-Ray   Fluorescence
                                Anions   by   Ion
                               Manual 4-AAP with
                                     4-AAP  with
                                    MBTH    with
                                   (Gravimetric,
                                  Chlorine in  New  and Used
                                  Oxidative  Combustion and
Test Method  for  Total
Petroleum   Products
Spectrometry {XRFJ
Test Method  for  Total
Petroleum  Products  by
Microcoulometry
Test Methods for  Total  Chlorine  in New and Used
Petroleum Products (Field Test Kit Methods)
Total  Coliform:     Multiple  Tube  Fermentation
Technique
Total Coliform:  Membrane Filter Technique
Nitrate
                      Automated Fern"cyanide AAI)
                      Automated FerricyanideAAII)
                       Mercuric Nitrate)
                       Silver Nitrate}
           Chloride  (Colorimetric,
           Chloride  (Colorimetric,
           Chloride (Titrimetric,
           Chloride (Titrimetric,
           Radium-228
                             FIVE - 1
                                               Revision 1
                                               September 1994

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                            CHAPTER SIX

                            PROPERTIES


The following methods are found in Chapter Six:
      Method
      Method
      Method
      Method
      Method
      Method
      Method
      Method
1312:
1320:
1330A:
9040A:
9041A:
9045B:
9050:
9080:
      Method 9081:
      Method 9090A:
      Method 9095:
      Method 9096:
      Method 9100:

      Method 9310:
      Method 9315:
Synthetic Precipitation Leaching Procedure
Multiple Extraction Procedure
Extraction Procedure for Oily Wastes
pH Electrometric Measurement
pH Paper Method
Soil and Waste pH
Specific Conductance
Cation-Exchange  Capacity   of  Soils  (Ammonium
Acetate)
Cat ion-Exchange Capacity of Soils (Sodium Acetate)
Compatibility Test for Wastes  and Membrane Liners
Paint Filter Liquids Test
Liquid Release Test (LRT) Procedure
Saturated   Hydraulic    Conductivity,   Saturated
Leachate Conductivity,  and Intrinsic Permeability
Gross Alpha and Gross Beta-
Alpha-Emitting Radium Isotopes
                             SIX  -  1
                                               Revision 1
                                               September 1994

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                                 CHAPTER SEVEN

                    INTRODUCTION  AND  REGULATORY  DEFINITIONS


7.1  IGNITABILITY

      7.1.1  Introduction

      This section discusses the  hazardous characteristic of ignitability.  The
regulatory background of this characteristic is summarized,  and the regulatory
definition of ignitability is presented.  The two testing methods associated with
this characteristic, Methods 1010 and 1020,  can be found in  Chapter Eight.

      The objective of the ignitability characteristic is to identify wastes that
either present  fire hazards  under routine storage, disposal,  and transportation
or are capable  of severely exacerbating a fire  once started.

      7.1.2  Regulatory Definition

      The following definitions  have  been taken  nearly  verbatim  from the RCRA
regulations  (40  CFR 261,21) and  the  DOT regulations (49 CFR §§  173.300 and
173.151).

      Characteristics Of Ignitabilitv Regulation

      A  solid   waste  exhibits  the   characteristic  of  ignitability  if  a
representative  sample of the waste has any of the following  properties:

      1.    It  is  a  liquid,  other  than an aqueous solution,  containing  < 24%
            alcohol by volume,  and it  has  a flash point <  60°C  (140°F),  as
            determined by a  Pensky-Martens  Closed Cup Tester, using  the test
            method specified in ASTM Standard D-93-79 or D-93-80, or a Setaflash
            Closed Cup Tester,  using the test method specified in ASTM standard
            D-3278-78, or as determined by an equivalent test method approved by
            the Administrator under the  procedures set forth  in Sections 260.20
            and 260.21.   {ASTM standards are  available  from ASTM,  1916 Race
            Street, Philadelphia, PA   19103.)

      2.    It  is not a liquid and is  capable,  under  standard temperature and
            pressure, of  causing  fire through friction, absorption of moisture,
            or   spontaneous   chemical   changes  and,  when  ignited,  burns  so
            vigorously and  persistently that it creates  a hazard.

      3.    It  is an ignitable  compressed gas, as defined in  49 CFR 173.300 and
            as  determined by the test methods described in that regulation or by
            equivalent test methods approved by the Administrator under Sections
            260.20 and 260.21.

      4.    It  is an oxidizer,  as defined in 49  CFR 173.151,
                                  SEVEN - 1                        Revision  2
                                                                   September 1994

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       gnitable Compressed

      For the purpose of this regulation the following terminology is defined:

      1.    Compressed  gas.   The  term  "compressed  gas"  shall  designate any
            material or mixture having in the  container an absolute pressure
            exceeding 40 psi at  21 °C  (70°F)  or, regardless of the pressure at
            21 °C  (70°F), having  an absolute pressure exceeding 104 psi at 54 °C
            (130°F), or any  liquid flammable  material  having a vapor pressure
            exceeding 40 psi absolute at 38°C  (100'F),  as determined by ASTM
            Test D-323.

      2.    ...I.gn.1table  compressed  gas.    Any   compressed gas,  as defined  in
            Paragraph 1, above,  shall be classed  as  an  "ignitable compressed
            gas" if any one of the following occurs:

            a.  Either  a mixture of 13%  or less (by volume)  with air forms a
                flammable mixture,  or  the flammable range with air is wider than
                12%,  regardless  of the  lower, limit.    These limits  shall  be
                determined  at atmospheric temperature and pressure.  The method
                of sampling and test procedure shall be  acceptable to the Bureau
                of Explosives.

            b.  Using the Bureau  of Explosives'  Flame Projection Apparatus (see
                Note,  below), the  flame  projects more than  18  in.  beyond the
                ignition source  with valve opened  fully, or the flame flashes
                back and burns at the  valve with any degree of valve  opening.

            c.  Using the Bureau of Explosives' Open Drum Apparatus (see Note,
                below),  there is  any significant  propagation of flame away from
                the ignition  source.

            d.  Using the Bureau of Explosives'  Closed Drum  Apparatus (see Note,
                below),  there is any explosion  of the  vapor-air mixture in the
                drum.

NOTE:       Descriptions  of  the  Bureau  of   Explosives'  Flame  Projection
            Apparatus,  Open Drum Apparatus, Closed Drum Apparatus, and method of
            tests may be procured  from the Association of American Railroads,
            Operations   and Maintenance  Dept.,  Bureau  of Explosives,  American
            Railroad Building,  Washington,  DC.   20036;  202-293-4048.

      Qxidizer (as defined  in 49 CFR 173.151)

      For the  purpose of this  regulation,  an oxidizer is any  material that yields
oxygen readily to  stimulate  the  combustion of  organic  matter (e.g.,  chlorate,
permanganate,  inorganic peroxide, or a nitrate).
                                   SEVEN  -  2                        Revision 2
                                                                   September 1994

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7.2   CORROSIVITY

      7.2.1  Introduction

      The corrosivlty characteristic, as defined in 40 CFR 261.22, is designed
to identify wastes that might pose a hazard to human health or the environment
due to their ability to:

      1.    Mobilize toxic metals if discharged into a landfill environment;

      2.    Corrode handling,  storage, transportation, and management equipment;
            or

      3.    Destroy human or animal  tissue in  the event of inadvertent contact.

      In order to identify such potentially hazardous materials, EPA has selected
two properties upon which to  base the definition  of a corrosive waste.   These
properties are pH and corrosivity toward Type SAE 1020 steel.

      The following sections present the  regulatory background and the regulation
pertaining to the definition of corrosivity.  The procedures for measuring pH of
aqueous wastes  are detailed in Method 9040, Chapter Six.   Method 1110, Chapter
Eight, describes how to determine whether  a waste  is corrosive to steel.   Use
Method 9095, Paint Filter Liquids Test,  Chapter Six, to determine free liquid.

      7-2.2  Regulatory Definition

      The  following  material   has  been  taken nearly verbatim from  the  RCRA
regulations.

      1.    A solid  waste  exhibits the  characteristic  of  corrosivity if  a
            representative  sample  of the  waste has  either  of the  following
            properties:

            a.   It is  aqueous  and has a  pH  < 2 or > 12.5, as determined by a pH
               meter  using either  the  test  method  specified in this  manual
                (Method 9040)  or  an equivalent  test method  approved  by  the
               Administrator  under  the  procedures set forth in Sections 260.20
               and  260.El.

            b.   It is  a liquid and  corrodes steel  (SAE 1020)  at rate > 6.35 mm
                (0,250  in.)  per year at  a test temperature of 55°C (130°F), as
               determined  by  the  test method  specified  in NACE  (National
               Association  of Corrosion  Engineers)  Standard  TM-01-69,   as
               standardized in this manual (Method 1110) or an equivalent test
               method  approved by the  Administrator  under  the procedures  set
               forth  in  Sections 260.20 and 260.21.
                                   SEVEN  -  3                        Revision 2
                                                                   Septenber 1994

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7,3   REACTIVITY

      7.3.1  Introduction

      The regulation in 40 CFR 261.23 defines  reactive wastes to include wastes
that have any of the following properties:  (1) readily undergo violent chemical
change;  (2) react violently or form potentially explosive mixtures with water;
(3) generate toxic fumes when mixed  with  water or,  in  the case of cyanide- or
sulfide-bearing wastes, when  exposed to mild  acidic or  basic  conditions; (4)
explode  when  subjected to  a  strong  initiating  force;  (5) explode  at normal
temperatures and pressures;  or (6) fit within the Department of transportation's
forbidden explosives,  Class  A explosives, or Class 8 explosives classifications.

      This definition  is  intended to  identify wastes  that, because  of their
extreme instability and tendency to react violently or explode, pose a problem
at all stages  of  the  waste  management process.   The definition  is  to a large
extent a paraphrase of the  narrative definition employed  by the National  Fire
Protection  Association.    The  Agency  chose  to  rely  almost   entirely  on  a
descriptive, prose definition  of reactivity  because most of the available tests
for measuring  the  variegated  class  of  effects embraced  by  the  reactivity
definition suffer from a number of deficiencies.

      7.3.2  Regulatory Definition

            7.3.2.1    Characteristic Of Reactivity  Regulation

                A  solid waste exhibits  the  characteristic of  reactivity  if a
            representative  sample  of the  waste  has   any of  the  following
            properties:

            1.   It is  normally  unstable  and readily undergoes  violent change
                without detonating.

            2.   It reacts  violently  with  water.

            3.   It forms potentially explosive mixtures with water.

            4.   When  mixed with  water,  it  generates  toxic gases,  vapors,  or
                fumes  in a  quantity sufficient to  present a danger  to human
                health  or  the  environment.

            5.   It is a cyanide- or sulfide-bearing waste which, when exposed to
                pH conditions  between  2  and  12.5,  can generate  toxic gases,
                vapors, or fumes in a quantity sufficient to present a danger to
                human health or the environment.  (Interim  Guidance for Reactive
                Cyanide and  Reactive Sulfide,  Steps  7.3.3  and  7.3.4  below, can
                be used to detect the presence  of  reactive cyanide and reactive
                sulfide in wastes.)

            6.   It is  capable  of detonation  or  explosive  reaction if it  is
                subjected  to  a  strong  initiating source  or  if  heated  under
                confinement.
                                   SEVEN  -  4                        Revision 2
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             7,  It is readily capable of detonation or explosive decomposition
                or reaction at standard temperature and pressure.

             8.  It is a forbidden explosive, as defined in 49 CFR 173.51, or  a
                Class A explosive,  as  defined in 49 CFR  173.53,  or a Class  B
                explosive, as defined in 49 CFR 173.88.


       7.3.3   Interim Guidance For Reactive  Cyanide

             7.3.3.1    The current EPA guidance level  is:

             Total releasable cyanide:  250  mg HCN/kg waste.

             7.3.3.2    Test Method to Determine Hydrogen Cyanide Released from
                       Wastes

1.0    SCOPE  AND APPLICATION

       1.1    This  method  is applicable to all wastes,  with the condition that
wastes that  are combined with acids do not  form explosive mixtures.

       1.2    This  method  provides  a  way to  determine the  specific  rate  of
release of hydrocyanic acid upon contact with an aqueous acid.

       1.3    This  test  measures  only the hydrocyanic acid  evolved  at the test
conditions.   It  is  not intended to measure forms  of  cyanide other than those
that are evolvable under the test conditions.

2.0    SUMMARY OF  METHOD

       2.1    An aliquot of acid is added to  a fixed weight of waste in a closed
system.    The generated  gas  is  swept   into  a  scrubber.    The   analyte  is
quantified.  The  procedure for quantifying  the cyanide is Method 9010, Chapter
Five,  starting with Step 7.2.7 of that method.

3.0    INTERFERENCES

      3.1    Interferences are undetermined.

4.0   APPARATUS AND MATERIALS (See Figure 1}

      4.1    Round-bottom  flask  - 500-mL, three-neck,   with 24/40  ground-glass
joints.

      4.2    Gas scrubber - 50 mL calibrated scrubber

      4.3    Stirring apparatus - To achieve approximately 30 rpm.   This may be
either a  rotating magnet and stirring  bar combination or  an  overhead motor-
driven propeller  stirrer.

      4.4    Addition funnel - With  pressure-equalizing tube and 24/40 ground-
glass joint  and Teflon sleeve,


                                   SEVEN  -  5                       Revision  2
                                                                   Septenter 1994

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      4,5   Flexible  tubing   -   For  connection  from   nitrogen  supply  to
apparatus.

      4.i   Water-pumped   or   oil-pumped  nitrogen   gas   -   With  two-stage
regulator.

      4.7   Rotometer - For monitoring nitrogen gas flow rate.

      4.8   Analytical balance - capable of weighing to 0.001 g.

5.0   REAGENTS

      5.1   Reagent  grade chemicals  shall  be  used  in  all  tests.    Unless
otherwise  indicated,  it  is intended  that all  reagents  shall  conform  to the
specifications  of  the  Committee  on  Analytical  Reagents  of  the  American
Chemical Society, where  such  specifications  are available.   Other grades may
be used, provided it  is  first  ascertained  that the reagent is of sufficiently
high  purity  to  permit  its   use  without  lessening  the  accuracy  of  the
determination.

      5.2   Reagent water.  All  references to water  in this method  refer to
reagent water, as defined in Chapter One.

      5.3   Sulfuric  acid (0.01N),  H?S04.   Add 2.8 ml  concentrated  H2SO  to
reagent water and dilute  to 1  L.  Withdraw 100 ml  of  this solution and dilute
to 1 L to make the 0.01N H2S04.

      5.4   Cyanide reference  solution,  (1000 mg/L).   Dissolve approximately
2.5 g of KOH and 2.51 g  of KCN in 1  liter of  reagent  water.  Standardize with
0.0192N AgNOg.   Cyanide  concentration  in  this  solution should be 1 mg/mL.

      5.5   Sodium hydroxide solution (1.25N), NaOH.   Dissolve 50 g of NaOH in
reagent water and dilute to 1  liter with reagent water.

      5.6   Sodium hydroxide solution  (0.25N), NaOH.   Dilute 200 ml  of 1.25N
sodium hydroxide solution (Step 5.5) to 1 liter with reagent water.

      5.7   Silver  nitrate   solution   (0.0192N).      Prepare   by   crushing
approximately 5  g  of AgN03 crystals  and drying to  constant weight  at 40°C.
Weigh 3.265  g  of  dried  AgNO,,  dissolve in  reagent  water,  and  dilute  to  1
liter.

6.0   SAMPLE COLLECTION, PRESERVATION AND HANDLING

      6.1   Samples  containing,   or  suspected  of containing,  sulfide or  a
combination of  sulfide  and cyanide  wastes should be  collected  with  a minimum
of aeration.   The sample bottle should  be  filled completely, excluding all
head space, and stoppered.  Analysis should commence  as  soon as possible, and
samples should be kept in a cool, dark place  until  analysis begins.

      6.2   It  is  suggested  that  samples of cyanide  wastes be tested  as
quickly as possible.  Although they can be preserved by  adjusting the sample
pH to 12 with  strong base, this  will  cause  dilution of  the sample,  increase
the  ionic  strength,  and,  possibly,   change  other  physical  or  chemical

                                  SEVEN  -  6                        Revision 2
                                                                   September 1994

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characteristics  of the  waste which  may affect  the rate  of release  of the
hydrocyanic acid.  Storage of samples should be under refrigeration and in the
dark.
      6.3   Testing should be performed in a ventilated hood.
7.0   PROCEDURE
      7.1   Add  50 ml  of  0.25N  NaOH  solution  (Step  5.6)  to  a  calibrated
scrubber and dilute with reagent water to obtain an adequate depth of liquid.
      7.2   Close the system  and  adjust the flow rate  of  nitrogen,  using the
rotometer.  Flow should be 60 raL/min.
      7.3   Add 10 g of the waste to be tested to the system.
      7.4   With the  nitrogen flowing,  add  enough  sulfuric acid to  fill the
flask half full.  Start the 30 minute test period.
      7.5   Begin stirring while the  acid  is entering the  round-bottom flask.
The stirring speed must remain constant throughout the test.
NOTE: The stirring should not be fast enough to create a vortex.
      7.6   After  30  minutes,  close  off  the  nitrogen   and  disconnect  the
scrubber.   Determine  the amount  of cyanide in  the scrubber by  Method 9010,
Chapter Five,  starting with Step 7.2.7 of the method.
NOTE: Delete  the  "C"  and  "D"  terms  from  the spectrophotometric  procedure
      calculation  and the  "E"  and  "F"  terms from  the   titration  procedure
      calculation  in  Method  9010.    These terms  are  not  necessary for the
      reactivity  determination  because  the  terms  determine  the  amount  of
      cyanide in the entire sample,  rather than  only in the aliquot  taken for
      analysis.
8.0   CALCULATIONS
      8.1   Determine  the specific rate of release of HCN,  using the  following
parameters:
            X = Concentration of HCN in diluted scrubber solution (mg/L)
                  (This is obtained from Method 9010.)
            L = Volume of solution in scrubber (L)
            W = Weight of waste used (kg)
            S = Time of measurement (sec.) = Time N2 stopped - Time N2 started
                                                         X  • L
            R - specific rate of release (mg/kg/sec.)  »	—
                                                         W  • S
            Total  releasable HCN (rag/kg) = R x S
                                  SEVEN  -  7                        Revision 2
                                                                   September 1994

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9.0   METHOD PERFORMANCE

      9.1   The operation of the  system  can be checked and verified using the
cyanide  reference  solution  (Step  5,4).    Perform  the  procedure  using  the
reference solution  as  a sample and determine  the  percent  recovery.   Evaluate
the  standard  recovery  based  on  historical  laboratory  data,  as  stated  in
Chapter One.

10.0  REFERENCES

      10.1  No references are available at this time.
                                  SEVEN - 8                        Revision 2
                                                                   Septenter 1994

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                                      FIGURE 1.

             APPARATUS TO DETERMINE HYDROSEN  CYANIDE RELEASED FROM WASTES
                                      Stirrer
      Flowmeter
N2ln
                    Reaction Flask
                                                                   Gas Scrubber
                                                    Waste Sample
                                    SEVEN - 9
Revision 2
Septater 1994

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      7.3.4  Interim GuidanceFor Reactive Sulfide

             7.3.4.1    The current EPA guidance level is:

                Total  releasable sulfide:  500 mg H2S/kg  waste.
            7.3.4.2    Test Method to Determine Hydrogen Sulfide Released from
                       Wastes

1.0   SCOPE AND APPLICATION

      1.1   This method  is applicable to all wastes, with  the condition that
waste that are combined with acids do not form explosive mixtures.

      1.2   This  method  provides  a  way to  determine  the  specific  rate  of
release of hydrogen sulfide ypon contact with an aqueous acid.

      1.3   This procedure releases  only the hydrogen  sulfide evolved at the
test conditions.   It is  not  intended to measure forms of  sulfide other than
those that are evolvable  under the test conditions.

2.0   SUMMARY OF METHOD

      2.1   An aliquot of acid is added to a fixed weight of waste in a closed
system.    The  generated   gas  is  swept  into  a  scrubber.     The  analyte  is
quantified.   The  procedure  for quantifying  the sulfide  is given  in Method
9030, Chapter Five, starting with Step 7.3 of that method.

3.0   INTERFERENCES

      3.1   Interferences  are undetermined.

4.0   APPARATUS AND MATERIALS (See Figure 2)

      4.1   Round-bottom  flask  -  500-mL, three-neck, with  24/40 ground-glass
joints.

      4.2   Sas scrubber  - 50 ml calibrated scrubber.

      4.3   Stirring apparatus - To achieve approximately 30 rpm.  This may be
either a  rotating  magnet  and stirring  bar combination or  an  overhead motor-
driven propeller stirrer.

      4.4   Addition funnel - With  pressure-equalizing  tube and 24/40 ground-
glass joint and Teflon sleeve.

      4.5   Flexible  tubing   -   For  connection  from  nitrogen   supply  to
apparatus.
                                  SEVEN - 10                       Revision 2
                                                                   Septenber 1994

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      4.6   Water-pumped   or  oil-pumped   nitrogen   gas   -   With  two-stage
regulator.

      4.7   Rotometer  - For monitoring nitrogen gas flow rate.

      4.8   Analytical balance - capable of weighing to 0.001 g.

5.0   REAGENTS

      5.1   Reagent  grade  chemicals shall  be  used   in  all  tests.    Unless
otherwise  indicated,  it  is  intended that  all  reagents shall  conform  to the
specifications  of  the  Committee  on  Analytical  Reagents  of the  American
Chemical Society,  where  such specifications are available.   Other grades may
be used, provided  it  is  first ascertained  that the reagent is of sufficiently
high  purity  to  permit   its  use  without  lessening  the   accuracy  of  the
determination.

      5.2   Reagent water.   All  references to water  in this method  refer to
reagent water, as defined  in Chapter One.

      5.3   Sulfuric acid  (0.01N), H,S04.   Add  2.8  ml concentrated  H.S04
 to reagent  water and dilute  to  1  L   Withdraw  100  ml of this  solution and
dilute to 1 L to make the 0.01N HES04.

      5.4   Sulfide reference solution  -  Dissolve 4.02 g  of  NagS *  9HJ) in
1.0 L of  reagent water.   This solution contains  570 mg/L hydrogen  sultide.
Dilute  this  stock solution  to cover the  analytical  range  required  (100-570
rag/L).

      5.5   Sodium hydroxide solution (1.25N), NaOH.   Dissolve 50 g of NaOH in
reagent water and dilute to 1 L with reagent water.

      5.6   Sodium hydroxide  solution  (0.25N), NaOH.   Dilute 200  ml  of 1.25N
sodium hydroxide solution  (Step 5.5} to 1 L with reagent water.


6.0   SAMPLE COLLECTION, PRESERVATION AND HANDLING

      6.1   Samples containing,  or  suspected of  containing,  sulfide  wastes
should be collected with  a minimum of aeration.   "The  sample bottle should be
filled completely, excluding  all  head space,   and  stoppered.   Analysis should
commence as soon as possible, and samples should be kept in a cool, dark place
until  analysis begins.

      6.2   It  is suggested  that  samples of sulfide  wastes  be tested as
quickly as possible.   Although they can be preserved  by  adjusting the sample
pH to 12 with strong  base and adding  zinc acetate to the  sample,  these will
cause dilution  of the sample,  increase the  ionic  strength,  and,  possibly,
change  other physical  or chemical  characteristics of the  waste which  may
affect the rate of release of the hydrogen sulfide.  Storage  of samples should
be under refrigeration and in the dark.

      6.3   Testing should be performed in a ventilated hood.


                                  SEVEN - 11                       Revision 2
                                                                   September 1994

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7.0   PROCEDURE

      7,1   Add  50  ml  of 0.25N NaOH  solution to  a calibrated  scrubber and
dilute with reagent water to obtain an adequate depth of liquid.

      7,2   Assemble  the  system and adjust  the flow rate  of nitrogen, using
the rotometer.  Flow  should be 60 mL/min,

      7,3   Add 10 g  of the waste to be tested to the system.

      7,4   With the  nitrogen  flowing, add  enough  sulfuric  acid  to fill  the
flask half full, while starting the 30 minute test period.

      7,5   Begin stirring while the acid  is entering the round-bottom flask.
The stirring speed must remain constant throughout the test.

NOTE: The stirring should not be fast enough to create a vortex.

      7.6   After  30  minutes,  close  off  the  nitrogen  and  disconnect  the
scrubber.   Determine the amount of sulfide  in  the scrubber  by  Method 9030,
Chapter Five, starting with Step 7.3 of that method.

      7.7   Substitute  the  following  for Step  7.3.2  in Method  9030:   The
trapping solution must  be brought  to  a pH of 2 before  proceeding.  Titrate a
small aliquot  of  the trapping solution  to  a pH 2  end  point  with 6N HC1  and
calculate the  amount  of HC1 needed to acidify the  entire  scrubber solution.
Combine  the small  acidified  aliquot  with  the  remainder  of the acidified
scrubber solution.
8.0   CALCULATIONS

      8.1   Determine the specific rate of release of H2S, using the following
parameters:


            X = Concentration of H.S  in scrubber (mg/L)
                (This is obtained from Method 9030.)

            L - Volume of solution In scrubber (1)

            W = Weight of waste used (kg)

            S = Time of experiment (sec.)  = Time N2 stopped - Time N2 started


            R = specific rate of release (mg/kg/sec.) =
X • L
            Total  releasable H2S (mg/kg)  = R x S
                                                         W • S
                                  SEVEN - 12                       Revision 2
                                                                   September 1994

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9,0   METHOD PERFORMANCE

      9.1   The operation of the  system  can  be checked and verified using the
sulfide  reference solution  (Step  5.4).    Perform  the  procedure  using  the
reference solution as  a  sample and determine  the  percent recovery.  Evaluate
the  standard  recovery  based  on  historical   laboratory  data,  as  stated  in
Chapter One.

10.0  REFERENCES

      10.1  No references are available at this time.
                                  SEVEN -  13                       Revision 2
                                                                   Septenter 1994

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                                      FIGURE 2.

             APPARATUS TO DETERMINE HYDROGEN  SULFIDE RELEASED FROM WASTES
      Flowmeter
N2 In m+*~J
             1N H2SO4
                    Reaction Flask
                                                                   Gas Scrubber
                                                   waste Sample
                                    SEVEN - 14
Revision 2
Septenter 1994

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 7.4   TOXICITY  CHARACTERISTIC  LEACHING  PROCEDURE

      7.4.1  Introduction

      The  Toxicity  Characteristic  Leaching  Procedure  (TCLP)  is  designed to
 simulate  the  leaching  a  waste will  undergo  if  disposed  of  in  a sanitary
 landfill.   This test is  designed  to simulate leaching that takes place in a
 sanitary  landfill  only.   The  extraction  fluid employed is  a  function  of the
 alkalinity  of  the  solid  phase of  the waste.   A  subsample  of  a  waste is
 extracted with  the appropriate  buffered acetic acid solution for 18 ± 2 hours.
 The  extract  obtained from the  TCLP  (the  "TCLP extract")  is then  analyzed to
 determine  if  any  of  the  thresholds  established   for  the   40  Toxicity
 Characteristic  (TC)  constituents (listed  in  Table 7-1)  have been  exceeded or
 if the  treatment standards established for the constituents listed in  40 CFR
 §268,41  have been  met  for the  Land  Disposal  Restrictions  (LDR) program.   If
 the TCLP extract contains  any one of the TC constituents in an amount equal to
 or  exceeding  the  concentrations  specified  in  40  CFR  §261.24,   the  waste
 possesses  the characteristic of toxicity  and is a  hazardous  waste.   If the
 TCLP  extract  contains   LDR   constituents   in   an   amount  exceeding  the
 concentrations  specified  in  40  CFR  §268.41,  the treatment  standard for that
 waste has not  been  met,  and   further  treatment  is  necessary  prior to land
 disposal.

      7.4.2  SummaryofProcedure

      The TCLP  consists of five steps (refer  to Figure 3):

      1.  Separation Procedure

      For  liquid wastes   (i.e...., those  containing  less than  0.5%  dry  solid
 material), the  waste,  after filtration through a 0.6  to  0.8  pm  glass  fiber
 filter,  is defined as the  TCLP extract.

      For wastes containing greater  than or equal  to  0.5% solids,  the liquid,
 if any,  is separated from  the solid phase and stored for later analysis.

      Z,  Particle Size Reduction

      Prior  to  extraction,  the solid  material  must pass  through  a  9.5-mm
 (0.375-in.)  standard sieve, have s. surface  area  per crarr o^ material equal tc
 or greater than  3.1  cm2, or, be  smaller than  1  cm in  its narrowest dimension.
 If the  surface  area  is smaller or  the particle  size larger than described
 above, the solid portion  of  the waste  is  prepared for extraction by crushing,
 cutting, or  grinding the  waste  to  the  surface area  or particle size described
 above.   (Special precautions  must be  taken  if the  solids are prepared  for
 organic volatiles extraction.)

      3.  Extraction of Solid Material

      The solid material  from  Step  2  is  extracted for  18 + 2  hours with an
 amount of extraction fluid equal to 20 times the weight  of the  solid  phase.
The extraction  fluid employed  is  a  function of  the  alkalinity of  the  solid
                                  SEVEN - 15                       Revision 2
                                                                   September 1994

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phase  of the  waste.    A special extractor  vessel  is  used when  testing for
volatile analytes.

      4.  Final Separation of the Extraction from the Remaining Solid

      Following  extraction,  the  liquid  extract is  separated from  the solid
phase  by  filtration  through   a 0.6  to  0.8  urn  glass  fiber   filter.    If
compatible,  the initial  liquid phase of the  waste  is  added  to  the  liquid
extract, and  these are  analyzed  together.   If incompatible, the liquids are
analyzed separately  and  the results  are mathematically combined to yield  a
volume-weighted average concentration.

      5.  Testing  (Analysis) of TCLP Extract

      Inorganic  and  organic  species are   identified   and  quantified  using
appropriate methods  in  the  6000,  7000,   and 8000  series  of methods  in  this
manual or by equivalent methods.

      7.4.3 Regulatory Definition

      Under  the   Toxicity  Characteristic,   a  solid  waste   exhibits   the
characteristic of  toxicity  if  the TCLP extract from a  subsample  of the waste
contains any   of  the  contaminants  listed  in  Table  7-1  at a  concentration
greater than or equal to the respective value given in that table.  If a waste
contains <0.5%  filterable   solids,  the  waste  itself,  after  filtering,  is
considered to be the extract for the purposes of analysis.

      Under  the  Land  Disposal  Restrictions  program,  a  restricted  waste
identified in  40  CFR §268.41 may be  land disposed  only if  a TCLP extract of
the waste or  a TCLP extract of the treatment  residue  of the waste  does not
exceed the  values  shown  in  Table CCWE  of  40  CFR  §268.41  for  any hazardous
constituent listed  in  Table CCWE for that  waste.   If a waste  contains <0.5%
filterable  solids, the waste itself,  after  filtering,  is considered to  be the
extract for the purposes of analysis.
                                  SEVEN - 16                       Revision 2
                                                                   September 1994

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                                  TABLE 7-1.

      MAXIMUM CONCENTRATION OF CONTAMINANTS FOR TOXICITY CHARACTERISTIC
Contaminant
Regulatory Level
     (mg/L)
Arsenic
Barium
Benzene
Cadmi urn
Carbon tetrachloride
Chlordane
Chlorobenzene
Chloroform
Chromium
o-Cresol
m-Cresol
p-Cresol
Cresol
2,4-D
1 ,4-Dichl oro benzene
1,2-Dichloroethane
1 , 1 -Di chl oroethyl ene
2,4-Dinitrotoluene
Endrin
Heptachlor (and its hydroxide)
Hexachl orobenzene
Hexachl oro-l,3-butadi ene
Hexachl oroethane
Lead
Lindane
Mercury
Methoxychlor
Methyl ethyl ketone
Nitrobenzene
Pentachl orophenol
Pyridine
Selenium
Silver
Tetrachl oroethyl ene
Toxaphene

SEVEN - 17

5.0
100.0
0.5
1.0
0.5
0.03
100.0
6.0
5.0
200. O1
200. O1
200. O1
200. O1
10.0
7.5
0.5
0.7
0.132
0.02
0.008
0.132
0,5
3.0
5.0
0.4
0.2
10.0
200.0
2.0
100.0
5.02
1.0
5.0
0.7
0.5
^continued)
Revision 2
Septa*erl994

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                                   Table 7-1
                                  (continued)
                                                 Regulatory Level
Contaminant
Trichloroethylene                                       0.5
2,4,5-Trichlorophenol                                 400.0
2,4,6-Trichlorophenol                                   2.0
2,4,5-TP (Silvex)                                       1.0
Vinyl chloride                                          0.2
1lf o-, m-,  and p-cresol  concentrations  cannot be  differentiated,  the total
cresol (D026) concentration  is  used.   The regulatory level  of total  cresol is
200 mg/L.

2Quantitation limit  is  greater than  the calculated  regulatory  level.   The
quantitation limit therefore becomes the regulatory level.
                                  SEVEN - 18                       Revision 2
                                                                   Septaiter 1994

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                          FIGURE 3.

  TOXICITY CHARACTERISTIC LEACHATE PROCEDURE FLOWCHART
 Iiqutd» from
telid* «ilk 06
- C ,8 am gl*sj
 fib.r filt.r
appro pna t* f iuid
1 ) Bottl* MtriclBr
foe non* voia t il»*
2) EKE d*vic« for




Reduc*
particia 31.21
io <9 S mm

                        SEVEN  -  19
Revision  2
Septent3er 1994

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  FIGURE 3
(continued)
                                   r* msicun t 0!
                              liquid xnd mnmiyxm
                                (m*lh«n*LiC«liy
                               covibin* rvaiui t «/
                               r»»ui t of «)i t r»ct
Canbin*
••tract «/
liquid
ph,***
of w«ct*


Analyse*
liquid


              STOP
 SEVEN  « 20
Revision  2
Septenter 1994

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                                 CHAPTER  EIGHT

                   METHODS  FOR  DETERMINING  CHARACTERISTICS


      Methods for determining the characterisitics of Ignitability for liquids,
Corrosivity for liquids, and  Toxicity  are  included.   Guidance for determining
Toxic Gas Generation  is found in Chapter Seven, Sections 7.3,3 and 7.3.4.
                                  EIGHT - 1                       Revision 1
                                                                  September 1994

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8.1   Ignitability

      The following methods are found in Section 8.1:
            Hethod 1010:      Pensky-Martens Closed-Cup Method for Determining
                              Ignitability
            Hethod 1020A:     Setaflash   Closed-Cup   Hethod  for  Determining
                              Ignitability
                                   EIGHT  -  2                       Revision 1
                                                                  Septenfcer 1994

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8.2   Corrosivity

      The following method  is  found in Section 8.2:


            Method 1110;       Corrosivity Toward Steel
                                   EIGHT - 3                       Revision  1
                                                                   September 1994

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8.3   Reactivity

      Refer to  guidance given in Chapter  Seven,  especially  Section  7.3.3 and
7.3.4.
                                   EIGHT -  4                       Revision 1
                                                                   September 1994

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 8,4    Toxicity

       The following methods  are  found in Section 8.4:
             Method I310A:      Extraction Procedure  (EP)  Toxicity Test  Method
                                and  Structural Integrity Test
             Method 1311:       Toxicity Characteristic Leaching  Procedure
                                    EIGHT - 5                       Revision- 1
                                                                    Septenfcer 1994
•U.S. G.P.O.-,1995-386-824: 33251

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                                  METHOD 1312

                  SYNTHETIC  PRECIPITATION LEACHING PROCEDURE


 1.0 SCOPE AND APPLICATION

      1.1    Method  1312 is  designed to determine the mobility of both organic
 and inorganic analytes present in liquids, soils, and wastes.

 2.0   SUMMARY OF METHOD

      2.1    For  liquid  samples  (jue_.,, those  containing  less than  0.5  % dry
 solid material),  the sample, after filtration  through  a  0.6 to 0.8 /xm glass
 fiber filter, is defined as  the 1312 extract.

      2.2    For samples containing greater than 0.5 % solids,  the liquid phase,
 if any,  is  separated from  the solid phase and  stored  for  later analysis; the
 particle size of the solid phase  is reduced,  if necessary.   The solid phase is
 extracted with an amount  of extraction fluid equal to 20 times  the weight of the
 solid phase.  The extraction fluid employed is a function of the region of the
 country where the sample  site is located if the sample is a  soil.  If  the sample
 is a waste  or wastewater,  the  extraction  fluid employed is a pH 4.2 solution.
 A special extractor vessel  is used when testing for volatile analytes  (see Table
 1 for a list of volatile compounds).  Following extraction, the liquid extract
 is separated from the solid  phase by  filtration  through a  0.6 to  0.8 pm glass
 fiber filter.

      2.3    If compatible (i.e.,  multiple phases will not form on combination),
 the initial  liquid phase  of the waste  is added  to the liquid extract, and these
 are analyzed together.  If  incompatible, the liquids  are  analyzed separately and
 the results are mathematically  combined  to  yield  a  volume-weighted  average
 concentration.

 3.0   INTERFERENCES

      3.1    Potential interferences that may be encountered during analysis are
 discussed in the individual  analytical methods,

 4.0   APPARATUS AND MATERIALS

      4.1    Agitation apparatus:   The  agitation  apparatus must be  capable of
 rotating the extraction vessel in an end-over-end fashion (see Figure 1) at 30
± 2 rpm.  Suitable devices known  to EPA are identified  in Table 2.

      4.2    Extraction Vessels

             4.2.1    Zero  Headspace Extraction Vessel  (ZHE).  This device is for
      use only  when  the  sample is  being  tested for the mobility of volatile
      analytes (i.e., those listed in  Table 1).  The ZHE (depicted in Figure 2)
      allows for  liquid/solid  separation  within the  device  and  effectively
      precludes headspace.   This type  of vessel allows for initial  liquid/solid
      separation, extraction, and final extract filtration  without opening the


                                   1312 -  1                       Revision 0
                                                                  September 1994

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      vessel (see Step 4.3.1).  These vessels shall have an internal volume of
      500-600 ml and be equipped to accommodate a 90-110 mm  filter.  The devices
      contain VITOhf1 0-rings which should be  replaced frequently.  Suitable ZHE
      devices known to EPA are identified in Table 3.

             For the  ZHE  to  be acceptable for use, the  piston  within  the ZHE
      should be  able  to  be moved with  approximately  15 psig or less.   If it
      takes more pressure to move the piston, the 0-rings in the device should
      be replaced.   If this does  not  solve the problem, the ZHE is unacceptable
      for 1312 analyses  and the manufacturer should be contacted.

             The ZHE should be checked for leaks after  every extraction.  If the
      device contains a  built-in  pressure gauge, pressurize the device  to 50
      psig, allow it to  stand unattended for 1 hour, and recheck the pressure.
      If the device does not  have a built-in pressure  gauge,  pressurize the
      device to 50  psig,  submerge it in water, and check for the presence of air
      bubbles escaping from any of the fittings.  If pressure is lost, check all
      fittings  and inspect  and  replace 0-rings,  if   necessary.    Retest  the
      device.  If leakage problems cannot be  solved, the manufacturer should be
      contacted.

             Some ZHEs use gas pressure  to actuate the ZHE piston, while others
      use mechanical pressure  (see Table 3).   Whereas  the  volatiles procedure
      (see  Step  7.3}  refers  to   pounds-per-square-inch   (psig),   for  the
      mechanically  actuated piston, the  pressure  applied  is measured in torque-
      inch-pounds.   Refer to  the manufacturer's  instructions  as  to  the proper
      conversion.

             4.2.2    Bottle   Extraction  Vessel.    When  the  sample  is  being
      evaluated using  the nonvolatile extraction,  a jar with sufficient capacity
      to hold  the  sample and  the  extraction fluid is  needed.   Headspace is
      allowed in this vessel.

             The extraction bottles may be constructed from various materials,
      depending on  the analytes to be analyzed and the nature of the waste (see
      Step 4.3.3).   It is recommended that borosilicate  glass bottles  be used
      instead  of other  types of  glass, especially  when  inorganics  are  of
      concern.   Plastic  bottles,  other than  polytetrafluoroethylene, shall not
      be used if organics are to  be investigated.  Bottles are available from a
      number of laboratory suppliers.   When  this  type  of extraction vessel is
      used, the filtration device discussed  in Step 4.3.2  is  used  for initial
      liquid/solid  separation and final  extract filtration.

      4,3    Filtration  Devices:   It is  recommended  that  all  filtrations be
performed in a hood.

             4.3.1    Zero-Headspace  Extraction Vessel  (ZHE):  When  the sample
      is evaluated  for volatiles,  the  zero-headspace extraction vessel described
      in Step 4.2.1  is  used for filtration.   The device shall   be  capable of
             is a trademark of Du Pont.
                                   1312 - 2                       Revision 0
                                                                  September 1994

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      supporting  and  keeping in place  the  glass fiber filter  and  be able to
      withstand the pressure needed to  accomplish separation (50 psig).

              NOTE:  When  it is suspected that the glass  fiber  filter has been
              ruptured, an  in-line glass fiber filter may be used to filter the
              material within the ZHE.

              4.3.2    Filter Holder:  When the sample is evaluated for other than
      volatile analytes,  a filter  holder capable of  supporting a  glass fiber
      filter and able to  withstand  the  pressure  needed to accomplish separation
      may be  used.  Suitable  filter  holders range  from simple  vacuum units to
      relatively complex systems capable of  exerting pressures of up to 50 psig
      or more.  The type  of filter  holder  used depends on the properties of the
      material to  be  filtered (see Step  4.3.3).   These devices shall  have a
      minimum internal volume of 300 ml  and be equipped to accommodate  a minimum
      filter size of 47 mm (filter  holders having an internal capacity of 1.5 L
      or greater,  and equipped to accommodate  a 142 mm diameter  filter,  are
      recommended).   Vacuum filtration can  only  be  used for wastes  with  low
      solids content (<10 %) and for highly  granular, liquid-containing wastes.
      All other  types of  wastes  should  be filtered  using  positive  pressure
      filtration.  Suitable filter holders  known to EPA are listed in Table 4.

              4.3.3    Materials  of  Construction:    Extraction  vessels  and
      filtration devices  shall be made of inert materials which will not leach
      or absorb sample components of interest.  Glass, polytetrafluoroethylene
      (PTFE), or type 316 stainless steel  equipment may be used when evaluating
      the mobility of both  organic and  inorganic  components.   Devices made of
      high-density  polyethylene  (HOPE),   polypropylene  (PP),   or  polyvinyl
      chloride (PVC) may be used only  when  evaluating the  mobility of metals.
      Borosilicate glass bottles are  recommended for use over  other  types of
      glass bottles, especially when  inorganics are analytes of concern.

      4.4     Filters:  Filters shall  be made of  borosilicate glass fiber, shall
contain no binder materials,  and  shall  have an effective pore  size  of 0.6 to
0.8-jum  .  Filters  known  to EPA which  meet these specifications  are identified
in Table. 5.   Pre-filters must not be  used.  When evaluating the  mobility of
metals,  filters shall  be  acid-washed prior to use by rinsing with IN nitric acid
followed by three consecutive  rinses with reagent water  (a  minimum of 1-L  per
rinse is recommended).   Glass  fiber filters are fragile  and should be handled
with care.

      4.5    pH Meters:  The meter should be accurate to + 0.05 units at 25"C.

      4.6    ZHE Extract Collection Devices:  TEDLAR*2 bags or glass, stainless
steel or PTFE gas-tight syringes are used to collect the initial liquid  phase and
the  final  extract  when   using the  ZHE  device.    These devices  listed  are
recommended for use under the following conditions:

             4.6.1    If  a  waste contains an  aqueous liquid phase or if a waste
      does not contain a  significant amount  of nonaqueous liquid (i.e., <1 % of
     2TEDLARffi  is a registered trademark of Du Pont.
                                   1312 - 3                       Revision 0
                                                                  September 1994

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      total waste), the TEDLAR* bag or a 600 ml syringe should be used to collect
      and combine the  initial liquid and solid extract.

             4.6.2    If a waste  contains  a significant  amount of nonaqueous
      liquid  in  the  initiaj  liquid phase  (i.e.,  >1  %  of total  waste),  the
      syringe or the TEDLAR* bag may be used for both the initial solid/liquid
      separation and the final extract filtration.  However,  analysts should use
      one or the other, not both.

             4.6.3    If the waste contains no  initial liquid  phase  (is 100 %
      solid) or  has  no significant solid phase (is  <0.5% solid)  ,  either the
      TEDLAR* bag or the syringe lay be used.   If the syringe is used, discard
      the  first  5  mL  of  liquid  expressed  from  the  device.    The  remaining
      aliquots are used for analysis.

      4.7    ZHE  Extraction  Fluid  Transfer  Devices:   Any device capable  of
transferring the extraction fluid into the ZHE without changing the nature of the
extraction  fluid  is  acceptable (e.g.,  a positive  displacement or peristaltic
pump, a gas-tight syringe, pressure filtration unit (see Step 4.3.2),  or other
ZHE device).

      4.8    Laboratory Balance:   Any  laboratory  balance accurate to  within ±
0.01 grams may be used (all weight measurements are to be within +0.1 grams).

      4.9    Beaker or Erlenmeyer  flask, glass, 500 mL.

      4.10   Watchglass,  appropriate diameter  to  cover   beaker  or Erlenmeyer
flask.

      4.11   Magnetic  stirrer.

5.0   REAGENTS

      5.1    Reagent  grade chemicals  shall  be used  in all  tests.    Unless
otherwise indicated,  it is  intended that  all  reagents  shall   conform  to  the
specifications of the Committee on  Analytical Reagents  of the American Chemical
Society, where such  specifications are available.   Other grades  may  be used,
provided it is  first ascertained that the reagent is of  sufficiently high purity
to permit its use without lessening the accuracy of the determination.

      5.2    Reagent  Water.   Reagent  water  is defined  as  water  in  which  an
interferant  is not  observed at or  above  the method's detection  limit  of the
analyte(s)  of  interest.   For nonvolatile  extractions, ASTM Type  II  water  or
equivalent meets the definition of  reagent water.   For  volatile extractions,  it
is recommended that reagent water be generated  by any of the following methods.
Reagent water should be monitored periodically for impurities.

             5.2.1    Reagent  water for  volatile extractions may be  generated
      by passing  tap  water through  a  carbon  filter bed  containing  about 500
      grams of activated carbon (Calgon Corp.,  Filtrasorb-300 or equivalent).
                                   1312 - 4                       Revision 0
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              5.2.2   A  water   purification   system  (Millipore  Super-Q   or
       equivalent)  may  also  be  used  to generate  reagent water  for  volatile
       extractions.

              5.2.3   Reagent water for volatile extractions may also be prepared
       by  boiling water  for  15  minutes.   Subsequently,  while maintaining  the
       water temperature  at 90 ± 5 degrees C, bubble a contaminant-free inert  gas
       (e.g. nitrogen) through the  water for 1  hour.  While still  hot,  transfer
       the water to a narrow mouth screw-cap bottle under zero-headspace and seal
       with a  Teflon-lined  septum and cap.

       5.3     Sulfuric acid/nitric acid {60/40 weight percent mixture) H2S04/HN03.
Cautiously mix 60 g of  concentrated  sulfuric acid with  40  g of concentrated
nitric  acid.    If preferred,  a more dilute   H2S04/HN03  acid mixture may  be
prepared and  used  in steps 5.4.1 and 5.4.2 making it easier to adjust the pH of
the extraction fluids.

       5.4     Extraction  fluids.

              5.4.1    Extraction fluid  #1:   This fluid is made  by adding  the
       60/40 weight percent mixture of sulfuric and  nitric acids (or  a  suitable
       dilution)  to reagent water (Step  5.2)  until  the  pH is  4.20 + 0.05.   The
       fluid is used  to  determine the  Teachability of soil from a site that  is
       east  of the  Mississippi  River,  and   the  Teachability  of  wastes   and
      wastewaters.

              NOTE:    Solutions are unbuffered and exact pH may not be attained.

              5.4.2   Extraction fluid  12:   This fluid is made  by adding  the
      60/40 weight percent mixture of sulfuric and nitric  acids  (or  a  suitable
      dilution)  to reagent water (Step  5.2)  until  the  pH is  5,00 + 0.05.   The
      fluid is used  to  determine the  Teachability of soil from a site that  is
      west of the Mississippi River.

              5.4.3    Extraction fluid  #3:  This  fluid  is reagent water (Step
      5.2) and is  used to determine cyanide and volatiles Teachability.

              NOTE: These extraction  fluids should be monitored frequently  for
              impurities. The pH should be checked  prior to use to ensure that
              these fluids  are made up  accurately.   If  impurities  are  found  or
              the pH  is not within  the above specifications, the fTuid  shall  be
              discarded and fresh extraction fluid prepared.

      5.5     Analytical  standards shall  be prepared according  to the appropriate
analytical method.

6.0   SAMPLE  COLLECTION, PRESERVATION,  AND HANDLING

      6.1     All samples shall be collected using an appropriate sampling plan.

      6.2     There may be requirements  on the minimal size of the field sample
depending upon the physical  state  or states  of the waste and the analytes  of
concern.  An  aliquot is  needed  for the  preliminary evaluations of the percent


                                   1312 - 5                       Revision  0
                                                                  September 1994

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solids  and  the  particle  size.    An aliquot  may  be  needed  to  conduct  the
nonvolatile  analyte extraction procedure.   If volatile organics  are of concern,
another aliquot may be needed. Quality  control measures may require additional
aliquots.   Further,  it  is always wise  to  collect  more  sample just  in case
something goes wrong with the initial attempt to conduct the test.

      6.3     Preservatives shall not be added to samples before  extraction.

      6.4     Samples  may  be  refrigerated  unless   refrigeration  results  in
irreversible physical change to the waste.   If precipitation occurs, the entire
sample (including precipitate) should be extracted.

      6.5     When  the sample is to  be  evaluated for volatile  analytes, care
shall be taken to minimize the loss  of volatiles.  Samples shall be collected and
stored in  a  manner intended  to  prevent  the loss of volatile  analytes (e...g.,
samples should be collected  in Teflon-lined septum  capped  vials and stored at
4°C.  Samples should be opened only immediately prior to extraction).

      6.6     1312 extracts should be  prepared for analysis  and analyzed as soon
as possible following extraction.  Extracts or portions of extracts for metallic
analyte determinations must be acidified with nitric acid  to  a  pH < 2» unless
precipitation occurs {see Step 7.2.14 if precipitation occurs).   Extracts should
be preserved for other analytes according to the guidance given  in the individual
analysis  methods.    Extracts  or  portions  of  extracts for  organic  analyte
determinations shall  not be  allowed  to  come into contact  with  the atmosphere
(i.e., no  headspace)  to prevent  losses.   See  Step  8.0 (Quality Control)  for
acceptable sample and extract holding times.

7.0   PROCEDURE

      7.1     Preliminary Evaluations

      Perform preliminary  1312  evaluations  on a minimum  100 gram  aliquot  of
sample.    This  aliquot  may  not  actually   undergo  1312   extraction.    These
preliminary evaluations include:  (1)  determination  of the  percent solids (Step
7.1.1); (2) determination of whether the  waste contains insignificant solids and
is,  therefore,  its  own   extract  after   filtration  (Step  7.1.2);  and  (3)
determination of whether the solid portion of the waste requires particle size
reduction (Step 7.1.3).

             7.1.1    Preliminary determination  of   percent  solids:    Percent
      solids is defined as  that fraction of a waste  sample  (as a percentage of
      the total sample) from  which no  liquid may be forced out by an applied
      pressure, as described below.

                      7.1.1.1     If  the  sample  will obviously  yield  no  free
             liquid when subjected  to pressure filtration (i.e.,  is 100% solid),
             weigh  out  a representative subsample  (100  g minimum)  and proceed
             to Step 7.1.3.

                      7.1.1.2     If   the  sample  is liquid   or  multiphasic,
             liquid/solid  separation  to make  a  preliminary determination  of
             percent solids is required.   This  involves the  filtration device


                                   1312  -  6                       Revision 0
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discussed in Step 4.3.2, and is outlined in Steps 7.1.1.3 through
7.1.1.9.

         7.1.1.3  Pre-weigh the filter and the container that will
receive the filtrate.

         7,1.1.4    Assemble filter holder and filter following the
manufacturer's  instructions.   Place  the  filter  on the  support
screen and secure.

         7.1.1.5   Weigh out  a subsample  of  the waste  (100 gram
minimum) and record the weight.

         7.1.1.6  Allow slurries to stand  to permit the solid phase
to settle.  Samples that settle slowly may be centrifuged prior to
filtration.   Centrifugation  is  to  be  used  only as  an aid  to
filtration.  If used, the liquid  should  be decanted  and filtered
followed by filtration  of the solid portion of the  waste through
the same filtration system.

         7.1.1.7  Quantitatively transfer the sample to the filter
holder (liquid and solid phases).  Spread  the  sample  evenly over
the surface  of  the filter.   If  filtration of the  waste at  4°C
reduces the amount  of expressed liquid over what would be expressed
at room  temperature,  then allow  the  sample to  warm up  to room
temperature in the  device  before  filtering.

         Gradually  apply vacuum or gentle pressure of  1-10  psig,
until  air or pressurizing gas moves through the  filter.   If this
point  is not reached under 10 psig,  and if no additional liquid has
passed through the  filter in any 2-minute  interval, slowly increase
the pressure in  10  psig  increments  to  a maximum of 50 psig.  After
each incremental  increase  of 10 psig,  if the  pressurizing gas has
not moved  through  the  filter,  and if  no additional  liquid  has
passed through the  filter  in any 2-minute interval, proceed to the
next 10-psig increment.  When the pressurizing gas begins to move
through  the  filter,  or when  liquid  flow has  ceased  at  50 psig
(i.e., filtration does not result  in any additional filtrate within
any 2-minute period), stop the filtration.

NOTE:    If  sample  material (>1 %  of  original   sample weight)  has
obviously adhered to  the container used  to transfer  the sample to
the filtration apparatus,  determine the weight  of this residue and
subtract it from the sample weight determined  in  Step  7.1.1.5 to
determine the weight  of the sample that  will  be filtered.

NOTE:  Instantaneous application of high  pressure  can  degrade the
glass  fiber filter  and may cause  premature plugging.

         7.1.1.8    The material in the filter holder is defined as
the solid phase  of  the sample,  and the filtrate is defined as the
liquid phase.
                      1312  -  7                        Revision 0
                                                     September 1994

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              NOTE:   Some samples,  such  as  oily wastes and some paint wastes,
              will  obviously contain some material  that appears  to  be  a liquid,
              but even  after applying vacuum or pressure filtration, as outlined
              in  Step 7.1.1.7, this material  may not  filter.   If  this  is the
              case,  the material  within  the  filtration device is defined as a
              solid.   Do not  replace the original filter  with  a fresh filter
              under  any circumstances.   Use  only one  filter.

                      7.1.1.9    Determine the  weight  of the liquid  phase by
              subtracting the weight of the filtrate container (see Step 7.1.1.3)
              from the total weight of the filtrate-filled container.   Determine
              the weight of the  solid  phase of  the  sample  by subtracting the
              weight  of the  liquid phase from the weight of  the total sample, as
              determined  in  Step  7.1.1.5  or  7.1.1.7.

                      Record  the  weight  of  the liquid  and   solid phases.
              Calculate  the  percent  solids as  follows:

                                Weight of solid (Step 7.1.1.9)
      Percent solids =  	  x 100

                        Total  weight of waste (Step 7.1.1.5 or 7.1.1.7}

              7.1.2    If the percent solids  determined  in Step 7.1.1.9 is equal
      to or greater  than 0.5%, then proceed either to Step 7.1.3 to  determine
      whether the  solid  material requires particle  size reduction or to Step
      7.1.2.1 if it is noticed that a small  amount of the filtrate  is  entrained
      in wetting  of the  filter.   If the  percent  solids  determined in  Step
      7.1.1.9 is less than  0.5%, then proceed to Step  7.2.9 if the nonvolatile
      1312 analysis is to be performed,  and to Step 7.3 with a fresh portion of
      the waste if the volatile  1312 analysis is to be performed.

                      7.1.2.1     Remove  the  solid phase and  filter  from  the
              filtration  apparatus.

                      7.1.2.2     Dry the filter and solid phase  at 100  + 20°C
              until  two successive weighings yield the  same value within + 1 %.
              Record  the  final weight.

              Caution:  The   drying  oven  should  ie  vented tc  a   hood  or  other
              appropriate device  to  eliminate the possibility of  fumes from the
              sample  escaping  into  the  laboratory.    Care  should  be  taken  to
              ensure  that the sample will not  flash  or violently  react  upon
              heating.

                      7.1.2.3     Calculate the  percent  dry  solids as follows:


Percent        (Weight of dry sample + filter)  - tared weight of filter
dry solids   = 	;	   x 100

                  Initial weight of sample (Step 7.1.1.5 or 7.1.1.7)
                                   1312 - 8                       Revision 0
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                7.1.2.4    If the percent dry  solids  is  less than 0.5%,
        then  proceed  to Step  7.2.9  if the nonvolatile  1312 analysis is to
        be  performed,  and  to  Step 7.3 if the volatile  1312 analysis is to
        be  performed.   If  the percent dry solids is greater than or equal
        to  0.5%,  and  if the nonvolatile 1312 analysis  is to be performed,
        return  to  the beginning of  this  Step  (7.1)  and,  with  a fresh
        portion  of sample, determine whether  particle size  reduction is
        necessary (Step 7.1,3).

        7.1.3    Determination of whether the sample requires particle-size
reduction  (particle-size  is  reduced  during  this step):   Using the solid
portion of the  sample, evaluate the  solid  for particle size.  Particle-
size reduction  is  required,  unless the solid has a surface area per gram
of material equal  to  or greater than 3.1 cm2,  or is smaller than  1 cm in
its  narrowest  dimension  (i. e., is capable  of passing through  a  9.5 mm
(0,375  inch)  standard  sieve).   If the surface  area  is smaller  or the
particle size larger  than described  above,  prepare  the solid portion of
the sample for extraction by crushing,  cutting, or grinding the waste to
a surface  area  or particle size as described  above.   If  the solids are
prepared for  organic volatiles extraction, special precautions  must be
taken (see Step  7.3.6).

        NOTE:   Surface  area  criteria are  meant for  filamentous  (e.g.,
        paper, cloth,  and similar) waste materials.  Actual measurement of
        surface area is not required,  nor is  it  recommended. For materials
        that  do  not obviously meet  the  criteria, sample-specific methods
        would  need to  be  developed  and  employed to measure  the  surface
        area. Such  methodology  is currently not available.

        7,1.4    Determination of appropriate extraction fluid:

                7.1.4.1    For  soils, if the sample  is  from a  site  that is
        east of the Mississippi  River, extraction fluid #1 should be used.
        If the sample is from  a  site that is  west of the Mississippi River,
        extraction  fluid 12 should be used.

                7.1,4.2    For  wastes and wastewater,  extraction fluid #1
        should be used.

                7.1.4.3    for  cyanide-containing  wastes  anc'/or  sc:Ts,
        extraction  fluid #3 (reagent water)  must be used because leaching
        of cyanide-containing samples under  acidic  conditions may result
        in the formation of hydrogen cyanide gas.

        7.1.5    If the  aliquot  of  the sample used for  the  preliminary
evaluation (Steps  7.1.1 - 7.1.4) was determined to be  100% solid at Step
7.1.1.1, then  it can  be  used  for  the  Step 7.2 extraction  (assuming at
least 100 grams  remain), and  the Step 7.3 extraction  (assuming at least 25
grams remain).   If the aliquot was  subjected to the procedure  in Step
7.1.1.7, then another aliquot  shall  be used for the volatile extraction
procedure  in Step 7.3.   The  aliquot  of  the waste  subjected  to  the
procedure in Step  7.1.1.7 might be  appropriate for  use  for  the Step 7.2
extraction if an adequate amount of solid (as determined by Step 7.1.1.9)


                             1312 - 9                       Revision 0
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      was obtained.  The amount of solid necessary is dependent upon whether a
      sufficient amount of extract will be produced to support the analyses.  If
      an  adequate  amount  of solid  remains,  proceed  to  Step  7.2.10 of  the
      nonvolatile 1312 extraction.

      7.2    Procedure When Volatiles Are Not Involved

      A  minimum sample   size  of  100  grams  (solid  and  liquid  phases)  is
recommended.  In some cases,  a larger sample size may be appropriate, depending
on the  solids  content of the waste  sample  (percent solids,  See Step 7.1.1),
whether the initial  liquid phase  of the waste will be miscible with  the aqueous
extract of the solid, and whether  inorganics, semivolatile organics,  pesticides,
and herbicides are  all analytes  of concern.   Enough solids  should be generated
for extraction  such that the volume of 1312 extract will  be sufficient to support
all of the analyses required.  If the amount of  extract generated  by a single
1312 extraction will  not  be sufficient to perform  all  of the analyses, more than
one extraction may be performed and the extracts from each combined and aliquoted
for analysis.

             7.2.1     If the sample will obviously yield no liquid when subjected
      to pressure filtration (i.e.,  is  100 % solid,  see Step  7.1.1), weigh out
      a subsample of the sample  (100  gram minimum) and proceed  to Step 7.2.9.

             7.2.2     If  the  sample  is  liquid  or  multiphasiCj liquid/solid
      separation is  required.  This involves the filtration  device described in
      Step 4.3.2 and is outlined  in  Steps 7.2.3 to 7.2.8.

             7.2.3   Pre-weigh the container  that  will receive the filtrate.

             7.2.4     Assemble  the  filter  holder  and  filter  following  the
      manufacturer's instructions.   Place the filter on the support screen and
      secure.   Acid wash the filter if evaluating the mobility  of  metals (see
      Step 4.4).

             NOTE:    Acid  washed filters may  be  used  for  all  nonvolatile
             extractions even when metals are not of concern.

             7.2.5   Weigh out a  subsample of the  sample (100  gram minimum)  and
      record the weight.   If the waste contains <0.5 % dry solids (Step 7.1.2),
      the liquid portion  of the waste, after f:"!trat:cr, 'is  defined  ss the 1312
      extract.  Therefore, enough  of the sample should be filtered  so  that  the
      amount of filtered liquid will  support  all of the analyses required of the
      1312 extract.  For  wastes  containing >0.5 %  dry  solids  (Steps  7.1.1  or
      7.1.2),  use the  percent solids  information obtained in  Step  7.1.1  to
      determine the  optimum  sample size  (100 gram  minimum)  for  filtration.
      Enough solids should be generated by filtration to support the  analyses to
      be performed  on the 1312 extract.

             7.2.6   Allow slurries to stand to permit the solid phase to settle.
      Samples  that  settle slowly may be centrifuged  prior to filtration.   Use
      centrifugation  only as  an  aid  to  filtration.    If  the   sample  is
      centrifuged,  the  liquid  should  be decanted  and filtered  followed  by
      filtration  of  the solid portion of the waste through  the  same filtration
      system.

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        7.2.7  Quantitatively transfer the sample (liquid and solid phases)
to the  filter  holder (see Step 4.3.2).  Spread  the  waste sample evenly
over the surface of the filter.  If filtration of the  waste at 4°C reduces
the  amount  of  expressed  liquid over  what would  be expressed  at  room
temperature, then allow the sample to warm up to room temperature in the
device before filtering.

        Gradually apply vacuum or gentle pressure of  1-10 psig, until air
or pressurizing gas moves  through  the filter.    If this point  if not
reached under 10 psig,  and if no additional liquid  has passed through the
filter in any 2-minute interval, slowly increase the pressure in 10-psig
increments to maximum of 50 psig.   After each incremental increase of 10
psig, if the pressurizing  gas has not moved through the filter, and if no
additional liquid has passed through the filter in any 2-minute interval,
proceed to the next 10-psig increment.   When the pressurizing gas begins
to move through the filter,  or when the liquid flow has ceased at 50 psig
(i.e..  filtration  does  not result in  any  additional filtrate  within  a
2-minute period), stop the filtration.

       NOTE:  If waste material (>1 % of the original sample weight) has
       obviously adhered to the container used to transfer the sample to
       the filtration apparatus, determine  the weight of this residue and
       subtract  it  from  the sample weight determined  in  Step  7.2.5,  to
       determine the weight of the waste sample that will be filtered.

       NOTE:Instantaneous  application  of  high pressure  can  degrade the
       glass fiber filter and may cause premature plugging.

       7.2.8  The material  in  the filter holder  is defined  as the solid
phase of  the  sample,  and the  filtrate  is  defined as the liquid  phase.
Weigh the filtrate.  The liquid phase  may now  be either analyzed (see Step
7.2.12) or stored at 4°C  until time of analysis.

       NOTE:  Some  wastes,  such as oily wastes and some paint wastes, will
       obviously contain  some material which appears to be a liquid.  Even
       after applying vacuum or pressure filtration,  as outlined in Step
       7.2.7, this  material  may not  filter.   If this is the  case,  the
       material within the  filtration device  is  defined  as  a solid,  and
       is carried through the extraction as a solid.   Do not replace the
       original filter w:th c fresh filter ^nder any circumstances.   Use
       only one filter.

       7.2.9    If the sample contains 0.5 %  dry  solids  (see
Step  7.1.1 or  7.1.2),  and  if  particle-size  reduction of the  solid  was
needed in Step 7.1.3, proceed to Step 7.2.10.  If the sample as received
passes a 9.5 mm  sieve, quantitatively  transfer the solid material into the
extractor bottle along with the filter used  to separate the initial liquid
from  the solid phase, and proceed  to  Step  7.2.11.

       7.2.10   Prepare the  solid portion of the sample for extraction by
crushing, cutting,  or grinding the waste to  a surface  area  or particle-
size  as described in Step 7.1.3.  When  the  surface area or particle-size
has been appropriately altered, quantitatively transfer the solid material

                             1312 - 11                       Revision 0
                                                            September 1994

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      Into an extractor bottle.  Include the filter used to separate the initial
      liquid from the solid phase.

             NOTE:  Sieving of the waste is not normally required.  Surface area
             requirements  are  meant  for filamentous  (e.g.,  paper,  cloth)  and
             similar waste materials.  Actual measurement of surface  area is not
             recommended.  If sieving is necessary, a Teflon-coated sieve should
             be used to avoid contamination of the  sample.

             7.2.11   Determine the amount  of  extraction  fluid to  add  to  the
      extractor vessel as follows:

                        20  x  % solids  (Step  7.1.1)  x weight  of  waste
                               filtered   (Step  7.2.5 or 7.2.7)
Weight of         =  	
extraction fluid
                                            100

             Slowly add this amount of  appropriate extraction  fluid (see  Step
      7.1.4) to the extractor vessel.  Close the extractor bottle tightly (it is
      recommended that Teflon tape be used  to  ensure  a tight seal), secure in
      rotary extractor  device,  and rotate  at  30  + 2 rpm  for 18 +  2  hours.
      Ambient temperature (j	e;.....,  temperature of room in which extraction takes
      place) shall be maintained  at 23 + 2°C during the extraction period.

             NOTE:  As  agitation  continues, pressure  may build up  within  the
             extractor bottle for some types of sample (e.g.. limed or calcium
             carbonate-containing  sample  may evolve gases   such  as  carbon
             dioxide).  To relieve excess pressure,  the extractor bottle may be
             periodically  opened  (e.g.,  after 15  minutes,  30 minutes, and  1
             hour) and vented into a hood.

             7.2.12   Following the 18  + 2 hour extraction, separate the material
      in the extractor  vessel  into its component  liquid  and  solid  phases by
      filtering through a  new  glass  fiber  filter,  as   outlined  in  Step  7.2,7.
      For final filtration of the 1312 extract,  the glass  fiber filter  may be
      changed,   if  necessary,  to  facilitate filtration.    Filter(s)  shall  be
      acid-washed (see Step 4,4)  if evaluating the mobility of metals.

             7.2.13   Prepare the  1312 extract  as  fcl'cws:

                      7.2.13.1   If the sample contained no initial liquid phase,
             the filtered liquid  material  obtained from Step 7.2.12 is defined
             as the 1312 extract.   Proceed to Step  7.2.14.

                      7.2.13.2   If compatible  (e.g..  multiple  phases  will  not
             result on combination), combine the  filtered liquid resulting from
             Step 7.2.12 with the initial  liquid  phase of  the  sample obtained
             in  Step  7.2.7.    This combined   liquid  is  defined  as  the  1312
             extract.  Proceed to Step 7.2.14.

                      7.2.13.3   If the  initial liquid phase of the waste,  as
             obtained from Step 7.2.7,  is not or may not be compatible with the
             filtered liquid resulting from Step  7.2.12, do not combine these

                                  1312 - 12                       Revision 0
                                                                  September  1994

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              liquids.   Analyze  these  liquids,  collectively defined as the  1312
              extract,  and combine the results mathematically, as described in
              Step  7,2.14.

              7,2.14   Following collection of  the  1312  extract,  the  pH of the
      extract should be recorded.  Immediately aliquot and preserve the extract
      for analysis.  Metals aliquots must be acidified with  nitric acid to  pH <
      2.  If precipitation  is observed upon addition  of nitric acid to a small
      aliquot of  the extract,  then  the  remaining portion of the  extract for
      metals analyses shall not  be acidified and the  extract  shall be analyzed
      as  soon  as  possible.     All  other  aliquots  must   be  stored  under
      refrigeration  (4"C)  until  analyzed.   The 1312 extract  shall  be prepared
      and analyzed according to  appropriate analytical methods,  1312 extracts
      to be analyzed for metals  shall  be acid digested except  in those instances
      where digestion causes loss of  metallic  analytes.  If an analysis of the
      undigested extract shows that the concentration of any regulated metallic
      analyte exceeds  the  regulatory level,  then the waste  is  hazardous and
      digestion of the  extract  is not necessary.   However,  data on undigested
      extracts  alone  cannot  be  used  to demonstrate that the  waste is  not
      hazardous.   If  the  individual phases   are  to be  analyzed  separately,
      determine the volume  of the individual  phases (to + 0.5 %),  conduct the
      appropriate  analyses, and  combine  the  results mathematically  by using a
      simple volume-weighted average:

                                        (VJ  (C,)  + (V2)  (C2)
      Final  Analyte Concentration  =  	
                                              V, +  V2
      where:

      V1 = The volume of the first phase (L).
      C, = The concentration of the analyte of concern in the first phase (mg/L).
      V2 = The volume of the second phase (L).
      C2 = The concentration of the analyte of concern in the second phase
           (mg/L).

              7.2.15   Compare the analyte concentrations in the 1312 extract with
      the  levels identified  in  the appropriate  regulations.   Refer to Section
      8.0 for quality assurance requirements.

      7.3     Procedure When Volatiles Are Involved

      Use  the ZHE  device to  obtain 1312  extract for  analysis of  volatile
compounds only.   Extract resulting from  the  use  of  the  ZHE  shall not be used to
evaluate the mobility of non-volatile analytes {e.g., metals, pesticides, etc.).

      The ZHE device has approximately a 500 ml  internal  capacity.  The ZHE can
thus accommodate a maximum of 25 grams of solid (defined as that fraction of a
sample from which no additional  liquid may  be forced out  by an applied pressure
of 50 psig),  due to the  need to add an  amount  of extraction fluid  equal  to 20
times the weight of the solid phase.
                                   1312  -  13                       Revision 0
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      Charge the ZHE with sample only once and  do  not open the device until the
final extract (of the solid)  has been collected.  Repeated filling  of the ZHE to
obtain 25 grams of solid is not permitted.

      Do not allow the  sample,  the  initial  liquid phase,  or the extract to be
exposed to the atmosphere for any more time than  is absolutely necessary.  Any
manipulation of these materials should be done  when cold  (4°C) to minimize loss
of volatiles.

             7.3.1    Pre-weigh the  (evacuated) filtrate  collection  container
      (see Step 4.6)  and set aside.   If using  a TEDLAR* bag, express all liquid
      from  the  ZHE  device  into  the bag,  whether  for  the  initial  or  final
      liquid/solid separation, and take  an  aliquot from  the  liquid in  the bag
      for analysis.  The containers listed in Step 4,6 are recommended for use
      under the conditions stated in Steps 4,6.1-4.6.3.

             7.3.2    Place  the ZHE piston within the  body of  the ZHE (it may be
      helpful first  to moisten  the piston  0-rings  slightly with extraction
      fluid).   Adjust the piston within the  ZHE body to a height that will
      minimize the distance  the piston will have to move once  the ZHE is charged
      with sample (based upon sample size requirements determined from Step 7.3,
      Step 7.1.1  and/or 7.1.2).  Secure the  gas inlet/outlet  flange  (bottom
      flange)  onto  the  ZHE  body  in  accordance  with  the  manufacturer's
      instructions.  Secure the glass fiber filter between the support screens
      and set aside.   Set liquid inlet/outlet flange  (top flange)  aside.

             7.3.3    If the sample  is 100%  solid (see Step 7.1.1),  weigh out
      a subsample (25 gram maximum)  of the waste,  record weight, and proceed to
      Step 7.3.5.

             7.3.4    If the  sample contains <0.5% dry solids (Step 7.1.2), the
      liquid portion  of  waste, after filtration, is defined as the 1312 extract.
      Filter enough  of  the  sample so that the  amount  of  filtered liquid will
      support all of the  volatile analyses required.  For  samples containing
      >0.5%  dry  solids  (Steps  7.1.1  and/or  7.1.2),   use  the percent solids
      information obtained in Step 7.1.1 to determine  the  optimum sample size to
      charge into the ZHE.  The recommended sample size is as follows:
        7.3,4.1    For  samples  containing <5%  solids  (see  Step

weight.
                   , weign  Ouz a  03 grain  subsampTs  of waste and  record the
                      7.3.4.2    For  wastes  containing  >5%  solids   (see  Step
             7.1.1),  determine  the  amount  of waste to charge into  the  ZHE as
             follows:

                                             25
Weight of waste to charge ZHE =  	   x 100
                                  percent solids (Step 7,1.1)

             Weigh out  a subsample of the  waste  of the appropriate  size and
      record the weight.
                                   1312  -  14           "            Revision 0
                                                                  September 1994

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        7.3,5    If particle-size  reduction  of the solid  portion  of the
sample  was  required  in Step 7,1.3,  proceed  to Step 7.3.6.  If particle-
size reduction was not required in Step 7.1,3, proceed to Step 7.3.7.

        7.3,6    Prepare the sample for extraction by crushing, cutting, or
grinding the solid portion of the  waste to a surface area or particle size
as described in Step 7.1.3.1.  Wastes and  appropriate reduction equipment
should  be  refrigerated,   if possible, to  4°C  prior to  particle-size
reduction.   The means  used to effect particle-size  reduction  must not
generate heat  in  and of itself.   If reduction of the solid phase of the
waste  is  necessary,  exposure  of  the waste  to the atmosphere  should be
avoided to the extent  possible.

        NOTE:    Sieving  of  the  waste  is not  recommended  due   to  the
        possibility   that   volatiles   may   be   lost.     The  use  of  an
        appropriately graduated ruler  is recommended  as  an  acceptable
        alternative.  Surface area requirements are meant for filamentous
        (e.g.,  paper,   cloth)  and   similar  waste  materials.    Actual
        measurement of  surface  area is not recommended.

        When  the  surface  area or particle-size  has  been  appropriately
altered, proceed to  Step 7.3.7.

        7.3.7    Waste slurries need not be allowed to stand to permit the
solid phase to settle.  Do  not centrifuge samples prior to filtration.

        7.3.8    Quantitatively transfer the entire sample (1 iquid and sol id
phases) quickly to the ZHE.   Secure  the  filter and support screens into
the top flange of the device and  secure the top flange to the ZHE body in
accordance with the manufacturer's instructions.  Tighten all ZHE fittings
and place the  device in the vertical  position  (gas inlet/outlet flange on
the bottom).  Do  not attach the  extraction  collection device to the top
plate.

        Note:   If sample  material (>1% of  original  sample  weight)  has
        obviously adhered to  the container used to transfer the sample to
        the ZHE, determine the weight  of this residue and subtract it from
        the sample weight determined in Step 7.3.4 to determine the weight
        of the waste  sample  that will be filtered.

        Attach  a  gas  line to the  gas  inlet/outlet  valve  (bottom flange)
and,  with the  liquid  inlet/outlet  valve (top flange) open, begin applying
gentle pressure of 1-10 psig (or more if necessary) to force all headspace
slowly  out  of  the ZHE device  into a hood.   At the  first  appearance of
liquid  from the  liquid inlet/outlet valve,  quickly close  the  valve and
discontinue pressure.   If  filtration  of  the waste  at  4°C  reduces  the
amount  of  expressed  liquid  over   what  would  be  expressed  at  room
temperature, then allow the  sample to warm up to room temperature in the
device  before filtering.   If the  waste  is 100 %  solid (see Step 7.1.1),
slowly increase the pressure to a  maximum  of 50 psig to force most of the
headspace out of the device  and proceed to Step 7.3.12.
                             1312  -  15                       Revision 0
                                                            September 1994

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             7.3.9    Attach  the  evacuated  pre-weighed  filtrate  collection
      container to  the liquid inlet/outlet valve  and  open the valve.   Begin
      applying gentle  pressure of  1-10 psig to force the  liquid  phase of the
      sample into the  filtrate collection  container.   If no additional liquid
      has passed through the  filter  in any 2-minute  interval,  slowly increase
      the pressure  in  10-psig increments to a  maximum of 50 psig.   After each
      incremental   increase of 10  psig, if  no additional  liquid  has passed
      through the filter in any Z-minute interval,  proceed to the next 10-psig
      increment.   When liquid flow  has ceased  such that  continued  pressure
      filtration at 50 psig does not  result in  any additional filtrate within a
      2-minute  period,  stop  the  filtration.    Close the  liquid  inlet/outlet
      valve, discontinue pressure to the piston, and disconnect  and weigh the
      filtrate collection container.

             NOTE:  Instantaneous application of high pressure can degrade the
             glass  fiber filter and may cause premature plugging.

             7.3.10   The material  in the ZHE  is defined as the solid phase of
      the sample and the filtrate  is  defined as the liquid phase.

             NOTE:  Some samples,  such as  oily wastes  and  some  paint wastes,
             will obviously contain some material which  appears to be a liquid.
             Even after  applying  pressure  filtration,  this material  will  not
             filter.   If this is the case, the material  within the filtration
             device is defined  as a solid,  and is  carried through  the 1312
             extraction as a solid.

             If the original waste contained <0.5 %  dry solids (see Step 7.1.2),
      this filtrate is defined as  the  1312 extract  and  is  analyzed directly.
      Proceed to Step  7.3.15.

             7.3.11   The liquid  phase  may  now be  either analyzed immediately
      (see Steps 7.3.13 through 7.3.15)  or stored at 4°C under minimal headspace
      conditions until time of analysis.   Determine the weight  of extraction
      fluid #3 to add  to the ZHE  as follows:
                                 20 x % solids (Step 7.1.1)  x weight
                               of waste filtered (Step 7.3.4 or 7.3.8)
Weight of extraction fluid =  	
                                                 100

             7.3.12   The following  steps  detail  how  to  add the  appropriate
      amount of  extraction  fluid  to the  solid  material  within  the ZHE  and
      agitation of the ZHE  vessel.   Extraction  fluid #3 is used  in  all  cases
      (see Step 5.4.3).

                      7.3.12.1  With  the ZHE in the vertical  position, attach a
             line from the extraction fluid reservoir to the liquid inlet/outlet
             valve.   The line used  shall  contain fresh extraction  fluid  and
             should be preflushed with fluid to eliminate any air pockets in the
             line.   Release  gas  pressure  on  the  ZHE  piston  (from the  gas
             inlet/outlet valve),  open the  liquid  inlet/outlet valve, and begin
             transferring extraction fluid  (by pumping  or similar  means)  into

                                   1312 - 16                       Revision 0
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       the ZHE.  Continue pumping extraction  fluid  into the ZHE until the
       appropriate amount of fluid has been introduced into the device.

                7.3.12,2   After  the  extraction  fluid  has  been  added,
       immediately close the liquid inlet/outlet valve and disconnect the
       extraction fluid line.  Check the ZHE to ensure that all valves are
       in  their closed  positions.    Manually rotate the  device  in  an
       end-over-end  fashion  2 or  3  times.   Reposition  the ZHE  in the
       vertical  position with  the liquid inlet/outlet  valve on  top.
       Pressurize the ZHE to 5-10 psig (if  necessary) and slowly open the
       liquid inlet/outlet valve to bleed out  any headspace (into a hood)
       that may have been introduced  due  to  the addition  of  extraction
       fluid.   This  bleeding shall  be done quickly and  shall  be stopped
       at the first  appearance of  liquid from the  valve.   Re-pressurize
       the ZHE  with  5-10  psig and  check all  ZHE  fittings  to ensure that
       they are closed.

                7.3.12.3   Place the ZHE in  the rotary extractor apparatus
       (if it is not  already there) and rotate at  30 +  2  rpm  for 18+2
       hours.   Ambient  temperature (i.e.,  temperature of room in  which
       extraction  occurs)  shall  be   maintained   at  23  +  2°C  during
       agitation.

       7,3.13   Following  the 18  ± 2   hour agitation period,   check the
pressure behind  the  ZHE  piston  by  quickly opening and closing  the gas
inlet/outlet valve and noting the escape of gas.  If the pressure has not
been maintained  (i.e.,  no gas  release observed),  the  ZHE is  leaking.
Check the ZHE  for  leaking as specified  in Step  4.2.1,  and perform the
extraction again with a new sample of  waste.   If  the pressure  within the
device has been maintained,  the  material  in the extractor  vessel  is once
again separated into  its  component  liquid and  solid phases.  If the waste
contained an initial  liquid  phase,  the liquid may  be filtered directly
into the  same filtrate collection  container  (i .e.,  TEDLAR" bag) holding the
initial   liquid  phase  of the  waste.    A  separate filtrate  collection
container must  be used if combining would create multiple phases, or there
is  not  enough  volume left within  the  filtrate   collection  container.
Filter through the glass  fiber filter, using  the  ZHE device as discussed
in Step 7.3.9.  All extracts shall  be filtered and  collected if the TEDLAff
bag is used,  if the extract is  multiphasic, or if the waste contained an
fnitiaT  liquid phase  (see Steps  4,5 and 7.3.1).

       NOTE:   An in-line glass  fiber  filter  may  be used to  filter the
       material within the ZHE  if it  is suspected that the glass  fiber
       filter has been ruptured

       7.3.14   If  the original sample contained no initial liquid phase,
the filtered liquid material  obtained  from  Step 7.3.13  is  defined as the
1312 extract.    If the  sample contained  an  initial  liquid phase,  the
filtered liquid material  obtained from Step 7.3.13 and the initial  liquid
phase (Step 7.3.9)  are collectively defined as the  1312  extract.

       7.3.15   Following  collection  of  the  1312  extract,  immediately
prepare  the extract for analysis  and store  with minimal  headspace at 4°C


                            1312  -  17                       Revision 0
                                                            September 1994

-------
      until  analyzed.   Analyze the  1312  extract  according to the appropriate
      analytical  methods.    If  the individual  phases  are  to   be  analyzed
      separately  (Le;,  are  not  miscible),  determine  the volume  of  the
      individual phases (to 0,5%), conduct the appropriate analyses, and combine
      the results mathematically by  using a simple volume- weighted average:
                               (Vt) (C,)  + (V2)  (C2)
      Final Analyte
      Concentration                  V, + V2

      where:

      V1 = The volume of the first phases (L).
      G! = The concentration of the analyte of  concern in the first phase (mg/L).
      V2 = The volume of the second phase (L).
      C2 = The concentration of the analyte  of concern in the second phase
           (mg/L).

             7.3.16  Compare the analyte concentrations in the 1312 extract with
      the levels identified in the appropriate regulations.  Refer to Step 8.0
      for quality assurance requirements.

8.0   QUALITY CONTROL

      8.1    A minimum of one blank (using the same extraction fluid  as used for
the samples) for every 20 extractions that have been conducted in an extraction
vessel.   Refer to Chapter One for additional quality control protocols.

      8.2    A  matrix spike  shall   be  performed for  each waste type  (e.g..
wastewater treatment sludge, contaminated soil, etc.)  unless the result exceeds
the regulatory level and the data is being used solely to demonstrate that the
waste property exceeds the regulatory level.  A minimum of one matrix spike must
be analyzed for each analytical batch.   As a minimum, follow the matrix spike
addition guidance provided in each analytical  method,

             8.2.1  Matrix spikes are to be added after filtration of the 1312
      extract and before preservation.   Matrix spikes  should not be added prior
      to 1312 extraction of the sample.

             8.2.2   In most cases,  matrix  spike levels should be  added  at a
      concentration equivalent to  the  corresponding regulatory  level.   If the
      analyte concentration  is less than one half the  regulatory  level,  the
      spike  concentration  may   be  as  low  as  one  half  of  the  analyte
      concentration, but may not  be  less than five times the method detection
      limit.  In order to  avoid differences in  matrix effects, the matrix spikes
      must be added to the same nominal volume of 1312  extract as that which was
      analyzed for the unspiked sample.

             8.2.3    The  purpose of  the  matrix  spike  is  to  monitor  the
      performance  of  the  analytical  methods  used,  and to  determine  whether


                                   1312  - 18                      Revision 0
                                                                  September 1994

-------
      matrix interferences exist.   Use of other internal  calibration methods,
      modification  of  the  analytical methods,  or  use  of  alternate analytical
      methods may be needed to accurately measure the analyte concentration in
      the  1312  extract when  the recovery  of the matrix  spike is  below the
      expected analytical method performance.

             8.2.4    Matrix  spike recoveries are  calculated  by the following
      formula:

             %R  (%  Recovery) = 100  (X. - XJ  / K
      where:
             Xs = measured  value for the spiked  sample
             Xu = measured  value for the unspiked sample,  and
             K  = known value  of  the spike in the sample.

      8.3  All  quality control measures described  in the appropriate analytical
methods shall be followed.
      8.4    The  use of  internal  calibration  quantitation  methods  shall  be
employed for a metallic contaminant if:  (1) Recovery of the contaminant from the
1312 extract  is  not at  least  50% and  the  concentration does not  exceed the
appropriate  regulatory  level,  and  (2)  The  concentration of  the  contaminant
measured in the extract is within 20% of the appropriate regulatory level.

             8,4.1.  The method  of standard  additions shall be employed as the
      internal  calibration quantitation method for each metallic contaminant.

             8.4.2   The method of  standard  additions  requires  preparing
      calibration standards in the sample matrix  rather than  reagent water or
      blank  solution.    It  requires  taking  four identical  aliquots of the
      solution and adding known amounts  of standard to three of these aliquots.
      The forth aliquot is the unknown.   Preferably,  the first addition should
      be prepared so that the  resulting concentration  is approximately 50% of
      the expected concentration of the  sample.  The second and third additions
      should be prepared so that the  concentrations are approximately 100% and
      150% of the expected concentration of the sample.   All  four aliquots are
      maintained at  the  same  final volume  by adding reagent water  or a  blank
      solution,  and may need dilution  adjustment to maintain the signals in the
      linear range of the  instrument technique.  All four aliquots are analyzed.

             8.4.3   Prepare  a plot,  or subject data to linear regression,  of
      instrument signals or external-calibration-derived concentrations as the
      dependant variable  (y-axis)  versus concentrations of the additions  of
      standards as the  independent variable (x-axis).   Solve for the intercept
      of the abscissa (the independent variable, x-axis)  which is the concentra-
      tion in the unknown.

             8.4.4   Alternately, subtract the instrumental signal orexternal-
      calibration-derived concentration of the  unknown  (unspiked)  sample from
      the instrumental signals or external-calibration-derived concentrations of
      the standard  additions.    Plot  or subject  to  linear regression of the
      corrected instrument signals or external-calibration-derived  concentra-


                                  1312  - 19                       Revision 0
                                                                  September 1994

-------
      tions  as the dependant variable versus the independent variable.  Derive
      concentrations for the unknowns using the internal calibration curve  as  if
      it were an external calibration curve.
      8.5
periods:
Samples must  undergo 1312  extraction within  the following  time
                      SAMPLE MAXIMUM HOLDING TIMES (days)








Volatiles
Semi-
volatiles
Mercury
Metals,
except
mercury
From: Field
Collec-
tion

To: 1312
extrac-
tion

14

14
28

180

From: 1312
extrac-
tion

To: Prepara-
tive
extrac-
tion
NA

7
NA

NA

From: Prepara-
tive
extrac-
tion

To: Determi-
native
analysis
14

40
28

180

Total
Elapsed
Time





28

61
56

360

NA = Not Applicable
If sample  holding  times  are exceeded, the values  obtained  will  be considered
minimal  concentrations.    Exceeding  the  holding  time  is  not  acceptable  in
establishing that a waste does not exceed the regulatory level.  Exceeding the
holding  tine  will  not  invalidate characterization  if  the  waste  exceeds the
regulatory level.

9.0   METHOD PERFORMANCE

      9.1    Precision results for semi-volatiles and metals:  An eastern soil
with high organic content and a western soil with low organic content were used
for the semi-volatile and metal leaching  experiments.  Both  types of soil were
analyzed prior to contaminant spiking.  The results are shown in Table 6.  The
concentration of contaminants leached from the soils were reproducible, as shown
by the moderate relative  standard deviations (RSDs)  of the recoveries (averaging
29% for the compounds and elements analyzed).

      9,2    Precision results for volatiles:   Four different soils were spiked
and tested for the  extraction of volatiles.  Soils One and Two were from western
and eastern Superfund sites.   Soils Three  and  Four were mixtures of a western
soil  with low organic content and  two  different municipal sludges.  The results
are shown  in  Table 7.   Extract  concentrations of volatile organics  from the
eastern soil were lower than from the western soil.  Replicate Teachings of Soils
                                   1312  -  20
                                                      Revision  0
                                                      September 1994

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Three and  Four showed lower  precision  than the leachates  from the Superfund
soils.

10.0  REFERENCES

1.    Environmental  Monitoring Systems  Laboratory,  "Performance  Testing of
      Method 1312; QA Support  for  RCRA  Testing:   Project Report".  EPA/600/4-
      89/022.   EPA Contract  68-03-3249  to Lockheed  Engineering  and Sciences
      Company,  June 1989.

Z,    Research  Triangle Institute,  "Inter!aboratory  Comparison of Methods 1310,
      1311, and 1312  for  Lead  in Soil".   U.S. EPA Contract 68-01-7075, November
      1988.
                                  1312 - 21                       Revision 0
                                                                  Septerrber 1994

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                         Table  1.   Volatile  Analytes1
Compound                                                       CAS  No.
Acetone                                                       67-64-1
Benzene                                                       71-43-2
n-Butyl alcohol                                               71-36-3
Carbon distil fide                                              75-15-0
Carbon tetrachloride                                          56-23-5
Chlorobenzene                                                108-iO-7
Chloroform                                                    67-66-3
1,2-Dichloroethane                                           107-06-2
1,1-Dichloroethylene                                          75-35-4
Ethyl acetate                                                141-78-6
Ethyl benzene                                                100-41-4
Ethyl ether                                                   60-29-7
Isobutanol                                                    78-83-1
Methanol                                                      67-56-1
Methylene chloride                                            75-09-2
Methyl ethyl ketone                                           78-93-3
Methyl isobutyl ketone                                       108-10-1
Tetrachloroethylene                                          127-18-4
Toluene                                                      108-88-3
1,1,1,-Trichloroethane                                        71-55-6
Trichloroethylene                                             79-01-6
Trichlorofluoromethane                                        75-69-4
UM-Trichloro-l^Z-trifluoroethane                         76-13-1
Vinyl chloride                                                75-01-4
Xylene                                                      1330-20-7
1  When  testing for any or all  of these analytes, the zero-headspace extractor
  vessel shall be  used  instead of  the  bottle  extractor.
                                   1312  -  22                       Revision 0
                                                                  Septenfcer 1994

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                 Table  2.   Suitable  Rotary Agitation Apparatus1
Company
Location
 Model No.
Analytical Testing and
  Consulting Services,
  Inc.

Associated Design and
  Manufacturing Company
Environmental Machine and
  Design, Inc.

IRA Machine Shop and
  Laboratory

Lars Lande Manufacturing
Millipore Corp.
Warrington, PA
 (215) 343-4490
Alexandria, VA
(703) 549-5999
Lynchburg, VA
(804) 845-6424

Santurce, PR
(809) 752-4004
 4-vessel extractor (DC20S);
 8-vessel extractor (DC20);
12-vessel extractor (DC20B)
 2-vessel
 4-vessel
 6-vessel
 8-vessel
12-vessel
24-vessel
(3740-2);
(3740-4);
(3740-6);
(3740-8);
(3740-12);
(3740-24)
 8-vessel (08-00-00)
 4-vessel (04-00-00)

 8-vessel (011001)
Whitmore Lake, MI 10-vessel (10VRE)
(313) 449-4116     5-vessel (5VRE)
Bedford, MA
(800) 225-3384
 4-ZHE or
 4 1-liter
 bottle extractor
 (YT300RAHW)
1  Any device that rotates the extraction vessel in an end-over-end fashion at 30
+2 rpm is acceptable.
                                   1312 - 23
                                  Revision 0
                                  September 1994

-------
              Table  3.   Suitable  Zero-Headspace  Extractor  Vessels1
Company
Location
Model No.
Analytical Testing &
  Consulting Services,  Inc.

Associated Design and
  Manufacturing Company

Lars Lande Manufacturing2
Millipore Corporation


Environmental Machine
and Design, Inc.
Warrington, PA
(215) 343-4490

Alexandria, VA
(703) 549-5999
C102, Mechanical
Pressure Device

3745-ZHE, Gas
Pressure Device
Whitmore Lake, MI  ZHE-11, Gas
(313) 449-4116     Pressure Device
Bedford, MA
(800) 225-3384

Lynchburg, VA
(804) 845-6424
YT30090HW, Gas
Pressure Device

VOLA-TOX1, Gas
Pressure Device
1  Any device  that  meets the specifications listed in Step 4.2.1 of the method is
suitable.

2  This  device uses a 11-0 mm filter.
                                   1312  -  24
                                  Revision 0
                                  September 1994

-------
                       Table  4.   Suitable Filter Holders1
Company
Nucleopore Corporation
Micro Filtration
Systems
Mi Hi pore Corporation
Location
Pleasanton, CA
(800) 882-7711
Dublin, CA
(800) 334-7132
(415) 828-6010
Bedford, MA
(800) 225-3384
Model/
Catalogue #
425910
410400
302400
311400
YT30142HW
XX1004700
Size
142 mm
47 mm
142 mm
47 mm
142 mm
47 mm
1 Any device capable of separating  the  liquid  from the solid phase of the waste
is suitable, providing that it is chemically compatible with the waste and the
constituents to be analyzed.  Plastic devices  (not listed above) may be used when
only  inorganic  analytes are  of concern.   The 142 ram  size  filter  holder is
recommended.
                       Table 5.  Suitable Filter Media1
Company
Mi Hi pore Corporation
Nucleopore Corporation
Whatman Laboratory
Products, Inc.
Micro Filtration
Systems
Location Model
Bedford, MA AP40
(800) 225-338^
Pleasanton, CA 211625
(415) 463-2530
Clifton, NJ 6FF
(201) 773-5800
Dublin, CA GF75
(800) 334-7132
(415) 828-6010
Pore
Size
(Mm)
0.7
0.7
0.7
0.7
1 Any filter that meets the specifications in Step 4.4 of the Method is suitable.
                                   1312  -  25
Revision 0
September 1994

-------
       TABLE 6 - METHOD 1312 PRECISION RESULTS  FOR  SEMI-VOLATILES AND METALS
Eastern Soil (oH 4.2)



FORTIFIED ANALYTES
bis(2-chloroethyl)-
ether
2 - Chlorophenol
1 , 4-Diehlorobenzene
1 , 2 -Dichlorobenzene
2-Methylphenol
Nitrobenzene
2 , 4-Dimethylphenol
Hexachlorobutadiene
Acenaphthene
2 , 4-Dinitrophenol
2 ,4-Dinitrotoluene
Hexachlorobenzene
famma BHC (Lindane)
eta BHC
METALS
Lead
Cadmium
Amount
Spiked
(MS)


1040
1620
2000
8920
3940
1010
1460
6300
3640
1300
1900
1840
7440
640

5000
1000
Amount
Recovered*
(MB)


834
1010
344
1010
1860
812
200
95
210
896**
1150
3.7
230
35

70
387

f ESP



12.5
6.8
12.3
8.0
7.7
10.0
18.4
12.9
8.1
6.1
5.4
12.0
16.3
13.3

4.3
2.3
Western Soil ft>H 5.0)
Amount
Recovered*
(Mg)


616
525
272
1520
1130
457
18
280
310**
23**
585
10
1240
65.3

10
91

% RSD



14.2
54.9
34.6
28.4
32.6
21.3
87,6
22.8
7.7
15.7
54.4
173.2
55.2
51.7

51.7
71.3
 * - Triplicate analyses.
** - Duplicate analyses; one value was rejected as an outlier at  the  90%
     confidence level using the Dixon Q test.
                                    1312  -  26
Revision 0
Septenber 1994

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                    TABLE 7 - METHOD 1312 PRECISION RESULTS FOR VQIATILES


Soil

No. 1

(Western)

Compound Name
Acetone
Acrylonitrile
Benzene
n- Butyl Alcohol
(1-Butanol)
Carbon disulflde
Carbon tetrachloride
Chlorobenzene
Chloroform
1, 2-Dichloroethane
1 , 1-Mchloroethane
Ethyl acetate
Ethylbenzene
Ethyl ether
Isooutanol (4-Methyl
-1-propanol)
Methylene chloride
Methyl ethyl ketone
(2-Butanone)
Methyl isobutyl
ketone
1,1,1, 2 - Tetrachloro -
ethane
1,1,2, 2 - Tetrachloro -
ethane
fetrachloroethene
Toluene
1,1,1-Trichloro-
ethane
1,1,2-Trichloro-
e thane
Trichloroethene
Trichloro-
f luorome thane
1,1,2-Trichloro-
trifluoroe thane
Vinyl chloride
Avg.
%Rec.*
44.0
52,5
47.8

55.5
21.4
40.6
64.4
61.3
73.4
31.4
76.4
56.2
48.0

0.0
47.5

56.7

81.1

69,0

85.3
45.1
59.2

47.2

76.2
54.5

20.7

18.1
10.2

iRSD
12.4
68.4
8.29

2.91
16.4
18.6
6.76
8.04
4.59
14.5
9.65
9.22
16,4

ND
30.3

5.94

10.3

6.73

7.04
12.7
8.06

16.0

5.72
11.1

24.5

26.7
20.3
Soil

No. 2

(Eastern)
Avg.
%Rec,*
43.8
50.5
34.8

49.2
12.9
22.3
41.5
54.8
68.7
22.9
75.4
23.2
55.1

0.0
42.2

61.9

88.9

41.1

58.9
15.2
49.3

33.8

67.3
39.4

12.6

6.95
7.17

IRSD
2.25
70.0
16.3

14.6
49.5
29.1
13.1
16.4
11.3
39.3
4.02
11.5
9.72

ND
42.9

3.94

2.99

11.3

4.15
17.4
10.5

22,8

8.43
19.5

60.1

58.0
72.8
Soil No
(Western
Sludge)
Avg.
%Rec . **
116.0
49.3
49.8

65.5
36.5
36.2
44.2
61.8
58.3
32,0
23,0
37.5
37.3

61.8
52.0

73.7

58.3

50.8

64.0
26.2
45.7

40.7

61.7
38.8

28.5

21.5
25.0
, 3
and


$RSD
11.5
44.9
36.7

37.2
51.5
41.4
32.0
29,1
33.3
54.4
119.8
36.1
31.2

37.7
37.4

31.3

32,6

31.5

25.7
44.0
35.2

40.6

28.0
40.9

34.0

67.8
61.0
Soil, No. 4
(Western and
Sludge)
Avg.
%Rec.*** %RSD
21.3 71.4
51.8 4.6
33.4 41.1

73.0 13.9
21.3 31.5
24.0 34.0
33.0 24.9
45.8 38.6
41.2 37.8
16.8 26.4
11.0 115.5
27.2 28,6
42.0 17.6

76.0 12.2
37.3 16.6

40.6 39.0

39.8 40.3

36.8 23.8

53.6 15.8
18.6 24.2
31.4 37.2

26.2 38.8

46,4 25.4
25.6 34.1

19.8 33. S

15.3 24,8
11.8 25.4
  * Triplicate analyses
 ** Six replicate analyses
*** Five replicate analyses
                                         1312 - 27
Revision 0
September 1994

-------
  Motor
(30±2rpm)
Extraction vmael Holder









                                                   n
      Figure 1.   Rotary Agitation Apparatus


                       UqukJ Irtst/Outt* VHv»
     TopFlangt.

 Support Screw*

            Fi
     Support Scratn'
 Bottom Rang*—*£
   Prt«suriz«d Gas •
                             SampJ*
                             PWon
                              Gas
                                  Prtssurt
                                  Gaugt
   Figure 2.  Zero-Headspace  Extractor (ZHE)
                    1312  -  28
Revision 0
September 1994

-------
                        METHOD  1312

     SYNTHETIC PRECIPITATION LEACHING  PROCEDURE
        Liquid
Prepare filtrate
 according to
  appropriate
   methods.
Analyze filtrate.
     Stop
                              Start
                             Select
                          representative
                             sample.
Separate liquid*
  from solids,
     filtrate
 become* SPLP
    extract.
                       Separate liquids
                         from solids.
   is
 particle
reduction
required?
                            Extract w/
                        appropriate fluid via:
                        1. Bottle extraction
                          for non-volatiies,
                        2. ZHE for volatiles.
                              Reduce particle
                             size to <9.5 mm.
                          1312  -  29
                                      Revision  0
                                      Septsiter 1994

-------
                         METHOD 1312

SYNTHETIC  PRECIPITATION LEACHING  PROCEDURE  (continued)
                         o

Discard
Solids
Solids

^
r
Separate liquids
from solids.
                              Extract
                             Is
                           extract
                         compatible
                         with initial
                           liquid
                           phase?
Prepare and analyze
    each liquid
    separately,
  mathematically
  combine results.
Combine extract
with liquid phase
of waste.
^
r
                                                      Stop
                    1    Prepare extract
according to
appropriate
methods.
^
r
Analyze extract.
^
r
                            Stop
                           1312 - 30
                  Revision 0
                  Septenter 1994

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                                  METHOD 3015

                 MICROWAVE ASSISTED ACID DIGESTION OF AQUEOUS
                             SAMPLES AND EXTRACTS


 1.0   SCOPE  AND APPLICATION

         1.1  This digestion procedure  is  used for the preparation of aqueous
 samples, nobility-procedure extracts, and wastes that contain suspended solids
 for  analysis,  by flame  atomic absorption spectroscopy (FLAA), graphite furnace
 absorption  spectroscopy (GFAA),  inductively coupled argon plasma  spectroscopy
 (ICP),  or  inductively  coupled irgon  plasma mass  spectrometry  (ICP-MS).   The
 procedure is a hot  acid  leach for determining available metals.  Due to  the rapid
 advances  in  microwave   technology,  consult  your  manufacturer's  recommended
 instructions for guidance on their microwave digestion system and  refer to the
 SW-846  "DISCLAIMER" when conducting analyses using Method 3015.

         1.2 Samples prepared by Method 3015 using nitric acid digestion may  be
 analyzed by FLAA,  GFAA,  1CP-AES, or ICP-MS  for the following:

                          Aluminum             Lead
                          Antimony       •     Magnesium
                          Arsenic*             Manganese
                          Barium               Molybdenum
                          Beryllium            Nickel
                          Cadmium              Potassium
                          Calcium              Selenium*
                          Chromium             Silver
                          Cobalt               Sodium
                          Copper               Thallium
                          Iron                 Vanadium
                                               Zinc


                          *Cannot be analyzed by FLAA

 2.0  SUMMARY OF METHOD

         2.1  A representative  45 ml  aqueous  sample is  digested  in 5  ml  of
 concentrated nitric acid in a fluorocarbon  (PFA or  TFM) digestion vessel for  20
 minutes using  microwave heating.   After the digestion process,  the sample  is
 cooled, and then filtered, centrifuged, or allowed to settle in a  clean sample
 bottle prior to analysis.

 3.0  INTERFERENCES

        3,1   Many samples  that  contain organics,  such as TCLP extracts, will
result in higher vessel   pressures which have the potential to cause venting  of
the vessels. Venting can result in either loss  of analytes and/or sample, which
must be avoided.   A smaller sample size can be used but the final water volume

                                   3015 - 1                       Revision 0
                                                                  September 1994

-------
prior to nitric acid addition must remain  at  45 mL.  This is required to retain
the heat characteristics of the calibration procedure.  Limits of quantitation
will change with sample quantity  (dilution) as with instrumentation."

4.0  APPARATUS AND MATERIALS

        4.1  Microwave apparatus  requirements

               4.1.1   The  microwave  unit   provides  programmable power with  a
        minimum  of 574 W,  which  can be  programmed to within  ± 10 W of the
        required  power.   Typical  units provide  a  nominal  600 W to  1200  W of
        power.   Temperature monitoring  and control of the microwave unit are
        desirable.

               4.1.2   The  microwave  unit  cavity  is  corrosion  resistant  and
        well ventilated.

               4.1.3  All electronics are  protected against corrosion for safe
        operation.

               4.1.4  The system requires  fluorocarbon (PFA or  TFM)  digestion
        vessels  (120 mL capacity) capable  of withstanding pressures  up to 7.5
        ± 0.7  atm  (110 ± 10 psig)  and capable of controlled  pressure relief at
        pressures  exceeding 7.5 ± 0.7 atm  (110 ± 10 psig).

               4.1.5  A rotating  turntable  is employed to insure  homogeneous
        distribution of microwave radiation within the unit.   The speed of the
        turntable  should be a minimum of 3 rpm.

               CAUTION:  Those laboratories  now using or contemplating the use of
               kitchen type microwave ovens for this method should  be aware of
               several significant safety  issues.  First,  when an acid such as
               nitric is used  to assist sample digestion  in microwave units in
               open vessels, or sealed vessels equipped with  venting  features,
               there is  the potential  for the  acid gases released to corrode the
               safety devices that  prevent the microwave magnetron from shutting
               off when  the door is opened.  This can  result in operator exposure
               to microwave energy. Use of a unit with corrosion resistant safety
               devices prevents this from occurring.

               CAUTION;  The second safety concern relates to  the use  of sealed
               containers without pressure relief valves in the unit.   Tempera-
               ture is the important variable controlling the reaction.  Pressure
               is needed to attain  elevated  temperatures but must be safely con-
               tained.  However, many digestion vessels constructed from certain
               fluorocarbons may  crack,  burst,  or   explode in  the oven  under
               certain  pressures.     Only  unlined   fluorocarbon  (PFA or  TFM)
               containers with pressure  relief mechanisms  or containers  with
               fluorocarbon (PFA or TFM) liners and pressure  relief mechanisms
               are considered acceptable at present.


                                   3015 -  2                       Revision 0
                                                                  September 1994

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               Users are  therefore  advised not to  use  kitchen type microwave
               ovens or to use sealed containers without pressure  relief  valves
               for microwave acid digestions by this method.   Use  of laboratory
               grade microwave equipment is required to prevent safety hazards.
               For further information consult reference  1.

               CAUTIQN:  In  addition,  there are many safety  and operational
               recommendations specific  to the model  and manufacturer  of the
               microwave  equipment  used  in  individual  laboratories.    These
               specific  suggestions  are beyond the scope  of  this  method and
               require the  analyst  to consult the  specific  equipment manual,
               manufacturer and literature for proper  and safe operation  of the
               microwave equipment and vessels.

         4.2 Volumetric graduated cylinder, 50 or 100 ml capacity or equivalent.

         4.3  Filter paper,  qualitative or equivalent.

         4.4  Analytical  balance,  300 g capacity, minimum accuracy ± 0.01 g.

         4.5  Filter funnel, glass or disposable polypropylene.

5.0  REAGENTS

         5.1   Reagent grade  chemicals shall  be  used in all  tests.   Unless
otherwise  indicated,  it  is intended that  all reagents  shall  conform  to the
specifications of the Committee on Analytical  Reagents of the American Chemical
Society, where such specifications  are available.   Other grades  may be used,
provided it is first ascertained that the reagent  is of sufficiently high purity
to permit its use without lessening the  accuracy of the determination.    If the
purity of a reagent is questionable, analyze the reagent to determine the level
of impurities.  The reagent blank  must  be less than the MDL in  order to be used.

         5.2  Reagent Water.   Reagent water shall  be interference free.  All
references to water in the method refer to reagent water unless  otherwise specif-
ied (Ref. 2).

         5.3   Concentrated nitric  acid,  HNO».   Acid should  be analyzed  to
determine levels of impurities.   If the method blank  is less than the MDL, the
acid can be used.

6.0  SAMPLE COLLECTION,  PRESERVATION, AND  HANDLING

         6.1  All  samples must have been  collected  using a  sampling  plan that
addresses the considerations discussed in  Chapter Nine of this  manual.

         6.2 All sample containers must be  prewashed with detergents, acids, and
water.   Plastic containers are preferable.  See Chapter Three,  Step  3.1.3 of this
manual, for further information.

         6.3 Aqueous  waste  waters must be acidified to a pH of <  2 with

                                   3015 -  3                       Revision 0
                                                                  September 1994

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7.0  PROCEDURE

        7.1  Calibration of Microwave Equipment

              NOTE:  If  the microwave unit  uses temperature feedback  control
              capable  of replicating the  performance  specifications  of  the
              method, then the calibration procedure may be omitted.

              7.1.1  Measurement  of  the  available  power  for   heating   is
        evaluated so that absolute power in watts may be  transferred from  one
        microwave unit to another.  For cavity  type microwave  equipment, this
        is  accomplished  by measuring the  temperature  rise in  1  kg of water
        exposed to microwave radiation for  a fixed period of time.   The  analyst
        can relate power in watts to the partial  power setting of the unit.   The
        calibration format required for laboratory microwave units  depends on
        the  type of electronic  system used  by the manufacturer to  provide
        partial microwave power.   Few  units have an accurate and precise linear
        relationship between percent power settings  and  absorbed power.  Where
        linear circuits have been  utilized, the calibration curve can be deter-
        mined  by a  three-point  calibration  method (7.1.3),  otherwise,   the
        analyst must use the multiple point calibration method (7.1.2).

              7.1.2  The multiple point  calibration involves the  measurement
        of absorbed power over a large range of power settings.   Typically,  for
        a 600 W unit, the following  power  settings are measured; 100,11,98,97,
        95,90,80,70,60,50, and 40%  using the procedure described in  section
        7.1.4.  This data is clustered about the customary working power  ranges.
        Nonlinearity has  been commonly encountered  at  the upper  end  of  the
        calibration.   If the unit's  electronics are  known to have  nonlinear
        deviations in  any region of  proportional  power  control,  it will   be
        necessary to make a  set of  measurements that bracket the power to be
        used.   The final  calibration point  should  be at  the partial power
        setting that will be used  in the test.   This  setting should be  checked
        periodically to  evaluate the integrity of the  calibration.    If  a
        significant change  is detected  {±10 W), then  the entire  calibration
        should be reevaluated.

              7.1.3  The three-point  calibration involves the measurement  of
        absorbed power  at three different power settings.  Measure  the power at
        100%  and 50%  using  the  procedure described  in  section  7.1.4,   and
        calculate the power setting corresponding to the required power in watts
        specified  in  the  procedure  from  the  (2-point)  line.   Measure  the
        absorbed power  at that partial power setting.  If the measured absorbed
        power does not  correspond  to the specified power within ±10 W,  use  the
        multiple point calibration in 7.1.2.   This point should also be used to
        periodically verify the integrity of the calibration.

              7.1.4  Equilibrate  a large volume of  water to room  temperature
        (23 ± 2  *C),  One  kg  of reagent water is weighed (1,000.0 g ± 0.1  g)
        into a fluorocarbon (PFA or  TFM) beaker  or a  beaker made of some other
        material that  does  not significantly absorb  microwave energy (glass

                                  3015 - 4                        Revision  0
                                                                  September 1994

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absorbs  microwave  energy  and  is  not  recommended).    The  initial
temperature of the water should be 23 ± 2 *C measured to ± 0.05  *C.  The
covered beaker  is  circulated  continuously  (in  the normal sample path)
through the microwave field for 2 minutes at the desired partial power
setting with  the unit's exhaust fan on maximum  (as  it will  be during
normal  operation).   The  beaker is  removed  and the  water  vigorously
stirred.   Use   a  magnetic stirring bar  inserted  immediately  after
microwave  irradiation  and record  the  maximum temperature within  the
first 30  seconds to  ±  0.05 °C.  Use a new  sample  for each  additional
measurement.  If the water is  reused both the water and the beaker must
have returned to 23 ± 2 *C.   Three measurements  at each power setting
should be made.

The absorbed power is determined by  the following relationship

                     P  • (K)  (Cp)  (m) (AT)

Eq.  1
Where :

P  -  the  apparent  power  absorbed  by  the  sample  in  watts  (W).
(W=joule-sec  )

K =  the conversion factor for  thermochemical  calories- sec"1  to watts
(-4.184)

C  - the heat capacity,  thermal  capacity,  or specific heat
    -g^-C'1), of water
m - the mass of the water sample 1n grams (g)

AT « the final temperature minus the initial temperature ("C)

t • the time in seconds (s)

Using the experimental conditions  of 2 minutes and 1  kg of distilled
water (heat capacity  at  25 "C is 0.9997 cal -g~1- T1)  the  calibration
equation simplifies to:

                       P  =  (AT)  (34.86)

      NOTE:  Stable line voltage is necessary for accurate and reproduc-
      ible calibration and operation.  The line voltage should be within
      manufacturer's specification, and during measurement and operation
      not vary  by more than  ±2  V.   A constant  power supply  may  be
      necessary for microwave use if the source of the  line voltage  is
      unstable.
                          3015  -  5                        Revision 0
                                                          September 1994

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         Electronic components  in most microwave units are matched to the units'
         function  and output.   When any part of  the high voltage  circuit, power
         source,  or  control   components  In  the  unit have  been  serviced  or
         replaced, it will be necessary to recheck the units' calibration power.
         If the power output has changed  significantly (±10 W), then the entire
         calibration should be  reevaluated.

         7.2  All  digestion vessels  and volumetric ware must be  carefully acid
washed  and rinsed with  reagent water.   When  switching between  high solids
(concentrated) samples and low solids  (low concentration)  samples all digestion
vessels should be cleaned by leaching  with hot (1:1)  hydrochloric acid (greater
than 80°C, but less  than boiling)  for a minimum of two hours followed with hot
(1:1) nitric acid  (greater than 8Q°C,  but  less than boiling) for a  minimum of two
hours,  rinsed with  reagent water,  and  dried  in a  clean environment.   This
cleaning procedure should also be used whenever the prior use of the digestion
vessels is unknown or  cross contamination from vessels is  suspected.  Polymeric
or glass  volumetric ware  and  storage  containers should  be cleaned by leaching
with more dilute  acids  (approximately 10%  V/V) appropriate  for the  specific
plastics used and then rinsed with reagent water and dried in a  clean environ-
ment.   In  addition, to avoid  precipitation  of  silver,  ensure  that all  HC1  has
been rinsed from the vessels.

         7.3  Sample Digestion

              7.3.1  Weigh the fluorocarbon  (PFAorTFM)  digestion vessel, valve
         and cap assembly  to 0.01 g prior to use.

              7.3.2  A 45 ml aliquot  of  a well  shaken sample  is  measured in a
         graduated cylinder.   This aliquot  is  poured into the  digestion vessel
        with  the number  of the vessel recorded  on the preparation  sheet.

              7.3.3  A  blank  sample of  reagent water is treated  in  the same
        manner along with spikes and duplicates.

              7.3.4  Add  5 mL  of concentrated  nitric acid tc  sach vessel that
        will  be used.  Check to make sure the pressure relief disks are in the
        caps  with the  smooth  side  toward the sample  and  start the caps  a few
        turns on the vessels.- Finish  tightening  the caps  in the capping station
        which will tighten them to a uniform torque  pressure  of  12 ft-lbs.
         (16 N-nt)  or to the manufacturers recommended specifications.  Weigh each
        capped vessel  to  the nearest 0.01 g.

              CAUTION: Toxic nitrogen oxide  fumes nay be evolved, therefore all
              work must be performed in a  properly operating ventilation system.
              The analyst should also be aware of the potential  for a vigorous
              reaction.   If a vigorous reaction occurs,  allow to  cool  before
              capping the vessel.

              7.3.5  Evenly distributed  the vessels  in  the  carousel  according
        to the manufacturer's recommended specifications.   Blanks are treated
        as  samples for the purpose  of balancing the  power  input.   When  fewer

                                  3015 - 6                        Revision 0
                                                                  September 1994

-------
 than  the  recommended  number of  samples  are digested,  the remaining
 vessels  should be filled with 45 ml of reagent water and  5 ml of nitric
 acid to achieve the full  compliment of vessels.   This provides an energy
 balance  since the microwave power absorbed is proportional to the total
 mass in  the cavity  (Ref,  1).

       7,3.6  Program the microwave unit according to the manufacturer's
 recommended specifications  and,  if used,  connect  the  pressure vessels
 to the central overflow vessel  with PFA-fluorocarbon tubes.  The chosen
 sequence will  bring the  samples  to 160"C  4 4"C  in  10  minutes and will
 permit a slow rise to 165-170 "C  during the second 10 minutes (Ref. 3),
 Start  the  turntable motor and  be sure the vent  fan  is running on high
 and the  turntable is turning.  Start  the microwave generator.

               7.3.6.1    Newer  microwave  units  are  capable  of  higher
       power that permit digestion  of  a larger  number of  samples per
       batch.   If the analyst wishes to digest more  samples at a tine,
       the  analyst  may use  different power settings  as  long as  they
      result  in  the same  time  and temperature  conditions  defined  in
      7.3.6.  That is,  any sequence of power that brings the samples to
       160*C ±  4*C  in 10 minutes and permits a  slow rise to 1S5-170*C
      during the second  10 minutes  (Ref. 2).

       Issues  of safety,  structural  integrity  (both  temperature  and
      pressure   limitations),   heat   loss,  chemical   compatibility,
      microwave absorption of vessel material, and energy transport will
      be considerations  made in  choosing  alternative  vessels.   If all
      of the considerations are met and the appropriate power settings
      are  provided  to reproduce the  reaction  conditions  defined  in
      7.3.6, then these  alternative vessels may be used  (Ref. 1,3)

       7.3.7   At  the end  of  the  microwave program,  allow  the  vessels
to cool  for at  least  5  minutes  in  the unit  before removal to  avoid
possible injury  if a vessel vents immediately after  microwave heating.
The samples may be  cooled outside the unit  by removing the carousel and
allowing the samples to cool  on the bench  or in a water bath.  When the
vessels have cooled to  room temperature, weigh and record the weight of
each vessel  assembly.    If  the  weight of the  sample  plus acid  has
decreased by more than 10% discard the sample.

      7.3.8  Complete  the  preparation of the  sample  by  carefully
uncapping and venting each vessel in a fume hood.  Transfer the  sample
to an  acid-cleaned   bottle.   If the  digested  sample contains  par-
ticulates whtch may clog nebulizers or interfere with  injection  of the
sample into the  instrument,  the  sample may be centrifuged,  allowed  to
settle or filtered.

          7.3.8.1  Centrifugation:  Centrifugalion at  2,000-3,000 rpm
      for 10 minutes is usually sufficient to clear the supernatant.
                           3015 -  7                       Revision 0
                                                          September 1994

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                  7.3.8.2   Settling:   Allow  the sample  to stand  until  the
               supernatant is  clear.   Allowing  a  sample to stand overnight will
               usually accomplish this.  If it does not, centrifuge or filter the
               sample.

                  7.3.8.3   Filtering: The filtering apparatus must be
               thoroughly cleaned  and prerinsed with dilute  (approximately 10%
               V/V)  nitric acid.   Filter the sample through   qualitative filter
               paper into a second acid-cleaned container.

               7.3.9  The  concentration values obtained  from analysis must be
         corrected for the  dilution factor from  the acid addition.   If the sample
         will  be  analyzed  by ICP-HS  additional dilution  will   generally  be
         necessary.   For example,  the sample may be diluted  by  a factor of 20
         with  reagent water and the acid strength adjusted back to 10% prior to
         analysis.  The dilutions  used should be  recorded and the measured con-
         centrations adjusted  accordingly  (e.g.,  for a 45 ml  sample and 5 ml of
         add  the correction factor  is 1.11).

8.0  QUALITY CONTROL

         8.1   All quality  control  measures  described  in Chapter  One,  of this
Manual,  should be followed.

         8.2  For each analytical  batch of samples processed,  analytical reagent
blanks (also field blanks  if they were taken) should be carried throughout the
entire sample preparation  and analytical  process.  These blanks will be useful
in determining if samples  are being contaminated.

         8.3   Duplicate  samples  should be  processed  on a  routine  basis.   A
duplicate sample is a real  sample brought through the whole sample preparation
and  analytical  process.   A  duplicate  sample  should  be processed  with  each
analytical batch or every  20 samples, whichever  is the greater number.

         8.4  Spiked  samples or standard reference materials  should be employed
to determine accuracy.   A spiked  sample  should be included  with each group of
samples  processed and whenever a new sample matrix is  being analyzed.

9.0  METHOD PERFORMANCE

         9.1   Refer  to  Table  1 for a  summary of  performance  data.
                                   3011 - 8                       Revision 0
                                                                  September 1994

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10,0  REFERENCES

1-       Introduction  to  Microwave  Sample  Preparation:  Theory  andPractice.
         Kingston,  H,  M.;  Jassie,  L.  B.,  Eds.; ACS Professional Reference Book
         Series: American  Chemical Society,  Washington, DC,  1988; Ch 6  & 11,

2.       1985 Annual Book of ASTM Standards.  Vol. 11.01; "Standard Specification
         for Reagent Water"; ASTM: Philadelphia, PA,  1985; D1193-77.

3.       Kingston,  H.  M.,  Final  Report  EPA IAG fDWI3932541-01-I, September 30,
         1988, Appendix A,

4.       Shannon, M.,  Alternate  Test Procedure Application,  USEPA Region V,
         Central Regional  Laboratory, 536  S. Clark Street, Chicago,  IL  60606,
         1989.

5,       Kingston,  H,  M.,  Walter,  P.  J.,  "Comparison  of Microwave  Versus
         Conventional Dissolution for Environmental Applications", Spectroscopy,
         vol. 7 No. 9,20-27,1992.

6.       Sosinski,  P., and Sze C.,  "Absolute  Accuracy Study, Microwave Digestion
         Method  3015  (Nitric  acid  only)";  EPA  Region  III Central  Regional
         Laboratory, 1991.
                                   3015 - 9                       Revision 0
                                                                  Septenter 1994

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                      TABLE 1
MICROWAVE DieESTION METHOD  3015  (Nitric Acid Only)
Elea
Al
At
At
At
Ba
Ba
Ba
Cd
Cd
Cd
Cd
Zn
Zn
In
Zn
As
As
Co
Co
K
K
Hi
Ni
Hi
fb
Pb
Pb
Po
Sb
£'*>
?~ '-
Se
Tt
Tl
V
V
8*
Be
Ca
Ca
Material
Tm-11
In- 12
T-107
T-109
Tm-11
Tm-12
T-107
Tm-11
Tm-12
T-107
T-109
Tm-11
Tm-12
T-107
T-109
T-107
T-109
Tm-11
Tin- 12
T-9S
T-109
Tw-11
Tn-12
T-109
Tdl-11
TIB- 12
T-107
'109
VP9BO-1
UP980-2
T-95
T-1C?
W980-1
UP980-2
Tra- 11
Tm-12
T-107
T-109
T-107
T-109
Certified
Nean
510.0
2687.0
220,0
113.0
450.0
2529.0
192.0
40.8
237.0
14.3
12.1
55.4
314.0
75.8
74.0
10.8
8.15
227.0
1067.0
4700,0
2330.0
264.0
1234.0
57.0
275.0
1526.0
26.0
34.9
16.9
101.5
60.1
11.0
50.0
6.3
491.0
2319.0
11.0
22.1
11700.0
35400.0
Observed
Nean
485.5
2770.6
213.5
117.7
441.4
2431 .4
196.6
44.6
242.3
12.4
10.3
55.9
316.5
81.6
69.9
12.8
90.6
242.6
1153.3
5080.3
2601.5
284.3
1293.0
60 .8
275.9
1359.0
30.0
39.3
18.3
108.9
65.9
13.0
55,1
7.0
532.6
2412.8
11.3
25.6
12364.0
38885.0
Std. Dev.
26.3
88.2
19.3
30.6
23.4
70.3
15.9
2.1
8
0.9
1.7
2.6
8.9
3.3
4.1
0.84
11.0
14.1
35.9
784
383.4
16.5
39.4
3.09
32.2
35.0
0.2
1.2
0.47
34.4
2.6
0.9
2
0.52
26.1
60.6
0.53
0.91
783.6
999
Relative
Standard
Deviation
5.4
3.2
9.0
2.6
5.3
2.9
8.1
4.7
3.3
7.2
16.5
4.6
2.8
4.0
5.8
6.5
12.2
5.8
3.1
15.4
14.7
5.8
3.0
5.0
11.7
2.6
0.66
3.0
2.6
31.6
3.94
6.9
3.6
7.4
4.9
2.5
4.7
3.6
6.3
2.6
Relative
•fas
-4.80%
3.11X
-2.95X
4.16%
•1.90X
-3.86%
2.44%
9.46%
2.25%
-12.94X
-14.55%
1.06X
0.82X
7.68%
-5. 46%
19.26%
11.26X
6.90%
8.09X
8.092
11.65X
7.71%
4.79%
6.72%
0.36X
2.49%
15.65%
12.69%
8.27%
7.33%
9.77%
19.00X
10.26%
11.66%
8.48%
4.05%
3.00%
15.97%
5.68%
9.84%
                     3015 - 10
Revision 0
Septaiter 1994

-------
TABLE 1  (continued)
Elan
Ca
Ca
Hg
Mg
Mg
Ma
Ma
Ma
Or
Cr
Cr
Cr
Cu
Cu
Cu
Cu
Fe
Fe
Fe
Fe
Hn
Hn
Mr.
Hn
*g
Katerial
T-107
T-109
T-95
T-107
T-109
T-95
T-107
T-109
Tm-11
Tm-12
T-107
T-109
Tm-11
Tm-12
T-107
T-109
Tm-11
Tin-IE
T-107
T-109
Tm-11
Tm-12
T-107
T-109
WS378-1
Certified
Mean
11700,0
35400.0
32800.0
2100.0
9310,0
190000.0
20700.0
12000.0
52.1
299.0
13,0
18.7
46.3
288.0
30.0
21.4
249.0
1089.0
52,0
106.0
46.0
263.0
45.0
34.0
48.0
Observed
Mean
12364,0
38885,0
35002.0
2246.7
10221.7
218130.0
22528.0
1379i,5
64.3
346.0
22.3
32.6
76.5
324.0
42.3
54.0
289.3
1182.5
63.8
134.0
SO. 9
304.4
52.6
46.8
19.4
Std. Dev.
783.6
999
1900
110.5
218.6
10700
1060
516.2
4,1
9.8
1.5
6.4
4.4
8.9
4.0
3.6
16.4
43.5
8.7
6.6
3.2
9.1
3.1
3.0
5,6
Relative
Standard
Deviation
6.3
2.6
5.4
4.9
2.1
4.9
4.7
3.7
6.4
2.8
6.7
19.6
5.7
2.7
9.4
6.7
5.7
3.7
13.6
4.9
5.2
3.0
5.8
6.4
2.9
Relative
Bias
5.68%
9,84%
6.71X
6.99%
9.79%
14.81%
8.83%
15,00%
23.51%
li.74%
71.77%
74.71%
65.36%
12.52%
41.17%
152.38%
16.18%
8.59%
22.69%
26.50%
32.48%
15.77%
17.Q9X
37,18%
-57.83%
     3015 - 11
Revision 0
Septartoer 1994

-------
                                METHOD 3015
MICROWAVE  ASSISTED ACID DIGESTION OF AQUEOUS  SAMPLES AND  EXTRACTS
           7,1 Ctfilmft*
             I
7.2 AeM *M
mnt
•II i
vw
 ftemnra.
                              7.3.3
                              4«
                                lnt»th*
7.3.$ U** M»*
       *l
                                7.1.* Ai

                               MNOgt*
                                7.1,1
                               M»»».l
                               oarvu
                             M«nk»tt
                                7.3,7 Alto*
                                     in
                                3015  - 12
                   Revision 0
                   Septenter 1994

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                                  METHOD 3051

               MICROWAVE ASSISTED ACID  DIGESTION OF SEDIMENTS.
                            SLUDGES,  SOILS, AND OILS


 1.0    SCOPE AND APPLICATION

       1.1  This method is applicable  to the microwave assisted acid digestion of
 sludges, sediments, soils,  and oils  for the  following elements:

       Aluminum    Cadmium        Iron          Molybdenum          Sodium
       Antimony    Calcium        Lead          Nickel              Strontium
       Arsenic     Chromium       Magnesium     Potassium           Thallium
       Boron       Cobalt         Manganese     Selenium            Vanadium
       Barium      Copper         Mercury       Silver        "      Zinc
       Beryl1i urn

       1.2   This  method is  provided  as  an alternative to Method  3050.   It is
 intended to provide a rapid multielement acid leach digestion prior to analysis
 so that decisions can  be  made about site  cleanup  levels,   the  need  for TCLP
 testing  of  a  waste   and   whether   a  BOAT  process   is  providing acceptable
 performance.   If a decomposition including  hydrochloric acid  is required for
 certain elements, it is recommended that Method 3050A be  used. Digests produced
 by the method are  suitable for analysis  by flame atomic  absorption (FLAA),
 graphite furnace atomic absorption (GFAA), inductively coupled plasma emission
 spectroscopy (ICP-ES)  and inductively coupled plasma mass spectrometry (ICP-MS).
 Due to the rapid advances in microwave technology, consult your manufacturer's
 recommended instructions for  guidance on  their  microwave  digestion system and
 refer to the SW-846 "DISCLAIMER" when conducting analyses using Method 3051.

 2.0  SUMMARY OF METHOD

      2.1   A representative  sample  of  up to  0.5 g  is digested  in  10  ml of
 concentrated nitric  acid  for 10 min using microwave heating with a  suitable
 laboratory microwave unit.   The sample and  acid are placed in  a fluorocarbon (PFA
 or TFM) microwave vessel.  The vessel  is  capped and heated in  the microwave unit.
After  cooling,  the  vessel   contents  are filtered,  centrifuged,  or allowed to
 settle and then diluted to  volume and analyzed by the appropriate  SW-846 method
 (Ref. 1).

3.0  INTERFERENCES

      3.1  Very reactive or volatile materials  that may create high pressures
when heated may cause venting of the vessels with potential  loss  of sample and
analytes.  The complete decomposition  of either carbonates, or  carbon  based
 samples, may cause  enough  pressure  to  vent  the  vessel  if  the  sample size is
greater than 0.25 g when used in the 120 mL vessels with a pressure  relief device
that has an upper limit of 7.5±  0.7  atm (110 ± 10 psi).
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4.0  APPARATUS AND MATERIALS

      4.1  Microwave apparatus requirements.

            4.1.1   The  microwave  unit  provides  programmable  power  with  a
      minimum of 574 W, which can be programmed to within ± 10 W of the required
      power.    Typical  units  provide  a  nominal  600  W to  1200  W of  power.
      Pressure,  or especially  temperature,   monitoring  and  control  of  the
      microwave unit are  desirable.

            4.1.2   The microwave  unit  cavity is corrosion resistant and  well
      ventilated.

            4.1.3  All  electronics are  protected against corrosion for  safe
      operation.

            4.1.4   The system  requires  fluorocarbon  (PFA  or TFH)  digestion
      vessels {120 ml capacity) capable of withstanding pressures  up to 7.5  ±
      0.7 atm  (110 ±  10  psi)  and  capable  of  controlled  pressure relief  at
      pressures exceeding 7.5  ± 0.7 atm (110  ± 10 psi).

            4.1.5  A rotating  turntable  is   employed  to  insure  homogeneous
      distribution of microwave radiation within  the  unit.   The  speed of  the
      turntable should  be a minimum of  3  rpm.

                  CAUTION:   Those laboratories  now using or contemplating  the
                  use of  kitchen type microwave  ovens for this  method should be
                  aware of  several signifant safety issues.  First, when an  acid
                  such  as nitric is used to assist sample digestion in microwave
                  units in  open vessels, or sealed vesselsequippedres, there is
                  the  potential  for the acid gases  released  to corrode  the
                  safety  devices  that  prevent  the microwave  magnetron  from
                  shutting  off when the  door is opened.   This can  result  in
                  operator  exposure to microwave  energy.   Use of a  unit  with
                  corrosion  resistant   safety  devices  prevents   this   from
                  occurring.

                  CAUTION:   The  second safety  concern relates  to the use  of
                  sealed  containers  without pressure relief valves in the unit.
                  Temperature   is  the  important  variable  controlling   the
                  reaction. Pressure is needed to attain elevated temperatures
                  but must  be safely contained.  However, many digestion  vessels
                  constructed  from certain  f1uorocarbons may crack,  burst,  or
                  explode in the unit under certain pressures.    Only  unlined
                  fluorocarbon  (PFA or TFH)   containers with  pressure relief
                  mecahnisms  or  containers  with  PFA-fluorocarbon liners  and
                  pressure  relief   mechanisms   are  considered  acceptable  at
                  present.

                  Users are therefore advised not to use kitchen type microwave
                  ovens or to  use  sealed containers  without  pressure relief

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                  valves for microwave acid digestions by this method.  Use of
                  laboratory-grade microwave  equipment  is  required to prevent
                  safety hazards.  For further details consult reference 2.

                  CAUTION;      There   are   many   safety    and   operational
                  recommendations specific to the model  and manufacturer of the
                  microwave equipment used  in individual  laboratories.  These
                  specific suggestions are beyond the scope of this method and
                  require the analyst to  consult  the  specific  equipment manual,
                  manufacturer and literature for proper and  safe operation of
                  the microwave equipment and vessels.

      4.2   Volumetric graduated cylinder,  50  or  100  ml capacity or equivalent.

      4.3   Filter paper, qualitative or equivalent.

      4.4  Filter funnel, glass or disposable polypropylene.

      4.5  Analytical balance, 300 g capacity, and minimum ± 0.01 g.

5.0  REAGENTS

      5.1  All acids should  be sub-boiling distilled  where possible to minimize
the  blank  levels due to  metallic contamination.   Other  grades may  be  used,
provided it is  first ascertained that the reagent  is of  sufficient purity to
permit  its  use  without  lessening the accuracy  of the determination.   If the
purity of a reagent is questionable,  analyze the  reagent to determine the level
of impurities.  The  reagent blank must be less than the MDL in  order to be used.

            5.1.1  Concentrated nitric acid, HN03.  Acid should be analyzed to
      determine levels of impurity.  If the method blank is less than the MDL,
      the acid can be used.

      5.2   Reagent  Water.   Reagent  water  shall be interference free.   All
references  to water  in  the method  refer  to  reagent water  unless  otherwise
specified (Ref.  3).

6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1   All  samples must  have been  collected  using  a sampling  plan  that
addresses the considerations discussed in Chapter Nine of this manual.

      6.2  All sample containers  must be prewashed  with  detergents,  acids and
water.  Plastic  and glass containers are both suitable. See Chapter Three, sec.
3.1.3 of this manual, for further information.

     6.3  Samples  must  be refrigerated  upon  receipt and analyzed  as  soon as
possible.
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7.0  PROCEDURE

      7.1  Calib -ation of Microwave Equipment

            NOTE:  If  the  microwave unit  uses  temperature  feedback  control
            capable of replicating the performance specifications of the method,
            then the calibration procedure may be omitted.

            7.1.1  Measurement of the available power for heating  is evaluated
      so that  absolute power in watts may be transferred from one microwave unit
      to another.  For cavity  type microwave equipment, this is accomplished by
      measuring  the temperature rise in  1 kg of  water  exposed  to  microwave
      radiation  for a fixed period  of  time.   The analyst can relate power in
      watts to the partial power setting of the  unit.  The  calibration format
      required for laboratory  microwave  units depends on the type of electronic
      system used by the manufacturer to provide  partial  microwave power.   Few
      units have an accurate  and precise linear relationship between  percent
      power settings  and  absorbed  power.    Where linear  circuits   have  been
      utilized,  the  calibration  curve   can  be  determined  by  a  three-point
      calibration method (7.1.3), otherwise,  the  analyst  must  use  the multiple
      point calibration  method (7.1.2).

            7.1.2  The multiple point calibration  involves the measurement of
      absorbed power over a large range  of power  settings.   Typically,  for a
      600 W unit, the following power settings are measured; 100, 99,  98,  97,
      95,  90,  80, 70,  60, 50,  and 40% using the procedure described  in section
      7.1.4.   This data  is clustered about  the customary  working power ranges.
      Nonlinearity has  been  commonly  encountered  at the  upper  end  of  the
      calibration.    If   the unit's  electronics  are  known  to  have  nonlinear
      deviations  in  any  region of  proportional  power  control,  it will  be
      necessary to make  a set of measurements  that  bracket the power to be used.
      The final calibration point should be at the partial power  setting  that
      will  be  used  in  the test.  This setting  should be checked periodically to
      evaluate the integrity of  the  calibration.   If a significant  change  is
      detected (±10 W),  then the entire  calibration should  be reevaluated.

            7.1.3   The   three-point  calibration  involves the  measurement  of
      absorbed power at  three  different power settings.  Measure  the power at
      100%  id 50% using athe  procedure  described  in  sact ion 7.1.4.    From the
      2-point  line calculate the  power  setting corresponding  to  the required
      power in watts specified  in the procedure.  Measure  the absorbed power at
      that partial power setting.    If  the measured  absorbed  power does  not
      correspond to the  specified power  within tlO W, use the multiple  point
      calibration in 7.1.2.   This point should  also  be  used to  periodically
      verify the integrity of  the calibration.

            7.1.4  Equilibrate a large volume  of  water to room temperature
      (23  ± 2°C).  One kg of reagent water  is  weighed  (1,000.0 g + 0.1  g)  into
      a  fluorocarbon beaker or a beaker made  of some  other material  that  does
      not  significantly  absorb microwave energy (glass absorbs microwave energy
      and  is not recommended).   The  initial temperature of the water should be

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23  ±  2"C  measured  to  ± 0,05'C,    The covered  beaker  is circulated
continuously  (in the normal sample path) through the microwave  field  for
2 minutes at the desired partial  power setting with the unit's exhaust  fan
on maximum (as it will  be during  normal operation).  The beaker is  removed
and the water vigorously stirred.   Use a magnetic stirring  bar inserted
immediately after microwave irradiation and record the maximum temperature
within  the  first 30  seconds  to ±  0.05°C.    Use  a new  sample  for each
additional measurement.   If the water is reused  both  the water  and  the
beaker must have returned to 23  t 2°C.  Three measurements at each power
setting should be made.

The absorbed  power is determined by the following relationship:

                       P - (K) (CJ  (m) (AT)
Eq. 1
Where:

P = the apparent power absorbed by the sample in watts (W)
(W=joule-sec*1)

K  =  the  conversion  factor  for  thermochemical  calories-sec"1  to  watts
(=4.184)

Cp = the heat capacity,  thermal  capacity,  or specific heat
(cal-g-1 T1) of water

m = the mass of the water sample in grams (g)

AT *  the final temperature minus the initial temperature  (°C)

t = the time in seconds (s)
Using the experimental  conditions of 2 minutes and 1 kg of distilled water
(heat capacity  at 25  °C  is  0.9997 cal-g^-'C1)  the calibration equation
simplifies to:

Eq. 2                    P = (AT)  (34.86)

      NOTE:     Stable  line  voltage   is  necessary  for  accurate  and
      reproducible calibration  and operation.   The  line voltage should be
      within  manufacturer's  specification,  and during  measurement  and
      operation should not  vary  by more than  ±2  V.   A constant power
      supply may be necessary for microwave use if the source of the
      line voltage is unstable.

      Electronic components  in  most  microwave  units are matched  to  the
      units'  function  and output.   When any  part of the  high  voltage


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            circuit, power source, or control components in the unit have been
            serviced or  replaced,  it will  be necessary  to  recheck the units'
            calibration.  If the power output has changed  significantly  (±10 W),
            then the entire calibration should be reevaluated.

      7.2   All  digestion vessels  and  volumetric ware must  be  carefully acid
washed and rinsed with reagent water.  When  switching between high concentration
samples and low concentration samples, all  digestion vessels should be cleaned
by leaching with hot (1:1) hydrochloric acid (greater than 80°C, but less than
boiling) for a minimum of two hours followed with hot (1:1) nitric acid (greater
than 80°C, but less than boiling)  for a minimum of two  hours  and  rinsed with
reagent water and dried  in a clean  environment.  This cleaning procedure should
also be used whenever the prior use of the digestion vessels  is unknown or cross
contamination from  vessels is suspected.  Polymeric or glass volumetric ware and
storage  containers should  be  cleaned  by leaching  with  more dilute  acids
(approximately 10%  V/V)  appropriate for the  specific  plastics used  and then
rinsed  with  reagent  water  and  dried  in a  clean environment.    To  avoid
precipitation of silver, ensure that all HC1 has been  rinsed from the vessels.

      7.3  Sample  Digestion

            7.3.1   Weigh the fluorocarbon (PFA or TFM)  digestion vessel,  valve
      and capassembly  to 0.001 g prior to use,

            7.3.2   Weigh  a  well-mixed  sample to the nearest 0.001  g  into the
      fluorocarbon   sample vessel  equipped  with  a  single-ported  cap and  a
      pressure relief valve.  For soils, sediments, and  sludges use no more than
      0.500 g.  For oils use no more than 0.250 g.

            7.3.3   Add  10  ±  0.1  mL concentrated nitric acid in a  fume hood.
      If a vigorous reaction occurs, allow the reaction to stop before capping
      the vessel.   Cap the vessel  and torque the  cap to  12  ft-lbs  (16  N-m)  or
      according to  the unit manufacturer's directions.   Weigh the vessels to the
      nearest 0.001 g.   Place the vessels in the microwave carousel.

            CAUTION:  Toxic nitrogen oxide  fumes may be evolved,  therefore all
            work must  be performed in a properly operating ventilation system.
            The analyst  should also  be  aware of the potential  for  a  vigorous
            reaction.    If a vigorous  reaction occurs,  allow to cool  before
            capping the  vessel.

            CAUTION:  When  digesting  samples  containing volatile  or easily
            oxidized organic compounds,  Initially weigh no more than 0.10  g and
            observe the  reaction  before capping  the  vessel.   If  a  vigorous
            reaction occurs, allow the reaction  to cease before  capping the
            vessel.   If no appreciable reaction occurs,  a sample weight  up  to
            0.25 g  can  be used.
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      CAUTION: All samples known or suspected of containing more than  5-
      10% organic material  should be predigested in a hood for at least  15
      minutes.

      7.3.4   Properly place the carousel  in the microwave unit  according
to the manufacturer's recommended specifications and, if used,  connect the
pressure  vessels  to  the central  overflow vessel  with PFA-fluorocarbon
tubes.  Any vessels  containing  10 ml of nitric acid for analytical blank
purposes are counted  as sample  vessels.  When fewer than the recommended
number of  samples are to  be  digested,  the remaining  vessels should  be
filled with 10  ml  of  nitric  acid to  achieve  the full complement  of
vessels.    This  provides  an  energy  balance  since the  microwave  power
absorbed  is proportional   to  the  total  mass  in  the  cavity  (Ref.  4).
Irradiate each group of sample vessels for 10 minutes.   The temperature  of
each  sample  should rise to 175 °C  in  less than 5,5 minutes  and  remain
between 170-180 °C for  the  balance of  the 10  minute irradiation period.
The pressure should  peak at less than 6 atm  for most  soil,  sludge,  and
sediment samples  (Ref. 5).   The pressure will  exceed these limits in the
case of high concentrations of  carbonate or organic compounds.  In these
cases the pressure will  be limited by the relief pressure of the  vessel  to
7.5 ± 0.7 atm (110 ±  10 psi).    All  vessels should be sealed according  to
the manufacturers recommended specifications.

            7.3.4.1  Newer microwave units are  capable of higher  power (W)
      that permits digestion of a larger number of  samples per batch.   If
      the analyst wishes to digest more samples at a time, the analyst may
      use different  values  of power  as  long as they result  in  the same
      time  and  temperature  conditions defined  in  7.3.4.  That is,  any
      sequence of power that  brings the  samples  to 175°C in  5.5 minutes
      and permits  a  slow  rise  to  175  -  180°C during  the remaining  4.5
      minutes (Ref. 5).

      Issues  of  safety,   structural  integrity  (both  temperature  and
      pressure limitations), heat loss, chemical compatibility, microwave
      absorption  of  vessel   material,  and  energy  transport  will    be
      considerations made  in choosing alternative vessels.  If all  of the
      considerations are met and the appropriate power  settings provided
      to  reproduce the reaction conditions defined  in  7.3.4,  then  these
      alternative vessels  may be used  (Ref. 1,2).

      7.3.5  At the  end of the microwave program,   allow the  vessels to
cool for a minimum of 5 minutes before removing  them from  the microwave
unit.   When the  vessels  have cooled to room temperature, weigh and record
the weight of each vessel  assembly.  If the weight of acid plus    sample
has decreased by more than  10  percent  from the original     weight,
discard the sample.  Determine the reason for the weight loss.  These are
typically attributed to loss of  vessel seal integrity, use of a digestion
time longer  than  10  minutes,  too  large a  sample,  or  improper heating
conditions.   Once the source of the  loss  has been    corrected, prepare
a new sample or set of samples for  digestion beginning  at 7.3.1.


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            7.3.6  Complete the preparation of the sample by carefully uncapping
      and venting each vessel  in a fume hood.  Transfer the  sample to an  acid-
      cleaned  bottle.   If the digested sample contains participates  which may
      clog  nebulizers or  interfere  with  injection  of  the sample  into the
      instrument, the sample may be centrifuged, allowed to settle,  or filtered.

                  7.3.6.1   Centrifugation:   Centrifugation at 2,000-3,000 rpm
            for  10 minutes is  usually sufficient to clear  the supernatant.

                  7.3.6.2   Settling:   Allow  the sample  to stand  until the
            supernatant  is  clear.   Allowing a sample  to  stand  overnight will
            usually accomplish this.  If  it does not, centrifuge or filter the
            sample.

                  7.3.6.3    Filtering:    The  filtering  apparatus  must  be
            thoroughly cleaned and prerinsed with dilute (approximately 10% V/V)
            nitric acid.   Filter the sample through   qualitative filter  paper
            into a second acid-cleaned container.

            7.3.7  Dilute the digest  to a known volume ensuring that the samples
      and standards are  matrix matched.   The  digest  is now ready for analysis
      for elements of interest using the appropriate SW-846 method.

      7.4 Calculations:  The concentrations determined  are  to be  reported on the
b  ;s of the actual weight of  the original sample.

8.0  QUALITY CONTROL

      8.1   All  quality  control data must  be maintained and   available for
reference or inspection for a period  of three years.  This  method is restricted
to use  by,  or  under  supervision  of,  experienced  analysts.    Refer to the
appropriate section of Chapter One  for additional quality  control guidance,

      8.2 Duplicate samples should  be processed on a routine basis.  A duplicate
sample is a sample brought through  the whole sample preparation  and analytical
process.  A duplicate sample should be processed with each analytical batch or
every 20 samples, whichever  is  the greater number. A duplicate sample  should be
prepared for each matrix type  (i.e.,  soil, sludge, etc.).

      8.3 Spiked samples or standard  reference materials should be included with
each  group of samples processed or every  20 samples,  whichever  is  the greater
number.   A spiked sample  should also be included whenever a new sample matrix is
being analyzed.

9.0  METHOD PERFORMANCE

      9.1  Precision:   Precision  data for  Method 3051, as  determined  by the
statistical  examination of  inter!aboratory test results, is located in Tables 1
and 2.
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       9.2  Repeatability:  If successive results are obtained by the same analyst
with  the same  apparatus under constant operating conditions on  identical  test
material, then the difference between these successive results will not, with 95%
probability, exceed the repeatability value.  For example, in  the case of lead,
an average of only 1 case  in 20 would exceed

                                    0.206 x

in the long ryn,  where  x is one result  in fjg/g  (Ref.  6).

       9,3  Reproducibility: If two successive measurements are made independently
by each of two different analysts working in different laboratories on identical
test  material, then the difference between  the  average  result for each  analyst
will  not, with 95% probability, exceed the reproducibility value.  For example,
in the case of lead, an average of only 1 case  in 20  would exceed

                                    0.303 x

in the long run,  where  x is the average of  two  successive measurements  in /Aj/g
(Ref.  2).

       As can be seen in Table 1, repeatability and reproducibility differ  between
elements, and usually depend on that element's  concentration.  Table  2 provides
an  example of  how  users  of  the method  can   determine  expected  values  for
repeatability and reproducibility; nominal values of lead have been used for this
model  (Ref. 6).

       9.4  Bias:   In  the case of SRM 1085 - Wear Metals in  Oil, the bias  of this
test  method  is different  for each element.  An  estimate  of bias, as shown in
Table  3, is:

                    Bias = Amount found - Amount expected.

       However,   the  bias  estimate  inherits  both   the  uncertainty  in   the
measurements made  using Method 3051 and the uncertainty on the certificate, so
whether the  bias  is  real or only due to measurement error must also  be con-
sidered.  The concentrations  found  for Al, Cr,  and Cu  using  Method  3051 fall
within their certified ranges on SRM 1085,  and 95%  confidence intervals  for Fe
and Ni overlap with their respective certified ranges; therefore,  the observed
biases for these  elements  are  probably  due  to  chance and should  be  considered
insignificant.  Biases should not be estimated at all for Ag and Pb because these
elements were not  certified.  Therefore,  the  only two elements considered  in this
table  for which the bias estimates are significant  are Mg and Mo.

10.0   REFERENCES

1.     TestMethods for  Evaluating Solid Waste,  Physical/Chemical Methods,  3rd
       ed;  U.S.  Environmental  Protection Agency,  Office  of  Solid  Waste  and
       Emergency Response.   U.S.  Government Printing  Office:   Washington,  DC,
       1986; SW-846.


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2.    Kingston, H. M. and L.  B. Jassie, "Safety Guidelines for Microwave Systems
      in  the  Analytical  Laboratory",    In  Introduction  to  Microwave  Acid
      Decomposition:  Theory and  Practice;  Kingston,  H.  M. and Jassie, L. B.,
      eds.; ACS Professional  Reference Book Series; American  Chemical Society:
      Washington, DC, 1988,

3.    1985 Annual Book  of ASTM Standards. Vol.  11.01; "Standard Specification
      for Reagent Water  ; ASTM, Philadelphia, PA, 1985, D1193-77.

4.    Introduction  to  Microwave  Sample  Preparation:  Theory  and  Practice,
      Kingston, H. H. and Jassie, L. B.,  Eds.; ACS Professional Reference Book
      Series; American Chemical Society:  Washington, DC,  1988.

5.    Kingston,  H.  M.    EPA  IAG  IDWI-393254-01-0 January 1-March  31,  1988,
      quarterly Report.

6.    Binstock, D. A., Yeager, W.  M.,  Grohse,  P.  M. and Cask/ill, A.  Validation
      of a Method for Determining  Elements  in Solid  Waste_by_H1croMave Diges-
      tion, Research  Triangle Institute  Technical  Report  Draft,  RTI  Project
      Number 321U-3579-24,  November,  1989, prepared  for  the Office  of Solid
      Waste, U.S. Environmental Protection Agency, Washington, DC 20450.

7.    Kingston,  H.  M,,  Walter,  P.   J.,  "Comparison  of  Microwave  Versus
      Conventional Dissolution for  Environmental  Applications", Spectroscopy,
      vol. 7 No. 9,20-27,1992.
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                                  TABLE 1.
         EQUATIONS RELATING REPEATABILITY AND REPRODUCIBILITY TO  MEAN
      CONCENTRATION  OF DUPLICATE DETERMINATION WITH 95 PERCENT CONFIDENCE
            Element          Repeatability          Reproducibility
Ag
AT
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Mg
Hn
Mo
Ni
Pb
Sr
V
Zn
0.195X8
0.232X
12. 9b
0.238X
0.082b
0.356X
0.385X
0.291X
0.187X
0.212X
0.257X
0.238X
1.96X1/2C
0.701X
0.212X
0.206X
0.283X
1.03X1/2
3.82X1/2
0.314X
0.444X
22. 6b
0.421X
0.082b
1.27X
0.571X
0.529X
0.195X
0.322X
0.348X
0.399X
4.02X1/2
0.857X
0.390X
0.303X
0.368X
2.23X1/2
7.69X1/2
"Log transformed variable based on one-way analysis of variance.
^Repeatability and reproducibility were independent of concentration.
c$quare root transformed variable based on one-way  analysis  of variance.
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                                   TABLE 2.
                  REPEATABILITY AND REPRODUCIBILITY FOR  LEAD
                                BY METHOD 3051
         Average Value      Repeatability       Reproducibility
               50                10.3                 15.2
              100                20.6                 30,3
              200                41,2                 60.6
              300                61.8                 90.9
              400                82.4               121
              500               103                 152

All results are in ing/Kg
                                   3051  -  12                       Revision  0
                                                                  September 1994

-------
                                   TABLE 3.
           RECOVERY AN0, BIAS DATA  FOR SRH  1085  -  HEAR  HETALS  IN OIL
     Element
 Amount
 Expected
(Certified
  Range)
 Amount
  Found*
(95% Conf
Interval)
Absolute
  Bias
 (w/g)
 Relative
  Bias
(Percent)
Significant
(due to more
than chance)
       Ag
       Al
       Cr
       Cu
       Fe
       Mg
       Mo
       Ni
       Pb
  (291)**
  296±4
  298+5
  295±10
  300+4
  297+3
  292+11
  303±7
  (305)**
All values in mg/Kg
 234116
 295+12
 293110
 28919
 311+14
 270111
 238111
 293+9
 279+8
   -1
   -5
   -6
   + 11
   -27
   -54
   -10
    0
   -2
   _2
   +4
   -9
   -18
   -3
    No
    No
    No
    No
    Yes
    Yes
    No
 *Results taken from table 4-7, Ref. 2.

 **Value not certified,  so  should not be used in bias detection and  estimation,
                                   3051  -  13
                                                   Revision 0
                                                   September 1994


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                                METHOD 3051
(MICROWAVE ASSISTED ACID DIGESTION OF  SEDIMENTS,  SLUDGES,  SOILS, AND OILS)
                                 3051 - 14
Revision 0
Septenter 1994

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                                 METHOD 3510B

                  SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION


1.0   SCOPE AND APPLICATION

      1.1   This method  describes  a  procedure  for isolating organic compounds
from  aqueous  samples.   The  method  also  describes  concentration  techniques
suitable for  preparing  the extract for the  appropriate determinative methods
described in Sec. 4,3 of Chapter Four.

      1.2   This method  is applicable to  the  isolation  and  concentration of
water-insoluble and slightly water-soluble organics in preparation for a variety
of chromatographic procedures.


2.0   SUMMARY OF METHOD

      2.1   A measured volume  of sample, usually 1 liter, at  a specified pH (see
Table 1),  is  serially  extracted with methylene  chloride using  a  separator^
funnel.   The extract is dried, concentrated (if necessary),  and, as necessary,
exchanged into a solvent compatible with the cleanup or determinative method to
be used (see Table 1 for appropriate exchange solvents).


3.0   INTERFERENCES

      3.1   Refer to Method 3500.

      3.2   Under basic extraction  conditions required to  separate analytes for
the packed columns of Method 8250,  the decomposition of some analytes has been
demonstrated.   Organochlorine  pesticides may dechlorinate, phthalate esters may
exchange, and  phenols may react to form tannates.   These  reactions increase with
increasing pH,  and  are decreased  by  the  shorter reaction times  available in
Method 3510.   Methods  3520/8270, 3510/8270, and  3510/8250,  respectively,  are
preferred over Method 3520/8250 for the analysis of these classes of compounds.


4.0   APPARATUS AND MATERIALS

      4.1   Separatory funnel  - 2 liter,  with Teflon stopcock.

      4.2   Drying column  - 20 mm  ID Pyrex chromatographic column  with  Pyrex
glass wool  at  bottom and a Teflon stopcock.

      NOTE:  Fritted  glass  discs are  difficult  to decontaminate  after  highly
            contaminated extracts  have been  passed through.   Columns  without
            frits may be  purchased.   Use a  small  pad of Pyrex  glass  wool  to
            retain the  adsorbent.   Prewash the glass wool  pad with 50  ml of
            acetone followed by 50 mL of elution  solvent  prior to packing the
            column with adsorbent.
                                  3510B  -  1                         Revision 2
                                                                September 1994

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       4.3    Kuderna-Danish  (K-D)  apparatus.

             4.3.1  Concentrator tube - 10 mL, graduated (Kontes K-570050-1025 or
       equivalent).   A ground-glass stopper  is  used to prevent evaporation  of
       extracts.

             4.3.2  Evaporatior    flask  -    500  ml  (Kontes   K-570001-500  or
       equivalent).    Attach  to  concentrator  tube with  springs,  clamps,  or
       equivalent.

             4.3.3  Snyder  column  - Three  ball  macro  (Kontes  K-503000-0121  or
       equivalent).

             4.3.4  Snyder  column  -  Two  ball micro  (Kontes  K-569001-0219  or
       equivalent).

             4.3.5  Springs -   1/2  inch (Kontes K-662750 or equivalent).

       4.4    Boiling chips -  Solvent extracted, approximately 10/40 mesh  (silicon
carbide or  equivalent).

       4.5    Water  bath  -  Heated,  with  concentric  ring  cover,  capable  of
temperature  control  (±5°C).   The bath should be used in a hood.

       4.6    Vials  - 2 ml, glass with Teflon  lined  screw-caps  or crimp tops.

       4.7    pH indicator paper - pH range including the desired extraction pH.

       4.8    Erlenmeyer flask  - 250 ml.

       4.9    Syringe - 5 mL.

       4.10   Graduated cylinder - 1 liter.


5.0    REAGENTS

       5.1    Reagent grade chemicals shall be  used in all  tests. Unless otherwise
indicated, it is intended that all reagents  shall  conform to the specifications
of the Committee on Analytical Reagents  of the American Chemical Society, where
such specifications are available. Other grades may be  used, provided it  is first
ascertained  that the  reagent  is of sufficiently high  purity to permit its use
without lessening the accuracy of the determination.  Reagents  should be stored
in glass to  prevent the leaching of contaminants from plastic  containers.

       5.2    Organic-free reagent water - All  references  to water  in  this method
refer  to organic-free reagent water,  as defined in Chapter One.

       5.3    Sodium  hydroxide  solution  (ION),  NaOH.   Dissolve  40 g  NaOH  in
organic-free reagent water and dilute to 100 ml,

       5,4    Sodium sulfate (granular, anhydrous),  Na2S04,  Purify  by heating  at
400°C for 4 hours in a shallow tray,  or by precleaning the sodium sulfate with


                                  3510B - 2                         Revision 2
                                                                September 1994

-------
methylene chloride.  If the sodium sulfate is precleaned with methylene chloride,
a method blank must be  analyzed, demonstrating that there is no interference from
the  sodium  sulfate.

       5.5    Sulfuric acid solution  (1:1  v/v), H2S04.  Slowly add 50 ml of H2S04
(sp. gr. 1.84}  to  50 ml of organic-free  reagent water.

       5.6    Extraction/exchange  solvents

             5.6.1  Methylene chloride, CH2C12 - Pesticide quality or  equivalent.

             5.6.2  Hexane, C6H14 - Pesticide quality or equivalent.

             5.6.3  2-Propanol,  CH3CH(OH)CH3 - Pesticide quality or equivalent.

             5.6.4  Cyclohexane, CQH12 -  Pesticide quality or equivalent.

             5.6.5  Acetonitrile,  CH3CN -  Pesticide quality or equivalent.


6.0    SAMPLE COLLECTION, PRESERVATION, AND HANDLING

       6.1    See  the introductory material  to this  chapter, Organic Analytes,
Sec. 4.1.


7.0    PROCEDURE

       7.1    Using  a  1  liter  graduated cylinder,  measure  1 liter (nominal)  of
sample  and  transfer  it  quantitatively  to the  separatory  funnel.  If high
concentrations  are anticipated,  a  smaller volume  may be  used and then diluted
with  organic-free  reagent water to  1  liter.   Add  1.0  mL of  the .surrogate
standards  to  all   samples,   spikes,  and   blanks  (see Hethod  3500 and  the
determinative method to be used,  for details on the  surrogate standard solution
and the matrix  spike solution).  For the sample in each analytical  batch selected
for spiking, add 1.0 ml of the matrix spiking standard.  For base/neutral-acid
analysis, the amount added of the surrogates and matrix spiking  compounds  should
result  in a  final  concentration  of  100 ng/jui of each base/neutral  analyte and
200 ng/jiL of each  acid analyte in  the  extract to  be analyzed (assuming a 1 yl
injection).  If Method  3640, Gel-Permeation Cleanup,  is to be used, add twice the
volume of surrogates and matrix spiking compounds since half the extract  is lost
due to  loading of  the  GPC column.

      7.2    Check  the   pH  of  the   sample  with  wide-range pH  paper and,   if
necessary,   adjust   the pH to that indicated  in  Table   1  for the specific
determinative method that will be used to  analyze the extract.

      7.3   Add 60 ml  of methylene  chloride to the separatory funnel.

      7.4    Seal and shake the  separatory funnel  vigorously for 1-2 minutes with
periodic venting to release excess  pressure.
                                   3510B -  3                         Revision 2
                                                                September 1994

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      NOTE: Methylene  chloride  creates   excessive   pressure  very  rapidly;
            therefore, initial  venting should  be  done  immediately  after the
            separatory funnel has been sealed and shaken once.  Venting of the
            separatory funnel should be into a hood to avoid needless exposure
            of the analyst to solvent vapors.

      7.5   Allow the  organic layer to  separate from  the  water phase  for a
minimum of 10 minutes.   If  the  emulsion  interface  between  layers is more than
one-third the  size  of the  solvent  layer,  the analyst  must  employ  mechanical
techniques to complete the phase separation.  The optimum technique depends upon
the sample and may  include  stirring, filtration  of the emulsion through glass
wool, centrifugation, or  other physical methods.  Collect the solvent extract in
an Erlenmeyer flask.   If  the emulsion cannot be broken  (recovery  of < 80% of the
methylene chloride,  corrected for the water solubility of methylene chloride),
transfer the  sample,  solvent, and emulsion  into the  extraction chamber  of a
continuous extractor and  proceed as described in Method 3520, Continuous Liquid-
Liquid Extraction.

      7.6   Repeat the extraction two more times using fresh portions of solvent
(Sees. 7.3 through 7.5).   Combine the three solvent extracts.

      7.7   If further pH adjustment and  extraction is  required, adjust the pH
of the aqueous phase to the desired pH  indicated in Table 1.   Serially extract
three  times  with  60  ml of  methylene  chloride,  as  outlined  in  Sees.  7.3
through 7.5.   Collect  and combine the  extracts  and label the  combined extract
appropriately.

      7.8   If performing SC/MS analysis (Method 8270),  the acid/neutral and base
extracts may be combined  prior to concentration.   However,  in  some situations,
separate concentration and analysis of the acid/neutral  and base  extracts may be
preferable (e.g.  if  for regulatory purposes the presence  or absence of specific
acid/neutral  or base compounds at low concentrations must be determined, separate
extract analyses  may be warranted}.

      7.9   Perform  the  concentration  {if  necessary) using  the  Kuderna-Danish
(K-D) Technique (Sees. 7.10.1 through 7.10.4).

      7.10  K-D Technique

            7.10.1     Assemble  a  Kuderna-Danish   (K-D)    concentrator  by
      attaching a 10 mL  concentrator tube to a 500 ml  evaporation flask.   Dry
      the extract by passing it  through a drying column containing about 10 cm
      of  anhydrous   sodium  sulfate.   Collect  the  dried  extract  in  a  K-D
      concentrator.   Rinse  the  Erlenmeyer  flask, which  contained the solvent
      extract,  with  20-30 mL of  methylene chloride  and  add  it  to the column to
      complete the quantitative  transfer.

            "".10.2     Add one or  two clean  boiling  chips  to the flask and
      attacr,  a three ball Snyder column.   Prewet the Snyder  column  by adding
      about 1  mL  of  methylene  chloride to the top of the  column.  Place the K-D
      apparatus on  a  hot water  bath (15-20°C  above the boiling point  of the
      solvent)  so that the concentrator tube is  partially immersed  in the hot
      water and the entire lower rounded surface of  the flask is  bathed with hot
                                  3510B - 4                         Revision 2
                                                                September 1994

-------
      vapor.   Adjust the  vertical  position  of the  apparatus and  the water
      temperature as required to  complete  the concentration  in 10-20 minutes.
      At the proper rate of distillation the balls of the column will actively
      chatter, but the  chambers  will  not flood.  When  the apparent volume of
      liquid reaches  1  ml,  remove the K-D  apparatus  from the  water bath and
      allow it to drain and cool  for at least 10 minutes.

            7.10.3      If a solvent exchange is required (as  indicated in Table
      I), momentarily  remove the  Snyder column,  add 50 ml of  the exchange
      solvent, a new boiling chip, and  reattach  the Snyder column.  Concentrate
      the extract, as described  in  Sec.  7.11,  raising  the temperature  of the
      water bath, if necessary,  to maintain proper distillation.

            7.10.4      Remove the Snyder  column  and  rinse  the  flask  and its
      lower joints into  the concentrator  tube with 1-2 roL of methylene chloride
      or  exchange  solvent.   If  sulfur  crystals  are a  problem,  proceed  to
      Method 3660 for cleanup.  The extract may be further concentrated by using
      the technique  outlined in  Sec.  7.11 or  adjusted to  10,0 ml with  the
      solvent last used.
               y

      7.11  If further concentration  is indicated in Table 1,  either the micro-
Snyder column technique  (7.11.1) or nitrogen blowdown technique  (7.11.2)  is used
to adjust the extract to the final volume required.

            7.11.1      Micro-Snyder Column Technique

                  7.11.1.1     If  further  concentration is indicated  in Table 1,
            add another clean boiling chip to the concentrator tube and attach
            a two ball micro-Snyder column.  Prewet the column by adding 0.5 ml
            of methylene chloride or exchange  solvent  to the top of the column.
            Place the K-D apparatus in a hot water bath so that the concentrator
            tube is partially immersed in the hot water.  Adjust the vertical
            position  of  the apparatus and the water temperature,  as required, to
            complete the concentration  in 5-10 minutes.   At the proper rate of
            distillation the balls of the column will  actively chatter, but the
            chambers  will not flood.  When the  apparent volume of liquid reaches
            0.5 ml, remove the K-D apparatus from the water bath  and  allow it to
            drain and cool  for at least  10  minutes.   Remove  the Snyder column
            and rinse the flask and its lower joints into the  concentrator tube
            with 0.2  ml  of  extraction solvent.  Adjust the final volume to 1.0-
            2.0 ml,  as indicated  in  Table 1, with solvent.

            7.11.2      Nitrogen  Blowdown Technique

                  7.11.2.1     Place  the concentrator tube in  a warm  bath (35°C)
            and evaporate the solvent volume to  0.5 ml using a gentle stream of
            clean, dry nitrogen {filtered through a column of activated carbon).

                  CAUTION:     New plastic tubing must not be used between the
                              carbon   trap  and  the  sample,   since  it   may
                              introduce interferences.
                                  3510B - 5                         Revision 2
                                                                September 1994

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                  7.11.2.2    The internal wall of the tube must be rinsed down
            several times with methylene chloride or  appropriate solvent during
            the operation.  During evaporation, the tube solvent level must be
            positioned to  avoid water  condensation.   Under normal  procedures,
            the extract must not be allowed to become dry.

                  CAUTION:    When the volume of solvent is reduced below 1 ml,
                              semi volatile analytes may be lost.

      7.12  The extract may now be analyzed  for the  target  analytes  using the
appropriate determinative  technique(s)  (see  Sec.  4.3  of  this Chapter).   If
analysis  of  the   extract  will  not  be  performed  immediately,  stopper  the
concentrator tube and store refrigerated.  If the  extract will be stored longer
than 2 days it should be  transferred  to a vial  with a Teflon lined screw-cap or
crimp top, and labeled appropriately.


8.0   QUALITY CONTROL

      8.1   Any reagent blanks or matrix spike samples  should  be  subjected to
exactly the same analytical procedures as those used  on actual  samples.

      8.2   Refer to  Chapter  One  for specific quality  control  procedures  and
Method 3500 for extraction and sample preparation procedures.


9.0   HETHOD PERFORMANCE

      9.1   Refer to the determinative methods for performance data.


10.0  REFERENCES

1.    U.S. EPA 40 CFR  Part 136, "Guidelines Establishing  Test Procedures for the
      Analysis of Pollutants Under the Clean Water Act; Final  Rule  and Interim
      Final Rule and Proposed Rule,"  October 26, 1984.
                                  3510B  - 6                         Revision 2
                                                                September 1994

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                                                          TABU  1.
                              SPECIFIC  EXTRACTION CONDITIONS  FOR VARIOUS DETERMINATIVE METHODS



Determinative
method
8040
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8140
8141
8250bc
8270bd
8310
8321
8410


Initial
extraction
PH
<2
as received
as received
as received
5-9
5-9
5-9
as received
as received
as received
as received
6-8
as received
>11
<2
as received
as received
as received


Secondary
extraction
PH
none
none
none
none
none
none
none
none
none
none
none
none
none
<2
>11
none
none
none
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
hexane
hexane
none
none
acetonitrile
methanol
methyl ene chloride
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
methylene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
hexane
-
-
-
-
methylene chloride
Volume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
10.0
10.0
-
-
-
-
10.0
Final

extract
volume
for

analysis (ml)
1.0,
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
10.0
10.0
1.0
1.0
1.0
1.0
0.0
10. 08
















(dry)
a  Phenols may be analyzed,  by Method  8040,  using a 1.0 ml 2-propanol extract by GC/FID.   Method 8040 also  contains  an optional
   derivatization procedure for phenols which results in a 10 ml hexane extract to be analyzed by GC/ECD.
b  The specificity of GC/MS may  make  cleanup of the extracts unnecessary.  Refer  to  Method 3600 for guidance on  the cleanup
   procedures available if required.
c  Loss of phthalate esters, organochlorine  pesticides and phenols can occur under these extraction conditions (see  Sec.  3.2).
d  Extraction pH sequence may be reversed to better separate acid and neutral waste components.   Excessive pH adjustments may
   result in the loss of some analytes (see Sec. 3.2).
                                                          3510B - 7
    Revision 2
September 1994

-------
                            METHOD 35106
          SEPARATORY  FUNNEL  LIQUID-LIQUID  EXTRACTION
7.1 Add surrogate
 standards to all
 camples, spikes,
   and blanks.
                                7.7 Collect
                               and combine
                             extracts and label
                                     7.8
                                   GC/MS
                               analysis (Metho
                                 8270} being
                                  performed?
  7.2 Chack
and adjust pH
  7.8 Combine
  base/neutral
 extracts prior
to concentration
   7.3 -  7.6
   Extract 3
    times.
                                 7,9 - 7.11
                                Concentrate
                                  extract.
      7.7
    Further
  extractions
   required?
                                  7.12
                                Ready for
                                analysis.
                             3510B  - 8
                                                                     Revision  2
                                                                September  1994

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                                  METHOD  3520B

                      CONTINUOUS LIQUID-LIQUID EXTRACTION
 1.0    SCOPE AND APPLICATION

       1.1   This  method  describes a procedure for isolating organic  compounds
 from  aqueous  samples.    The method  also describes  concentration techniques
 suitable  for preparing  the  extract  for the  appropriate  determinative  steps
 described  in Sec. 4.3 of  Chapter  Four.

       1.2   This  method  is  applicable  to the isolation  and  concentration of
 water-insoluble and  slightly soluble organics in preparation  for a variety of
 chromatographic procedures.

       1.3   Method 3520 is designed  for extraction solvents with greater density
 than  the  sample.   Continuous extraction  devices  are available for extraction
 solvents that are less dense than the sample.   The analyst  must  demonstrate the
 effectiveness  of  any such automatic  extraction device  before  employing it in
 sample extraction.


 2.0   SUMMARY OF METHOD

      2.1   A  measured  volume of sample, usually 1  liter,  is placed into a
 continuous liquid-liquid  extractor,  adjusted, if necessary,  to a specific pH {see
 Table  1),  and  extracted  with organic solvent  for 18-24  hours.   The extract is
 dried, concentrated {if necessary),  and,  as  necessary, exchanged into  a solvent
 compatible with the cleanup or determinative method being employed  (see Table 1
 for appropriate exchange solvents).


 3.0   INTERFERENCES

      3.1   Refer to Method  3500.

      3.2   Under basic extraction conditions  required to separate analytes for
 the packed columns of Method 8250, the decomposition of some analytes has been
 demonstrated.  Organochlorine pesticides  may dechlorinate,  phthalate esters may
 exchange, and phenols may react to form tannates.   These  reactions increase with
 increasing pH,  and  are decreased by the shorter  reaction times  available  in
 Method 3510.   Methods  3520/8270, 3510/8270,  and  3510/8250,  respectively, are
 preferred over Method 3520/8250 for  the analysis of these classes of compounds,


 4.0   APPARATUS AND MATERIALS

      4.1   Continuous liquid-liquid extractor -  Equipped with Teflon or glass
 connecting joints and stopcocks  requiring no  lubrication  (Kontes 584200-0000,
 584SOO-0000,  583250-0000, or equivalent).

      4.2   Drying column  -  20  mm ID Pyrex chromatographic column  with Pyrex
glass wool  at bottom and  a Teflon stopcock.

                                  3520B  - 1                         Revision 2
                                                                September 1994

-------
      NOTE: Fritted  glass discs  are  difficult to  decontaminate  after  highly
            contaminated  extracts have been passed  through.   Columns without
            frits  may  be purchased.   Use  a small pad  of Pyrex  glass wool  to
            retain  the  adsorbent,  Prewash  the glass wool pad with 50  ml  of
            acetone  followed  by  50 mL of elution solvent prior to packing  the
            column with adsorbent,

      4.3   Kuderna-Danish  (K-D)  apparatus

            4.3.1 Concentrator tube -  10 ml graduated (Kontes K-570050-1025 or
      equivalent).   A  ground glass stopper  is  used  to prevent evaporation  of
      extracts.

            4.3.2 Evaporation  flask   -     500  ml  (Kontes  K-570001-500   or
      equivalent).   Attach to  concentrator  tube with  springs,  clamps,   or
      equivalent.

            4.3.3 Snyder  column  -  Three ball  macro  (Kontes  K-503000-0121  or
      equivalent).

            4.3.4 Snyder  column   -   Two ball  micro  (Kontes  K-569Q01-0219  or
      equivalent).

            4.3.5 Springs -  1/2  inch  (Kontes K-662750 or equivalent).

      4,4   Boiling chips -  Solvent extracted, approximately 10/40  mesh (silicon
carbide or equivalent).

      4.5   Water  bath  -  Heated,  with  concentric  ring  cover,  capable   of
temperature control  (+ 5°C).  The bath should be used in a hood.

      4.6   Vials - 2 mL, glass with Teflon lined screw-caps or crimp tops.

      4.7   pH indicator paper -  pH range including the desired extraction  pH.

      4.8   Heating mantle  - Rheostat controlled.

      4.9   Syringe - 5 ml.


5.0   REAGENTS

      5.1   Reagent grade chemicals shall be used in all  tests. Unless otherwise
indicated, it is intended that all reagents  shall  conform  to the specifications
of the Committee on Analytical  Reagents of the American Chemical Society,  where
such specifications are available. Other grades  may be used, provided it,is first
ascertained that the reagent  is  of sufficiently high  purity to permit its  use
without lessening the accuracy of the determination. Reagents should be stored
in glass to prevent the leaching  of contaminants from plastic containers.

      5.2   Organic-free reagent water -  All  references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
                                   3520B  -  2                         Revision 2
                                                                September 1994

-------
       5.3    Sodium  hydroxide  solution  (ION), NaOH.    Dissolve  40  g  NaOH  in
organic-free reagent water  and dilute to  100  ml.

       5.4    Sodium sulfate  (granular, anhydrous), Na2S04.   Purify  by heating  at
400*0 for 4  hours in a shallow tray, or by precleaning  the sodium  sulfate with
methylene chloride.   If the sodium sulfate  is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium  sulfate,

       5.5    Sulfuric acid solution  (1:1 v/v), H2S04.   Slowly  add  50 ml  of H2S04
(sp. gr, 1.84) to 50 ml of  organic-free reagent water.

       5.6    Extraction/exchange solvents

             5.6.1 Methylene chloride, CH2C12  - Pesticide quality or equivalent.

             5.6.2 Hexane, C6H14 -  Pesticide quality or  equivalent.

             5.6.3 2-Propanol,  (CH3)2CHOH - Pesticide  quality  or equivalent.

             5.6,4 Cyclohexane, C6H12 - Pesticide quality or equivalent.

             5.6.5 Acetonitrile, CH3CN -  Pesticide quality or equivalent.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1    See  the  introductory  material to this chapter,  Organic Analytes,
Sec. 4.1.


7.0   PROCEDURE

      7.1    Using a 1 liter  graduated cylinder, measure out 1  liter  (nominal) of
sample  and  transfer  it quantitatively  to the continuous extractor.   If high
concentrations are anticipated, a smaller volume may  be used and  then diluted
with organic-free reagent water to 1  liter. Check the pH of the sample with wide-
range pH paper and adjust the pH,  if necessary,  to the pH indicated  in Table 1
using  1:1  (V/V)  sulfuric  acid or  10 N sodium hydroxide.   Pipet  1.0 mL of the
surrogate standard spiking solution  into each  sample  into  the extractor and mix
well.  (See Method 3500 and  the determinative  method to  be used, for details on
the surrogate standard  solution and  the  matrix spike solution.)  For the sample
in each analytical batch selected  for spiking, add 1.0 mL  of the matrix spiking
standard.   For base/neutral-acid  analysis,  the  amount of the surrogates  and
matrix  spiking  compounds   added  to  the  sample  should   result   in a  final
concentration of 100 ng/^L  of each  base/neutral  analyte and  200  ng/^L of each
acid analyte in  the  extract to be  analyzed  (assuming  a  1 jtL  injection).   If
Method 3640,  Gel-Permeation Cleanup,  is  to  be used,  add twice the volume  of
surrogates and matrix spiking  compounds since half the extract is lost due to
loading of the GPC column.

      7.2   Add 300-500 mL of methylene chloride  to the distilling, flask.  Add
several boiling chips to the flask.


                                  35208 - 3                          Revision 2
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      7.3   Add sufficient water to the extractor to ensure proper operation and
extract for 18-24 hours.

      7.4   Allow to cool; then detach the boiling flask.   If extraction at a
secondary pH is not required (see Table 1), the extract is dried and concentrated
using one of the techniques referred to in Sec, 7.7.

      7.5   Carefully,  while  stirring, adjust the pH of the aqueous phase to the
second pH  indicated  in Table 1.   Attach  a clean distilling  flask  containing
500 ml of methylene  chloride  to  the continuous extractor.   Extract  for 18-24
hours, allow to cool, and detach  the distilling flask.

      7.6   If performing GC/MS analysis  (Method 8270), the acid/neutral and base
extracts  may be combined prior to  concentration.   However,  in  some  situations,
separate  concentration  and analysis of the acid/neutral  and base extracts may be
preferable (e.g.  if for regulatory purposes the presence or absence of specific
acid/neutral  and  base  compounds  at low  concentrations must be  determined,
separate  extract analyses may be warranted).

      7.7   Perform concentration  (if necessary) using the  Kuderna-Danish (K-D)
Technique (Sees.  7.8.1  through 7.8.4).

      7.8   K-D Technique

            7.8.1  Assemble a Kuderna-Danish (K-D) concentrator  by attaching a 10
      mL  concentrator tube to a 500  mL evaporation flask.    Dry the  extract  by
      passing it through a drying column  containing  about 10 cm of anhydrous
      sodium sulfate.  Collect the dried extract in a K-D concentrator.   Rinse
      the flask which contained the  solvent extract with 20-30 mL  of methylene
      chloride and add  it to  the column  to complete the quantitative transfer.

            7.8.2  Add one or  two clean  boiling  chips  to the  flask  and attach a
      three ball  Snyder column.   Prewet  the Snyder column by adding  about 1  mL
      of  methylene chloride to the top  of the  column.   Place the K-D apparatus
      on  a hot water bath (15-20°C above the  boiling point of the  solvent)  so
      that the concentrator tube is partially immersed in the hot water and the
      entire lower  rounded  surface  of  the flask  is bathed  with  hot  vapor.
      Adjust the  vertical  position of the  apparatus and the  water  temperature,
      as  required, to  complete the  concentration  in 10-20 minutes.   At  the
      proper rate of distillation the balls of the column will actively chatter,
      but the chambers  will  not  flood.   When the apparent volume of  liquid
      reaches 1 ml, remove the K-D apparatus from the water bath and allow it to
      drain and cool for  at  least 10 minutes.   Remove the Snyder  column  and
      rinse the flask and its  lower  joints into the concentrator tube with 1-2
      mL  of extraction  solvent.

            7.8.3  If a  solvent exchange  is required (as indicated  in Table 1),
      momentarily  remove^ the  Snyder  column, add 50  mL  of the exchange solvent,
      a  new  boiling  chip,  and reattach  the  Snyder column.   Concentrate  the
      extract,  as  described in Sec.  7.9, raising the temperature of  the  water
      bath,  if necessary,  to  maintain proper distillation.
                                  3520B - 4                         Revision  2
                                                                September  1994

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            7.8.4 Remove  the  Snyder  column and rinse the  flask and its lower
      joints  into  the concentrator tube with  1-2 ml  of  methylene chloride or
      exchange solvent.   If sulfur crystals are a  problem,  proceed to Method
      3660  for cleanup.   The  extract  may be further concentrated by using the
      techniques outlined  in  Sec.  7.9 or adjusted to  10.0  ml with the solvent
      last  used.

      7.9   If further concentration  is indicated in Table  1, either the micro-
Snyder column technique (7.9.1) or nitrogen blowdown technique  (7.9.2) is used
to adjust the extract to the final volume required.

            7.9.1 Micro-Snyder Column Technique

                  7.9.1.1     Add another one or two clean  boiling chips to the
            concentrator tube and  attach  a two ball miero-Snyder column. _Prewet
            the  column  by  adding 0.5 mL  of  methylene  chloride or  exchange
            solvent to the top of  the  column.   Place the K-D apparatus in a hot
            water bath so  that the concentrator tube  is  partially immersed in
            the hot water.  Adjust the vertical position of the apparatus and
            the water temperature, as  required, to complete  the  concentration in
            5-10 minutes.  At the proper rate of distillation the balls of the
            column will  actively chatter, but the chambers will  not flood.  When
            the  apparent   volume  of  liquid reaches  0.5 mL,  remove  the  K-D
            apparatus from the water  bath and allow  it to drain  and cool for at
            least 10 minutes.  Remove  the Snyder column, rinse the flask and its
            lower joints  into  the concentrator tube with  0.2  ml  of methylene
            chloride or exchange  solvent, and adjust the final  volume to 1.0 to
            2.0 ml, as indicated in Table 1, with  solvent.

            7.9.2 Nitrogen Blowdown Technique

                  7.9.2.1     Place the concentrator tube in  a  warm  bath  (35°C)
            and evaporate the solvent  volume to 0.5  ml using a gentle stream of
            clean,  dry nitrogen (filtered through a column of activated carbon).

                  CAUTION:    New plastic tubing must not  be  used between the
                              carbon   trap  and  the  sample,   since   it  may
                              introduce interferences.

                  7.9.2.2     The  internal  wall of the tube must be rinsed down
            several  times with methylene  chloride or appropriate solvent during
            the operation.  During evaporation, the  tube  solvent level must be
            positioned to  avoid water condensation.   Under normal  procedures,
            the extract must not be allowed to become  dry.

                  CAUTION:    When the volume of solvent is reduced below 1 ml,
                              semivolatile analytes  may  be  lost.

      7.10  The extract may now be analyzed  for the target analytes using the
appropriate determinative  technique(s)   (see  Sec.  4.3 of  this Chapter).   If
analysis  of  the  extract  will  not   be  performed  immediately,  stopper  the
concentrator tube and store refrigerated.   If the extract will be stored longer
                                  3520B  -  5                         Revision 2
                                                                September 1994

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than 2 days it should  be transferred to a vial with a Teflon lined screw-cap or
crimp top, and labeled appropriately.


8.0   QUALITY CONTROL

      3.1   Any reagent  blanks,  matrix spike,  or replicate  samples  should be
subjected to  exactly  the same analytical  procedures  as those  used  on actual
samples.

      8.2   Refer to  Chapter  One for  specific quality  control  procedures and
Method 3500 for extraction and sample-preparation procedures.


9.0   METHOD PERFORMANCE

      9.1   Refer to the determinative methods for performance data.


10.0  REFERENCES

1.    U.S. EPA 40 CFR Part 136, "Guidelines  Establishing  Test Procedures for the
      Analysis of Pollutants Under the Clean Water Act;  Final  Rule and Interim
      Final  Rule and Proposed Rule," October 26,  1984.
                                  3S20B - 6                         Revision 2
                                                                September 1994

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                                                          TABLt  1.
                              SPECIFIC  EXTRACTION CONDITIONS  FOR VARIOUS DETERMINATIVE METHODS



Determinative
method
8040
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8140
8141
8250b'c
8270M
8310
8321
8410


Initial
extraction
pH
<2
as received
as received
as received
5-9
5-9
5-9
as received
as received
as received
as received
6-8
as received
>11
<2
as received
as received
as received


Secondary
extraction
pH
none
none
none
none
none
none
none
none
none
none
none
none
none
<2
>11
none
none
none
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
hexane
hexane
none
none
acetonitrile
methanol
methylene chloride
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
methylene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
hexane
-
-
-
-
methylene chloride
Volume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
10.0
10.0
-
-
-
-
10.0
Final
extract
volume
for
analysis
1.0,10
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
10.0
10.0
1.0
1.0
1.0
1.0




(ml)
.oa
















0.0 (dry)
a  Phenols may be analyzed,  by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID.   Method 8040 also  contains  an optional
   derivatization procedure for phenols which results in a 10 ml hexane extract to be analyzed by GC/ECD.
b  The specificity of GC/MS may make cleanup of the extracts unnecessary.  Refer  to  Method  3600 for guidance on  the cleanup
   procedures available if required.
c  Loss of phthalate  esters, organochlorine pesticides and phenols can occur under these  extraction conditions  (see  Sec. 3.2).
d  If  further  separation of  major  acid  and  neutral  components  is required, Method 3650,  Acid-Base  Partition  Cleanup, is
   recommended.  Reversal of the Method  8270 pH sequence is not recommended  as analyte losses are more  severe under the base first
   continuous extraction (see Sec. 3.2).
                                                          3520B - 7
    Revision 2
September 1994

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                             METHOD  3520B
              CONTINUOUS LIQUID-LIQUID EXTRACTION
     start
^
7
r
1 Add appropriate
surrogate and
matrix spiking
solutions.
                                          7.7 - 7.8
                                     Concentrate extract
7.2 Add methylene
    chloride to ,
  distilling flask.
     7.8.3 Is
     iolvent
     exchange
     required7
     7,8.3 Add
  exchange solvent;
eoncsntntion extract
 7.3 Add reagent
water to extractor
 extract for 18-24
      hours.
    7.9 Further
concentrate extract
   if necessary;
adjust final volume.
 7.5 Adjust pH of
 aqueous phase;
extract for 18-24
 hours with clean
      flask.
7.10 Analyze using
organic techniques.
      7,6
     GC/'MS
    analysis
 {Method 8270)
   performed?
       8000
      Series
     Methods
7.6 Combine acid
 and base/neutral
 extracts prior to
  concentration.
                              3520B -  8
                                    Revision  2
                               September 1994

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                                 METHOD 3540B

                              SOXHLET EXTRACTION
1.0   SCOPE AND APPLICATION
      1,1   Method  3540  is a  procedure  for extracting nonvolatile  and semi-
volatile organic compounds from solids such  as  soils,  sludges, and wastes.  The
Soxhlet extraction process ensures intimate contact of the sample matrix with the
extraction solvent.

      1,2   This method is applicable to the  isolation and concentration of water
insoluble and slightly water  soluble  organics  in  preparation  for a variety of
chromatographic procedures.


2.0   SUMMARY OF METHOD

      2.1   The solid sample is mixed with anhydrous sodium sulfate,  placed in
an extraction thimble or between two plugs of glass wool, and extracted using an
appropriate  solvent  in  a  Soxhlet  extractor.    The  extract  is then  dried,
concentrated  (if  necessary),  and,   as  necessary,  exchanged  into  a  solvent
compatible with the cleanup or determinative step being employed.


3.0   INTERFERENCES

      3.1   Refer to Method 3500.
4.0   APPARATUS AND MATERIALS

      4.1   Soxhlet extractor - 40 m ID, with 500 mL round bottom flask.

      4.2   Drying column  -  20 mm ID Pyrex chromatographic  column  with Pyrex
glass wool  at bottom.

      NOTE: Fritted  glass  discs are difficult  to decontaminate  after highly
            contaminated extracts  have  been  passed through.   Columns  without
            frits nay  be  purchased.   Use a  small  pad of Pyrex glass  wool  to
            retain the  adsorbent.   Prewash the glass  wool  pad with 50 mL  of
            acetone followed by 50 ml of elution  solvent  prior to packing the
            column with adsorbent.

      4.3   Kuderna-Danish (K-D) apparatus

            4.3.1 Concentrator tube - 10 mL, graduated  (Kontes K-57005Q-1Q25 or
      equivalent}.   A  ground glass stopper is used to  prevent evaporation  of
      extracts.

            4.3.2 Evaporation  flask  -    500  mL   (Kontes  K-570001-500  or
      equivalent).  Attach  to  concentrator   tube  with  springs,   clamps,  or
      equivalent.

                                   3540B - 1                         Revision 2
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            4.3.3 Snyder  column  - Three  ball  macro  (Kontes  K-503000-0121 or
      equivalent),
            4.3,4 Snyder  column   -  Two  ball  micro  (Kontes  K-5690Q1-0219 or
      equivalent).
            4.3.5 Springs - 1/2 inch {Kontes K-662750 or equivalent).
      4.4   Boiling chips -  Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
      4.5   Water  bath  -  Heated,  with  concentric  ring  cover,  capable  of
temperature control (± 5°C).  The  bath  should be used in a hood.
      4.6   Vials - Glass, 2 ml capacity,  with Teflon  lined  screw or crimp top.
      4.7   Glass or paper thimble or glass wool - Contaminant free.
      4.8   Heating mantle - Rheostat controlled.
      4.9   Disposable glass pasteur pipet and bulb.
      4.10  Apparatus for determining percent dry weight.
            4.10.1      Oven - Drying.
            4.10.2      Desiccator.
            4.10.3      Crucibles  -  Porcelain or disposable aluminum.
      4.11  Apparatus for grinding
      4.12  Analytical balance -  0.0001 g.
5.0   REAGENTS
      5.1   Reagent grade inorganic chemicals shall  be used in all tests.  Unless
otherwise indicated,  it  is  intended that all  reagents  shall conform  to  the
specifications of the  Committee on Analytical Reagents of the American Chemical
Society, where  such specifications  are available.   Other grades may be used,
provided it  is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening  the accuracy of the determination.
      5.2   Organic-free reagent water. All references to water in this method
refer to organic-free reagent water,  as defined in Chapter One.
      5.3   Sodium sulfate (granular, anhydrous),  Na2S04.  Purify by heating at
400°C for 4  hours in a shallow tray,  or by precleaning the sodium  sulfate with
methylene chloride.  If the sodium  sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no  interference from
the sodium sulfate.
                                  3540B - 2                         Revision 2
                                                                September 1994

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      5.4   Extraction solvents
            5,4.1 Soil/sediment and aqueous  sludge  samples  shall be extracted
      using either of the following solvent systems;
                  5.4.1.1     Acetone/Hexane    (1:1)    (v/v),    CH3COCH3/C6HU.
            Pesticide quality or equivalent.
                  NOTE: This solvent system  has lower  disposal  cost and lower
                        toxicity.
                  5.4.1.2     Methylene     chloride/Acetone    (1:1    v/v),
            CH2C12/CH3COCH3. Pesticide quality or equivalent.
            5.4.2 Other samples shall  be extracted using the following:
                  5.4.2.1     Methylene chloride, CH2C12-  Pesticide quality or
            equivalent.
                  5,4.2.2     Toluene/Methanol   (10:1)   (v/v),   C6H5CH3/CH3OH.
            Pesticide quality or equivalent.
      5.5   Exchange solvents
            5.5.1 Hexane, CSH14.  Pesticide quality or equivalent.
            5.5,2 2-Propanol, (CH3)2CHOH.   Pesticide  quality  or  equivalent.
            5.5.3 Cyclohexane,  CeH12.  Pesticide quality or equivalent.
            5.5.4 Acetonitrile, CH3CN.   Pesticide quality  or equivalent.

6.0   SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING
      6.1   See the introductory material  to this chapter, Organic Analysis, Sec.
4.1.

7.0   PROCEDURE
      7.1   Sample Handling
            7.1.1 Sediment/soil samples  - Decant and  discard  any  water layer on
      a sediment sample.  Mix sample thoroughly, especially composited samples.
      Discard any foreign objects such  as sticks, leaves,  and rocks.
            7.1.2 Waste  samples  -  Samples consisting  of  multiphases  must  be
      prepared by the phase  separation method  in Chapter Two before extraction.
      This procedure is for solids  only.
            7.1.3 Dry waste samples amenable  to  grinding  -  Grind or otherwise
      subdivide the waste so that it either passes through a 1 mm sieve or can
                                  3540B  -  3                         Revision 2
                                                                September 1994

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      be  extruded  through a 1 mm hole.   Introduce sufficient sample into the
      grinding apparatus  to yield at least 10 g after grinding.

            7.1.4  Gummy,  fibrous,  or oily materials not  amenable to grinding
      should  be  cut,  shredded,  or otherwise broken  up to  allow mixing,  and
      maximum exposure of the sample surfaces for  extraction.  The professional
      judgment of the analyst  is  required for handling these difficult matrices,

      7.2   Determination  of  sample % dry  weight - In certain  cases,  sample
results are desired  based on  dry weight  basis.   When such data are desired, a
portion of sample for this determination  should  be weighed out at  the same time
as the portion used  for analytical determination.

      HARMING:    The  drying  oven  should  be contained in  a hood  or  vented.
                  Significant laboratory  contamination may result from a heavily
                  contaminated hazardous waste sample.

      However, samples known or suspected to  contain significant concentrations
of toxic, flammable, or explosive constituents should not be oven dried because
of concerns for personal  safety.  Laboratory discretion is advised.  It may be
prudent to delay oven drying of  the weighed-out portion until other analytical
results are available.

            7,2.1  Immediately after weighing  the sample for extraction, weigh 5-
      10 g of the sample  into, a  tared crucible.   Determine the % dry weight of
      the sample by  drying  overnight  at  105°C.  Allow  to  cool  in a desiccator
      before weighing:

            % dry weight  = q of  dry sample x 100
                             g of sample

      7.3   Blend 10 g of  the  solid sample with 10 g of anhydrous sodium sulfate
and place in an extraction thimble.  The extraction thimble  must drain freely for
the duration of the  extraction  period.   A glass  wool  plug above and below the
sample in the Soxhlet  extractor  is  an  acceptable  alternative for the thimble.
Add 1.0 ml of the surrogate standard spiking solution onto the  sample {see Method
3500 for details on  the surrogate standard and matrix spiking solutions).   For
the sample in  each  analytical batch selected for spiking,  add  1.0  ml  of  the
matrix spiking standard.  For base/neutral-acid analysis, the amount added of the
surrogates and matrix spiking compounds should result in a final concentration
of 100 ng/^iL of each base/neutral analyte and 200  ng/jiL  of each acid analyte in
the extract to be  analyzed  (assuming  a 1 #L  injection).   If Method  3640,  Gel
Permeation Chromatography Cleanup, is to be used,  add  twice  the  volume  of
surrogates and matrix spiking compounds  since half the  extract  is lost  due to
loading of the GPC column.

      7.4   Place approximately 300  mL of the extraction solvent  (Sec. 5.4)  into
a 500 ml  round bottom flask containing one or two clean boiling chips.   Attach
the flask to the  extractor  and extract the sample for  16-24  hours at  4-6
cycles/hr.

      7.5   Allow the extract to cool  after the  extraction is complete.
                                   3540B  - 4                         Revision 2
                                                                September 1994

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      7.6   Assemble  a Kuderna-Danish  (K-D)  concentrator  (if  necessary)  by
attaching a 10 mi concentrator tube to a 500 ml evaporation flask.

      7,7   Dry  the  extract by passing it through  a drying column containing
about 10 cm  of anhydrous  sodium sulfate.  Collect  the  dried  extract in a K-D
concentrator.  Wash the extractor flask and sodium  sulfate column with 100 to 125
ml of extraction solvent to complete the quantitative transfer.

      7.8   Add one or two clean boiling chips to the flask and attach a three
ball Snyder column.  Prewet the Snyder  column by adding  about 1 ml of methylene
chloride to the top of the column.   Place  the K-D  apparatus  on a hot water bath
(15-20°C above the boiling point of the solvent)  so that the concentrator tube
is partially immersed  in the hot water and the entire lower rounded surface of
the  flask  is  bathed  with  hot  vapor.    Adjust the  vertical  position  of  the
apparatus and the water temperature,  as required,  to complete the concentration
in 10-20 minutes.  At  the  proper rate  of  distillation the balls of the column
will actively chatter,  but the chambers  will not flood.  When  the apparent volume
of liquid reaches 1-2 ml, remove the K-D apparatus from the water bath and allow
it to drain and cool for at least 10 minutes.

      7.9   If  a solvent  exchange  is  required  (as indicated  in Table  1),
momentarily remove the Snyder  column,  add  approximately 50  ml  of the exchange
solvent and a new boiling chip, and reattach the Snyder column.  Concentrate the
extract as described in Sec. 7.8, raising  the temperature  of the water bath, if
necessary,  to  maintain proper distillation.   When the apparent  volume again
reaches 1-2 ml,  remove the  K-D  apparatus  from  the water batch  and allow it to
drain and cool for at least 10 minutes.

      7.10   Remove the Snyder column and rinse the flask and its lower joints
into the concentrator tube with 1-2 ml of methylene chloride or exchange solvent.
If sulfur  crystals  are a  problem,  proceed to Method  3660  for cleanup.   The
extract may be further concentrated by using the  techniques described  in Sec.
7.11 or adjusted to 10.0 ml with the solvent last used.

      7.11   If further concentration is  indicated in Table 1,  either micro Snyder
column technique (Sec. 7.11.1) or nitrogen blowdown technique (Sec. 7.11.2)  is
used to adjust the extract to the final  volume  required.

            7.11.1       Micro Snyder Column Technique

                  7.11,1.1     Add another  one or two  clean boiling chips to the
            concentrator tube  and attach a two ball micro Snyder column.  Prewet
            the column by  adding about 0.5 ml of methylene chloride or exchange
            solvent to the  top of the column.  Place the K-D apparatus in a hot
            water bath so that the concentrator tube  is partially  immersed in
            the hot water.  Adjust the vertical position  of the  apparatus  and
            the water temperature, as required,  to  complete the concentration in
            5-10 minutes.   At  the proper  rate of  distillation  the balls of the
            column  will actively chatter, but the  chambers will not flood.  When
            the  apparent  volume of  liquid  reaches 0.5  ml,   remove  the  K-D
            apparatus from the water bath  and allow it to drain and cool for at
            least 10 minutes.   Remove the Snyder column and rinse the flask and
            its  lower  joints  with  about  0.2  ml  of  solvent  and  add  to  the


                                  3540B - 5                         Revision 2
                                                                September 1994

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            concentrator  tube.    Adjust  the  final  volume to  1.0-2.0  mL,  as
            indicated in Table 1, with solvent.

            7.11.2      Nitrogen Slowdown Technique

                  7.11.2.1    Place the concentrator tube in  a warm water bath
            {approximately  35°C)  and  evaporate  the  solvent  volume   to  the
            required  level  using  a  gentle  stream  of  clean,  dry  nitrogen
            (filtered through a column of activated carbon).

                  CAUTION:    Do not use plasticized tubing between the carbon
                              trap and the sample.

                  7.11.2.2    The internal  wall  of the  tube must be rinsed down
            several times  with  the  appropriate solvent during  the operation.
            During evaporation,  the  solvent level in the tube must be positioned
            to prevent water from condensing  into  the sample (i.e., the solvent
            level should be below the level  of  the water  bath).   Under normal
            operating conditions, the extract should not  be  allowed  to become
            dry.

                  CAUTION:    When the volume of solvent is reduced below 1 ml,
                              semi volatile analytes may be lost.

      7.12  The extracts obtained may now  be analyzed  for the  target analytes
using the appropriate organic technique(s)  (see Sec. 4.3 of this  Chapter).  If
analysis  of  the extract  will  not  be  performed immediately,  stopper  the
concentrator tube and store in a  refrigerator.  If the extract will  be stored
longer than 2  days,  it should be transferred to a vial with a Teflon lined screw
cap or crimp top, and labeled appropriately.


8.0   QUALITY CONTROL

      8.1   Any reagent blanks or matrix spike  samples should  be  subjected to
exactly the same analytical procedures as those used on actual  samples.

      8.2   Refer to Chapter  One for specific  quality  control procedures and
Method 3500 for extraction and sample preparation  procedures.


9.0   METHOD PERFORMANCE

      9.1   Refer to the determinative methods for performance  data.


10.0  REFERENCES

1.     U.S. EPA 40 CFR Part 136, "Guidelines  Establishing Test Procedures for the
      Analysis of Pollutants Under the Clean  Water Act; Final  Rule and Interim
      Final Rule and Proposed Rule," October  26, 1984.
                                  3540B  - 6                         Revision 2
                                                                September 1994

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                                                  TABU 1.
                      SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040"
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8140
8141
8250"'c
8270a'c
8310
8321
8410
Extraction
PH
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
hexane
hexane
none
none
acetonitrile
methanol
methyl ene chloride
Exchange Volume
solvent of extract
required required
for for
cleanup cleanup (ml)
hexane
hexane
hexane
methylene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
hexane
--
--
--
--
methylene chloride
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
10.0
10.0
--
--
--
--
10.0
Final
extract
volume
for
analysis (ml)
1.0, 10. Ob
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
10.0
10.0
1.0
1.0
1.0
1.0
0.0 (dry)
8 To obtain separate acid and base/neutral extracts, Method 3650 should be performed following concentration
  of the extract to 10.0 ml.

b Phenols may be analyzed by Method 8040 using a 1.0 ml 2-propanol extract and analysis by  GC/FID.  Method 8040
  also contains an optical derivatization procedure for  phenols  which  results  in  a  10 ml  hexane extract to be
  analyzed by GC/ECD.

  The specificity of GC/MS may make  cleanup  of  the  extracts  unnecessary.
  on the cleanup procedures available if required.
Refer to Method 3600 for guidance
                                                  3540B -  7
                       Revision 2
                   September  1994

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                                           METHOD 3540B
                                       SOXHLET  EXTRACTION
        7.1
   Use appropriate
   sample handling
      technique
        7.2
 Determine sample %
     dry weight
       7.3
  Add appropriate
surrogate and matrix
 spiking standards
       7.4
   Add extraction
  solvent to flask:
 extract for 16-24
      hours
       7.5
   Cool extract
       7.6
  Assemble K-D
   concentrator
        7.7
   Dry and collect
   extract in K-D
   concentrator
        7,8
  Concentrate using
   Sryder column
 and K-D apparatus
       7.9
     Is servant
exchange required?
                           T.12
                       Analyze using
                     organic techniques
 Proceed
toMetfwd
 3660 far
 deanup
 8000
 Series
Methods
       7.9
   Add exchange
     solvent,
reogncentrate extract
                                             35408 -  8
                                                              Revision  2
                                                         September  1994

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                                  METHOD 3541

                         AUTOMATED SOXHLET EXTRACTION
 1.0   SCOPE AND APPLICATION

      1.1   Method 3541 describes the extraction of organic  analytes from soil,
 sediment, sludges, and waste solids.  The method uses a commercially available,
 unique, three stage extraction system to achieve analyte recovery comparable to
 Method 3540, but in a much  shorter time.  There are two differences between this
 extraction method  and  Method  3540.   In the initial extraction stage of Method
 3541, the sample-loaded extraction thimble is immersed into the boiling solvent.
 This ensures very  rapid intimate contact between the specimen and solvent and
 rapid extraction of  the organic  analytes.  In the second  stage the thimble is
 elevated above the  solvent, and  is  rinse-extracted as  in  Method 3540.   In the
 third stage, the  solvent is evaporated,  as would  occur  in  the Kuderna-Danish
 (K-D) concentration step in Method 3540.  The concentrated  extract is then ready
 for cleanup (Method 3600) followed  by measurement of the organic analytes.

      1.2   The method is applicable to the extraction and concentration of water
 insoluble  or  slightly  water  soluble  polychlorinated  biphenyls  (PCBs)  in
 preparation for gas  chromatographic determination using either Method  8080 or
 8081.   This method is applicable to  soils, clays,  solid  wastes and sediments
 containing from 1 to 50 ^g of PCBs  (measured as Arochlors) per gram of sample.
 It has been statistically evaluated  at 5 and 50 Mi/9 of Arochlors 1254 and 1260,
 and  found to  be  equivalent  to Method  3540  (Soxhlet Extraction).    Higher
 concentrations of PCBs  are measured following volumetric dilution with hexane.

      1.3   The method  is  also  applicable the extraction  and concentration of
 semivolatile organics  in preparation for GC/MS analysis by  Method  8270  or by
 analysis using specific GC or HPLC  methods.


 2.0   SUMMARY OF METHOD

      2.1   PCBs:  Moist solid samples (e.g., soil/sediment samples) may be air-
dried and ground prior to extraction or chemically dried with anhydrous sodium
 sulfate.  The prepared  sample is  extracted using 1:1 (v/v) acetone:hexane in the
automated Soxhlet  following the same  procedure as outlined  for  semivolatile
organics in Sec.  2.1.  The  extract is  then concentrated and exchanged into pure
hexane prior to final gas chromatographic PCB measurement.

      2.2   Other semivolatile organics:  A 10-g solid sample (the sample is pre-
mixed with  anhydrous  sodium  sulfate for certain matrices)  is placed  in  an
extraction thimble and usually extracted with  50 ml of 1:1 (v/v) acetone/hexane
for 60 minutes in the  boiling extraction  solvent.   The  thimble with sample is
then raised into the rinse  position  and  extracted  for an additional 60 minutes.
 Following the extraction steps,   the extraction solvent is  concentrated to 1 to
2 ml.
                                   3541 - 1                         Revision 0
                                                                September 1994
                                       \

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3.0    INTERFERENCES

       3.1   Refer to Method 3500.

       3.2   The extraction thimble and the o-rings used to seal the extraction
cup  are  both  a  source  of interference.   Both should be checked by including a
method blank and following the extraction procedure as written.  Solvent rinsing
or   extraction,  prior  to  use,  may  be  necessary   to  eliminate  or  reduce
interferences.   Viton  seals  contributed  least  to the  interference  problem,
however,  even they  contributed some  interference  peaks when  the  extraction
solvent  was analyzed by the electron capture detector.  Use  of butyl or EPDM
rings  are not  recommended since  they were  found to  contribute significant
background when  the  extraction  solvent was  1:1  v/v  hexane/acetone  or 1:1 v/v
methylene chloride/acetone.


4.0   APPARATUS AND MATERIALS

      4.1   Automated Soxhlet Extraction System - with temperature-controlled oil
bath (Soxtec,  or equivalent).  Tecator bath oil (catalog number 1000-1886) should
be used with the Soxtec.  Silicone oil  must not be used because it destroys the
rubber parts.  See Figure 1.  The apparatus is used in a hood.

      4.2   Accessories and consumables for the automated Soxhlet  system.  {The
catalog  numbers  are  Fisher Scientific  based on the  use of the  Soxtec  HT-6,
however, other sources that are equivalent are acceptable.)

            4.2.1  Cellulose  extraction   thimbles  -  26  mm   ID  x  60  mm
      contamination free, catalog number 1522-0034, or equivalent.

            4.2.2  Glass  extraction cups (80 ml)  -  (set of  six required for the
      HT-6), catalog number 1000-1820.

            4.2.3  Thimble  adapters  -  (set   of  six  required  for the  HT-6),
      catalog number 1000-1466.

            4.2.4  Viton  seals  -  catalog number  1000-2516.

      4.3   Syringes - 100 and  1000 ^i and 5 ml.

      4.4   Apparatus for Determining Percent Dry Weight

            4.4.1  Drying Oven.

            4.4.2  Desiccator.

            4.4.3  Crucibles, porcelain.

            4.4.4  Balance, analytical.

      4.5   Apparatus for grinding -  Fisher Cyclotec,  Fisher Scientific catalog
number 1093, or equivalent.
                                   3541 - 2                         Revision 0
                                                                September 1994

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      4.6   Spatula
      4.7   Graduated cylinder - 100 ml,
      4.8   Aluminum weighing dish - VWR Scientific  catalog number 25433-008 or
equivalent,
      4,9   Graduated, conical-bottom glass tubes - 15 mL,  Kimble catalog number
45166 or equivalent, or 10 ml KD concentrator tube.

5.0   REAGENTS
      5.1   Reagent grade chemicals shall be used in  all  tests. Unless otherwise
indicated, it is intended that all  reagents shall conform  to the  specifications
of the Committee on Analytical Reagents of  the American  Chemical  Society, where
such specifications are available. Other grades may be used, provided it  is first
ascertained that the reagent  is  of sufficiently high  purity  to permit its use
without lessening the accuracy of the determination.
      5.2   Organic-free reagent water.  All  references  to water  in this method
refer to organic-free reagent water, as defined in Chapter One.
      5.3   Sodium sulfate (granular, anhydrous),  Na2S04.  Purify by heating at
4QQ°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride.  A method blank must be analyzed,  demonstrating that there
is no interference from the sodium sulfate.
      5.4   Extraction solvents:
            5.4.1  Organochlorine  pesticides/PCB extraction:
                   5.4.1.1    Acetone/hexane    (1:1    v/v),     CH3COCH3/C6H14.
            Pesticide quality or equivalent.
            5.4.2  Semi volatile  organics extraction:
                   5.4.2.1    Acetone/hexane    (1:1    v/v),     CH3COCH3/C6H14.
            Pesticide quality or equivalent.
                   5.4.2,2    Acetone/methyline    chloride    (1:1    v/v),
            CH3COCH3/CH2C12.  Pesticide quality or equivalent.
      5.5   Hexane, C6H14.  Pesticide quality or equivalent.

6.0   SAMPLE COLLECTION,  PRESERVATION, AND HANDLING
      6.1   See the  introductory material  to this  chapter,  Organic Analytes,
Sec. 4.1.
                                   3541 - 3                         Revision 0
                                                                September 1994

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7.0   PROCEDURE

      7.1   Sample handling

            7.1.1  Sediment/soil  samples  -  Decant and discard any water layer
      on  a sediment  sample.   Mix  sample  thoroughly,  especially composited
      samples.  Discard any  foreign objects such as s:icks, leaves, and rocks.

                   7.1.1.1    PCBs or high-boiling organochlorine pesticides -
            Air-dry the sample at room temperature for 48 hours  in  a glass tray
            or on hexane-cleaned aluminum  foil, or dry the sample by mixing with
            anhydrous  sodiui sulfate until  a free-flowing  powder  is obtained
            (see Sec. 7.2).

                   NOTE:      Dry, finely ground soil/sediment allows the best
                              extraction efficiency for non-volatile, non-polar
                              organics, e.g., PCBs, 4,4'-DDT, etc.   Air-drying
                              is not appropriate  for  the analysis  of the more
                              volatile  organochlorine  pesticides   (e.g.  the
                              BHCs) or  the  more volatile of  the semivolatile
                              organics  because  of  losses  during  the  drying
                              process.

            7.1.2  Dried  sediment/soil  and  dry   waste  samples  amenable  to
      grinding - Grind or otherwise subdivide the waste so that it either passes
      through a 1 mm  sieve or can  be  extruded through a 1 mm hole.  Introduce
      sufficient sample into  the grinding apparatus to yield  at least 20 g after
      grinding.     Disassemble   grinder   between   samples,   according   to
      manufacturer's  instructions, and clean with  soap and  water,  followed by
      acetone and hexane rinses.

            NOTE:  The same warning on loss  of volatile analytes applies to the
                   grinding  process.   Grinding  should  only  be  performed when
                   analyzing for non-volatile organics.

            7.1.3  Gummy, fibrous, or  oily  materials  not amenable  to grinding
      should  be  cut,  shredded, or  otherwise broken  up to allow  mixing,  and
      maximum exposure of the sample  surfaces for extraction.   If  grinding of
      these materials is preferred, the  addition and mixing of anhydrous sodium
      sulfate  with  the  sample  (1:1) may improve  grinding  efficiency.   The
      professional judgment   of  the  analyst  is  required  for  handling  such
      difficult matrices.

            7.1.4  Multiple phase waste samples - Samples consisting of multiple
      phases  must be  prepared by the  phase separation method  in  Chapter  Two
      before extraction.  This procedure is for solids only.

      7.2   For sediment/soil (especially gummy clay)  that is moist and cannot
be air-dried because of loss of volatile analytes  - Mix 5 g of sample with 5 g
of anhydrous sodium sulfate in a small  beaker using a spatula.  Use this approach
for any solid  sample  that requires  dispersion of the sample particles to ensure
greater solvent contact throughout the sample mass.
                                   3541 - 4                         Revision 0
                                                                September 1994

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       7.3   Determination of sample percent dry weight -  In certain cases, sample
 results  are desired  based  on dry weight basis.   When such data  are  desired,  a
 portion  of sample for this determination should be weighed out at the same  time
 as the portion  used  for  analytical  determination,

       WARNING:      The drying oven  should  be contained  in  a hood  or  vented.
                    Significant  laboratory  contamination may  result from  the
                    drying  of a  heavily contaminated hazardous waste  sample.

            7.3.1   Immediately  after weighing the  sample for extraction, weigh
       5-10 g of the sample  into  a tared  crucible.  Determine the % dry weight of
       the sample  by  drying overnight at 105°C.   Allow to cool in a  desiccator
       before weighing:

            % dry weight •= q of dry  sample x  100
                              g of  sample

       7.4   Check the heating oil level  in the automated  Soxhlet unit and add oil
 if needed.  See service manual  for details.   Set  the temperature  on the  service
 unit at  140°C  when using hexane-acetone (1:1, v/v) as the extraction solvent.

       7.5   Press the "MAINS" button; observe that the switch lamp is now "ON".

       7.6   Open the cold water tap for the  reflux condensers.  Adjust the  flow
 to 2 L/niin to prevent solvent loss through the condensers.

       7.7   Weigh 10 g  of  sample  into extraction thimbles.  For  samples mixed
 with anhydrous sodium sulfate,  transfer the  entire contents of the beaker (Sec.
 7.2)  to  the  thimble.    Add  surrogate  spikes to  each  sample and  the matrix
 spike/matrix spike duplicate to the  selected  sample.

      NOTE: When  surrogate  spikes   and/or  matrix  spikes contain   relatively
            volatile compounds (e.g., trichlorobenzenes,  BHCs, etc.),  steps  7.8,
            7.9, and 7.10 must be performed  quickly to avoid  evaporation losses
            of these compounds.   As the spike is  added to the sample in  each
            thimble,  the  thimble  should  immediately  be  transferred  to   the
            condenser and lowered into  the extraction solvent.

      7.8   Immediately transfer the thimbles containing  the weighed samples  into
 the condensers.  Raise the  knob  to the "BOILING"  position.  The magnet will  now
 fasten to the thimble.  Lower the knob  to the "RINSING"  position.  The thimble
will now hang just below the condenser  valve.

      7.9   Insert the extraction cups  containing  boiling chips,  and  load  each
with 50 ml of  extraction solvent  (normally  1:1  (v/v) hexane  .-acetone, see  Sec.
 5.4).  Using the cup holder,  lower  the locking handle, ensuring that  the safety
 catch engages.  The  cups  are now clamped Into position.  (The  seals must  be  pre-
 rinsed or pre-extracted with extraction solvent prior to initial  use.)

      7.10  Move the extraction knobs to the  "BOILING"  position.  The thimbles
 are now immersed in solvent.  Set the timer for 60 minutes.  The condenser valves
must be in the "OPEN" position.   Extract for  the preset  time.
                                   3541 - 5                         Revision 0
                                                                September 1994

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       7.11   Move  the  extraction  knobs  to  the  "RINSING" position.  The  thimbles
will  now  hang  above the  solvent  surface.   Set  timer for  60 minutes.  Condenser
valves are  still  open.   Extract  for  the preset time.

       7.12   After rinse  time has elapsed,  close the condenser valves by turning
each  a quarter-turn,  clockwise.

       7.13   When  all  but 2 to  5 ml  of solvent have  been collected,  open the
system and  remove the cups.

       7.14   Transfer  the contents of  the cups to 15 ml  graduated, conical-bottom
glass tubes.   Rinse the  cups using hexane  {methylene  chloride if 1:1 methylene
chloride-acetone  was  used for extraction  and analysis is  by  GC/MS) and  add the
rinsates  to the glass tubes.  Concentrate  the extracts to 1 to 10 ml.  The final
volume is dependent  on  the determinative  method and the  quantitation limit
required.   Transfer a portion to a GC  vial  and store  at  4°C  until  analyses are
performed.

       NOTE:         The  recovery solvent  volume   can be  adjusted  by adding
                    solvent  at the top of  the condensers.    For  more   details
                    concerning  use of  the  extractor,  see the operating manual
                    for the  automated extraction system.

       7.15          Shutdown

             7.15.1       Turn "OFF" main switch.

             7.15.2       Turn "OFF" cold water  tap.

             7.15.3       Ensure that  all condensers are free  of solvent.  Empty
       the solvent that is recovered in  the evaporation step into an appropriate
       storage  container.

       7.16   The extract  is now ready for cleanup or analysis, depending on the
extent  of interfering co-extractives.  See Method 3600 for guidance on cleanup
methods and Method 8000 for guidance  on determinative  methods,.  Certain cleanup
and/or  determinative  methods  may require a solvent exchange prior  to  cleanup
and/or determination.


8.0    QUALITY  CONTROL

      8.1    Refer to  Chapter One for general quality  control  procedures and to
Method 3500  for specific extraction and sample preparation QC procedures.

      8.2    Before processing any samples,  the analyst should demonstrate through
the analysis of an organic-free  solid matrix (e.g., reagent  sand)  method blank
that  all  glassware  and  reagents are  interference-free.    Each  time a set of
samples is  extracted, or when there is  a change  in  reagents,  a  method blank
should be processed as a safeguard against chronic laboratory contamination.  The
blank samples should be carried through all stages  of the  sample preparation and
measurement.   This  is  especially  important  because of  the  possibility  of
interferences  being extracted from the extraction cup seal.


                                   3541 - 6                         Revision 0
                                                                September 1994
   \

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       8.3   Standard quality assurance practices should be used with this method.
Field  duplicates  should  be  collected  to  validate the precision of  the  sampling
technique.   Each  analysis batch of 20 or  less  samples must contain:  a method
blank,  either a  matrix  spike/matrix  spike duplicate  or a matrix  spike  and
duplicate  sample  analysis,  and  a  laboratory  control  sample,  unless   the
determinative  method  provides  other  guidance.   Also,  routinely  check  the
integrity of the  instrument  seals.

       8.4   Surrogate  standards  must  be  added to all samples when  specified in
the appropriate determinative method.


9.0    METHOD PERFORMANCE

       9,1   Multi-laboratory accuracy and precision data were obtained  for PCBs
in soil.  Eight laboratories spiked Arochlors 1254  and  1260  into three  portions
of 10  g  of  Fuller's  Earth on three non-consecutive days followed by immediate
extraction using Method  3541.  Six of  the laboratories  spiked each Arochlor at
5 and  50 mg/kg and two laboratories  spiked each Arochlor at 50 and 500 mg/kg.
All extracts were  analyzed by Oak Ridge National Laboratory, Oak Ridge, TN, using
Method 8081.  These data are listed  in a table  found in Method 8081,  and were
taken  from Reference 1.

       9.2   Single-laboratory  accuracy  data were  obtained  for  chlorinated
hydrocarbons, nitroaromatics, haloethers, and organochlorine pesticides in a clay
soil.  The  spiking concentrations  ranged from 500  to 5000 M9/kg,  depending  on
the sensitivity of the analyte  to  the electron  capture detector.   The spiking
solution was mixed into the soil  during addition and then immediately transferred
to the extraction device  and immersed  in  the  extraction solvent.   The data
represents  a  single  determination.    Analysis  was  by capillary column   gas
chroraatography/electron   capture  detector  following   Methods  8081   for   the
organochlorine  pesticides,   8091   for  the  nitroaromatics,  8111   for   the
hydrocarbons, and 8121 for the chlorinated  hydrocarbons.  These data are listed
in a table located in  their respective methods and  were  taken from Reference  2,

      9,3.  Single-laboratory  accuracy and precision  data  were  obtained   for
semivolatile organics  in soil by spiking  at a  concentration of 6 mg/kg  for each
compound.  The spiking  solution was mixed into the soil  during addition  and then
allowed  to  equilibrate  for approximately  1  hr prior  to extraction.   Three
determinations  were   performed  and  each  extract  was  analyzed   by   gas
chromatography/mass spectroroetry following  Method 8270.  The low recovery of  the
more  volatile compounds  1s  probably  due  to   volatilization  losses  during
equilibration.  These  data are listed  in a Table  located in Method 8270  and were
taken from Reference 2.
10.0  REFERENCES

1.    Stewart,  J.    "Intra-Laboratory Recovery  Data for  the  PCB  Extraction
      Procedure";  Oak Ridge National  Laboratory,  Oak Ridge,  TN,  37831-6138;
      October 1989.
                                   3541 - 7                         Revision 0
                                                                September 1994


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2.    Lopez-Avila,  V.  (Beckert,  W., Project Officer), "Development of a Soxtec
      Extraction Procedure  for Extracting  Organic  Compounds  from  Soils  and
      Sediments",  EPA 600/X-91/140,  US EPA, Environmental  Monitoring Systems
      Laboratory-Las Vegas,  October 1991.
                                  3541 - 8                          Revision 0
                                                                September 1994

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             Figure 1
Automated Soxhlet  Extraction  System
          Condenser
            Thimble


        Glass Wool Plug

            Sample


    Aluminum beaker (cup)
           Hot plate
             3541  - 9
    Revision 0
September 1994

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                              METHOD 3541
                     AUTOMATED SOXHLET EXTRACTION
       Start
       7.1
  Use appropriate
  sample handling
    technique.
       7.2
 Add anhydrous
    necessary
       7.3
Determine percent
   dry weight.
       7.4
    Check oil
     level in
   Soxhlet unit.
    ©
        7.5
   Press "Mains"
      button.
        7.6
  Open Cold water
  tap.  Adjust flow.
        7.7
 Weigh sample into
 extraction thimbles.
   Add surrogate
       spike.
        7.8
 Transfer samples
 into condensers.
 Adjust position of
magnet and thimble.
        7.9
  Insert extraction
   cups and toad
    with solvent.
                                  7.10
                             Move extraction
                                knobs to
                              "Boiling" for
                                60 mins.
                                 ©
                                 3S41 -  10
       7.11
  Move extraction
     knobs to
   "Rinsing" for
     60 mins.
                                    7.12
                                   Close
                              condenser valves.
                                                               I
      7.13
  Remove cups.
      7.14
Transfer contents
   to collection
  vials, dilute or
  concentrate to
     volume.
7.15
Shutdown
i
t
                                   Stop
                                          Rtvlsion 0
                                     September 1994

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                                 METHOD 3550A

                             ULTRASONIC EXTRACTION


See DISCLAIMER-1.  See manufacturer's specifications for operational settings.


1.0   SCOPE AND APPLICATION

      1.1   Method 3550  is a  procedure  for extracting  nonvolatile  and semi-
volatile organic compounds from solids such as  soils, sludges, and wastes.  The
ultrasonic  process  ensures  intimate  contact  of the  sample matrix with  the
extraction solvent.

      1.2   The  method  is divided  into two sections,  based on  the expected
concentration  of organics  in  the  sample.    The  low  concentration  method
(individual organic components of < 20 mg/kg)  uses a larger sample size and a
more rigorous extraction procedure (lower concentrations are more difficult to
extract).  The medium/high concentration method (individual organic components
of > 20 mg/kg) is much simpler and therefore faster.

      1.3   It is highly recommended  that  the  extracts  be  cleaned up prior to
analysis.  See Chapter Four (Cleanup), Sec. 4.2.2, for applicable methods.


2.0   SUMMARY OF METHOD

      2.1   Low concentration method  -  A 30 g  sample  is mixed  with anhydrous
sodium sulfate to form a free-flowing powder.  This is solvent extracted three
times using ultrasonic extraction.   The extract is separated  from the sample by
vacuum filtration or centrifugation.   The  extract is ready for  cleanup and/or
analysis following concentration.

      2.2   Medium/high  concentration  method  - A  2  g  sample  is mixed  with
anhydrous  sodium sulfate  to form  a  free-flowing  powder.   This  is  solvent
extracted once using ultrasonic extraction.  A portion of the  extract  is removed
for cleanup and/or analysis.


3.0   INTERFERENCES

      3.1   Refer to Method 3500.


4.0   APPARATUS AND  MATERIALS

      4.1   Apparatus for grinding dry waste samples.

      4.2   Ultrasonic preparation  - A horn type device equipped with  a titanium
tip, or a device that will give equivalent performance, shall be used.
                                   3550A  -  1                         Revision 1
                                                                September 1994

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             4.2,1  Ultrasonic Disrupter - The disrupter must have a minimum power
      wattage  of 300  watts,  with pulsing  capability.   A  device designed to
      reduce the cavitation  sound  is recommended.   Follow the  manufacturers
      instructions  for preparing the disrupter for extraction of samples with
      low  and  medium/high  concentration.
             Use  a 3/4" horn for the low concentration method and  a 1/8" tapered
      raicrotip attached to a 1/2" horn for the medium/high concentration method.
      4.3    Sonabox - Recommended with above disrupters for decreasing cavitation
 sound (Heat  Systems -  Ultrasonics, Inc., Model 432B or equivalent).
      4.4    Apparatus  for  determining percent dry weight.
             4.4.1 Oven - Drying.
             4,4.2 Desiccator.
             4.4.3 Crucibles - Porcelain or disposable aluminum.
      4.5    Pasteur glass  pipets  - 1 ml, disposable.
      4.6    Beakers -  400  ml.
      4.7    Vacuum  or  pressure filtration apparatus.
             4.7.1 Buchner  funnel.
             4.7.2 Filter paper - Whatman No. 41 or equivalent.
      4.8    Kuderna-Danish  (K-D) apparatus.
             4.8.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or
      equivalent).   A  ground  glass stopper is used  to  prevent evaporation of
      extracts.
             4.8.2 Evaporation   flask  -   500   ml   (Kontes   K-570001-500  or
      equivalent).  Attach  to  concentrator  tube with  springs,  clamps,  or
      equivalent.
             4,8.3 Snyder column  - Three  ball  macro  (Kontes  K-503000-0121  or
      equivalent),
             4.8.4 Snyder  column   -  Two  ball  micro  (Kontes  K-5690Q1-Q219  or
      equivalent),
             4.8.5 Springs  - 1/2  inch (Kontes K-662750 or equivalent).
      4.9    Boiling chips - Solvent extracted,  approximately 10/40 mesh (silicon
carbide  or equivalent).
                                   3550A  -  2                         Revision 1
                                                                September 1994

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       4.10  Water  bath  -  Heated,  with  concentric  ring  cover,  capable  of
 temperature control (+ 5°C).   The batch  should  be  used in a hood.

       4.11  Balance -  Top loading, capable of accurately weighing to the nearest
•0.01 g.

       4.12  Vials - 2 ml, for GC  autosarapler,  with  Teflon lined  screw caps or
 crimp tops.

       4.13  Glass scintillation  vials -  20 mL,  with Teflon  lined  screw caps.

       4.14  Spatula -  Stainless  steel or Teflon.

       4.15  Drying column - 20  mm ID Pyrex chrotnatographic column with  Pyrex
 glass wool at bottom.

       NOTE:       Fritted glass  discs  are  difficult  to  decontaminate  after
                   highly  contaminated  extracts   have  been   passed   through.
                   Columns without frits  may be purchased.  Use a  small  pad of
                   Pyrex glass  wool to retain the  adsorbent.   Prewash  the glass
                   wool pad with  50 mL of acetone  followed by  50 mL of elution
                   solvent prior  to packing the  column with  adsorbent.

       4.16  Syringe -  5 mL.


 5.0   REAGENTS

       5.1    Reagent grade inorganic chemicals shall be used in all tests.  Unless
 otherwise  specified, it is intended that  all  inorganic  reagents shall conform to
 the specifications of the Committee  on Analytical  Reagents  of the  American
 Chemical Society,  where such specifications are available.  Other grades may be
 used,  provided it  is first ascertained that the reagent is of  sufficiently high
 purity to  permit  its  use  without lessening the  accuracy of the determination.

       5.2    Organic-free  reagent  water.  All references to water in this method
 refer to organic-free  reagent  water,  as  defined in Chapter One.

       5.3    Sodium sulfate  (granular,  anhydrous),  Na2S04.   Purify  by heating at
 400°C for  4 hours  in  a shallow tray,  or  by precleaning the sodium  sulfate with
 methylene  chloride.  If the sodium sulfate is precleaned with methylene  chloride,
 a method blank must be  analyzed, demonstrating that there is no interference from
 the sodium sulfate.

       5.4    Extraction solvents.

             5.4.1  Low  concentration  soil/sediment  and aqueous sludge  samples
       shall  be extracted  using a  solvent  system  that gives optimum,  reproducible
       recovery for the matrix/analyte combination  to  be  measured.    Suitable
       solvent choices  are given  in Table 1.
                                   3550A - 3
    Revision 1
September 1994
                        \

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4.1.
            5.4.2 Methylene   chloride:Acetone,   CH2C;j:CH3COCH3   (1:1,   v:v).
      Pesticide quality or equivalent.

            5.4.3 Methylene chloride, CH2C12.  Pesticide quality or equivalent.

            5.4.4 Hexane, C6H14.  Pesticide quality or equivalent.

      5.5   Exchange solvents.

            5.5.1 Hexane, C6H14.  Pesticide quality or equivalent.

            5.5.2 2-Propanol, (CH3)2CHOH,   Pesticide  quality  or equivalent.

            5.5.3 Cyclohexane, C6H12.  Pesticide quality or equivalent.

            5.5.4 Acetonitrile, CH3CN.  Pesticide  quality  or  equivalent.

            5.5.5 Methanol ,  CH3OH.   Pesticide quality or equivalent.


      SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1   See the introductory material to this Chapter, Organic Analytes, Sec.
7.0   PROCEDURE

      7.1   Sample handling

            7.1.1 Sediment/soil  samples - Decant  and discard any water layer on
      a sediment sample.  Mix sample thoroughly, especially composited samples.
      Discard any foreign objects such as  sticks, leaves, and rocks.

                  7.1.1.2     Determine the dry weight of the sample (Sec. 7.2)
            remaining after decanting.   Measurement of soil pH may be required.

            7.1.2 Waste samples  -  Samples   consisting  of multiphases must  be
      prepared by the phase separation  method in Chapter Two before extraction.
      This procedure is for solids only.

            7.1.3 Dry waste samples amenable to  grinding -  Grind  or otherwise
      subdivide the waste so that it either passes through a 1 mm sieve  or can
      be extruded through  a  1 mm hole.  Introduce sufficient  sample  into the
      grinder to yield at least  100 g after grinding.

            7.1.4 Gummy,  fibrous  or oily  materials  not amenable to  grinding
      should be  cut,  shredded,  or  otherwise  broken up  to allow mixing,  and
      maximum exposure of the sample surfaces for extraction.  The professional
      judgment  of  the analyst  is required  for   handling  of  these  difficult
      matrices.
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      7.2   Determination  of percent dry  weight  -  In certain  cases,  sample
results are desired based on  a dry weight basis.  When such data are desired, or
required, a portion of sample for this determination should be weighed out at the
same time as the portion used for analytical determination,

      WARNING:    The drying oven should  be contained  in a  hood  or  vented.
                  Significant laboratory contamination may result from drying a
                  heavily contaminated hazardous waste sample.

      However, samples known  or  suspected to  contain significant  concentrations
of toxic, flammable, or explosive constituents should not be overdried  because
of concerns for personal safety.  Laboratory discretion is advised.   It may be
prudent to delay overdrying  of  the weighed-out  portion until other analytical
results are available.

            7.2.1 Immediately after weighing  the sample for extraction, weigh 5-
      10 g of the sample into a tared crucible.   Determine the % dry weight of
      the sample by drying overnight  at  I05°C.  Allow to  cool  in a desiccator
      before weighing:

            % dry weight = g of dry sample x 100
                              g of sample

      7.3   Extraction method for samples expected to  contain  low  concentrations
of organics and pesticides (< 20 mg/kg):

            7.3.1 The following step  should be performed rapidly to avoid  loss
      of the more  volatile extractables.   Weigh approximately  30 g  of  sample
      into a 400 ml beaker.  Record  the  weigh to the  nearest 0.1 g.   Nonporous
      or wet samples (gummy or clay type) that do not  have a free-flowing sandy
      texture must  be  mixed  with 60 g  of  anhydrous  sodium sulfate, using  a
      spatula.  If required,  more, sodium sulfate may  be added.   After addition
      of  sodium  sulfate, the  sample should  be free  flowing.    Add  1  ml  of
      surrogate standards to all  samples,  spikes, standards,  and  blanks  (see
      Method 3500 for details on the  surrogate standard solution  and the matrix
      spike solution).   For  the sample  in each analytical  batch selected for
      spiking, add  1.0 ml of the matrix spiking standard.  For base/neutral-acid
      analysis, the amount added of the surrogates and matrix spiking compounds
      should result in a final  concentration of  100 ng/fiL of each base/neutral
      analyte and 200 ng/pL of each  acid analyte in the extract  to be analyzed
      (assuming a 1 ^L injection).   If Method 3640, Gel-Permeation Cleanup,  is
      to  be  used,  add   twice  the volume  of  surrogates  and  matrix  spiking
      compounds since half of  the  extract is lost due to loading of the GPC
      column.   Immediately add  100 ml of 1:1 methylene chloride:acetone.
            7.3.2 Place the  bottom surface  of the  tip  of  the  1207 3/4  in.
      disrupter horn about 1/2 in.  below the surface of the solvent,  but above
      the sediment laver.
      7.3.2 Place  the  bottom surface  of the  tip of  the 1207  3/4 in.
     jjter horn abou'
the sediment layer.

      7.3.3 Extract ultrasonically for 3 minutes, with output control knob
set at  10  (full power)  and  with  mode  switch  on Pulse  (pulsing energy
                                  3550A - 5                         Revision 1
                                                                September 1994

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rather  than continuous energy)  and  percent-duty cycle knob  set  at 50%
(energy on  50% of time and off 50% of time).  Do not use microtip probe.

      7.3.4 Decant the extract and filter  it through Whatman No. 41 filter
paper (or equivalent) in a Buchner funnel  that is attached  to  a clean 500
ml filtration flask.  Alternatively,  decant the  extract  into a centrifuge
bottle and  centrifuge at low  speed to remove  particles.

      7.3.5 Repeat the extraction two  or  more times with two additional
100 roL portions of solvent.  Decant off the solvent  after each ultrasonic
extraction.  On  the  final  ultrasonic extraction,  pour the entire sample
into the Buchner funnel and rinse with extraction solvent.   Apply a vacuum
to  the  filtration  flask,  and  collect the  solvent extract.   Continue
filtration  until all  visible  solvent is removed from the funnel,  but do
not attempt to completely dry the sample,  as  the continued  application of
a  vacuum  may result  in  the  loss of some analytes.   Alternatively,  if
centrifugation is used in  Sec.  7.3.4,  transfer  the  entire sample  to the
centrifuge  bottle.  Centrifuge at low speed,  and then decant the solvent
from the bottle,

      7.3.6 Assemble a Kuderna-Danish (K-D) concentrator (if necessary) by
attaching  a 10  ml  concentrator tube  to  a 500  ml evaporator  flask.
Transfer filtered extract to a 500 ml evaporator flask and  proceed to the
next section.

      7,3.7 Add one to two clean boiling chips to the evaporation  flask,
and attach a three ball Snyder column,  Prewet the Snyder column by adding
about 1 ml  methylene  chloride to the top.   Place the K-D apparatus on  a
hot water  bath  (80-90 °C)  so that  the concentrator tube  is partially
immersed in the  hot water and  the  entire lower rounded  surface  of the
flask is  bathed  with  hot  vapor.   Adjust  the vertical position  of the
apparatus  and  the  water  temperature,  as  required,   to  complete  the
concentration in 10-15 min.  At  the proper  rate of distillation the balls
of the column will  actively chatter,  but the  chambers will  not flood with
condensed  solvent.   When  the apparent volume  of  liquid  reaches  1 ml,
remove the  K-D apparatus and  allow it  to  drain  and  cool for at  least 10
min.

      7.3.8 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column,  add  50 ml of  the exchange solvent
and a new boiling chip, and re-attach the Snyder column.  Concentrate the
extract as described in Sec.  7.3.10,  raising  the temperature of the water
bath,  if necessary, to maintain  proper distillation.   When the  apparent
volume again reaches  1-2 ml, remove the  K-D apparatus and allow  it  to
drain and cool  for at least 10 minutes.

      7.3.9 Remove the Snyder column and  rinse the  flask  and its  lower
joints into the  concentrator  tube  with 1-2 ml  of methylene  chloride  or
exchange solvent.   If sulfur crystals  are a  problem,  proceed to  Method
3660 for cleanup.  The extract may be  further concentrated by using the
technique outlined in Sec.  7.3.10 or  adjusted  to 10.0 ml with the solvent
last used.
                             3550A  -  6                         Revision 1
                                                          September 1994

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            7.3.10       If further concentration is indicated in Table 1,  either
      micro  Snyder  column technique  {Sec.  7.3.10.1)  or nitrogen  blow  down
      technique  (Sec.  7.3,10.2)  is  used to  adjust the  extract  to  the  final
      volume required.

                  7,3.10.1   Micro  Snyder Column  Technique

                         7.3.10.1.1        Add a clean boiling chip and  attach a
                  two ball micro Snyder column to the concentrator tube.  Prewet
                  the  column  by  adding approximately  0.5  mL  of  methylene
                  chloride or exchange  solvent through  the  top.   Place the
                  apparatus in the hot water bath.  Adjust the vertical  position
                  and  the water temperature,  as  required,  to  complete the
                  concentration  in  5-10 minutes.   At  the  proper  rate of
                  distillation the  balls of  the column will actively  chatter,
                  but the  chambers will  not flood.  When  the liquid reaches an
                  apparent volume of approximately 0.5 ml,  remove  the apparatus
                  from the water bath  and allow to drain  and cool for  at  least
                  10 minutes.   Remove  the micro Snyder  column  and  rinse its
                  lower  joint with approximately 0.2 ml of appropriate solvent
                  and add  to the concentrator tube.  Adjust the  final volume to
                  the  volume required  for  cleanup  or for  the determinative
                  method  (see Table  1).

                  7,3.10.2   Nitrogen Slowdown Technique

                         7.3.10,2.1        Place the concentrator tube in  a warm
                  water  bath  (approximately  35 °C) and  evaporate the  solvent
                  volume to the required level using a gentle stream of clean,
                  dry nitrogen (filtered through a column  of activated carbon).

                         CAUTION:     Do  not use  plasticized tubing between the
                                     carbon trap and the sample.

                         7.3.10.2.2        The internal wall of  the tube must be
                  rinsed down several times with the appropriate solvent during
                  the operation.  During evaporation, the solvent level in the
                  tube must be positioned to prevent water from condensing  into
                  the sample (i.e., the solvent  level  should be  below the  level
                  of the water bath).   Under  normal operating  conditions, the
                  extract  should not be  allowed to  become dry,

                        CAUTION:    When the volume of solvent  is  reduced  below
                                     1 ml, semivolatile analytes may be lost,

      7.4.   If analysis of the extract will not be performed immediately, stopper
the concentrator tube and store refrigerated.    If the  extract will  be stored
longer than 2 days,  it should be transferred to a  vial with a Teflon lined cap
and labeled appropriately.
                                   3550A -  7                         Revision 1
                                                                September 1994

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      7.5   Extraction method for samples expected to contain high concentrations
of organics {> 20 tng/kg):

            7.5.1 Transfer approximately 2 g (record weight to the nearest 0.1
      g) of sample to a 20 ml  vial.  Wipe the mouth of the  vial with a tissue to
      remove any sample material.  Record the exact weight  of sample taken.  Cap
      the  vial  before  proceeding with  the next  sample   to  avoid  any  cross
      contamination.

            7.5.2 Add  2  g of anhydrous  sodium sulfate to  sample  in  the  20 ml
      vial and mix well.

            7.5.3 Surrogate  standards  are added to  all   samples,  spikes,  and
      blanks (see Method 3500 for details on the surrogate  standard solution and
      on the matrix spike solution).  Add 1.0 ml of surrogate spiking solution
      to sample mixture.  For the sample in each analytical batch selected for
      spiking, add 1.0 ml of the matrix spiking  standard.   For base/neutral-acid
      analysis, the amount added of  the  surrogates and matrix spiking compounds
      should result in a final concentration of 100 ng/^L  of each base/neutral
      analyte and 200 ng/^L of each acid analyte in the extract to be analyzed
      (assuming a 1 ^L injection).  If Method 3640, Gel-Permeation Cleanup, is
      to  be used,  add  twice the  volume  of  surrogates   and  matrix  spiking
      compounds since half the extract is lost due to loading of the GPC column.

            7.5.4 Immediately add whatever  volume  of solvent is  necessary to
      bring the  final  volume  to  10.0  ml considering  the added  volume  of
      surrogates and matrix  spikes.  Disrupt the sample with the 1/8 in. tapered
      microtip ultrasonic probe for 2 minutes  at output control  setting  5 and
      with mode  switch on pulse  and  percent duty  cycle  at 50%.   Extraction
      solvents are:

            1.    For nonpolar compounds  (i.e.,  organochlorine  pesticides and
                  PCBs), use hexane or appropriate solvent.

            2.    For extractable priority pollutants, use methylene  chloride.

            7.5.5 Loosely pack disposable Pasteur pipets  with 2  to 3 cm  Pyrex
      glass wool  plugs.  Filter the extract through the glass wool and collect
      5.0  ml  in a  concentrator tube  if further  concentration  is  required.
      Follow Sec. 7.3.10  for details  on concentration.   Normally, the  5.0 ml
      extract  is concentrated to approximately 1.0  raL or less.

            7.5.6 The extract is ready for cleanup or analysis, depending on the
      extent of interfering  co-extractives.


8.0   QUALITY  CONTROL

      8.1    Any reagent blanks or matrix spike  samples should be subjected to
exactly the same analytical  procedures as those used on actual  samples.
                                  3550A - 8                         Revision 1
                                                                September 1994
                        \

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      8.2   Refer to  Chapter  One for specific  quality  control  procedures and
Method 3500 for extraction and sample preparation procedures.


9.0   METHOD PERFORMANCE

      9.1   Refer to the determinative method for performance data.


10.0  REFERENCES

1.    U.S. EPA 40 CFR  Part 136, "Guidelines Establishing  Test  Procedures for the
      Analysis of Pollutants Under the Clean Water Act;  Finil Rule and Interim
      Final Rule and Proposed Rule," October 26, 1984.

2.    U.S. EPA,  Interlaboratory  Comparison Study:   Methods for  Volatile and
      Serai-Volatile Compounds,  Environmental  Monitoring Systems  Laboratory,
      Office of Research and Development, Las Vegas,  NV,  EPA 600/4-84-027, 1984.

3.    Christopher S. Hein,  Paul J, Marsden, Arthur S. Shurtleff, "Evaluation of
      Methods 3540  (Soxhlet) and 3550 (Sonication) for Evaluation of Appendix IX
      Analytes form Solid Samples",  S-CUBED,  Report for  EPA Contract 68-03-33-
      75, Work Assignment No.  03, Document No.  SSS-R-88-9436, October 1988.
                                  3550A - 9                         Revision 1
                                                                September 1994
                  \

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                                                  TABLE 1.
                                  EFFICIENCY OF EXTRACTION SOLVENT SYSTEMS3
Solvent Systemd
Compound CAS No.b ABNC
4-Bromophenyl phenyl ether 101-55-3
4-Chloro-3-methylphenol 59-50-7
bis(2-Chloroethoxy)methane 111-91-1
bis(2-Chloroethyl) ether 111-44-4
2-Chloronaphthalene 91-58-7
4-Chlorophenyl phenyl ether 7005-72-3
1,2-Dichlorobenzene 95-50-1
1,3-Dichlorobenzene 541-73-1
Diethyl phthalate 84-66-2
4,6-Dinitro-o-cresol 534-52-1
2,4-Dinitrotoluene 121-14-2
2,6-Dinitrotoluene 606-20-2
Heptachlor epoxide 1024-57-3
Hexachlorobenzene 118-74-1
Hexachlorobutadiene 87-68-3
Hexachlorocyclopentadiene 77-47-4
Hexachloroethane 67-72-1
5-Nitro-o-toluidine 99-55-8
Nitrobenzene 98-95-3
Phenol 108-95-2
1,2,4-Trichlorobenzene 120-82-1
a Percent recovery of analytes spiked
b Chemical Abstracts Service Registry
c Compound Type: A = Acid, B = Base,
d A = Methylene chloride
B = Methylene chloride/Acetone (1/1)
C = Hexane/Acetone (1/1)
D = Methyl t-butyl ether
N
A
N
N
N
N
N
N
N
A
N
N
N
N
N
N
N
B
N
A
N
at 200
Number
%R
64.2
66.7
71.2
42.0
86.4
68.2
33.3
29.3
24.8
66.1
68.9
70.0
65.5
62.1
55.8
26.8
28.4
52.6
59.8
51.6
66.7
mg/kg

SO
6.5
6.4
4.5
4.8
8.8
8.1
4.5
4.8
1.6
8.0
1.6
7.6
7.8
8.8
8.3
3.3
3.8
26.7
7.0
2.4
5.5
%R
56.4
74.3
58.3
17.2
78.9
63.0
15.8
12.7
23.3
63.8
65.6
68.3
58.7
56.5
41.0
19.3
15.5
64.6
38.7
52.0
49.9
SO
0.5
2.8
5.4
3.1
3.2
2.5
2.0
1.7
0.3
2.5
4.9
0.7
1.0
1.2
2.7
1.8
1.6
4.7
5.5
3.3
4.0
into NIST sediment



%R
86.7
97.4
69.3
41.2
100.8
96.6
27.8
20.5
121.1
74.2
85.6
88.3
86.7
95.8
63.4
35.5
31.1
74.7
46.9
65.6
73.4
SRM 1645

SO
1.9
3.4
2.4
8.4
3.2
2.5
6.5
6.2
3.3
3.5
1.7
4.0
1.0
2.5
4.1
6.5
7.4
4.7
6.3
3.4
3.6


%R
84.5
89.4
74.8
61.3
83.0
80.7
53.2
46.8
99.0
55.2
68.4
65.2
84.8
89.3
76.9
46.6
57.9
27.9
60.6
65.5
84.0


SO
0.4
3.8
4.3
11.7
4.6
1.0
10.1
10.5
4.5
5.6
3.0
2.0
2.5
1.2
8.4
4.7
10.4
4.0
6.3
2.1
7.0


%R
73.4
84.1
37.5
4.8
57.0
67.8
2.0
0.6
94.8
63 4
64. a
59.8
77.0
78.1
12.5
9.2
1.4
34.0
13.6
50.0
20.0


SO
1.0
1.6
5.8
1.0
2.2
1.0
1.2
0.6
2.9
2.0
2.3
0.8
0.7
4.4
4.6
1.7
1.2
4.0
3.2
8.1
3.2


N = neutral












































E = Methyl t-butyl ether/Methanol (2/1)
                                                 3550A  -  10
    Revision 1
September 1994

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                                                  TABLE 2.
                      SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS



Determinative
method
8040"
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8250"'c
8270C
8310
8321
8410



Extraction
PH
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
none
none
acetonitrile
methanol
methylene chloride
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
methylene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
--


--
methylene chloride
Volume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
' --
--
--
--
10.0
Final
extract
volume
for
analysis (ml)
1.0, 10. Ob
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
1.0
1.0
1.0
1.0
0.0 (dry)
" To obtain separate acid and base/neutral extracts, Method 3650 should be performed following concentration
  of the extract to 10.0 ml.

b Phenols may  be  analyzed,  by Method 8040, using  a  1.0  ml 2-propanol  extract by GC/FID.   Method  8040 also
  contains an  optical  derivatization procedure  for  phenols  which results in  a  10  ml hexane  extract  to be
  analyzed by GC/ECD.

  The specificity of GC/MS may  make  cleanup  of the  extracts  unnecessary.
  on the cleanup procedures available if required.
Refer to Method 3600 for guidance
                                                 3550A - 11
                       Revision 1
                   September 1994

-------
                            METHOD  3550A
                      ULTRASONIC EXTRACTION
                                7.1 Prepare *empiae
                              uiing appropriate method
                                for th* WMt* matrix
                                  7,2 Determine th*
                                 percent dry we
                                   of tne eempla
7.5.2 Add anhydrous
  sodium »ulfat« to
      •ample
                                     7.5.2
                                   It organic
                                 concentration
                                exp act*d  to be
                                  < 2O mg/kg?
7.3.1 Add surrogate
  standard* to ill
  •ampl»f. tpifcet,
    •nd blank*
 7.S.3 Add »urrogate
   «t«nd«rd« to ill
  • ample*,  (pikee,
     and blank*
                                                                 7.3.2 - 7.3.S
                                                              Sonicate •ample at
                                                                 lea*t 3 time*
   7.5.4 Adjust
  volume: disrupt
aampl* with taperad
 mtcrotip ultratomc
      probe
                                                                  7.3.7 Dry and
                                                                 collect extract in
                                                                 K-D concentrator
                               7.5.5 Rlter
                            through gloee wool
                                                               7.3.8 Concentrate
                                                               extract and collect
                                                               in K-D concentrator
                             3550A -  12
                                                                           Revision 1
                                                                     September 1994

-------
                       METHOD 3550A
                         continued
7.3.9 Add exchange
     solvent;
concentrate extract
Yes
 7.3,1O Use Method
  3660 for cleanup
                                       Yes
 7.3.9 is
* •orvent
exchenge
required?
          7.3,10 Do
        sulfur cry>t*lf
            form?
                                                7.3.11 Furthtr
                                              concentrate and/or
                                                adjust volume
                                                 (Cleanup or   ]
                                                  analyze    J
                        3550A -  13
                            Revision  1
                       September 1994

-------
                                 METHOD 3580A
                                WASTE DILUTION
1.0   SCOPE AND APPLICATION
      1.1   This method  describes  a solvent  dilution  of a  non-aqueous  waste
sample prior to cleanup  and/or analysis.   It is designed for  wastes that may
contain organic chemicals at a  concentration greater than 20,000 mg/kg and that
are soluble in the dilution solvent.
      1.2   It is recommended that an aliquot of the diluted sample be cleaned
up.  See this chapter, Organic Analytes, Section 4.2.2 (Cleanup).
2.0   SUMMARY OF METHOD
      2.1   One gram of sample is weighed  into a capped tube, and the sample is
diluted to 10.0 ml with an appropriate solvent.

3.0   INTERFERENCES
      3.1   Refer to Method 3500.
4.0   APPARATUS AND MATERIALS
      4.1   Glass scintillation vials:   At least 20 mL, with Teflon or aluminum
foil lined screw-cap, or equivalent.
      4.2   Spatula:  Stainless steel or Teflon.
      4.3   Balance:  Capable of weighing 100 g to the nearest 0.01 g.
      4.4   Vials and caps:  2 mL for GC autosampler.
      4.5   Disposable pipets:  Pasteur.
      4.6   Test tube rack.
      4.7   Pyrex glass wool.
      4.8   Volumetric flasks, Class A:  10 mL (optional).

5.0   REAGENTS
      5.1   Sodium sulfate (granular, anhydrous),  Na2S04.  Purify by heating at
400°C for 4 hours  in a shallow tray, or by precleaning the  sodium sulfate with
methylene chloride.   If the sodium sulfate is precleaned with methylene chloride,

                                  3580A -  1                         Revision 1
                                                                     July 1992

-------
a method blank must be analyzed,  demonstrating that there is no interference from
the sodium sulfate.

      5.2   Methylene chloride,  CH2C12  -  Pesticide quality or equivalent.

      5.3   Hexane, C6H14 - Pesticide quality or equivalent.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to this  chapter,  Organic Analytes,
Section 4.1.


7.0   PROCEDURE

      7.1   Samples consisting  of multiphases must  be prepared by  the phase
separation method (Chapter Two)  before extraction.

      7.2   The sample dilution may be  performed  in a 10 mL volumetric flask.
If  disposable  glassware is  preferred,  the  20  mL  scintillation vial  may be
calibrated for use.  Pipet  10.0  mL of extraction solvent  into the scintillation
vial and mark the bottom of the meniscus.  Discard this solvent.

      7.3   Transfer approximately 1 g of each phase of the sample to separate
20 mL vials or  10 mL volumetric flasks  (record weight to the  nearest 0.1 g).
Wipe the mouth  of the vial with a tissue to remove  any sample material.  Cap the
vial before proceeding with the next sample to avoid any cross-contamination.

      7.4   Add 2.0 mL surrogate spiking solution to  all samples and blanks.  For
the sample  in  each analytical batch  selected  for spiking, add  2.0  mL  of the
matrix spiking  standard.  For base/neutral-acid analysis, the amount added of the
surrogates and matrix spiking compounds should result in a final concentration
of 200 ng//LtL of each base/neutral  analyte and 400 ng//iL of each  acid  analyte in
the extract to be analyzed  (assuming a  1 pL injection).   If Method 3640, Gel-
permeation cleanup, is to be used,  add twice the volume of surrogates  and matrix
spiking  compounds  since half the  extract  is lost  due to loading of the GPC
column.  See Method 3500 and the determinative method to  be used  for  details on
the surrogate standard and matrix  spiking solutions.

      7.5   Immediately dilute  to 10  mL with  the  appropriate  solvent.   For
compounds to be analyzed by GC/ECD, e.g., organochlorine pesticides and PCBs, the
dilution  solvent  should be  hexane.    For  base/neutral  and  acid semivolatile
priority pollutants, use methylene chloride.  If the dilution is to  be cleaned
up by gel permeation chromatography (Method 3640),  use methylene  chloride as the
dilution solvent for all compounds.

      7,6   Add 2.0 g of anhydrous sodium sulfate to the  sample.

      7.7   Cap and shake the sample for 2 min.
                                   3580A - 2                        Revision  1
                                                                     July 1992

-------
      7.8   Loosely pack disposable Pasteur pi pets with 2-3 cm glass wool plugs.
Filter the extract through the glass wool and collect 5 ml of the extract in a
tube or vial.

      7.9   The extract is ready for cleanup or analysis, depending on the extent
of interfering co-extractives.


8.0   QUALITY CONTROL

      8.1   Any reagent blanks and matrix spike samples should be subjected to
exactly the same analytical  procedures as those used on actual  samples.

      8.2   Refer to  Chapter  One for specific quality  control  procedures and
Method 3500 for extraction and sample preparation procedures.


9.0   METHOD PERFORMANCE

      9.1   Refer to the determinative methods for performance data.


10.0  REFERENCES

      10.1  None applicable.
                                  3580A  - 3                         Revision 1
                                                                     July 1992

-------
                        METHOD  3580A
                       WASTE DILUTION
       STftRT
                           7. 1  Use phase
                         separation method
                            (Chapter 2)
7 . 3 Transfer 1 g of
   each phase to
 separata vials or
      flasks
 74  Add surrogate
spiking solution to
  all tatnple* and
      blank*
  7 . 4  Add tna t r i K
spiking standard to
•ample selected for
      spiking
  7 S  DiAute with
apprapnate sol vent
 7 6  Add anhydrous
 ammonium »yi £»t»
 7 ?  Cap and shak*
7,8 Filtar through
    glass wool
Cleanup or analyse
                           3580A -  4
                      Revision 1
                       July  1992

-------

-------
                                 METHOD 3600B

                                    CLEANUP
1.0   SCOPE AND APPLICATION

      1.1   Method 3600 provides general guidance on selection of cleanup methods
that are appropriate for the target analytes of  interest.  Cleanup methods are
applied to the extracts prepared by one of the  extraction methods, to eliminate
sample interferences.  The following table lists the cleanup methods and provides
a brief description of the type of cleanup,

                            SW-846 CLEANUP METHODS
 Method I     Method  Mame                              Cleanup Type


 3610         Alumina  Cleanup                         Adsorption

 3611         Alumina Cleanup &  Separation             Adsorption
              for  Petroleum  Waste

 3620         Fieri si 1   Cleanup                        Adsorption

 3630         Silica  Gel   Cleanup                      Adsorption

 3640         Gel-Permeation Cleanup                   Size-Separation

 3650         Acid-Base  Partition  Cleanup              Acid-Base Partitioning

 3660         Sulfur  Cleanup                          Oxidation/Reduction

 3665         Sulfuric Acid/Permanganate               Oxidation/Reduction
              Cleanup


      1.2   The purpose of applying a cleanup method  to an extract is to remove
interferences  and  high boiling material  that  may result  in:    (1)  errors  in
quantisation  (data may be  biased low  because of  analyte  adsorption  in  the
injection port or front of the  GC  column or biased high because of overlap with
an interference peak);  (2) false positives because of  interference peaks falling
within the analyte retention time window; (3)  false negatives caused by shifting
the  analyte  outside the  retention  time  window; (4)  rapid deterioration  of
expensive capillary columns; and,  {5} instrument downtime  caused by cleaning and
rebuilding of detectors  and  ion sources.  Most extracts of soil and waste require
some degree of cleanup,  whereas, cleanup for water extracts may be unnecessary.
Highly  contaminated  extracts  (e.g.   sample  extracts of oily  waste or  soil
containing oily residue) often  require a  combination of  cleanup methods.   For
example,  when analyzing  for  organochlorine pesticides  and PCBs,  it  may  be
necessary to  use  gel permeation  chromatography  (GPC),  to eliminate  the  high
boiling  material   and  a  micro  alumina  or  Florisil   column  to  eliminate
interferences with the analyte peaks on the GC/ECD.

                                   36008 -  1                         Revision 2
                                                                September 1994
         \

-------
      1,3   The following techniques have been  applied  to extract purification:
adsorption  chromatography;  partitioning  between  immiscible  solvents;  gel
permeation chromatography; oxidation of interfering substances with acid, alkali,
or oxidizing  agents.   These  techniques  may be  used  individually or in various
combinations, depending on the extent and nature of the co-extractives,

            1,3.1       Adsorption column chromatography - Alumina {Methods 3610
      and 3611), Florisil  (Method  3620),  and silica gel  (Method 3630) are useful
      for separating  analytes of  a relatively  narrow  polarity  range away from
      extraneous,  interfering  peaks  of a  different  polarity.    These  are
      primarily  used  for cleanup  of  a  specific chemical  group  of relatively
      non-polar analytes,  i.e.,  organochlorine  pesticides,  polynuclear aromatic
      hydrocarbons   (PAHs),   nitrosamines,  etc..     Solid  phase  extraction
      cartridges have been added as an option.

            1.3.2       Acid-base  partitioning  (Method  3650)  -  Useful  for
      separating acidic or basic  organics  from neutral  organics.   It has been
      applied to analytes such as  the  chlorophenoxy herbicides and phenols.  It
      is very useful  for  separating the neutral PAHs  from the  acidic phenols
      when analyzing a site contaminated with creosote and pentachlorophenol.

            1.3.3       Gel permeation chromatography  (GPC)  (Method 3640) - The
      most  universal   cleanup  technique  for   a  broad  range  of  semivolatile
      organics   and   pesticides.     It   is   capable   of  separating   high
      molecular-weight, high  boiling material from the  sample analytes.  It has
      been used successfully  for  all  the semivolatile  base, neutral,  and acid
      compounds associated with  the EPA Priority Pollutant and  the Superfund
      Target  Compound  list  prior  to  GC/MS  analysis  for semivolatiles  and
      pesticides.  GPC may not be applicable to  elimination  of  extraneous peaks
      on a chromatogram which interfere with the analytes of interest.  It is,
      however,  useful  for the removal  of  high boiling materials  which  would
      contaminate  injection  ports and  column  heads,  prolonging  column  life,
      stabilizing the instrument,  and reducing  column  reactivity.

            1.3,4       Sulfur cleanup  (Method  3660)  - Useful  in  eliminating
      sulfur from sample extracts,  which may cause chromatographic interference
      with analytes of interest.

      1.4   Several of the methods are also useful for fractionation of complex
mixtures of analytes.  Use the solid phase extraction cartridges in Method 3630
(Silica Gel) for separating the PCBs away from  most  organochlorine pesticides.
Method 3611  (Alumina) is for  the fractionation of aliphatic, aromatic and polar
analytes.  Method 3620 (Florisil)  provides fractionation of the organochlorine
pesticides.

      1.5   Cleanup  capacity is  another factor  that  must be  considered  in
choosing a cleanup technique.   The adsorption  methods (3610, 3620,  and  3630)
provide the option of using standard column chromatography techniques or solid
phase extraction  cartridges.   The  decision  process  in selecting  between  the
different options available generally depends on the amount of interferences/high
boiling material in the  sample extract and the degree of cleanup required by the
determinative method.  The solid phase extraction cartridges  require less elution
solvent and less time,  however, their cleanup  capacity is  drastically reduced
when comparing a 0.5 g or 1.0 g Florisil cartridge to  a 20 g standard Florisil

                                   3600B -  2                         Revision 2
                                                                September 1994

-------
 column.  The same factor enters into the choice of the 70 g gel  permeation column
 specified  in Method 3640 versus  a high efficiency column.

       1.6   Table  1  indicates  the  recommended  cleanup  techniques  for the
 indicated groups of compounds.  This information can also be used as guidance for
 compounds  that are not  listed.   Compounds that are chemically  similar to  these
 groups  of compounds  should  behave similarly  when  taken  through the cleanup
 procedure,however, this must be demonstrated by determining recovery of standards
 taken  through the method.


 2.0    SUMMARY OF METHOD

       2.1   Refer to the specific cleanup method for a summary  of the procedure.


 3.0    INTERFERENCES

       3.1   Analytical interferences may be  caused by contaminants in solvents,
 reagents,  glassware,  and  other sample  processing hardware.    All  of  these
 materials must be routinely demonstrated  to  be free of interferences, under the
 conditions of the analysis, by running laboratory reagent blanks.

      3.2   More extensive procedures  than those  outlined  in the methods may be
 necessary for reagent purification.


 4.0   APPARATUS AND MATERIALS

      4.1   Refer to  the  specific  cleanup  method for apparatus and  materials
 needed.
5.0   REAGENTS

      5.1   Refer to the specific cleanup method for the reagents needed.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory material  to this  chapter,  Organic Analytes,
Section 4.1.


7.0   PROCEDURE

      7.1   Prior to  using  the  cleanup  procedures, samples  normally  undergo
solvent extraction.   Chapter  Two,  Section 2.0,  may  be used  as a  guide  for
choosing the appropriate extraction  procedure based  on the physical composition
of the waste and on the  analytes of interest in the matrix (see also Method 3500
for  a  general  description  of the  extraction  technique).    For  some  organic
liquids, extraction prior to cleanup may not be  necessary.
                                  3600B  - 3                         Revision 2
                                                                September 1994

-------
      7.2   Most soil/sediment and waste sample extracts will require some degree
of cleanup.  The extract is then analyzed by  one of the determinative methods.
If interferences still preclude analysis for the analytes of interest, additional
cleanup may be required.

      7.3   Many of the determinative methods  specify cleanup methods that should
be  used   when   determining  particular  analytes   (e.g.   Method  8061,  gas
chromatography of phthalate esters, recommends using either Method 3610 (Alumina
column cleanup)  or Method 3620 (Florisil column cleanup) if interferences  prevent
analysis.   However, the  experience of  the   analyst  may  prove  invaluable in
determining which cleanup  methods  are  needed.   As  indicated in Section 1.0 of
this method, many matrices may require a combination of cleanup procedures in
order to ensure proper analytical determinations.

      7.4   Guidance for cleanup is specified  in each of the methods that  follow.
The amount of extract cleanup required  prior  to the final determination  depends
on the concentration of  interferences in the sample,  the  selectivity of both the
extraction procedure and  the determinative method and  the required detection
limit.

      7.5   Following cleanup, the  sample is  concentrated to whatever volume is
required  in  the determinative method.    Analysis follows  as  specified  in the
determinative procedure.


8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control  procedures.

      8.2   The analyst must  demonstrate that the  compounds  of interest are
being quantitatively recovered by the cleanup technique  before the cleanup is
applied  to  actual   samples.    For  sample extracts  that  are  cleaned up,  the
associated  quality  control   samples  (e.g.   spikes,   blanks,  replicates,  and
duplicates) must also be processed through the same cleanup procedure.

      8.3   The  analysis  using each determinative  method (GC,  GC/MS, HPLC)
specifies  instrument  calibration  procedures using  stock standards.    It  is
recommended that cleanup  also be  performed  on a series  of the  same  type of
standards to  validate  chromatographic  elution  patterns  for the  compounds of
interest and to verify the absence of interferences  from reagents.


9.0   METHOD PERFORMANCE

      9.1   Refer to the specific cleanup method for performance data.


10.0  REFERENCES

      10.1  Refer to the specific cleanup method.
                                  3600B - 4                         Revision 2
                                                                September 1994

-------
                                   TABLE 1.
       RECOMMENDED CLEANUP TECHNIQUES FOR  INDICATED GROUPS OF COMPOUNDS
Analyte Group
Determinative11
   Method
   Cleanup
Method Options
Phenols
Phthalate esters
Nitrosamines
Organochlorine pesticides & PCBs
PCBs
Nitroaromatics and cyclic ketones
Polynuclear aromatic hydrocarbons
Chlorinated hydrocarbons
Organophosphorus pesticides
Chlorinated herbicides
Semi volatile organics
Petroleum waste
PCODs and PCDFs by LR/MS
PCDDs and PCDFs by HR/MS
N-methyl carbamate pesticides
8040
8060/80$ 1
8070
8080/8081
8080/8081
8090
8100/8310
8120/8121
8140/8141
8150/8151
8250/8270
8250/8270
8280
8290
8318
363Db, 3640, 3650, 8040C
3610, 3620, 3640
3610, 3620, 3640
3620, 3640, 3660
3665
3620, 3640
3611, 3630, 3640
3620, 3640
3620
8150d, 8151d, 3620
3640, 3650, 3660
3611, 3650
8280
8290
8318
   The GC/MS Methods, 8250 and 8270,  are  also appropriate determinative methods
   for all analyte groups,  unless  lower  detection  limits are required.

   Cleanup applicable  to derivatized phenols.

   Method 8040 includes a derivatization  technique  followed by GC/ECD analysis,
   if interferences  are encountered  using GC/FID.

   Methods 8150 and  8151  incorporate an  acid-base  cleanup  step  as an integral
   part of the methods.
                                  3600B  - 5
                                Revision  2
                            September 1994

-------
                   METHOD 3600B
                      CLEANUP
 x-	x
       Start
        I	
       7,1
    Do solvent
     extraction
       I
       7.2
  Analyze anaJyte
 by a determinative
method torn Sec. 4.3
      7.2 Are
     analytes
  undeterminable
      due to
       7.3
USB dSBnup method
  mm ini •i^jfc^ b^
                                       7,5
                                ConoentratBsampte
                                 to requifsd volume
                        3600B  - 6
                               Revision  2
                          September 1994

-------
                                 METHOD 3630B

                              SILICA GEL CLEANUP
1.0   SCOPE AND APPLICATION

      I.I   Silica  gel  is a  regenerative  adsorbent of  amorphous  silica with
weakly acidic properties.  It is produced from sodium silicate and sulfuric acid.
Silica gel can be used in column chromatography for the separation of analytes
from  interfering  compounds  of a different chemical polarity.   It  may be used
activated, after heating to 150 - 160°C, or deactivated with up to  10% water.

      1.2   This method includes guidance for  standard  column cleanup of sample
extracts  containing polynuclear  aromatic  hydrocarbons, derivatized  phenolic
compounds, organochlorine pesticides, and PCBs as Aroclors.

      1.3   This  method  also  provides  cleanup  procedures using  solid-phase
extraction  cartridges  for   pentafluorobenzyl   bromide-derivatized  phenols,
organochlorine pesticides, and PCBs as Aroclors.   This technique' also provides
the best separation of PCBs from most single component organochlorine pesticides.
When only PCBs are to be measured, this method can be used  in conjunction with
sulfuric acid/permanganate cleanup (Method 3665).

      1.4   Other analytes may be cleaned  up  using  this  method if  the analyte
recovery meets the criteria specified in Sec.  8.0,


2.0   SUMMARY OF METHOD

      2.1   This method  provides  the option  of  using either  standard  column
chromatography techniques or solid-phase extraction  cartridges.  Generally, the
standard column chromatography techniques use  larger amounts of adsorbent and,
therefore, have a greater cleanup capacity.

      2.2   In the standard column cleanup protocol, the column is  packed with
the required amount  of adsorbent, topped with a water adsorbent, and then loaded
with the sample to be analyzed.  Elution  of the analytes is  accomplished with a
suitable solvent(s)  that leaves the  interfering  compounds  on  the column.   The
eluate is then concentrated (if necessary).

      2.3   The cartridge cleanup protocol  uses  silica solid-phase extraction
cartridges packed with 1 g or 2 g of adsorbent.   Each cartridge  is solvent washed
immediately prior to use.   Aliquots of sample  extracts  are  loaded  onto  the
cartridges, which are then eluted with suitable solvent(s).  A vacuum manifold
is required  to  obtain reproducible  results.   The collected  fractions  may  be
further concentrated prior to gas chromatographic analysis.

      2.4   The appropriate gas chromatographic method is listed at the end of
each  technique.   Analysis  may also  be  performed by  gas  chromatography/mass
spectrometry (Method 8270).
                                   3630B  -  1                         Revision 2
                                                                September 1994

-------
3.0   INTERFERENCES

      3.1   Solvents, reagents, glassware,  and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms.  All  these materials  must be demonstrated  to be free from
interferences under the conditions of the analysis, by analyzing  reagent blanks.
See Sec. 8 for guidance on a reagent blank check.

      3.2   Phthalate  ester  contamination  may  be  a  problem with  certain
cartridges  The more inert  the  column  and/or  cartridge material  (i.e., glass or
Teflon),  the  less  problem with  phthalates.    Phthalates  create interference
problems for all method analytes, not just the  phthalate esters themselves.

      3.3   More extensive procedures  than  those outlined  in this method may be
necessary for reagent purification.


4.0   APPARATUS AND MATERIALS

      4.1   Chromatographic column - 250 mm  long  x  10 mm  ID;  with Pyrex glass
wool at bottom and a Teflon stopcock.

      NOTE: Fritted glass  discs  are difficult to  decontaminate  after  highly
            contaminated extracts have  been  passed  through.   Columns  without
            frits may  be  purchased.   Use  a  small  pad of Pyrex  glass wool  to
            retain the  adsorbent.  Prewash  the glass wool  pad with 50  ml  of
            acetone followed by  50 ml of elution  solvent  prior  to packing the
            column with adsorbent.

      4.2   Beakers - 500 ml.

      4.3   Vials - 2,  10, 25  ml, glass with Teflon lined screw-caps  or crimp
tops.

      4.4   Muffle furnace.

      4.5   Reagent bottle - 500  raL.

      4.6   Erlenmeyer flasks - 50 and 250 mL.

      4.7   Vacuum   manifold:    VacElute    Manifold   SPS-24    (Analytichem
Inte national),  Visiprep  (Supelco,  Inc.)   or equivalent,  consisting of  glass
vacuum basin, collection rack and funnel, collection vials,  replaceable stainless
steel  delivery  tips,  built-in   vacuum bleed  valve  and  gauge.   The system  is
connected to a vacuum  pump  or water aspirator through  a vacuum trap made from a
500 ml sidearm  flask fitted with  a one-hole stopper and  glass  tubing.


5.0   REAGENTS

      5.1   Reagent grade inorganic chemicals shall be used in all tests.  Unless
otherwise indicated,  it is intended  that  all  reagents  shall  conform to  the
specifications of the  Committee on Analytical Reagents of the American  Chemical
Society, where  such specifications are  available.  Other grades may  be  used,

                                  3630B -  2                         Revision 2
                                                                September 1994
                              \

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provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.

      5,2   Organic-free reagent water.  All  references to water  in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Silica gel for chromatography columns.

            5.3.1 Silica Gel for Phenols and  Polynuclear Aromatic Hydrocarbons:
      100/200 mesh desiccant (Davison Chemical grade 923 or equivalent).  Before
      use, activate for at least 16 hr.  at 130°C in a shallow glass tray, loosely
      covered with foil.

            5.3,2 Silica Gel for Organochlorine pesticides/PCBs:    100/200 mesh
      desiccant  (Davison Chemical  grade  923 or  equivalent).    Before  use,
      activate for  at  least 16 hr. at  130°C  in a  shallow glass  tray, loosely
      covered with foil.  Deactivate it to 3.3% with reagent water  in a SOO ml
      glass jar.   Mix  the  contents thoroughly and allow  to  equilibrate  for 6
      hours.  Store  the  deactivated silica gel  in  a  sealed glass jar inside a
      desiccator.

      5.4   Silica cartridges:  40 pm particles, 60 A pores. The cartridges with
which this method was developed consist of 6 ml serological-grade polypropylene
tubes, with the 1 g of silica held between two polyethylene or stainless steel
frits with 20 pm pores.   2 g silica cartridges are  also used in this  method, and
0.5 g cartridges are available.  The compound  elution patterns must  be verified
when cartridges other than the specified size are used.

      5.5   Sodium sulfate  (granular,   anhydrous), Na2S04.  Purify  by heating at
400°C for 4  hours in a shallow tray,  or by precleaning the sodium sulfate with
methylene chloride.   A method blank must be analyzed in order to demonstrate that
there is no interference from the sodium sulfate.

      5.6   Eluting solvents

            5.6.1 Cyclohexane,   C6H12 -  Pesticide quality  or equivalent.

            5.6.2 Hexane, CeH14 - Pesticide quality or  equivalent.

            5.6.3 2-Propanol, (CH3)2CHOH - Pesticide quality or equivalent.

            5.6.4 Toluene,  C6H5CH3  - Pesticide quality  or  equivalent.

            5.6.5 Methylene chloride,  CH2C12 - Pesticide quality or equivalent.

            5.6.6 Pentane,  C6H12 -  Pesticide quality or equivalent.

            5.6.7 Acetone,  CH3COCH3 - Pesticide quality or equivalent.

            5.6.8 Diethyl Ether, C2HSOC2HS.   Pesticide quality or  equivalent.
      Must be  free of  peroxides  as indicated  by test  strips  (EM  Quant,  or
      equivalent).  Procedures for removal of peroxides  are  provided with the
                                  3630B  -  3                         Revision 2
                                                                September 1994

-------
      test strips.   After cleanup,  20 ml of ethanol  preservative must be added
      to each liter of ether.

6.0   SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

      6.1   See the introductory material to this chapter, Organic Analytes, Sec.
4.1.


7.0   PROCEDURE

      7.1   General  Guidance

            7.1.1 The procedure contains two cleanup options for the derivatized
      phenols and organochlorine pesticides/Aroclors, but only one technique for
      the   polynuclear   aromatic   hydrocarbons    (PAHs)    (standard   column
      chromatography). Cleanup techniques by standard column chromatography for
      all analytes  are found  in  Sec.  7.2.   Cleanup techniques  by  solid-phase
      cartridges for  derivatized phenols and PAHs are found in Sec.  7.3.   The
      standard column  chromatography techniques are packed with a greater amount
      of silica gel adsorbent  and,  therefore,  have a greater cleanup  capacity.
      A rule  of thumb relating  to cleanup capacity  is  that  1  g  of  sorbent
      material will  remove  10  to  30 mg  of total  interferences.    (However,
      capacity  is   also   dependent  on  the  sorbent  retentiveness   of   the
      interferences.)   Therefore,  samples  that  exhibit  a greater degree  of
      sample interference  should be cleaned up by the standard  column technique.
      However, both techniques have limits on the amount of interference  that
      can be removed.   If the  interference  is  caused by high boiling  material,
      then Method 3640 should be used prior to this method.   If the interference
      is caused by  relatively  polar compounds  of  the same boiling range as  the
      analytes,  then multiple  column or cartridge cleanups  may be required.   If
      crystals of sulfur  are noted in the extract,  then Method 3660  should  be
      utilized prior to this method.  The cartridge cleanup techniques  are often
      faster and use  less  solvent,  however they have less cleanup capacity.

            7.1.2 Allow the  extract to reach room temperature  if it  was in  cold
      storage.  Inspect  the  extracts  visually to  ensure  that  there are  no
      particulates  or  phase  separations  and that the volume is  as stated in  the
      accompanying  documents.   Verify that the solvent is compatible  with  the
      cleanup procedures.  If  crystals of sulfur are visible or if the presence
      of sulfur is  suspected,  proceed with Method  3660.

            7.1.3 If the extract solvent is methylene chloride, for most cleanup
      techniques, it  must be exchanged to hexane.   (For the PAHs,  exchange  to
      cyclohexane  as  per Sec.  7.2.1).    Follow  the  standard  Kuderna-Danish
      concentration technique  provided in each extraction method.  The  volume of
      methyl ene chloride  should have been reduced to  1 -  2 ml.  Add  40 ml  of
      hexane, a  fresh  boiling chip and repeat the concentration as written.  The
      final  volume  required  for  the cleanup  techniques  is normally  2  mL.
                                  3630B - 4                         Revision  2
                                                                September  1994

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7.2   Standard Column Cleanup Techniques

      7.2.1 Polynuclear aromatic hydrocarbons

            7.2.1.1     Before the  silica  gel  cleanup technique  can be
      utilized, the extract solvent  must be exchanged to cyclohexane. The
      exchange  is  performed  by  adding 4  ml  of cyclohexane  following
      reduction of the  sample  extract  to  1-2 ml using the  macro Snyder
      column.   Attach  the two ball micro  Snyder column and  reduce the
      volume to 2 ml.

            CAUTION:     When the  volume of solvent is reduced below 1 ml,
                        semivolatile analytes  may  be  lost.    If  the
                        extract goes to dryness, the extraction  must be
                        repeated.

            7.2.1.2     Prepare a slurry of 10  g  of  activated silica gel
      (Sec. 5.3.1)  in methylene chloride and place this into  a  10  mm ID
      chromatographic column.  Tap the column to settle the silica gel and
      elute the methylene  chloride.  Add  1  to  2 cm of anhydrous sodium
      sulfate to the top of the silica  gel.

            7.2.1.3     Pre-elute the column with 40 ml of  pentane.  The
      rate for all  elutions should be about 2 rnL/min.   Discard the eluate
      and, just prior to exposure of the sodium sulfate layer to the air,
      transfer the  2  ml cyclohexane  sample  extract onto the column  using
      an additional 2 ml cyclohexane to  complete the transfer.  Just prior
      to exposure of the  sodium  sulfate layer  to the  air,  add 25  ml of
      pentane  and  continue the  elution  of  the  column.    Discard  this
      pentane eluate.

            7.2.1,4     Next,  elute the column with  25  ml of  methylene
      chloride/pentane  (2:3)(v/v)  into a 500 ml K-D  flask equipped with a
      10 ml  concentrator  tube.   Concentrate the collected fraction  to
      whatever volume is required (1-10 ml).  Proceed with  HPLC  (Method
      8310) or GC analysis (Method 8100).  Validated components that elute
      in this fraction  are:

            Acenaphthene
            Acenaphthylene
            Anthracene
            Benzo(a)anthracene
            Benzo(a)pyrene
            Benzo(b)f1uoranthene
            Benzo(g,h,i)perylene
            Benzo(k)f1uoranthene
            Chrysene
            Dibenzo(a,h)anthracene
            Fluoranthene
            Fluorene
            Indeno(l,2,3-cd)pyrene
            Naphthalene
            Phenanthrene
            Pyrene

                            3630B - 5                         Revision 2
                                                         September 1994

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7.Z.2  Derivatized Phenols

      7.2.2.1     This silica gel  cleanup  procedure is performed on
sample  extracts  that  have   undergone  pentafluorobenzyl  bromide
derivatization, as described  in  Method 8040.   The sample extract
must be in 2 ml of hexane at this point.

      7.2.2.2     Place 4.0 g of activated silica gel (Sec. 5.3.1)
into a 10 mm  ID chromatographic column.   Tap the column to settle
the silica gel and add about 2 g of anhydrous sodium sulfate to the
top of the silica gel.

      7.2.2.3     Pre-elute the column  with  6 ml  of hexane.   The
rate for all  elutions should be about 2 mL/rain.  Discard the eluate
and, just prior to exposure of the sodium  sulfate layer to the air,
pipet onto the column 2 ml of  the hexane solution that contains the
derivatized sample or  standard.  Elute  the column  with  10.0  mL of
hexane and discard the eluate.

      7,2.2.4     Elute the column, in order, with 10.0 mL of 15%
toluene in hexane  (Fraction  1);  10.0 mL of  40%  toluene in hexane
(Fraction 2);  10.0 ml of 75% toluene in  hexane  (Fraction  3);  and
10.0 ml of  15% 2-propanol  in toluene  (Fraction 4).  All  elution
mixtures are prepared  on a volume:volume  basis.   Elution patterns
for the phenolic derivatives are shown in Table 1.   Fractions may be
combined,   as   desired,  depending  upon the   specific  phenols  of
interest  or  level of  interferences.   Proceed  with GC  analysis
(Method 8040).

7.2.3 Organochlorine  Pesticides  and Aroclors

      7.2.3.1      Transfer a  3 g  portion of deactivated  silica gel
(Sec. 5.3.2) into a 10 mm ID glass chromatographic column and top it
with 2 to 3 cm of anhydrous  sodium sulfate.

      7.2.3.2      Add  10 ml of hexane to  the  top  of the column to
wet and rinse  the  sodium sulfate and  silica gel.   Just  prior to
exposure of the sodium sulfate layer to air, stop the hexane eluate
flow by closing the stopcock on the chromatographic  column.  Discard
the eluate.

      7.2.3.3      Transfer the sample extract  (2 mL in hexane) onto
the column.  Rinse the  extract vial twice  with 1  to 2 mL of hexane
and add each rinse to  the column.  Elute  the column  with  80  mL of
hexane (Fraction  I)   at a  rate  of about  5  mL/min.    Remove  the
collection flask and   set it aside for  later  concentration.   Elute
the column  with  50  mL of hexane  (Fraction   II)  and collect  the
eluate.  Perform a third elution with  15  mL  of  methylene chloride
(Fraction   III).   The  elution  patterns  for  the  organochlorine
pesticides,  Aroclor-1016, and  Aroclor-1260 are shown in  Table 2.

      7.2.3.4      Prior  to  gas  chromatographic   analysis,   the
extraction solvent must  be exchanged  to hexane. Fractions may be
combined,    as   desired,    depending    upon    the    specific

                       3630B - 6                         Revision  2
                                                    September 1994

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      pesticides/Aroclors of  interest  or  level  of  interferences.   If
      mixtures of Aroclors  and pesticides are expected,  it is  best to
      analyze  Fraction  I  separately,  since  it  contains  the  Aroclors
      separated from most  pesticides.  Proceed with  GC analysis  as  per
      Method 8081.

7.3   Cartridge Cleanup Techniques

      7.3.1 Cartridge Set-up and Conditioning

            7.3.1.1      Arrange the 1  g  silica cartridges (2 g for phenol
      cleanup) on the manifold in the  closed-valve  position.  Other size
      cartridges may  be used, however the data presented in the Tables are
      all   based  on  1   g  cartridges  for  pesticides/Aroclors  and  2  g
      cartridges for  phenols.  Therefore, supporting recovery data must be
      developed for other sizes.  Larger cartridges  will probably  require
      larger volumes  of elution solvents.

            7.3.1.2      Turn on the vacuum pump and set pump vacuum to 10
      inches  (254   mm)  of   Hg.   Do   not  exceed   the manufacturer's
      recommendation  for manifold vacuum. Flow rates can be  controlled by
      opening and closing cartridge valves.

            7.3.1.3      Condition the  cartridges by adding 4 mL  of hexane
      to each cartridge.  Slowly open the cartridge valves to allow hexane
      to pass through the sorbent beds to the lower  frits.  Allow a  few
      drops per cartridge to pass through  the manifold  to remove  all  air
      bubbles. Close the valves and allow the solvent to soak the entire
      sorbent bed for 5  minutes.   Do not turn off the vacuum.

            7.3.1.4      Slowly open cartridge valves  to allow the hexane
      to pass through the cartridges.   Close the cartridge valves when
      there is still  at  least  1 ran  of  solvent above the sorbent bed.   Do
      not  allow cartridges  to  become dry.  If cartridges go dry,  repeat
      the  conditioning  step.

      7.3.2 Derivatized  Phenols

            7.3.2.1      Reduce the  sample extract volume to E ml prior to
      cleanup. The  extract  solvent must be hexane and  the phenols must
      have undergone  derivatization by pentafluorobenzyl bromide,  as  per
      Method 8040.

            7.3.2.2      Transfer the extract to  the  2  g cartridge that  has
      been conditioned  as described in  Sec.  7.3.1.  Open the  cartridge
      valve to allow the extract to  pass through  the  cartridge   bed  at
      approximately 2 mL/minute.

            7.3.2.3      When the entire extract  has  passed through  the
      cartridges, but before the cartridge  becomes  dry,  rinse the sample
      vials with an additional  0.5 ml of hexane, and add the rinse to  the
      cartridges to complete the quantitative transfer.
                            3630B - 7                         Revision  2
                                                          September 1994

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       7.3.2.4      Close the cartridge valve and turn off  the  vacuum
after  the  solvent  has passed through, ensuring that the cartridge
never  gets dry.

       7.3.2.5      Place a  5 mL vial  or  volumetric flask into the
sample  rack corresponding  to the  cartridge  position.   Attach  a
solvent-rinsed stainless steel solvent guide to the manifold cover
and align with the collection vial.

       7.3.2.6     Add 5 mL of hexane to the cartridge.  Turn  on the
vacuum  pump  and  adjust  the  pump  pressure to 10 inches {254 mm) of
Hg.  Allow the solvent to soak the sorbent bed for 1 minute or less.
Slowly  open  the  cartridge  valve, and  collect  the eluate (this is
Fraction 1,  and  should be discarded).

      NOTE:  If cartridges smaller than 2 g are used, then Fraction
             1  cannot  be discarded,  since  it contains  some  of the
             phenols.

       7.3.2.7     Close the cartridge valve,  replace the collection
vial, and add 5 ml of toluene/hexane (25/75, v/v)  to the cartridge.
Slowly  open  the  cartridge  valve  and collect the  eluate  into the
collection vial.   This  is  Fraction  2, and should be retained for
analysis.

      7.3.2.8     Adjust the final volume  of the eluant to a known
volume which will result in analyte concentrations appropriate for
the  project  requirements   (normally  1 -  10 mL).   Table 3  shows
compound recoveries  for 2  g silica  cartridges.   The  cleaned  up
extracts are ready for analysis by Method  8040.

7.3.3 Organochlorine Pesticides/Aroclors

NOTE: The   silica  cartridge   procedure   is   appropriate   when
      polychlorinated biphenyls are known  to be present.

      7.3.3.1     Reduce the sample  extract volume to 2 mL prior to
cleanup.  The extract solvent must be hexane.

      7.3.3.2     Use the 1  g cartridges conditioned as described in
Sec. 7.3.1.

      7.3.3.3     Transfer the extract to  the cartridge.  Open the
cartridge valve to allow the extract to pass through the cartridge
bed at approximately 2 mL/minute,

      7.3.3.4     When the  entire extract has passed  through  the
cartridges, but before the cartridge becomes dry,  rinse the sample
vials with  an additional 0.5 ml of solvent, and  add the rinse to the
cartridges to complete the quantitative transfer.

      7.3.3.5     Close the cartridge valve and turn off the vacuum
after the solvent has passed  through,  ensuring  that the cartridge
never goes  dry.

                      3630B - 8                         Revision  2
                                                    September 1994

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                  7.3.3.6      Place  a 5 ml vial  or  volumetric flask into the
            sample  rack corresponding  to the  cartridge  position.   Attach a
            solvent-rinsed  stainless  steel solvent guide to the manifold cover
            and align with  the collection  vial.

                  7.3.3.7      Add 5 ml of hexane to the cartridge.  Turn on the
            vacuum  pump  and adjust  the pump  pressure to 10 inches (254 mm) of
            Hg.  Allow the solvent to  soak  the sorbent bed for  1 minute or less.
            Slowly  open  the cartridge  valve  and collect the  eluate into the
            collection vial  (Fraction  1).

                  7.3.3.8      Close the cartridge valve,  replace the  collection
           .vial, and  add  5 ml  of diethyl  ether/hexane (50/50,  v/v)  to the
            cartridge.   Slowly open the cartridge valve and collect  the eluate
            into the collection vial  (Fraction  2).

                  7.3.3.9      Adjust  the  final  volume  of  each  of the  two
            fractions  to   a  known   volume   which  will   result  in  analyte
            concentrations appropriate for the project  requirements (normally 1
            - 10 ml).  The  fractions may be combined prior to final  adjustment
            of volume,  if analyte fractionation is not  required.  Table 4 shows
            compound recoveries  for  1  g   silica  cartridges.   The  cleaned  up
            extracts are ready for analysis by Method 8081.


8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for  specific  quality  control  procedures and
Method 3600 for cleanup procedures.

      8.2   A reagent blank (consisting of the elution  solvents) must be passed
through the column or cartridge and checked for the compounds of interest, prior
to the use of this method.  This same performance check is required with each new
lot of adsorbent or  cartridges.  The  level of interferences must be below the
method detection limit before this method  is performed on actual  samples.

      8.3   The analyst must demonstrate that the compounds of interest are being
quantitatively recovered before applying this method to actual  samples.  See the
attached Tables for-acceptable recovery data.   For compounds that have not been
tested, recovery must be > 85%.

            8.3.1 Before  any  samples  are processed  using  the  solid-phase
      extraction cartridges, the efficiency of the cartridge must be verified.
      A recovery check  must be performed using standards of the target analytes
      at known concentration.  Only  lots  of cartridges that  meet the recovery
      criteria for the spiked compounds can be used to process the samples.

            8.3.2 A check  should also be performed on each individual  lot of
      cartridges and for every 300 cartridges of a particular lot.

      8.4   For sample  extracts  that  are cleaned up  using  this  method,  the
associated quality control  samples should also be processed through this cleanup
method.
                                   3630B  -  9                         Revision 2
                                                                September 1994

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9.0   METHOD PERFORMANCE

      9.1   Table  1  provides  performance information on the  fractionation of
phenolic derivatives using standard column chromatography.

      9.2   Table  2  provides  performance information on the  fractionation of
organochlorine pesticides/Aroclors using standard column chromatography.

      9.3   Table 3 shows recoveries of derivatized phenols obtained using 2 g
silica cartridges.

      9,4   Table  4  shows  recoveries   and  fractionation  of  organochlorine
pesticides obtained using 1  g silica cartridges.


10.0  REFERENCES

      1.     U.S. EPA 40 CFR  Part 136,  "Guidelines Establishing Test Procedures
            for the Analysis of Pollutants Under the Clean Water Act; Final Rule
            and Interim Final  Rule and Proposed Rule,"  October 26,  1984.

      2.     U.S EPA  "Evaluation  of Sample  Extract Cleanup Using  Solid-Phase
            Extraction Cartridges," Project  Report, December 1989,
                                  3630B  -  10                         Revision 2
                                                                September 1994

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                                    TABLE 1
                   SILICA  GEL  FRACTIONATION OF PFBB DERIVATIVES
                                        Percent Recovery by Fraction3

Parameter                          123
2-Chlorophenol
2-Nitrophenol
Phenol
2 , 4-Dimethyl phenol
2,4-Dichlorophenol
2,4, 6-Tri chl orophenol
4-Cnloro-3 -methyl phenol
Pentachl orophenol
4-Nitrophenol
90

90
95
95
50 50
84
75 20

1
9
10
7
1

14

1

90






90
a  Eluant composition:

    Fraction 1 - 15% toluene in hexane.
    Fraction 2 - 40% toluene in hexane.
    Fraction 3 - 75% toluene in hexane.
    Fraction 4 - 15% 2-propanol in toluene.

Data from Reference 1 (Method 604)
                                  3630B - 11                        Revision 2
                                                                September 1994

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                              TABLE 2
       DISTRIBUTION ANP PERCENT RECOVERIES OF ORGANOCHLORINE
PESTICIDES AND PCBs A'   OCLORS IN SILICA GEL COLUMN FRACTIONSa-b'cde
      Fraction I
Fraction II
Fraction III
Total Recovery
Compound
alpha-BHCf
beta-BHC
gamma -BHC
delta-BHC
Heptachlor
Aldrin
Heptachlor epoxide
Technical chlordane
Endosulfan I
4,4'-DDE
Dieldrin
Endrin
Endosulfan II
4, 4 '-ODD'
Endrin aldehyde
Endosulfan sulfate
4, 4' -DDT'
4,4'-Methoxychlor
Toxaphene*
Aroclor-1016
Aroclor-1260
COIIL.
1




109(4
97(5

14(5

86(5









86(4
91(4





•1)
.6)

.5)

.4)









.0)
•1)
Cone.
2




118(8
104(1

22(5

94(2









87(6
95(5





•7)
.6)

.3)

.8)









•1)
.0)
Cone. Cone. Cone.
1 2 1
82(1
107(2
91(3
92(3


95(4
19(6.8) 39(3.6) 29(5
95(5

96(6
85(10
97(4
102(4
81(1
93(4
86(13.4) 73(9.1) 15(17
99(9
15(2.4) 17(1.4) 73(9



•7)
•1)
.6)
.5)


•7)
.0)
•1)

.0)
.5)
•4)
.6)
•9)
•9)
•7)
•9)
•4)


Cone.
2
74(8
98(12
85(10
83(10


88(10
37(5
87(10

87(10
71(12
86(10
92(10
76(9
82(9
8.7(15
82(10
84(10



.0)
.5)
•7)
.6)


•2)
•1)
•2)

.6)
.3)
•4)
•2)
.5)
•2)
.0)
•7)
•7)


Cone.
1
82(1.
107(2.
91(3.
92(3.
109(4.
97(5.
95(4.
62(3.
95(5.
86(5.
96(6.
85(10.
97(4.
102(4.
81(1.
93(4.
101(5.
99(9.
88(12.
86(4.
91(4.

7)
1)
6)
5)
1)
6)
7)
3)
1)
4)
0)
5)
4)
6)
9)
9)
3)
9)
0)
0)
1)
Cone.
2
74(8.0)
98(12.5)
85(10.7)
83(10.6)
118(8.7)
104(1.6)
88(10.2)
98(1.9)
87(10.2)
94(2.8)
87(10.6)
71(12.3)
86(10.4)
92(10.2)
76(9.5)
82(9.2)
82(23.7)
82(10.7)
101(10.1)
87(6.1)
95(5.0)
                             3630B - 12
                                                      Revision 2
                                                  September 1994

-------
                                               TABLE 2
                                             (Continued)
Effluent composition:  Fraction  I, 80  ml  hexane;  Fraction  II,  50 ml hexane; Fraction III, 15 ml methylene
chloride.

Concentration 1 is 0.5 /ug per column  for BHCs, Heptachlor, Aldrin, Heptachlor epoxide, and Endosulfan  I;  1.0
/ng  per  column for  Dieldrin, Endosulfan  II,  4,4'-DDD,  4,4'-DDE,  4,4'-DDT, Endrin,  Endrin  aldehyde,  and
Endosulfan sulfate;  5 /ug per column for  4,4'-Methoxychlor and technical Chlordane;  10  /ug per column  for
Toxaphene, Aroclor-1016,  and Aroclor-1260.

For Concentration 2,  the amounts spiked are 10 times as  high as those for Concentration  1.

Values given represent the average  recovery of three determinations; numbers in parentheses are the standard
deviation; recovery cutoff point is 5 percent.

Data obtained with standards, as indicated in footnotes  b and c, dissolved  in 2 ml hexane.

It has been found that because of batch-to-batch variation in the silica gel  material, these compounds  cross
over in two fractions and the amounts recovered in each  fraction are difficult to reproduce.
                                              3630B  -  13                                          Revision  2
                                                                                             September  1994

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                                      TABLE 3
                  PERCENT RECOVERIES AND ELUTION PATTERNS FOR  18
                        PHENOLS FROM 2 g SILICA CARTRIDGES8
                                                    Fraction 2
                                                Average     Percent
      Compound                                  Recovery      RSD
Phenol
2-Methyl phenol
3-Methyl phenol
4-Methyl phenol
2, 4-Di methyl phenol
2-Chlorophenol
2,6-Dichlorophenol
4-Chl oro-3-methyl phenol
2,4-Dichlorophenol
2,4,6-Trichloropheriol
2, 3, 6-Tri chl orophenol
2, 4, 5-Tri chl orophenol
2,3, 5-Tri chl orophenol
2,3,5,6-Tetrachlorophenol
2,3,4, 6-Tetrachl orophenol
2, 3, 4-Tri chl orophenol
2,3 , 4, S-Tetrachl orophenol
Pentachl orophenol
74.1
84.8
86.4
82.7
91.8
88.5
90.4
94.4
94.5
97.8
95.6
92.3
92.3
97.5
97.0
72.3
95.1
96.2
5.2
5.2
4.4
5.0
5.6
5.0
4.4
7.1
7.0
6.6
7.1
8.2
8.2
5.3
6.1
8.7
6.8
8.8
a     Silica cartridges  (Supelco,  Inc.) were  used;  each cartridge was conditioned
      with 4 ml of hexane prior to use.  Each  experiment was performed  in duplicate
      at three spiking concentrations  (0.05 /ig,  0.2  M9i  and 0.4 ^g per  compound per
      cartridge).   Fraction  1  was eluted  with  5  ml  hexane  and  was discarded.
      Fraction 2 was eluted with 5 ml  toluene/hexane (25/75,  v/v).

Data from Reference 2
                                    3630B - 14                          Revision 2
                                                                    September  1994
                                                      \

-------
                                      TABLE 4
           PERCENT RECOVERIES AND ELUTION PATTERNS FOR 17 ORGANOCHLORINE
                PESTICIDES AND AROCLORS FROM 1 g SILICA CARTRIDGES8
Compound
     Fraction 1
Average     Percent
Recovery      RSD
     Fraction 2
Average     Percent
Recovery      RSD
alpha-BHC
gamma -BHC
beta-BHC
Heptachlor
delta-BHC
Aldrin
Heptachlor epoxide
Endosulfan I
4,4'-DDE
Dieldrin
Endrin
4,4'-DDD
Endosulfan II
4, 4' -DDT
Endrin aldehyde
Endosulfan sulfate
4,4'-Methoxychlor
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1264
0
0
0
97.3 1.3
0
95.9 1.0
0
0
99.9 1.7
0
0
10.7 41
0
94.1 2.0
0
0
0
124
93.5
118
116
114
108
112
98.7
94.8
94.3
0
90.8
0
97.9
102
0
92.3
117
92.4
96.0
0
59.7
97.8
98.0







2.3
1.9
3.0

2.5

2.1
2.3

2.0
2.6
3.3
2.2

2.6
2.1
2.4







a     Silica cartridges  (Supelco,  Inc.  lot SP0161) were  used;  each cartridge was
      conditioned with 4 mL hexane prior to use.  The organochlorine  pesticides were
      tested separately  from  PCBs.   Each organochlorine pesticides experiment was
      performed in duplicate, at three spiking concentrations (0.2 ^g, 1.0 pig, and
      2.0  ^g  per compound  per cartridge).   Fraction 1  was  eluted with  5  ml  of
      hexane.  Fraction 2 with 5 ml of diethyl  ether/hexane (50/50, v/v).  PCBs were
      spiked at 10 jig per cartridge  and were eluted with 3 mL of hexane.   The values
      given for PCBs are the percent recoveries for a single determination.

Data from Reference 2
                                    3630B - 15
                                          Revision 2
                                      September 1994

-------
                                            METHOD  3630B
                                       SILICA  GEL  CLEANUP
                  7.2 Standard
                Column Cleanup
                                                                             7,3.1 Cartridg
                                                                                S*t-up *
                                                                              Conditioning.
   7.2.2,1  Do PF8B
   derivatizatten an
   temple extract
      (8040),
   7.2.2.2 Piece
 activated ailica gel
 in ehromaiographic
    column; add
anhydrous Ne2SO*.
  7.2.2.3 Praaluta
column with hexan*;
    pioat n»xan«
tolutton onto column;
      •lut*.
7.2.2.4 Elut* column
    with specified
     solvanta.
      Analyze
      SV GC
      (Method
      80401.
 7.2.3.1 Deactivate
  »ilici gal, prepare
      column.
                                I
                           7.2.3.2 ilute the
                              <3C colun^
                             with heiene.
  7.2.3.3 Trenefer
extract onto column
   and a Jute wltrt
 (pacified lolvantt.
7.3.4 Exchange tne
  •lution ao
-------
  METHOD  3630B
   (continued)
      0
      !PAHs»
    7.2 Standard
  Column Cleanup.
 7.2.1.1 Exchange
 extract solvent to
cyclohexana during
  K-D procedure.
 7,2.1.2 Prepare
 slurry activated
 silica gel, prepare
     column.
  7.2.1.3 Prielute
   column with
 pontano, transfer
extract onto column
  and eluto with
     pentane.
   7.2,1.4 Elute
   colymn with
 CH2CI2 /pentane;
    concentrate
 collected fraction;
   adjust volume.
     Analyze
  by GC Method
     8100 or
      GC/MS
     Method
      8270.
   3630B -  17
     Revision  2
September  1994

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                                 METHOD 3640A

                            GEL-PERHEATION CLEANUP
1.0   SCOPE AND APPLICATION

      1.1   Gel-permeation  chromatography  {GPC} is  a size exclusion  cleanup
procedure  using  organic solvents  and hydrophobic gels  in the  separation  of
synthetic raacromolecules (1).  The packing gel is porous and is characterized by
the range or uniformity (exclusion range) of that pore size.   In the choice of
gels, the exclusion  range must be larger than the molecular size of the molecules
to be separated (2).  A cross-linked divinyl benzene-styrene copolymer (SX-3 Bio
Beads or equivalent}  is specified for this method.

      1.2   General  cleanup application - GPC is recommended for the elimination
from the sample of  lipids,  polymers,  copolymers, proteins, natural  resins and
polymers, cellular components, viruses, steroids, and dispersed high-molecular-
weight compounds (2).   GPC is appropriate for both polar and non-polar analytes,
therefore, it  can be  effectively used to cleanup extracts containing  a  broad
range of analytes.

      1.3   Specific application -  This method  includes guidance for cleanup of
sample extracts containing the following analytes from the RCRA Appendix VIII and
Appendix IX lists:
      Compound Name                                            CAS No.'
      Acenaphthene                                             83-32-9
      Acenaphthylene                                          208-96-8
      Acetophenone                                             98-86-2
      2-Acetylaminofluorene                                    53-96-3
      Aldrin                                                  309-00-2
      4-Aminobiphenyl                                          92-67-1
      Aniline                                                  62-53-3
      Anthracene                                              120-12-7
      Benomyl                                               17804-35-2
      Benzenethiol                                            108-98-5
      Benzidine                                                92-87-5
      Benz(a)anthracene                                        56-55-3
      Benzo(b)fluoranthene                                    205-99-2
      Benzo(a)pyrene                                           50-32-8
      Benzo(ghi)perylene                                      191-24-2
      Benzo(k)fluoranthene                                    207-08-9
      Benzole acid                                             61-85-0
      Benzotrichloride                                         98-07-7
      Benzyl alcohol                                          100-51-6
      Benzyl chloride                                         100-44-7
      alpha-BHC                                               319-84-6
      beta-BHC                                                319-85-7
                                  3640A - 1                         Revision 1
                                                                September 1994

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Compound Name
gamma-BHC
delta-BHC
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2 -sec-butyl- 4, 6-dinitrophenol (Dinoseb)
Carbazole
Carbendazim
alpha-Chlordane
gamma-Chlordane
4-Ch1oro-3-methyl phenol
4-Chloroaniline
Chi orobenzi late
Bis{2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl ) ether
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenol
3-Chlorophenol
4-Chlorophenyl phenyl ether
3-Chloropropionitrile
Chrysene
2-Cresol
3-Cresol
4-Cresol
Cyclophosphamide
ODD
DDE
DDT
Di-n-butyl phthalate
Diallate
Dibenzo{a,e)pyrene
Dibenzo(a,i)pyrene
Dibenz(a,j)acridine
Dibenz( a, h) anthracene
Dibenzofuran
Di benzoth i ophene
1 ,2-Di brorno-3-chl oropropane
1,2-Dibromoethane
trans- l,4-Dichloro-2-butene
cis-l»4-Dichloro-2-butene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3' -Dichlorobenzidi ne
2,6-Dlchlorophenol
2,4-Dichlorophenoxyacetic acid (2,4-D)
2,4-Dichlorophenol
CAS No."
58-89-9
319-86-8
101-55-3
85-68-7
88-85-7
86-74-8
10605-21-7
5103-71-9
5566-34-7
59-50-7
106-47-8
510-15-6
111-91-1
111-44-4
108-60-1
91-58-7
95-57-8
106-48-9
108-43-0
7005-72-3
542-76-7
218-01-9
95-48-7
108-39-4
106-44-5
50-18-0
72-54-8
72-55-9
50-29-3
84-74-2
2303-16-4
192-65-4
189-55-9
224-42-0
53-70-3
132-64-9
132-65-0
96-12-8
106-93-4
110-57-6
1476-11-5
95-50-1
106-46-7
541-73-1
91-94-1
87-65-0
94-75-7
120-83-2
3640A - 2
    Revision 1
September 1994

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Compound Name
2,4-Dichlorotoluene
1 ,3-Di chl oro-2-propanol
Dieldrin
Diethyl phthalate
Dlmethoate
Dimethyl phthalate
p-Di methyl ami noazobenzene
7,12-Dimethyl-benz(a)anthracene
2,4-Dimethylphenol
3,3-Dimethylbenzidine
4,6-Dinitro-o-cresol
1,3-Dinitrobenzene
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
Diphenyl ether
1 , 2 - Di phenyl hydr az i ne
Disulfoton
Endosulfan sulfate
Endosulfan I
Endosulfan II
Endrin
Endrin aldehyde
Endrin ketone
Ethyl methane sulfonate
Ethyl methacrylate
Bis(2-ethylhexyl) phthalate
Famphur
Fluorene
Fluoranthene
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachlorobutadiene
Hexachl orocycl opentadiene
Hexachl oroethane
Hexachl oropropene
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
cis-Isosafrole
trans- I sosaf role
Kepone
Malononitrile
Merphos
Methoxychlor
3-Methylcholanthrene
CAS No/
95-73-8
96-23-1
60-57-1
84-66-2
60-51-5
131-11-3
60-11-7
57-97-6
105-67-9
119-93-7
534-52-1
99-65-0
51-28-5
121-14-2
606-20-2
122-39-4
101-84-8
122-66-7
298-04-4
1031-07-8
959-98-8
33213-65-9
72-20-8
7421-93-4
53494-70-5
62-50-0
97-63-2
117-81-7
52-85-7
86-73-7
206-44-0
76-44-8
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
1888-71-7
193-39-5
465-73-6
78-59-1
17627-76-8
4043-71-4
143-50-0
109-77-3
150-50-5
72-43-5
56-49-5
3640A - 3
    Revision 1
September 1994

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Compound Name
2-Methyl naphthalene
Methyl parathion
4,4'-Methylene-bis(2-chloroaniline)
Naphthalene
1,4-Naphthoquinone
2-Naphthylamine
1-Naphthylamine
5-Nitro-o-toluidine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
2-N1trophenol
4-Nitrophenol
N-Ni trosodi-n- butyl ami ne
N-Nitrosodiethanolatnine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Ni trosodi -n-propyl amine
N-Ni trosomethyl ethyl ami ne
N-Nitrosomorpholine
N-Ni trosopi peri dine
N-Nitrosopyrol idine
Di-n-octyl phthalate
Parathion
Pentachl orobenzene
Pentachl oroethane
Pentachl oronitrobenzene (PCNB)
Pentachl orophenol
Phenacetin
Phenanthrene
Phenol
1,2-Phenylenediamine
Phorate
2-Picoline
Pronamide
Pyrene
Resorcinol
Safrole
1 , 2 , 4, 5-Tetrachl orobenzene
2, 3, 5, 6-Tetrachl oronitrobenzene
2 » 3 , 5 , 6-Tetrachl orophenol
2,3, 4 , 6-Tetrachl orophenol
Tetraethyl dithiopyrophosphate (Sulfotep)
Thiosemicarbazide
2-Toluidine
4-Toluidine
CAS No.a
91-57-6
298-00-0
101-14-4
91-20-3
130-15-4
91-59-8
134-32-7
99-55-8
88-74-4
99-09-2
100-01-6
98-95-3
79-46-9
100-02-7
924-16-3
1116-54-7
55-18-5
62-75-9
86-30-6
621-64-7
10595-95-6
59-89-2
100-75-4
930-55-2
117-84-0
56-38-2
608-93-5
76-01-7
82-68-8
87-86-5
62-44-2
85-01-8
108-95-2
95-54-5
298-02-2
109-06-8
23950-58-5
129-00-0
108-46-3
94-59-7
95-94-3
117-18-0
935-95-5
58-90-2
3689-24-5
79-19-6
106-49-0
95-53-4
3640A - 4
    Revision 1
September 1994

-------
      Compound Name                                             CAS No."
Thiourea, l-(o-chlorophenyl)
Toluene-2,4~diamine
1, 2, 3-Triehloro benzene
1 , 2 » 4-TH chl orobenzene
2 , 4 , 6-Tri chl orophenol
2 j4 , 5-Tri chl orophenol
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)
2,4,5-Trichlorophenoxypropionic acid (2,4,5-TP)
Warfarin
5344-82-1
95-80-7
87-61-6
120-82-1
88-06-2
95-91-4
93-76-5
93-72-1
81-81-2
      *  Chemical Abstract Services Registry Number.

      Table  1 presents average percent recovery and percent RSD data for these
analytes,  as well as the  retention volumes of  each  analyte on  a  single GPC
system.   Retention volumes  vary  from  column  to column.    Figure  1 provides
additional information on  retention volumes for certain classes of compounds.
The data for the semivolatiles were determined by  GC/MS, whereas, the pesticide
data were  determined  by  GC/ECD or GC/FPD.   Compounds not  amenable  to GC were
determined by HPLC.   Other analytes may  also be  appropriate for this cleanup
technique, however, recovery through the  GPC should be >70%,

      1.4    Normally, this method  is most efficient for removing high boiling
materials that condense in the injection  port area of a gas ehromatograph (GC)
or  the  front  of  the  GC   column.    This  residue will  ultimately  reduce  the
chromatographic  separation efficiency or  column capacity because of adsorption
of the target analytes on  the  active sites,  Pentachlorophenol  is especially
susceptible to this problem,  GPC,  operating on the principal  of size exclusion,
will not usually remove interference  peaks that appear in the ehromatogram since
the molecular size of these compounds is relative similar to  the target analytes.
Separation cleanup techniques, based on other molecular characteristics (i.e.,
polarity), must  be used to eliminate this type of interference.


2.0   SUMMARY OF METHOD

      2.1   The  column   is  packed with  the  required  amount  of  preswelled
absorbent, and is  flushed  with solvent for  an  extended  period.   The column is
calibrated and then loaded  with the sample extract to  be  cleaned up.  Elution is
effected with a  suitable solvent(s) and the product is then concentrated,


3.0   INTERFERENCES

      3.1   A reagent blank should be analyzed for the compound of  interest prior
to  the  use  of  this method.   The  level  of interferences  must  be  below the
estimated quantitation limits  (EQLs) of  the analytes of interest before this
method is perfoned on actual samples.


                                   3640A  - 5                        Revision 1
                                                                September 1994

-------
      3.2   More extensive procedures than  those outlined in this method may be
necessary for reagent purification.


4.0   APPARATUS

      4.1   Gel-permeation chromatography  system  -  6PC Autoprep Model  1002  A
or B,  or equivalent,  Analytical  Biochemical  Laboratories,  Inc.  Systems  that
perform  very  satisfactorily  have  also  been assembled  from  the  following
components -  an HPLC pump, an auto sampler or a valving  system with sample loops,
and a  fraction collector.  All  systems,  whether automated  or  manual,  must meet
the calibration requirements of Sec. 7.2.2.

            4.1.1 Chromatographic column -  700 mm x 25  mm ID glass column.  Flow
      is upward.   (Optional)  To  simplify switching from the UV detector during
      calibration to the GPC collection device during extract cleanup, attach  a
      double  3-way  valve  (Rheodyne  Type  50  Teflon Rotary  Valve  #10-262 or
      equivalent) so that the column exit flow can be  shunted either  to the UV
      flow-through cell  or to the SPC collection device.

            4.1.2 Guard  column  -  (Optional)  5 cm,  with appropriate  fittings to
      connect to the  inlet side of  the  analytical  column  (Supelco  5-8319 or
      equivalent).

            4.1.3 Bio Beads (S-X3)  - 200-400  mesh,  70  g (Bio-Rad Laboratories,
      Richmond, CA,  Catalog 152-2750 or  equivalent).   An additional 5 g of Bio
      Beads are required if the optional  guard column is employed.  The quality
      of Bio Beads may vary from lot to  lot because  of excessive fines in  some
      lots.    The  UV  chromatogram of the Calibration  solution should  be  very
      similar to that in  Figure 2, and the  backpressure  should be  within 6-
      10 psi.  Also,  the gel swell ratio 1n methylene chloride should  be in the
      range of 4.4 - 4.8 mL/g.  In addition  to fines having  a detrimental effect
      on chromatography,  they  can   also  pass  through   the  column screens  and
      damage the  valve.

            4.1.4 Ultraviolet detector - Fixed wavelength (254 nm) with a semi-
      prep  flow-through  cell.

            4.1.5 Strip  chart recorder, recording integrator or laboratory data
      system.

            4.1.6 Syringe - 10  mL with Luerlok fitting.

            4.1.7 Syringe filter assembly,  disposable  - Bio-Rad "Prep  Disc"
      sample  filter assembly #343-0005,  25 ram, and 5  micron filter  discs or
      equivalent.    Check  each  batch for  contaminants.   Rinse  each  filter
      assembly (prior to use) with  methylene  chloride  if necessary.

      4.2    Analytical balance  -  0.0001  g.

      4.3    Volumetric flasks,  Class A -  10 mL  to  1000 mL

      4.4    Graduated cylinders


                                  3640A - 6                        Revision  1
                                                                September  1994

-------
5.0  REAGENTS

      5.1   Methylene chloride, CH2C12,   Pesticide quality or equivalent.

            5.1.1 Some  brands  of methylene chloride  may contain unacceptably
      high  levels  of acid  (HC1).   Check the pH  by  shaking  equal  portions of
      methylene chloride and water, then check the pH of the water layer.

                  5.1.1.1      If the  pH  of the  water layer is < 5,  filter the
            entire  supply  of  solvent through  a  2  in.  x 15  in.  glass  column
            containing  activated  basic   alumina.    This  column  should  be
            sufficient  for  processing approximately  20-30 liters  of solvent.
            Alternatively,  find a different supply of methylene chloride.

      5.2   Cyclohexane, C6H12.   Pesticide  quality or  equivalent,

      5.3   n-Butyl chloride, CH3CH2CH2CH2C1.  Pesticide quality or equivalent.

      5.4   GPC  Calibration  Solution.     Prepare  a  calibration  solution  in
methylene chloride containing the following analytes  (in elution order):

      Compound                              mg/L
      corn oil                             25,000
      bis(2-ethylhexyl) phthalate           1,000
      methoxychl or                           200
      perylene                                20
      sulfur                                  80

      NOTE: Sulfur is not  very soluble  in  methylene  chloride,  however,  it is
            soluble in warm corn oil.  Therefore, one approach is to weigh out
            the corn oil, warm  it and transfer the weighed amount of sulfur into
            the warm corn oil.  Mix it and then transfer  into a volumetric flask
            with methylene chloride, along with the other calibration compounds.

      Store the calibration  solution in an amber glass bottle with a Teflon lined
screw-cap at 4°C, and protect from light.   (Refrigeration  may cause the corn oil
to precipitate.  Before use,  allow the calibration solution  to  stand  at room
temperature until the corn  oil dissolves.)  Replace  the calibration standard
solution every 6 months, or more frequently if necessary,

      5.5   Corn Oil Spike for Gravimetric Screen.  Prepare a solution of corn
oil in methylene chloride (5 g/100 ml).


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the introductory material  to this chapter,  Organic Analytes, Sec.
4.1.
                                  3640A  -  7                         Revision 1
                                                                September 1994

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7.0  PROCEDURE

      7.1   It  Is  very important to  have consistent  laboratory  temperatures
during an entire 6PC run,  which  could  be 24 hours or more.  If temperatures are
not consistent,  retention times will  shift,  and the  dump and collect  times
determined by the calibration standard will no longer be appropriate.  The ideal
laboratory temperature to prevent outgassing  of  the  tnethylene chloride is 72°F.

      7.2   SPC Setup and Calibration

            7.2.1 Column Preparation

                  7.2.1.1     Weigh out 70 g of Bio Beads  (SX-3),  Transfer them
            to a quart  bottle with a  Teflon  lined cap or  a 500 ml  separatory
            funnel  with a large  bore  stopcock, and add approximately 300 ml of
            methylene chloride.   Swirl the container to  ensure the  wetting of
            all  beads.   Allow the beads  to  swell  for a minimum  of 2  hours.
            Maintain enough  solvent  to sufficiently  cover the  beads  at  all
            times.   If a guard column  is to  be used, repeat the above with 5 g
            of  Bio  Beads in  a   125 ml  bottle  or  a  beaker,  using  25  ml  of
            methylene chloride.

                  7.2.1.2     Turn  the  column  upside down  from  its   normal
            position,  and  remove the  inlet  bed  support  plunger  (the  inlet
            plunger is longer than the outlet plunger).   Position and tighten
            the outlet bed support plunger as near the  end as  possible,  but no
            closer than 5 cm (measured from  the  gel  packing to the collar).

                  7.2.1.3     Raise  the end  of the outlet tube  to keep  the
            solvent in the GPC column, or close the column outlet stopcock if
            one is  attached.   Place a  small  amount of  solvent  in the  column to
            minimize the formation of  air  bubbles  at the  base  of poured  column
            packing.

                  7.2.1.4     Swirl the bead/solvent slurry to get a homogeneous
            mixture and,  if the  wetting  was  done in  a quart bottle, quickly
            transfer  it  to a  500 mL separatory  funnel  with  a  large  bore
            stopcock.  Drain the excess methylene chloride directly into  the
            waste beaker,  and then start draining the slurry into  the column by
            placing the separatory funnel  tip against  the column wall.    This
            will  help to minimize bubble formation.  Swirl occasionally to keep
            the slurry  homogeneous. Drain  enough to  fill  the column.   Place the
            tubing  from the column outlet into a waste  beaker below the column,
            open the stopcock (if attached)   and  allow the excess solvent  to
            drain.   Raise  the tube to stop the flow and close the  stopcock when
            the top of the gel  begins to  look dry.   Add  additional  methylene
            chloride to just rewet the gel.

                  7.2.1.5     Wipe  any remaining  beads  and  solvent from  the
            inner walls of  the  top  of  the  column  with  a laboratory tissue.
            Loosen   the  seal   slightly on  the  other   plunger  assembly   (long
            plunger) and insert  it  into the column.   Make  the seal just  tight
                                  3640A - 8                         Revision 1
                                                                September 1994

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enough  so  that  any  beads  on  the  glass  surface will  be  pushed
forward, but loose enough so that the plunger can be pushed  forward.

      CAUTION:    Do  not tighten the seal  if beads  are between  the
                  seal  and  the glass  surface  because this  can
                  damage the seal and cause leakage.

      7.2.1.6     Compress  the  column  as  much  as possible without
applying excessive  force.   Loosen  the  seal and gradually pull  out
the plunger.  Rinse and wipe off the plunger.   Slurry any remaining
beads and  transfer  them into  the  column.   Repeat Sec.  7.2.1.5  and
reinsert the plunger.  If the  plunger cannot be inserted and  pushed
in  without allowing  beads to  escape  around  the  seal,  continue
compression of the beads without tightening the seal, and loosen  and
remove the plunger  as described.   Repeat  this  procedure until  the
plunger is  successfully inserted.

      7.2.1.7     Push  the  plunger until  it  meets the  gel, then
compress the column bed about four centimeters.

      7.2.1.8     Pack the optional 5 cm column with approximately
5 g  of  preswelled   beads   (different  guard columns  may  require
different  amounts).   Connect the guard  column  to the  inlet of  the
analytical  column.

      7.2.1.9     Connect the column inlet  to the  solvent reservoir
(reservoir  should be placed higher than the top of the column)  and
place the  column outlet  tube  in  a waste  container.    Placing a
restrictor  in the outlet tube will  force air out of the column more
quickly.    A  restrictor can  be made  from a  piece of  capillary
stainless  steel  tubing  of  1/16"  OD x  10/1000"  ID x  2".   Pump
methylene chloride through the  column at a  rate of 5 mL/min for  one
hour,

      7.2.1.10    After washing the  column  for at least  one hour,
connect the column outlet tube, without the  restrictor, to the inlet
side of the UV detector.  Connect  the  system outlet to the outlet
side  of  the  UV  detector.   A  restrictor  (same  size  as  in Sec.
7.2.1.9) in the outlet tube from the UV detector will prevent bubble
formation which causes a noisy UV baseline.   The restrictor will  not
effect flow rate.   After  pumping  methylene chloride  through  the
column for  an  additional  1-2  hours, adjust the  inlet  bed  support
plunger until  approximately  6-10 psi backpressure is achieved.  Push
the plunger in to  increase pressure or slowly pull  outward to reduce
pressure.

      7.2.1.11    When the GPC  column is not to be used for several
days, connect the column outlet  line to  the column inlet to prevent
column drying and/or channeling.  If channeling  occurs, the gel must
be removed  from  the column, reswelled, and repoured  as  described
above.   If  drying  occurs,  methylene   chloride  should be  pumped
through the column  until the observed  column pressure  is constant
and the column appears wet.  Always recalibrate after column drying
has occurred to verify retention volumes have not changed.

                       3640A - 9                         Revision 1
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7.2.2 Calibration of the GPC Column

      7.2.2.1     Using a  10 ml  syringe,  load  sample loop #1 with
calibration solution (Sec.  5,6).  With the ABC automated system, the
5 ml  sample loop requires a minimum  of  8 ml of  the calibration
solution.  Use a firm, continuous pressure to push the sample onto
the loop.  Switch the  valve so that GPC flow is  through the UV flow-
through cell.

      7.2.2.2     Inject the calibration  solution  and obtain a UV
trace  showing  a discrete  peak  for each  component.   Adjust  the
detector and/or recorder sensitivity to produce a UV trace similar
to Figure  2 that meets  the  following  requirements.   Differences
between manufacturers' cell volumes and detector sensitivities may
require a dilution  of  the  calibration  solution to  achieve similar
results.  An analytical  flow-through detector  cell  will  require a
much  less   concentrated  solution  than  the semi-prep  cell,  and
therefore the analytical  cell is not acceptable for use.

      7.2.2.3     Following  are  criteria  for evaluating  the  UV
chromatogram for column condition.

            7.2.2.3.1   Peaks  must  be observed,  and  should  be
      symmetrical,  for all  compounds in the calibration solution.

            7.2.2.3.2   Corn oil  and phthalate peaks  must  exhibit
      >85% resolution.

            7.2.2.3.3   Phthalate  and  methoxychlor   peaks   must
      exhibit >85% resolution.

            7.2.2.3.4   Methoxychlor and perylene peaks must exhibit
      >85% resolution.

            7.2.2.3,5   Perylene   and  sulfur  peaks  must  not  be
      saturated and must exhibit  >90% baseline  resolution.

            7.2.2.3.6   Nitroaromatic  compounds  are  particularly
      prone to adsorption.   For  example,  4-nitrophenol  recoveries
      may be low due  to  a portion of  the  analyte  being  discarded
      after the  end of the  collection time.   Columns should  be
      tested with the  semivolatiles matrix  spiking  solution.   GPC
      elution should continue until  after  perylene  has  eluted,  or
      long  enough to recover at least 85% of the analytes, whichever
      time  is longer,

      7.2.2.4     Calibration  for   Semivolatiles   -  Using   the
information from the  UV  trace,  establish appropriate  collect  and
dump  time  periods   to  ensure collection  of  all  target  analytes.
Initiate  column   eluate  collection   just   before   elution   of
bis(2-ethylhexyl) phthalate and after the elution of the corn oil.
Stop  eluate  collection  shortly  after the  elution   of  perylene.
Collection  should be  stopped before sulfur elutes.   Use  a  "wash"
time  of 10  minutes after the elution of sulfur.   Each laboratory is

                      3S40A - 10                         Revision 1
                                                    September 1994

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required to establish its specific time sequences.  See Figure 2 for
general guidance on retention time.   Figure 1  illustrates retention
volumes for different classes of compounds.

      7.2.2,5     Calibration for Organoehlorine Pesticides/PCBs -
Determine  the  elution  times  for   the   phthalate,  methoxychlor,
perylene, and sulfur.  Choose a dump time which  removes >85%  of the
phthalate, but  collects  >95% of the methoxychlor.  Stop collection
after the elution of perylene, but before  sulfur elutes.

      7.2,2.6     Verify the flow rate by  collecting column  eluate
for 10 minutes in a graduated cylinder and measure the volume, which
should be 45-55 ml (4.5-5.5  mL/min).  If the flow rate  is outside of
this range,  corrective  action must  be taken,  as described  above.
Once the flow rate is within the range of  4,5-5.5 mL/min, record the
column pressure (should be 6-10 psi)  and  room  temperature.  Changes
in  pressure,  solvent  flow  rate, and  temperature  conditions  can
affect analyte retention times,  and  must  be monitored.  If the flow
rate and/or column pressure do not fall within the above ranges,  a
new column should be prepared.   A UV trace that does  not meet the
criteria  in  Sec. 7.2.2.3 would also  indicate  that a  new column
should be prepared.  It may  be necessary  to obtain a new lot of Bio
Beads if the column fails all the criteria.

      7,2.2.7     Reinject   the    calibration    solution    after
appropriate collect and dump cycles have been set,  and the solvent
flow and column pressure have been established,

            7.2.2.7.1   Measure and record the volume  of collected
      GPC eluate in a graduated cylinder.   The volume of GPC eluate
      collected  for each  sample extract  processed may  be  used  to
      indicate problems with the system during sample  processing.

            7.2.2.7.2   The retention  times for bis(2-ethylhexyl)
      phthalate  and perylene  must  not vary more than  +5%  between
      calibrations.   If  the retention  time shift  is >5%,  take
      corrective action.  Excessive retention time shifts are caused
      by:

                  7.2.2.7.2.1 Poor laboratory temperature control or
            system leaks.

                  7.2.2.7.2.2 An unstabilized column that requires
            pumping methylene chloride through it for  several more
            hours or overnight.

                  7.2.2.7.2.3 Excessive  laboratory  temperatures,
            causing outgassing of the methylene chloride.

      7.2.2.8     Analyze a GPC blank by loading 5 ml  of methylene
chloride into  the GPC.   Concentrate the  methylene chloride that
passes through the system during  the  collect cycle using a Kuderna-
Danish  (KD)   evaporator.    Analyze   the   concentrate  by  whatever
detectors will  be used for the analysis of future samples.  Exchange

                      3640A - 11                        Revision  1
                                                    September 1994

-------
      the  solvent,  if necessary.   If  the  blank exceeds  the estimated
      quantitation  limit  of  the  analytes,  pump  additional  methylene
      chloride  through  the system for  1-2  hours.   Analyze  another 6PC
      blank  to ensure  the system  is  sufficiently clean.    Repeat the
      methylene chloride pumping, if necessary.

7.3   Extract Preparation

      7.3.1 Adjust  the extract  volume  to 10.0 ml.  The  solvent extract
must  be  primarily  methylene  chloride.    All   other  solvents,  e.g.
1:1 methylene chloride/acetone,  must be concentrated to 1  ml (or  as low as
possible if  a  precipitate  forms) and  diluted to 10.0  ml with tnethylene
chloride.  Thoroughly mix the extract  before proceeding.

      7.3.2 Filter the extract through a 5 micron  filter disc by attaching
a syringe filter assembly containing the filter disc to a 10 ml syringe.
Draw the sample extract  through the  filter assembly and  into the 10 ml
syringe.  Disconnect  the filter assembly before  transferring  the sample
extract into a  small  glass container,  e.g.  a 15 ml culture tube with a
Teflon lined screw cap.   Alternatively, draw the extract into the syringe
without the  filter  assembly.   Attach  the filter assembly  and  force the
extract through the filter and  into the  glass  container.   The latter is
the preferred technique  for  viscous extracts  or extracts with  a lot of
solids.  Particulate  larger than 5 microns  may scratch the valve, which
may result in a system leak and  cross-contamination of sample extracts in
the sample loops.   Repair of the damaged valve is quite expensive.

      NOTE: Viscosity of a  sample extract  should not exceed the viscosity
            of  1:1  water/glycerol.   Dilute  samples   that  exceed  this
            viscosity.

7.4   Screening the Extract

      7.4.1 Screen  the  extract  to  determine  the weight of  dissolved
residue by  evaporating a  100  ^L  aliquot to  dryness  and weighing  the
residue.  The weight of dissolved residue  loaded on the GPC column cannot
exceed 0.500 g.   Residues  exceeding 0.500 g will very likely result in
incomplete extract cleanup and  contamination of  the SPC  switching valve
(which results in cross-contamination  of sample extracts).

            7.4.1.1     Transfer 100  ^L  of the  filtered extract  from
      Sec.   7.3.2 to a tared aluminum  weighing dish.

            7.4.1.2     A suggested evaporation technique  is to use a heat
      lamp.    Set  up  a  250  watt heat  lamp  in  a  hood   so that it  is
      8 + 0.5 cm from a  surface covered  with  a clean  sheet of  aluminum
      foil.   Surface temperature should be 80-100°C (check temperature by
      placing a thermometer on the foil and under the  lamp).   Place the
      weighing dish under the lamp using  tongs.  Allow it to  stay under
      the lamp for  1  min.   Transfer  the weighing dish to an  analytical
      balance or a micro  balance and weigh to the nearest  0.1 mg.  If the
      residue weight is less than 10 mg/100 jtL,  then further weighings are
      not necessary.  If  the residue weight  is greater  than 10  mg/100 /iL,


                            3640A -  12                        Revision 1
                                                          September 1994

-------
      then determine if constant weight has been achieved by placing the
      weighing  dish  and  residue back under the heat  lamp  for  2 or more
      additional  0.5  min.   intervals.    Reweigh  after each   interval.
      Constant  weight  is achieved when three weights agree within ±10%.

            7.4.1.3     Repeat the above residue analysis on a  blank and
      a  spike.   Add  100  pi of the same methylene  chloride used for the
      sample extraction to a weighing dish and determine residue  as above.
      Add 100 pi of a corn oil spike (5 g/100 ml) to another weighing dish
      and repeat the residue determination.

      7.4.2 A residue weight of 10 mg/100 jiL of extract  represents 500 mg
in 5  ml  of extract.    Any  sample  extracts  that exceed  the 10  mg/100 pi
residue weight  must be diluted so that the 5 ml loaded  on the 6PC column
does  not exceed 0.500  g.  When  making  the  dilution, keep in  mind that a
minimum  volume  of  8  ml  is  required  when  loading the  ABC 6PC  unit.
Following is a calculation that  may be  used to determine what dilution is
necessary if the residue exceeds 10 mg.

      Y ml taken  =     10 ml final    x    10 mg maximum
      for dilution        volume          X mg of residue

Example:

      Y ml taken  =     10 ml final    x    10 mq maximum
      for dilution        volume          15 mg of residue

      Y mL taken for dilution  -  6.7 ml

      Therefore, taking  6.7 ml of sample  extract  from  Sec. 7.3.2,  and
diluting to 10 mL with  methylene chloride, will result  in 5 mL of diluted
extract loaded on the GPC column that contains 0.500 g of residue.

      NOTE: This dilution factor must be included  in the  final  calculation
            of analyte  concentrations.  In the above example, the dilution
            factor is 1.5.

7.5   GPC Cleanup

      7.5.1 Calibrate  the   GPC  at least  once  per  week following  the
procedure outlined in Sees.  7.2.2 through 7.2.2.6.   Ensure that UV trace
requirements,   flow  rate and  column  pressure  criteria  are  -acceptable.
Also,  the  retention  time shift must be  <5% when  compared to  retention
times  in the last calibration UV trace.

            7.5.1.1      If these criteria are  not  met,  try cleaning the
      column by loading one or more 5  mL portions  of butyl chloride and
      running  it through  the  column.   Butyl  chloride  or  9:1  (v/v)
      methylene   chloride/methanol   removes   the   discoloration   and
      particulate that  may have precipitated out of  the methylene chloride
      extracts.  Backflushing (reverse flow) with  methylene  chloride to
      dislodge  particulates  may restore  lost  resolution.   If  a  guard
      column is being used,  replace  it  with a new one.  This  may correct


                            3640A -  13                         Revision 1
                                                          September 1994

-------
            the  problem.    If  column  maintenance does  not  restore acceptable
            performance,  the column must  be  repacked with new  Bio  Beads and
            calibrated.

            7.5.2 Draw a minimum of 8 ml of extract  (diluted,  if necessary, and
      filtered)  into a 10 ml syringe.

            7.5.3 Attach  the  syringe  to the turn lock  on  the injection port.
      Use  firm,  continuous pressure to  push  the sample onto  the  5-mL sample
      loop.  If the sample is difficult to load,  some  part of the system may be
      blocked.   Take  appropriate corrective action.  If the  back  pressure is
      normal (6-10 psi),  the blockage  is  probably in the valve.  Blockage may be
      flushed  out  of the  valve  by reversing  the  inlet and outlet  tubes and
      pumping  solvent through  the tubes.   (This should be  done  before sample
      loading.)

            NOTE: Approximately 2 ml of the extract remains  in  the lines between
                  the injection  port  and the  sample  loop;  excess  sample also
                  passes through the sample loop to waste.

            7.5.4 After loading a loop, and before removing  the  syringe from the
      injection port,  index the 6PC  to the next loop.  This will prevent loss of
      sample caused by unequal pressure  in the loops.

            7.5.5 After loading  each  sample loop,  wash the loading  port with
      methylene chloride in a PTFE wash bottle  to minimize cross-contamination.
      Inject  approximately  10 ml  of  methylene chloride to rinse the  common
      tubes.

            7.5.6 After loading all the  sample loops, index the  6PC  to  the 00
      position,  switch  to the  "RUN"  mode  and start  the  automated  sequence.
      Process each sample using the  collect  and dump cycle times established in
      Sec. 7.2.2.

            7.5.7 Collect each sample  in  a 250 ml  Erlenmeyer flask, covered with
      aluminum foil  to reduce solvent evaporation,  or directly into a Kuderna-
      Danish evaporator.   Monitor sample volumes  collected.   Changes  in sample
      volumes collected may indicate one or more of the following problems:

                  7.5.7.1     Change in solvent flow rate, caused by channeling
            in the column or changes in column pressure.

                  7.5.7.2     Increase in column  operating  pressure due to the
            absorption of particles  or gel fines onto either the guard column or
            the analytical column gel, if a guard column is not used.

                  7.5.7.3     Leaks in the  system or  significant variances in
            room temperature.

      7.6   Concentrate the extract  by the standard K-D technique {see  any of the
extraction methods,  Sec.  4.2.1  of this  chapter).  See the determinative methods
(Chapter Four, Sec.  4.3)  for the final volume.
                                  3640A - 14                        Revision 1
                                                                September 1994

-------
      7.7   It  should  be remembered  that  only half of  the  sample extract  is
processed by the GPC {5 ml of the 10 ml extract is  loaded onto  the  GPC column),
and thus, a dilution factor of 2  (or 2 multiplied by any dilution factor  in Sec.
7.4.2) must be used for quantitation of the sample  in the determinative method.


8.0   QUALITY CONTROL

      8.1   Refer to Chapter  One and Method 3600 for specific quality control
procedures.

      8.2   The analyst should demonstrate that the compound(s) of  interest are
being quantitatively recovered before applying this method to  actual samples.

      8.3   For  sample  extracts  that  are cleaned  up  using this  method,  the
associated quality control samples must also be processed through this cleanup
method.


9.0   METHOD PERFORMANCE

      9.1   Refer to Table 1 for  single laboratory performance data.


10.0  REFERENCES

1.    Wise, R.H.; Bishop, D.F.; Williams, R.T.; Austern, B.M.  "Gel Permeation
      Chromatography in  the  GC/MS Analysis of Organics  in  Sludges";  U.S.  EPA
      Municipal  Environmental Research Laboratory:   Cincinnati, Ohio 45268.

2,    Czuczwa,  J.; Alford-Stevens, A.  "Optimized Gel Permeation Chromatographic
      Cleanup for Soil,  Sediment, Waste and Waste Oil Sample Extracts for GC/MS
      Determination of Semivolatile Organic Pollutants, JAOAC,  submitted April
      1989.

3.    Marsden,  P.J.; Taylor, V.; Kennedy, M.R,  "Evaluation of Method 3640 Gel
      Permeation  Cleanup";   Contract  No.  68-03-3375,   U.S.  Environmental
      Protection Agency, Cincinnati, Ohio, pp. 100, 1987.
                                  3640A - 15                        Revision 1
                                                                September 1994

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                  TABLE 1
GPC RECOVERY AND RETENTION VOLUMES FOR RCRA
          APPENDIX  VIII  ANALYTES
Compound
Acenaphthene
Acenaphthylene
Acetophenone
2 - Acety 1 ami nof 1 uorene
Aldrin
4-Aminobi phenyl
An i 1 i ne
Anthracene
Benomyl
Benzenethiol
Benzidine
Benz(a) anthracene
Benzo ( b) f 1 uoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Benzo(k)fl uoranthene
Benzoic acid
Benzotrichloride
Benzyl alcohol
Benzyl chloride
alpha-BHC
beta-BHC
gamma -BHC
delta-BHC
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-butyl-4,6-dinitrophenol (Dinoseb)
Carbazole
Carbendazim
alpha-Chlordane
gamma-Chlordane
4-Chloro-3-methyl phenol
4-Chloroaniline
Chi oroberzi late
Bis(2-ch jroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl } ether
2-CMoronaphthalene
2-Chlorophenol
3-Chlorophenol
4-Chlorophenol
4-Chlorophenyl phenyl ether
3-Chloropropionitrile
Chrysene
2-Cresol
% Rec1
97
72
94
97
99
96
93
89
131
92
95
100
93
93
90
91
66
93
95
99
84
94
93
102
93
104
103
99
131
97
93
87
88
92
89
76
83
89
90
86
87
98
80
102
91
% RSD2
2
10
7
2
9
7
4
2
8
11
5
3
5
3
6
4
7
7
17
4
13
9
4
7
1
3
IB
5
8
2
2
1
3
5
1
2
2
1
1
3
2
2
5
1
1
Ret. Vol.3 (ml
196-235
196-235
176-215
156-195
196-215
176-215
196-235
196-235
146-195
196-235
176-215
196-235
196-235
196-235
196-235
196-235
176-195
176-215
176-215
176-215
196-215
196-215
196-215
216-251
176-215
136-175
176-195
196-255
146-195
196-235
196-215
196-255
196-235
176-235
156-195
156-215
156-195
196-235
196-215
196-215
196-215
176-215
176-215
196-235
196-215
                3640A - 16
    Revision 1
September 1994

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                                    TABLE  1  (continued)
\
Compound
3-Cresol
4-Cresol
Cyclophosphamide
ODD
DDE
DDT
Di-n-butyl phthalate
Dial late
Di benzo ( a , e) pyrene
Dibenzo(a»i)pyrene
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
Dibenzofuran
Dibenzothiophene
1 ,2-Dibromo-3-chloropropane
1,2-Dibromoethane
trans-l,4-Dichloro-2-butene
cis~l,4-Dichloro-2-butene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1 , 4-Di chl orobenzene
3,3'-Dichlorobenzidine
2,6-Dichlorophenol
2,4-Dichlorophenoxyacetic acid (2,4-D)
2,4-Dichlorophenol
2,4-Dichlorotol uene
l,3-Dichloro-2-propanol
Dieldrin
Diethyl phthalate
Dimethoate
3,3'-Dimethoxybenzidinea
Dimethyl phthalate
p-Dimethy 1 ami noazobenzene
7,12-Dimethyl-benz(a)anthracene
2, 4-Dimethyl phenol
3, 3' -Dimethyl benzi dine
4,6-Dinitro-o-cresol
1,3-Dinitrobenzene
2,4-Dinitrophenol
2»4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
Diphenyl ether
1,2-Diphenylhydrazine
Disulfoton
Endosulfan sulfate
Endosulfan I
% Rec1
70
88
114
94
94
96
104
97
94
99
117
92
94
94
83
121
107
106
81
81
81
98
86
80
87
70
73
100
103
79
15
100
96
77
93
93
100
99
118
93
101
95
67
92
81
94
99
%RSD2
3
2
10
4
2
6
3
6
10
8
9
5
1
3
2
8
5
5
1
1
1
3
3
NA
2
9
13
5
3
15
11
1
1
1
2
2
1
2
7
4
2
6
12
1
15
2
8
Ret. Vol.3 (ml
196-215
196-215
146-185
196-235
196-235
176-215
136-175
156-175
216-235
216-235
176-195
196-235
176-235
196-235
176-215
196-215
176-195
176-215
196-235
196-235 '
196-235
176-215
196-215
76-215
96-215
196-235
176-215
196-215
136-195
146-185
156-195
156-195
176-215
176-215
176-215
156-215
156-195
156-195
176-195
156-195
156-175
176-235
196-215
176-215
146-165
176-195
176-215
                                         3640A  -  17
    Revision 1
September 1994

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TABLE 1 (continued)
Compound
Endosulfan II
Endrin
Endrin aldehyde
Endrin ketone
Ethyl methane sulfonate
Ethyl methacrylate
Bis(2-ethylhexyl) phthalate
Famphur
Fluorene
Fluoranthene
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachl orobutadi ene
Hexachl orocyclopentadiene
Hexachl oroethane
Hexachl oropropene
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
cis-Isosafrole
trans-Isosafrole
Kepone
Malononitrile
Merphos
Methoxychlor
3-Methyl chol anthrene
2-Methy 1 naphthal ene
Methyl parathion
4,4' -Methyl ene-bi s(2-chl oroani 1 ine)
Naphthalene
1,4-Naphthoquinone
2-Naphthylamine
1-Naphthylamine
5-Nitro-o-toluidine
2-Nitroanillne
3-Nitroaniline
4-Nitroanil ine
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
N-Nitroso-di-n-butylamine
N-Nitrosodiethanolamine
N-Ni trosodi ethyl ami ne
N-Nitrosodimethyl atnine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
% Rec1
92
95
97
94
62
126
101
99
95
94
85
91
108
86
89
85
91
79
98
68
go
88
102
111
93
94
74
67
84
96
95
73
94
96
77
96
96
103
86
95
77
89
104
' 94
86
99
85
%RSD2
6
6
1
4
7
7
1
NA
1
1
2
11
2
2
3
I
Z
13
5
7
4
16
NA
9
12
6
12
6
13
1
7
7
8
6
2
8
2
8
2
3
3
4
3
2
13
2
4
Ret, Vol.3 (ml
196-215
196-215
176-215
176-215
176-235
176-195
120-145
126-165
176-235
196-235
195-215
156-195
196-235
176-215
176-215
196-235
196-235
216-255
196-235
156-195
176-215
156-195
196-235
156-195
126-165
156-195
176-195
196-215
146-185
176-215
196-215
176-215
196-235
196-235
176-195
176-215
176-215
176-215
176-195
176-195
196-215
156-175
146-185
156-175
156-li5
156-195
156-175
    3640A - 18                        Revision 1
                                  September 1994

-------
                                 TABLE 1 (continued)
Compound
N-Nitrosomethyl ethyl ami ne
N-Nitrosomorphol i ne
N-Nitrosopi peri dine
N-Nitrosopyrol idine
Di-n-octyl phthalate
Parathion
Pentachl orobenzene
Pentachl oroethane
Pentachl oronitrobenzene (PCNB)
Pentachl orophenol
Phenacetin
Phenanthrene
Phenol
1 , 2-Phenyl enedi ami ne
Phorate
2-Picoline
Pronamide
Pyrene
Resorcinol
Safrole
Streptozotocina
1,2,4, 5-Tetrachl orobenzene
2,3,5,6-Tetrachloro-nitrobenzene
2,3,4,6-Tetrachlorophenol
2,3,5,6-Tetrachlorophenol
Tetraethyl dithiopyrophosphate (Sulfotep)
Thiosemicarbazide
2-Toluid1ne
4-Toluidine
Thiourea, I-(o-chlorophenyl)
Toluene-2,4-diamine
1 , 2 ,3-Tri chl orobenzene
1, 2, 4-Trichl orobenzene
2 ,4, 5-Trichl orophenol
2,4,6-Trichlorophenol
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)
2,4, 5-Tri chl orophenoxypropi oni c aci d
Warf ari n
% Rec1
83
86
84
92
83
109
95
74
91
102
100
94
83
91
74
99
105
98
70
93
6
96
85
95
96
89
74
92
87
75
69
87
89
77
95
71
67
94
%RSD2
7
4
4
1
4
14
2
1
8
1
3
2
2
1
NA
14
15
2
6
1
48
2
9
1
7
14
3
3
8
11
7
1
1
1
1
23
NA
2
Ret. Vol.3 (ml
156-175
156-195
156-195
156-175
120-156
146-170
196-235
196-235
156-195
196-215
156-195
196-235
156-195
196-215
116-135
156-215
156-195
215-235
196-215
176-215
225-245
196-235
176-215
196-215
196-215
116-135
146-185
176-235
176-231
166-185
176-215
196-235
196-235
216-235
216-235
156-235
216-215
166-185
NA = Not applicable, recovery presented as the average of two determinations.

8  Not an appropriate analyte for this method.

1  The percent recovery is based on an average of three recovery values.

2  The % relative standard deviation is determined from three recovery values.

3  These Retention Volumes are  for guidance  only  as  they  will  differ from column to
   column and from system to system.


                                     3640A - 19                        Revision 1
                                                                   September 1994

-------
                          Figure 1
         6PC RETENTION VOLUME OF CLASSES  OF ANALYTES
                                  W////////////M
                                   W///////////////.
                                   PAH't

                                   CHLORO8ENZENES
         PHTHALATB -—
OROANOPHOSPHATE
    PESTICIDES
   CORN Oil.-*
                                   NJTROSAMINE3, N1TROAROMATJCS

                                               AROMATIC AMINES
                           MTftOPHiNOi.3

                           """"" CHLOROPHENOLS

                                   ORQANOCHLORINE
                                   P§STIClOeS/PCB'»
                                            HERBICIDES (8 ISO)
                                           — POP
                                                         C-Collect
 10
20
    30        40

Q   TIME (minutes)
50
60
70
                         3640A -  20
                                             Revision  1
                                         September 1994
                                                               \
                                                                 \

-------
                                    Figure 2
                  UV CHROMATQGRAN OF THE  CALIBRATION SOLUTION
      Injection
      5 M.S
      on column
                                              —  0 minutes
      Corn oil
      25 rag/oL
      B is (2 -ethyIheay 1) phctnia te
      1.0 rag/nL
      Methoxychlor
      0.2 mg/nL
                                      	1	:	  .......:."' 30 minutes
      Perylene
      0.02 mg/oL
      Sulfur
      0.08 og/aL
                                                                   15 iflinuces
                                                 45  miauces
700 am X25 nra
70 g Bio-Beads SX
Bed length - 490
CH-Ci,  at 5.0 u
254 na
                                           ,'1  •;"'
»•»_	. .       .:.   _  	  . _.   ;	   _. 	 ...    _ ,1
_r_	_.,_„______	,	;	 	'	.  60 minutes
                                   3640A  -  21
                                                     Revision 1
                                                 September 1994

-------
                                               METHOD  3640A
                                       GEL-PERMEATION  CLEANUP
                               7.1 Ensure ambient tamp, consistent
                                      throughout GPC run.
                                  7.2 GPC Setup and Calibration
      7.2.1 Column Preparation
  7,2.1.1 Place Bio Beads and MeCI
      in a container.  Swirl and
        allow beads to swell.
    7,2.1.2 Remove column inlet bed
  support plunger.  Position and tighten
outlet bed support plunger to column end.
   7.2.1.3 Ensure GPC column outlet
 contains solvent. Place small amount
     solvent in column to minimize
          bubble formation.
   7.2.1.4 Transfer bead mixture into
   sep. tunnel.  Drain excess solvent:
   drain beads into column. Keep
       beads wet throughout
    7.2.1.5 Loosen seal on opposite
  plunger assembly, insert into column.
 7.2.1,6 Compress column. Slurry
remaining beads and repeat Section
 7.2.1.5 and column compression
                                                                            7.2.1.7 Compress column bed
                                                                              approximately tour cm.
  7.2.1,8 Pack option 5 cm. guard
     column w/ roughly 5 gm.
        preswelleci beads.	
   7.2.1.9 Connect column inlet to
  solvent reservoir.  Pump MeCI at
         5 ml/min. for 1 hr.
 7.2.1,10 Connect column outlet to
  UV-Vis detector. Place restrictor
  at detector outlet. Run MeCI for
   additional 1 -2 hrs,  Compress
  column bed to provide 6-10 psi
         backpressure.
                                                                        7.2.1.11 Connect outlet tine ID column
                                                                        inlet when column not in use,  Repack
                                                                        column when channeling is observed.
                                                                        Assure consistent backpressure when
                                                                           beads are rewetted after drying.
                                               3640A  -  22
                        Revision  1
                  September  1994

-------
                                        METHOD 3640A
                                          continued
  7.2.2 Calibration at the GPC column
               i
    7.2.2.1 Load sample loop wrtfi
          calibration solution.
               I
  7.2.2,2 Inject calibration soln.; adjust
     recorder or detector sensitivity
  to produce similar UV trace 33 Fig, 2.
                1
     7.2,2.3 Evaluation criteria for
         UV chrorratogram.
  7.2.2.4 Calibration tor Semivolatiles
    Use information torn UV trace to
     obtain collect and dump times,
Initiate collection before bis(2-ethylhexyl)
 phthalate, stop after perylene. Stop run
          before sulfur elutas.
               I
 7,2.2.5 Calibration for Organochterine
          Pesfletdes/PCBs	
  Choose dump time which removes
   > 35% phthaiate, but collects at
   times > 95% methoxychlor. Stop
   collection between perylene and
           sulfur eluttbn.
  7.2.2.6 Verify column flow rate and
        backpressure. Correct  .
     inconsistencies when criteria
            are not met.
7.2.2.7 fieinject calibration soln. when
  collect and dump cycles are set,
    and column criteria are met.
                                                                     7.2.2.7.T Measure and record
                                                                        volume of GPC eluate
 7.2.2.7.2 Correct for retention 8me
       shifts of > +/- 5% for
    bis<2-ethythexyt) phthalate
          and perytene.
7.2.2.8 Inject and analyze OPC blank
   for column cleanliness. Pump
   through MeCI as column wash.
                                         3640A  -  23
                           Revision  1
                    September  1994

-------
                                          METHOD 3640A
                                            continued
         7.3 Extract Preparation
  7,3.1 Adjust extract volume to 10 ml.
    Primary solvent should be MeCI.
                1
 7.3.2 Filter extract through S micron filter
    disc/syringe assembly into small
           glass container.
       7.4 Screening the Extract
   7.4.1 Screen extract by determining
       residue wt. of 1 00 uL aliquot.
    7.4.1 .1 Transfer 1 00 uL of fitered
   extract from Section 7.3.2 to tared
       aluminum weighing dish.
                1
 7.4. 1 .2 Evaporate extract solvent under
 heating lamp. Weigh residue to nearest
             0.1 mg.
                1
7.4.1.3 Repeat residue analysis of Section
   7.4 . 1 .2 w/blank and spike sample.
 7.4 ,2 Use dilution example to determine
    necessary dilution when residue
            wts, > I0mg
          7.5 GPC Cleanup
  7.5.1 Calibrate GPC weekly.  Assure
  column criteria, UV trace, retention
      time shift criteria are met.
 7.S.1.1 Clean column w/butyl chloride
      loadings, or replacement of
	guard column.	
                                                                 7.5.S Draw 8 mL extract into syringe.
 7.5.3 Load sample into injection loop.
   7.5.4 Index GPC to next loop to
        prevent sample loss.
               I
                                                                                                                     \
  7.5.S Wash sample port w/MeCI
    between sample loadings.
 7.5.6 At end of loadings, index GPC to
   00, switch to 'RUN' mode, start
        automated sequence
                                                                              I
7.5.7 Collect sample into aluminum foil
  covered Erlenmeyer flask or into
    Kuderna- Danish evaporator.
                                                                   7.6 Concentrate extract by std.
                                                                     Kuderna- Danish technique.
                                                                7.7 Note dilution (actor of GPC method
                                                                      into final determinations.
                                           3640A  -  24
                              Revision  1
                         September  1994

-------
                                 METHOD 3650A

                          ACID-BASE  PARTITION  CLEANUP

1.0   SCOPE AND APPLICATION
      1.1
manual.
Method 3650 was formerly Method 3530 in the second edition of this
      1.2   Method  3650 is  a  liquid-liquid  partitioning  cleanup method  to
separate  acid  analytes,  e.g.   organic  acids  and  phenols,  from  base/neutral
analytes, e.g.  amines, aromatic hydrocarbons, and halogenated organic compounds,
using pH  adjustment.   It  may be used for cleanup of  petroleum waste  prior to
analysis or further cleanup (e.g., alumina cleanup).  The following compounds can
be separated by this method:
Compound Name
                     CAS No.1
Fraction
Benz(a)anthracene
Benzo(a)pyrene
Benzo (b) f 1 uoranthene
Chlordane
Chlorinated dibenzodioxins
2-Chlorophenol
Chrysene
Creosote
Cresol(s)
Dichlorobenzene(s)
Dichlorophenoxyacetic acid
2, 4-Dimethyl phenol
Dinitrobenzene
4,6-Dinitro-o-cresol
2,4-Dinitrotoluene
Heptachlor
Hexachlorobenzene
Hexachlorobutadiene
Hexachloroethane
Hexachlorocyclopentadiene
Naphthalene
Nitrobenzene
4-Nitrophenol
Pentachlorophenol
Phenol
Phorate
2-Picoline
Pyridine
Tetrachlorobenzene(s)
Tetrachlorophenol (s)
Toxaphene
Trichlorophenol (s)
2,4,5-TP (Silvex)
56-55-3
50-32-8
205-99-2
57-74-9

95-57-8
218-01-9
8001-58-9


94-75-7
105-67-9
25154-54-5
534-52-1
121-14-2
76-44-8
118-74-1
87-68-3
67-72-1
77-47-4
91-20-3
98-95-3
100-02-7
87-86-5
108-95-2
298-02-2
109-06-8
110-86-1


8001-35-2

93-72-1
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Acid
Base-neutral
Base-neutral and Acid
Acid
Base-neutral
Acid
Acid
Base-neutral
Acid
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Acid
Acid
Acid
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Acid
Base-neutral
Acid
Acid
   Chemical  Abstract Services Registry Number,

                                   3650A  -  1
                                                        Revision 1
                                                         July 1992

-------
 2.0   SUMMARY OF METHOD

       2.1   The solvent extract from a prior solvent extraction method is shaken
•with water  that  is strongly basic.  The acid  analytes partition into the aqueous
 layer, whereas,  the basic and neutral compounds stay in the organic solvent.  The
 base/neutral  fraction  is concentrated  and is then ready for further cleanup,  if
 necessary,  or analysis.  The aqueous  layer  is acidified and extracted  with  an
 organic  solvent. This  extract is concentrated (if necessary)  and is then ready
 for analysis  of the  acid analytes.


 3.0   INTERFERENCES

       3.1   More extensive procedures  than those outlined in this method may be
 necessary for reagent  purification.

       3.2   A method blank must be run for  the compounds of interest  prior  to
 use of the  method.   The interferences  must  be  below the method  detection limit
 before this method  is  applied to  actual samples,


 4.0   APPARATUS AND  MATERIALS

       4.1   Drying column  -  20 mm  ID Pyrex chromatographic column  with Pyrex
 glass wool  at bottom,  or equivalent.

       NOTE: Fritted  glass discs are difficult to clean after highly contaminated
             extracts have been passed through  them.   Columns without frits are
             recommended.   Use  a  small pad  of Pyrex  glass  wool to  retain the
             adsorbent.   Prewash the  glass wool  pad  with  50  mL  of  acetone
             followed by  50  ml  of elution  solvent prior to packing  the column
             with adsorbent.

       4.2   Kuderna-Danish (K-D)  apparatus

             4.2.1 Concentrator tube -  10 mi graduated  (Kontes  K570Q50-1025  or
       equivalent).   A ground glass stopper is used to prevent evaporation of the
       extracts.

             4.2.2 Evaporation  flask  - 500  ml  (K-570001-0500  or  equivalent).
       Attach  to concentrator tube with springs,  clamps, or  equivalent.

             4.2.3 Snyder  column  -  Three ball macro  (Kontes  K-503000-0121  or
       equivalent).
             4.2.4 Snyder  column  -  Two  ball  micro   (Kontes  K569001-0219  or
       equivalent).
 tops.
             4.2.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).

       4.3   Vials - Glass, 2 ml capacity with Teflon lined screw-caps or crimp
       4.4   Water bath - Heated, concentric ring cover,  temperature control  of
 ± 2°C.   Use  this  bath  in  a  hood.

                                   3650A - 2                         Revision 1
                                                                      July 1992

-------
      4.5   Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).

      4.6   pH indicator paper - pH range including the desired extraction pH.

      4.7   Separatory funnel - 125 ml.

      4.8   Erlenmeyer flask - 125 ml.


5.0   REAGENTS

      5.1   Reagent  grade  inorganic  chemicals shall  be  used  in  all  tests.
Unless otherwise  indicated,  it  is intended that all  inorganic  reagents shall
conform to the specifications  of  the Committee on Analytical  Reagents  of the
American Chemical  Society, where such specifications are available. Other grades
may be used, provided it is first ascertained that the reagent is of sufficiently
high  purity  to  permit  its  use  without  lessening  the  accuracy  of  the
determination.

      5.2   Organic-free reagent water - All  references  to  water  in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Sodium hydroxide, NaOH,  (ION)  -  Dissolve 40 g of sodium hydroxide
in 100 ml of organic-free reagent water.

      5.4   Sulfuric acid, H?S04,  (1:1 v/v in water) - Slowly add 50 ml H2S04 to
50 ml of organic-free reagent water.

      5.S   Sodium sulfate  (granular, anhydrous), Na2SO,  -  Purify by heating at
400°C for 4 hours in  a shallow tray, or by precleaning the sodium sulfate with
methylene chloride.  If the sodium  sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is  no interference from
the sodium sulfate.

      5.6   Solvents:
                                      \
            5.6.1 Methylene chloride, CH2C12  -  Pesticide quality or equivalent.

            5.6.2 Acetone,  CH3COCH3 - Pesticide quality or equivalent.

            5.6.3 Methanol, CH3OH - Pesticide quality or equivalent.

            5.6.4 Diethyl  Ether,  C2H5OC2H5 - Pesticide  quality  or equivalent.
      Must  be free of  peroxides  as  indicated by test  strips  (EM  Quant,  or
      equivalent).  Procedures for  removal of  peroxides are provided with the
      test strips.  After cleanup, 20 ml of ethyl alcohol preservative must be
      added to each liter of ether.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material to  this chapter,  Organic Analytes,
Section 4.1.

                                  3650A - 3                         Revision 1
                                                                     July 1992

-------
7.0   PROCEDURE

      7.1   Place 10 mL of the solvent extract from a prior extraction procedure
into a 125 mL separatory funnel.

      7.2   Add 20 mL of methylene chloride to the separatory funnel.

      7.3   Slowly add 20 mL of prechilled  organic-free reagent water which has
been previously adjusted to a pH of 12-13 with ION sodium hydroxide.

      7.4   Seal and  shake the separatory funnel for at least  2  minutes with
periodic venting to release excess pressure.

      NOTE: Methylene   chloride   creates   excessive   pressure   very  rapidly;
            therefore,  initial  venting should be done immediately  after the
            separatory  funnel has been sealed and shaken once.   The separatory
            funnel should be vented into a  hood to prevent unnecessary exposure
            of the analyst to the organic vapor.

      7.5   Allow the  organic  layer  to separate  from the aqueous  phase  for a
minimum of 10 minutes.   If the  emulsion  interface between layers  is more than
one-third the  size  of the solvent layer,  the analyst must  employ mechanical
techniques to  complete the  phase separation.  The  optimum technique depends upon
the sample, and may include stirring, filtration  of the emulsion through glass
wool, centrifugation, or other physical methods.

      7.6   Separate the  aqueous  phase  and  transfer  it  to a  125 ml Erlenmeyer
flask.   Repeat  the  extraction two more  times using  20 mL aliquots  of dilute
sodium hydroxide (pH 12-13).   Combine the aqueous extracts.

      7.7   Water soluble  organic acids and phenols will be primarily in the
aqueous phase.  Base/neutral  analytes will be in the methylene chloride.   If the
analytes  of  interest  are  only in the aqueous  phase,  discard the  methylene
chloride and proceed  to  Section 7.8.  If the analytes of interest  are only  in the
methylene chloride,  discard the aqueous phase and proceed to  Section 7.10.

      7.8   Externally cool the 125 ml Erlenmeyer flask with ice while adjusting
the  aqueous phase  to a  pH of 1-2 with  sulfuric acid  (1:1).   Quantitatively
transfer the  cool  aqueous phase to a  clean  125 mL  separatory funnel.  Add 20 mL
of methylene chloride to the separatory funnel and shake  for at least 2 minutes.
Allow the methylene  chloride  to separate from  the  aqueous phase and collect the
methylene chloride in an Erlenmeyer flask.

      7.9   Add 20 mL of methylene chloride to the separatory funnel and extract
at pH 1-2 a second time.  Perform a third extraction in the same manner combining
the extracts  in the Erlenmeyer flask.

      7.10  Assemble  a  Kuderna-Danish  (K-D) concentrator  (if necessary)  by
attaching a 10 mL concentrator tube to a 500 mL evaporation  flask.

      7.11  Dry both acid  and base/neutral fractions by passing them through a
drying column containing about 10 cm of anhydrous sodium sulfate.   Collect the
dried  fractions in  K-D  concentrators.    Rinse  the  Erlenmeyer  flasks  which

                                   3650A -  4                        Revision 1
                                                                     July 1992

-------
'contained  the solvents and  the columns with  20  ml of  methylene  chloride to
complete the  quantitative transfer.

       7.12  Concentrate both acid and base/neutral  fractions as follows:  Add
one  or two boiling  chips  to the  flask  and attach a  three  ball macro-Snyder
column.  Prewet the Snyder column by adding about  1  ml  of methylene chloride to
the top of the column.   Place the K-D  apparatus on a hot water bath  (80-90°C) so
that the concentrator tube is partially immersed  in  the warm  water.  Adjust the
vertical position  of the apparatus  and  the water  temperature  as  required to
complete the concentration in 15-20 minutes. At the proper rate of distillation,
the balls of  the column will  actively chatter but the  chambers will not flood.
When the apparent volume of  liquid reaches  1 ml, remove  the  K-D  apparatus from
the water  bath  and  allow  it to  cool.  Remove  the  Snyder column and rinse the
flask  and its lower  joints into  the concentrator tube  with 1-2 ml of methylene
chloride.  Concentrate the extract to the  final volume using either the micro-
Snyder column technique (7.12.1)  or nitrogen blowdown  technique  (7.12.2).

            7.12.1      Micro-Snyder Column Technique

                  7.12.1.1    Add another  one  or  two  boiling  chips  to  the
            concentrator tube and attach  a  two ball micro-Snyder column.  Prewet
            the column by adding  0.5  ml  of methylene chloride to the top of the
            column.   Place  the K-D apparatus in a hot water bath  (80-90°C) so
            that the concentrator tube is  partially immersed  in  the hot water.
            Adjust   the  vertical  position of  the  apparatus  and the water
            temperature  as  required  to  complete  the concentration  in  5-10
            minutes.  At the proper rate  of distillation the balls of the column
            will  actively chatter but the  chambers will  not flood.   When the
            apparent volume  of  the  liquid reaches  0.5 ml,  remove  the  K-D
            apparatus  and allow  it to cool.  Remove  the Snyder column and rinse
            the flask  and  its lower joints into the concentrator tube with 0.2
            mL  of methylene  chloride.   Adjust  the final volume to  1  ml with
            methylene  chloride.

            7.12.2      Nitrogen Blowdown  Technique

                  7.12.2.1     Place the  concentrator tube in a warm water bath
             (35°C) and evaporate the solvent volume to  1.0-2.0 ml using  a gentle
            stream   of  clean,  dry  nitrogen  (filtered  through  a column  of
            activated  carbon).

                  CAUTION;     Do not  use plasticized tubing  between the carbon
                               trap and the  sample.

                  7.12.2.2     The internal  wall of the  concentrator tube must be
            rinsed  down several  times with the appropriate solvent during the
            operation.   During  evaporation,  the tube solvent  level  must be
            positioned  to avoid condensation  water.   Under normal procedures,
            the extract must not be  allowed to become  dry.

                  CAUTION;    When the volume of solvent  is  reduced below 1 ml,
                               semivolatile  analytes may  be lost.

       7.13  The acid fraction is now ready for analysis.  If the base/neutral

                                   3650A -  5                        Revision  1
                                                                     July 1992

-------
fraction requires further cleanup by  the  alumina column cleanup for petroleum
waste (Method 3611), the solvent may have to be changed to hexane.   If a solvent
exchange is required, momentarily  remove the Snyder column, add approximately 5
ml of  the  exchange  solvent  and  a new  boiling  chip,  and reattach the Snyder
column.  Concentrate the extract as described in Section 7.12.1.1, raising the
temperature of the  water bath,  if necessary,  to maintain proper distillation.
When the apparent volume again reaches 1 ml,  remove the K-D apparatus from the
water bath and allow it to drain and cool  for at least 10 minutes.  Repeat the
exchange 2 more  times.   If no further cleanup  of  the base/neutral extract is
required, it is also ready for analysis.


8.0   QUALITY CONTROL

      8.1   Refer  to Chapter One  for general  quality  control  procedures and
Method 3600 for cleanup procedures.

      8.2   The  analyst must demonstrate that  the compounds of  interest are
being quantitatively recovered before applying this method to actual samples.

      8.3   For  simples that  are cleaned using this method,  the associated
quality control samples must be processed through this cleanup method.


9.0   METHOD PERFORMANCE

      9.1   Refer to the determinative methods  for performance data.


10.0  REFERENCES

1-    Test Methods;  Methods  for  Organic Chemical Analysis  of Municipal and
      Industrial Mastewater;   U.S.  Environmental Protection  Agency. Office of
      Research and Development. Environmental Monitoring and Support Laboratory.
      ORD Publication Offices of Center for Environmental Research  Information:
      Cincinnati, OH, 1982;  EPA-600/4-82-057.
                                   3650A - 6                        Revision 1
                                                                     July 1992

-------
                                                  METHOD  3650A
                                       ACID-BASE  PARTITION CLEANUP
      START
 'l  I  Place extract
 or organic liquid
    waste into
 separator? funnel
 7  2 Add methy.ene
    chlorida
7.3  Add prechiiled
  dilute sodium
? 4  Seal and shake
 separate*')' funnel
     7 S Allow
   separa Iion of
organic layer f r ens
   aqueous phase
                                                       S Complete phase
                                                       separation with
                                                        mechanica1
                                                        techniques
                               7 . 6 Tram for
                             aqueous  phase to
                               flask;  repeat
                             en traction  twice;
                              combine aqueous
                                 BKt racta
7 7  Discard aqueous
       phase
                                                                      Aqueous
                                               7.?  Discard o
                                                      phase
                                                                            7.S Adjust  pH .ith
                                                                           sulfunc  acid; t rani
                                                                           far aquaous  phaie tc
                                                                           clean separatory fun
                                                                            nel;  add methylena
                                                                             chloride;  shake,
                                                                            all01* phase separa-
                                                                           tion;  collect solven
                                                                              phase  in  flash
7  10  Assemole K - D
   appa ra tus
                                                                            7 9 Perform 2 more
                                                                               en tractions•
                                                                                combine all
                                                                                 atttracts
                                                     3650A  -  7
                                                                            Revision  1
                                                                             July  1992

-------
         METHOD 3650A
          (Continued)
7 11  Dry extracts,
collec t extracts in
 K - D  concentrator;
 rinse flask  wilh
methyletie chloride
 ? 12 Concentrate
  both fractions
                             a 1 vent
     Ana 1y ze
   f ra c t i ana by
    app r opr LSt te
   de te r mma 14. ve
     method
           3650A  -  8
Revision 1
 July  1992

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                                 METHOD 3660A

                                SULFUR CLEANUP
1.0   SCOPE AND APPLICATION
      1.1   Elemental sulfur is encountered  in many sediment samples (generally
specific to different areas in the country), marine algae, and some industrial
wastes.  The  solubility  of sulfur in various solvents  is  very  similar to the
organochlorine  and  organophosphorus  pesticides.     Therefore,   the  sulfur
interference follows along  with the pesticides through the normal extraction and
cleanup techniques.  In general,  sulfur will usually elute entirely in Fraction
1 of the Florisil  cleanup  (Method 3620).

      1.2   Sulfur will  be quite evident  in  gas ehromatograms obtained  from
electron capture detectors, flame photometric detectors operated in the sulfur
or phosphorous  mode, and  Coulson electrolytic  conductivity detectors  in the
sulfur mode.  If the gas  ehromatograph is operated at the normal  conditions for
pesticide analysis, the sulfur interference  can completely mask the region from
the solvent peak through  Aldrin.

      1.3   Three  techniques for the elimination of sulfur are detailed within
this method: (1) the use  of copper powder;  (2) the use of mercury; and (3) the
use of tetrabutyl ammonium sulfite.  Tetrabutylammonium sulfite causes the least
amount of degradation of a broad range of pesticides and organic compounds, while
copper  and  mercury may  degrade  organophosphorus  and  some  organochlorine
pesticides.


2.0   SUMMARY OF METHOD

      2.1   The sample  to undergo cleanup is mixed with either copper, mercury,
or tetrabutylammonium (TBA) sulfite.   The mixture is shaken and  the extract is
removed from the sulfur cleanup reagent.


3.0   INTERFERENCES

      3.1   Removal of sulfur using  copper:

            3.1.1  The copper must be very reactive.   Therefore, all  oxides of
      copper must  be removed so that the copper has a shiny, bright appearance.

            3.1.2  The  sample  extract must  be  vigorously  agitated  with  the
      reactive copper for at least one minute.


4.0   APPARATUS AND MATERIALS

      4.1   Mechanical  shaker or mixer -  Vortex Genie or equivalent.

      4.2   Pipets, disposable - Pasteur  type.


                                  3660A - 1                         Revision 1
                                                                     July 1992

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      4.3   Centrifuge tubes, calibrated - 12 ml.

      4,4   Glass bottles or vials -  10 ml  and  50  mLf  with Teflon-lined screw
caps or crimp tops.

      4.5   Kuderna-Danish  (K-D) apparatus.

            4.5,1 Concentrator tube -  10  ml graduated  (Kontes K-570050-1025 or
      equivalent).  A  ground  glass stopper is used to prevent  evaporation of
      extracts.

            4.5.2 Evaporation   flask  -    500 ml  (Kontes   K-570001-500   or
      equivalent).   Attach  to  concentrator tube  with  springs,  clamps,  or
      equivalent.

            4.5.3 Snyder column  -   Three  ball macro  (Kontes  K-503000-0121 or
      equivalent).

            4.5.4 Snyder column  -   Two  ball micro  (Kontes  K-569001-0219 or
      equivalent).

            4.5.5 Springs -  1/2 inch (Kontes K-662750 or equivalent).


5.0   REAGENTS

      5.1   Reagent grade chemicals shall  be used in all tests. Unless otherwise
indicated, it is intended that all  reagents  shall conform to the specifications
of the Committee on Analytical  Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first
ascertained that the reagent  is  of sufficiently  high  purity to  permit its use
without lessening the accuracy of the determination.

      5.2   Organic-free reagent water - All  references to water in this method
refer to organic-free reagent water,  as defined in Chapter One.

      5.3   Nitric acid, HNOj, dilute.

      5.4   Solvents

            5.4.1 Acetone, CH3COCH3  - Pesticide  quality or  equivalent.

            5.4.2 Hexane, C6H14 - Pesticide quality or  equivalent.

            5.4.3 2-Propanol, CH3CH(OH)CH3 -  Pesticide  quality or equivalent.

      5.5   Copper powder - Remove oxides by treating with dilute nitric acid,
rinse with organic-free reagent water to remove all traces of acid, rinse with
acetone and dry under a stream of nitrogen.  (Copper, fine granular Mallinckrodt
4649 or equivalent).

      5.6   Mercury, triple distilled.

      5.7   Tetrabutylammonium (TBA) sulfite reagent

                                   3660A - 2                        Revision 1
                                                                     July  1992

-------
            5.7.1 Tetrabutylammonium hydrogen sulfate, [CH3(CH2)3]4NHS04.

            5.7.2 Sodium sulfite, Na2S03.

            5.7.3 Prepare  reagent  by  dissolving  3.39  g  tetrabutylammonium
      hydrogen  sulfate  in  100   ml  organic-free  reagent  water.  To  remove
      impurities, extract  this solution  three  times with  20 ml  portions  of
      hexane.  Discard the hexane extracts, and add 25 g sodium sulfite to the
      water solution.   Store  the resulting solution, which  is  saturated with
      sodium sulfite, in an amber bottle  with a Teflon-lined  screw cap.   This
      solution can be stored at room temperature for at least one month.


6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1   See the  introductory  material to this chapter,  Organic Analytes,
Section 4.1.


7.0   PROCEDURE

      7.1   Removal  of sulfur using copper

            7.1.1 Concentrate  the sample  to exactly  1.0 mL  or  other  known
      volume.  Perform  concentration using  the  Kuderna-Danish (K-D) Technique
      (Method 3510,  Sections 7.10.1 through 7.10.4).

            CAUTION:    When  the  volume  of solvent  is  reduced  below  1  mL,
                        semi volatile analytes may be lost.

            7.1.2 If  the  sulfur  concentration  is  such  that  crystallization
      occurs, centrifuge  to settle the crystals,  and carefully draw off the
      sample extract with  a  disposable pipet leaving the excess sulfur  in the K-
      D tube.  Transfer 1.0 mL of the extract to a calibrated centrifuge  tube.

            7.1.3 Add approximately 2 g of cleaned  copper  powder (to the 0.5 mL
      mark) to the centrifuge tube.  Mix  for  at least 1 min  on  the mechanical
      shaker.

            7.1.4 Separate  the  extract from the  copper by  drawing  off  the
      extract with a disposable pipet and  transfer  to  a clean vial.  The volume
      remaining still represents  1.0 mL of extract.

            NOTE; This separation is necessary to prevent further degradation of
                  the pesticides.

      7.2   Removal  of sulfur using mercury

      NOTE; Mercury is a highly toxic metal.  All  operations involving mercury
            should be  performed   in  a  hood.   Prior  to  using mercury,  it  is
            recommended that the  analyst become acquainted with proper handling
            and cleanup techniques associated with this metal.

            7.2.1 Concentrate the  sample  extract to  exactly  1.0 mL  or  other

                                  3660A - 3                         Revision 1
                                                                     July 1992

-------
known  volume.    Perform  concentration  using  the Kuderna-Danish  (K-D)
Technique (Method 3510, Sections 7.10.1 through 7.10.4).

      CAUTION:     When  the  volume  of solvent  is reduced  below  1  ml,
                  semi volatile analytes may be lost.

      7.2.2 Pi pet 1.0 ml of  the  extract into a clean concentrator tube or
Teflon-sealed vial.

      7.2.3 Add  one  to  three  drops of  mercury to  the vial  and  seal.
Agitate the contents of the  vial  for 15-30 sec.  Prolonged shaking (2 hr)
may be required.  If so, use a mechanical shaker.

      7.2.4 Separate  the sample  from the  mercury by  drawing  off  the
extract with a disposable pipet and transfer to a clean vial.

7.3   Removal of sulfur using TBA sulfite

      7.3.1 Concentrate  the  sample extract to  exactly 1.0  ml  or  other
known  volume.    Perform  concentration  using  the Kuderna-Danish  (K-D)
Technique (Method 3510, Sections 7.10.1 through 7.10.4).

      CAUTION:     When  the  volume  of solvent  is reduced  below  1  ml,
                  semivolatile analytes may be lost.

      7.3.2 Transfer 1.0 ml  of the extract to a 50 ml clear glass bottle
or vial with a Teflon-lined  screw-cap.  Rinse the concentrator tube with
1 ml of hexane, adding the rinsings to the 50 ml bottle.

      7.3.3 Add 1.0 ml TBA  sulfite  reagent  and  2  ml  2-propanol, cap the
bottle, and shake for at  least  1 min.   If  the  sample is colorless  or if
the initial  color is unchanged, and if clear crystals (precipitated sodium
sulfite)  are  observed,   sufficient  sodium  sulfite is  present.   If  the
precipitated  sodium  sulfite  disappears,  add   more  crystalline  sodium
sulfite in approximately  0.100  g portions  until  a solid residue remains
after repeated shaking.

      7.3.4 Add 5 ml organic free reagent water and shake for at least 1
iin.  Allow the sample to stand for 5-10 min.  Transfer the hexane  layer
(top) to a concentrator tube and concentrate the extract to approximately
1.0  ml  with the  micro  K-D  Technique (Section 7.3.5)  or  the  Nitrogen
Slowdown Technique (Section  7.3.6).  Record the actual volume of the final
extract.

      7.3.5 Micro-Snyder Column Technique

            7.3.5.1     Add  another one or  two clean boiling  chips to the
      concentrator tube and  attach a two ball  micro-Snyder column.  Prewet
      the column  by adding  about  0.5 ml  of hexane to the top of  the
      column.   Place  the K-D apparatus in a hot water  bath so that  the
      concentrator tube  is  partially  immersed  in  the hot water. Adjust
      the vertical position  of the apparatus and the water temperature, as
      required, to  complete the concentration  in  5-10  minutes.  At  the
      proper rate of distillation  the  balls  of  the column will actively

                             3660A  - 4                         Revision 1
                                                               July 1992

-------
            chatter, but the chambers will not flood.  When the apparent volume
            of liquid reaches 0.5 ml, remove the K-D  apparatus  from the water
            bath and allow  it to drain and cool  for  at  least 10 minutes.  Remove
            the Snyder  column  and rinse the flask and its lower  joints  with
            about 0.2 ml of solvent and  add to the concentrator tube.   Adjust
            the final volume to approximately  1.0 ml with hexane.

            7.3.6 Nitrogen  Slowdown Technique

                  7.3.6.1     Place the concentrator tube in  a warm water bath
            (approximately  35°C) and evaporate the solvent volume to 1.0-2.0 ml,
            using a  gentle  stream of clean,  dry nitrogen  (filtered through a
            column of activated carbon).

                  CAUTION:     Do not use plasticized tubing between the carbon
                              trap and the sample.

                  7.3.6.2     The internal wall of  the tube must be rinsed down
            several   times with  the appropriate solvent during  the operation.
            During evaporation,  the solvent level  in the tube must be positioned
            to prevent water from  condensing into the  sample (i.e., the solvent
            level should be below  the level of the water  bath).   Under normal
            operating conditions,  the extract should  not  be  allowed to become
            dry.

                  CAUTION:     When the volume of  solvent is reduced  below 1 ml,
                              semi volatile analytes may be lost.

      7.4   Analyze  the cleaned  up  extracts  by gas  chromatography  (see  the
determinative methods, Section 4.3 of this chapter).


8.0   QUALITY CONTROL

      8.1   Refer to Chapter  One  for specific quality  control  procedures and
Method 3600 for cleanup procedures.

      8.2   All  reagents  should   be. checked  prior  to  use  to  verify  that
interferences do not exist.


9.0   METHOD PERFORMANCE

      9.1   Table 1  indicates the effect of using copper and  mercury to remove
sulfur on the recovery of certain pesticides.


10.0  REFERENCES

1.    Loy, E.W., private communication.

2.    Goerlitz, D.F. and L.M.  Law,  Bulletin for Environmental  Contamination and
      Toxicology, 6, 9  (1971).


                                   3660A - 5                         Revision 1
                                                                     July 1992

-------
3.    U.S.  EPA Contract  Laboratory Program,  Statement of  Work  for  Organic
      Analysis, Revision, July 1985.
                                   3660A - 6                        Revision 1
                                                                     July 1992

-------
                                  Table 1.
                  EFFECT OF MERCURY AND COPPER ON PESTICIDES
                                       Percent Recovery8 using:
  Pesticide                         Mercury                 Copper
Aroclor 1254
Lindane
Heptachlor
Aldrin
Heptachlor epoxide
DDE
DDT
BHC
Dieldrin
Endrin
Chi orobenzi late
Malathion
Diazinon
Parathion
Ethion
Trithion
97.10
75.73
39.84
95.52
69.13
92.07
78.78
81.22
79.11
70.83
7.14
0.00
0.00
0.00
0.00
0.00
104.26
94.83
5.39
93.29
96.55
102.91
85.10
98.08
94.90
89.26
0.00
0.00
0.00
0.00
0.00
0.00
a Percent recoveries  cited are averages  based  on duplicate analyses  for all
  compounds  other than  for  Aldrin and  BHC.    For  Aldrin,  four and  three
  determinations were  averaged to obtain the result  for mercury  and  copper,
  respectively.  Recovery of BHC using copper is based on one analysis.
                                  3660A  - 7                         Revision 1
                                                                     July 1992

-------
                               METHOD  3660A
                              SULFUR CLEANUP
                           7.1.1
                        Concentrate
                          sample
                         extract,
    7.1.2
 Centrifuge
and draw off
   sample
  extract -
                           7,1.2
                         Transfer
                        extract to
                        centrifuge
                           tub*.
    7.2.1
 Concentrate
   •ample
  extract,
 7.2.2  Pipat
extract into
concentrator
tube or vial -
  7.2.3  Add
  mercury,
  agitate -
                                          L
   7.4.1
Concentrate
  •ample
 extract.
   7.3,2
 Transfer
extract  to
centrifuge
   tube.
 7,3.3  Add
TBA-.ulfite
    and
2-propanol.
 agitate
                                   3660A  -  8
                                  Revision 1
                                    July 1992

-------
                           METHOD 3660A
                             continued
           7
  7.1.3 ftdd
   copper
powder, mix.
   7,2-4
 Separate
sample from
 mercury,
    7.1,4
  Separate
extract Irorr
   copper.
 '7.3-3 Add
more  3odium
 sulfite;
  shake.
J                  \nalyze entract
                  ling appropriate
                   determinativ
                    procedure.
                              3660A  -  9
                                                    Revision  1
                                                     July  1992

-------

-------
                                  METHOD 3665

                      SULFURIC ACID/PERMANGANATE CLEANUP
1.0   SCOPE AND APPLICATION

      1.1   This method is suitable for the rigorous cleanup of sample extracts
prior to  analysis  for polychlorinated biphenyls.  This method  should  be used
whenever  elevated  baselines  or overly  complex  chromatograms  prevent accurate
quantitation of PCBs.  This method cannot  be used to cleanup extracts for other
target  analytes,   as  it  will  destroy  most  organic  chemicals  including  the
pesticides Aldrin, Dieldrin,  Endrin,  Endosulfan (I  and  II),  and  Endosulfan
sulfate.
2.0   SUMMARY OF METHOD

      2.1   An  extract is  solvent  exchanged  to  hexane, then  the hexane  is
sequentially treated with (1)  concentrated  sulfuric acid  and, if necessary,  (2)
5% aqueous potassium permanganate.  Appropriate caution must  be taken with these
corrosive reagents.

      2,2   Blanks and replicate analysis samples must  be subjected to the same
cleanup as the samples associated with them.

      2.3   It is important that all  the extracts be exchanged to hexane before
initiating the following treatments.


3.0   INTERFERENCES

      3.1   This technique will  not  destroy chlorinated  benzenes,  chlorinated
naphthalenes (Halowaxes), and a number of chlorinated pesticides.


4.0   APPARATUS

      4.1   Syringe or Class A volumetric pipet, glass; 1.0, 2.0 and 5.0 ml.

      4.2   Vials - 1, 2 and 10  mL, glass with  Teflon lined screw caps or crimp
tops.

      4.3   Kuderna-Danish (K-D) apparatus.

            4.3.1 Concentrator tube - 10 mL graduated (Kontes K-570050-1025 or
      equivalent).  A ground  glass  stopper is used to prevent  evaporation of
      extracts.

            4.3.2 Evaporation    flask  - 500  mL  (Kontes    K-570001-500   or
      equivalent).    Attach  to  concentrator  tube  with  springs,  clamps,  or
      equivalent.
                                   3665 - 1                         Revision 0
                                                                September 1994

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            4.3.3 Snyder  column -  Three  ball  macro  (Kontes  K-503000-0121 or
      equivalent).

            4,3.4 Snyder  column  -  Two  ball  micro  (Kontes  K-569001-0219 or
      equivalent).

            4.3.5 Springs - 1/2 inch  (Kontes K-662750 or equivalent).

      4.4   Vortex mixer.


5.0   REAGENTS

      5.1   Reagent grade inorganic  chemicals shall be used in  all tests. Unless
otherwise  indicated,  it  is  intended  that all  reagents  shall conform  to the
specifications of the Committee on Analytical Reagents of the American Chemical
Society, where  such  specifications are  available.  Other grades may  be used,
provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.

      5.2   Organic-free reagent water.  All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Sulfuric acid/Water, HjSQ^O, (1:1, v/v).

      5.4   Hexane, CeH14  - Pesticide  grade or equivalent.

      5.5   Potassium permanganate,  KMn04,  5  percent  aqueous solution  (w/v).


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See  the introductory material to this chapter,  Organic Analytes, Sec.
4.1.


7.0   PROCEDURE

      7.1   Sulfuric acid cleanup

            7,1.1 Using a syringe  or a volumetric pipet, transfer 1.0 or 2.0 mL
      of the hexane extract to a 10 ml vial  and, in a fume hood,  carefully add
      5 mL  of the 1:1 sulfuric acid/water solution.

            7.1.2 The volume of hexane extract used depends on the requirements
      of the  GC  autosampler  used  by  the  laboratory.    If  the  autosampler
      functions  reliably with  1 ml of sample volume,  1.0 mL of extract should be
      used.  If  the autosampler requires more than 1 mL of sample volume, 2.0 mL
      of extract should be used.

            CAUTION:     Make  sure  that  there  is no  exothermic  reaction  nor
                        evolution of gas prior to proceeding.
                                   3665 - 2                         Revision 0
                                                                September 1994

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       7.1.3  Cap the vial tightly and  vortex for one minute.  A vortex must
be visible  in  the  vial.

       CAUTION:     Stop the vortexing immediately if the  vial  leaks, AVOID
                   SKIN CONTACT,  SULFURIC ACID BURNS.

       7.1.4  Allow  the phases to  separate for at least 1 minute.  Examine
the top (hexane) layer;  it should not be highly colored nor should it have
a visible emulsion or cloudiness.

       7.1.5  If a   clean  phase  separation   is  achieved,  proceed  to
Sec. 7.1.8.

       7.1.6  If the hexane layer is  colored  or the emulsion persists for
several minutes, remove the sulfuric acid layer  from the vial and dispose
of it  properly.  Add another 5 ml of the clean 1:1 sulfuric acid/water.

       NOTE:  Do not remove any hexane at this stage of the procedure.

       7.1.7  Vortex the  sample  for  one minute  and  allow the  phases  to
separate.

       7.1.8  Transfer the  hexane  layer to a clean 10 ml vial.

       7.1.9  Add an additional 1 ml of hexane to the sulfuric acid layer,
cap and  shake.  This  second  extraction is  done  to ensure quantitative
transfer of  the PCBs and Toxaphene.

       7.1.10      Remove  the  second hexane layer and combine  with  the
hexane from  Sec. 7.1.8.

7.2    Permanganate cleanup

       7.2.1  Add 5  ml of the 5  percent aqueous  potassium  permanganate
solution to  the combined hexane fractions from 7.1.10.

      CAUTION:     Make  sure  that there is  no  exothermic  reaction  nor
                   evolution of gas prior to  proceeding.

      7.2.2  Cap the vial tightly and vortex  for 1 minute.   A vortex must
be visible in the  vial.

      CAUTION:     Stop the vortexing  immediately if the vial  leaks.  AVOID
                   SKIN CONTACT, POTASSIUM PERMANGANATE BURNS.

      7.2.3  Allow  the phases to separate for at least 1  minute.  Examine
the top (hexane) layer,  it should not be highly colored nor should it have
a visible emulsion or cloudiness.

      7.2.4  If  a  clean   phase  separation   is   achieved,   proceed   to
Sec.  7.2.7.
                             3665 - 3                         Revision 0
                                                          September 1994

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      7,2.5 If the hexane layer  is  colored  or  the emulsion persists for
several minutes,  remove  the permanganate solution  from the vial  via a
glass pipette and dispose of it properly.  Add another 5 ml of the clean
aqueous permanganate solution.

      NOTE: Do not remove any hexane at this stage of the procedure.

      7.2.6 Vortex the sample and allow the phases to separate.

      7.2.7 Transfer the hexane layer to a clean 10 ml vial.

      7.2.8 Add an additional 1 ml  of  hexane  to the permanganate layer,
cap the vial  securely and shake.  This second extraction  is done to ensure
quantitative transfer of the PCBs and Toxaphene..

      7.2.9 Remove the second  hexane layer  and combine with the hexane
from Sec.  7.2.7.

7.3   Final preparation

      7.3,1 Reduce  the volume  of  the combined  hexane layers  to  the
original  volume  (]  or  2  ml)  using   the   Kuderna-Oanish   Technique
(Sec. 7.3,1.1).

            7.3.1.1      Add  one or  two clean boiling  chips  to  the flask
      and  attach  a three  ball Snyder column.  Prewet the Snyder column by
      adding about 1 mL of hexane to the top  of  the column.  Place the K-D
      apparatus on a hot water bath (15-20°C above  the  boiling point of
      the  solvent) so that the concentrator tube is partially immersed in
      the  hot water  and the  entire lower rounded surface of the flask is
      bathed  with hot  vapor.    Adjust  the  vertical  position  of  the
      apparatus and  the water temperature,  as  required, to  complete the
      concentration  in  10-20 minutes.   At the proper rate of distillation
      the  balls of the column will  actively chatter,  but the chambers will
      not  flood.   When the  apparent volume of  liquid  reaches  1-2  ml,
      remove the  K-D apparatus from the water  bath and allow it to drain
      and  cool for at least  10 minutes.

            7.3.1.2      Remove the Snyder column and rinse  the  flask and
      its  lower joints  into  the concentrator tube with 1-2  mL  of hexane.
      The  extract may be further concentrated  by  using  either  the micro
      Snyder column  technique (Sec.  7.3.2) or nitrogen blowdown  technique
      (Sec. 7.3.3).

      7.3.2 Micro Snyder  Column Technique

            7.3.2.1      Add  another  one or two  clean boiling chips to the
      concentrator tube and  attach a two ball micro Snyder column.  Prewet
      the  column  by adding   about  0.5 ml of  hexane  to the top  of the
      column.   Place the K-D apparatus in a hot water  bath so that the
      concentrator tube is partially immersed  in  the  hot water.   Adjust
      the  vertical position of the apparatus  and the water temperature, as
      required, to complete  the  concentration  in 5-10 minutes.   At the


                             3665 -  4                         Revision 0
                                                          September 1994

-------
            proper  rate  of distillation the balls of the column will actively
            chatter, but the chambers will not flood.  When  the  apparent volume
            of liquid  reaches  0.5  ml,  remove the K-D apparatus from the water
            bath and allow it to drain  and cool for at least  10 minutes.  Remove
            the  Snyder column and rinse  the flask  and  its  lower joints with
            about 0.2 ml of hexane  and  add to the concentrator tube.  Adjust the
            final volume to  1.0-2.0 mL, as  required, with hexane.

            7.3.3 Nitrogen Slowdown Technique

                  7.3.3,1      Place the concentrator tube in a warm water bath
            (approximately  35°C)   and  evaporate  the  solvent  volume  to  the
            required  level  using  a   gentle  stream  of  clean,  dry  nitrogen
            (filtered through  a column of activated  carbon).

                  CAUTION:     Do not use  plastidzed tubing between the carbon
                               trap and the  sample.

                  7.3.3.2      The internal wall  of the  tube must be rinsed down
            several times  with the appropriate  solvent  during  the  operation.
            During evaporation, the solvent  level in the tube must be positioned
            to prevent water from condensing into the sample (i.e., the solvent
            level should be  below  the  level  of  the water bath).  Under normal
            operating conditions,  the  extract should not be allowed  to become
            dry.

            7.3.4 Remove  any  remaining  organochlorine  pesticides  from  the
      extracts using Florisil Column Cleanup (Method 3620) or Silica Gel Cleanup
      (Method 3630).

            7.3.5 The  extracts obtained  may  now  be  analyzed  for the  target
      analytes using the appropriate  organic technique(s) (see Sec. 4.3 of this
      Chapter).  If analysis of the extract will not be  performed immediately,
      stopper the concentrator tube and store in a refrigerator.  If the extract
      will be  stored longer than 2 days, it should be transferred to a vial with
      a Teflon lined screw cap or crimp top, and labeled appropriately.
8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control procedures.


9.0   METHOD PERFORMANCE

      9.1   No performance data are currently available.


10.0  REFERENCES

      None required.
                                   3665 - 5                         Revision 0
                                                                September 1994

-------
                                 METHOD  3665
                 SULFURIC  ACID/PERMANGANATE CLEANUP
    St»rt
 7.1.1 Carafullv
combtn* hsxane
   with 1:1
  H2SO4/H20
   solution.
    7.1.2
 Tran»f»r th«
  appropriate
  volyntn to
     vial.
 7.1.3 - 7,1.4
  Cap. vortex
   and allow
    phaaa
  ovparetian.
    7.1.8
  Tranifar
 h«x*n« layar
 to clean yiei.
  7.1.9 Add
  haxana to
 H2S04 layar,
cap and shake
   7.1,10
 Combing two
hexana levers.
                         7.1.6 Remove
                          and di»po««
                        H2S04 iclution,
                        add clean H2SO4
                           solution.
7.1.7 Cap,
vortsx, and
allow phasa
laparation.
                                                     7.2.1 Add
                                                      KMn04
                                                      sotution.
                                                     7.2.2 - 7.2.3
                                                     Cap, vort»x,
                                                      and  allow
                                                        phase
                                                     separation.
/ 7.2.4 ta \.
f Dh«»« \ to w
t Mpvation ) 	
>. clean? /
JYea
7.
Trai
h«xan
to cla
1
2.7
risfaf
an vni.
f
7.2.8 Add
haxane to
KMnO4 layar.
cap and ahaka.
\
r
7.2.9 Combine
two riaxan*
lay«r».
af


>.

7.2.5 Ramova
and diapote
add clean KMnO4
aolution.
V
7,2.6 Cap
vortex and
taparation.

7.3.1 - 7.3.3
Reduce volumn
using K-D
and/or nitrogen
^r

7.3.4 Ut«
M*tho« 3620 or
Method 3630 to
further remove
contaminant! .
                                                                                  7.3.5 Stopper
                                                                                       ants
                                                                                    refrig*rat«
                                                                                    for fMfthar
                                                                                    analyara.
                                                                                       Stop
                                   3665  -  6
                                                       Revision  0
                                                 September  1994

-------
                                •  METHOD 4010

                SCREENING  FOR PENTACHLOROPHENOL BY IMMUNOASSAY
 1.0  SCOPE AND APPLICATION

      1.1  Method  4010  is  a procedure  for screening  solids  such  as soils,
 sludges,   and  aqueous   media   such  as   waste   water  and   leachates   for
 pentachlorophenol  (PCP)  (CAS Registry 87-86-5).

      1.2  Method 4010 is recommended for screening samples to determine whether
 PCP  is  likely to be  present at concentrations above 0.5 ing/Kg  for solids or
 0.005 mg/L  for aqueous  samples.   Method  4010 provides  an estimate  for the
 concentration of PCP  by  comparison with a standard.

      1.3  Using the  test kits  from which this method was  developed,  95  % of
 aqueous samples containing 2 ppb or less  of  PCPs will produce a negative result
 in the 5 ppb test configuration.  Also, 95 % of soil samples containing 125 ppb
 or less of PCBs will produce a negative result in the 500 ppb test configuration.

      1.4  In cases where the exact concentration of PCP is required, additional
 techniques (i.e.,  gas chromatography (Method 8040}  or  gas chroraatography/mass
 spectrometry (Method  8270)} should be used.


 2.0  SUMMARY OF METHOD

      2.1    Test  kits  are  commercially  available for  this  method.    The
manufacturer's  directions should  be followed.    In  general,  the method  is
 performed using a water  sample  or  an extract of a soil  sample.   Sample and an
 enzyme conjugate reagent  are added to immobilized antibody.  The enzyme conjugate
 "competes" with  PCP present  in  the sample for  binding  to  immobilized anti-PCP
 antibody.  The test is interpreted by comparing  the response produced by testing
 a sample to the response produced by testing standard(s)  simultaneously.


3.0  INTERFERENCES

      3.1  Compounds that are chemically similar may cause a positive test (false
positive) for PCP.  The test kit  used  in preparation of this method was evaluated
 for interferences.  Table 1 provides the concentration of compounds found to give
 a false positive test at the indicated concentration.

      3.2  Other compounds have been tested for cross reactivity with PCP, and
 have been demonstrated to not interfere with the specific  kit tested.  Consult
the  information  provided by the manufacturer  of  the kit used  for additional
 information regarding cross reactivity with other compounds.

      3.3  Storage and use temperatures may modify the method performance. Follow
the manufacturer's directions for storage and use.
                                    4010-1                          Revision 0
                                                                   August 1993

-------
 4.0  APPARATUS AND MATERIALS

      4.1  PENTA RISc Test Kits (EnSys, Inc.), or equivalent.  Each commercially
 available test kit will supply or specify the apparatus  and  materials necessary
 for  successful completion of the test.


 5.0  REAGENTS

      5.1   Each commercially  available  test kit  will  supply  or  specify the
 reagents necessary for successful completion of the test.


 6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See the  introductory material  to this chapter,  Organic Analytes,
 Section 4.1.
7.0  PROCEDURE

      7.1  Follow the manufacturer's instructions for the test kit being used.
Those test kits used must meet or exceed the performance indicated in Tables 2-3.


8.0  QUALITY CONTROL

      8.1  Follow the manufacturer's instructions for the test kit being used for
quality control procedures specific to the test kit used.  Additionally, guidance
provided in Chapter One should be followed.

      8.Z   Use of  replicate  analyses,  particularly  when results  indicate
concentrations  near  the action  level,   is  recommended  to  refine information
gathered with the kit.

      8.3  Do not use test kits past their expiration date.

      8.4  Do not use tubes or reagents designated for use with other kits.

      8.5  Use the test kits  within their specified storage  temperature and
operating temperature limits.

      8.6  Method 4010 is intended for field or laboratory  use.  The appropriate
level of quality assurance should accompany  the application of this method to
document data quality.


9.0  METHOD PERFORMANCE

      9.1  This method  has  been applied to  a  series of  groundwater, process
water,  and wastewater samples  from  industries which use  PCP,  and the results
compared with  6C/MS  determination  of  PCP  (Method  8270).   These  results are
provided in Table 2.  These results represent determinations by two laboratories,


                                    4010-2                          Revision 0
                                                                   August 1993

-------
      9.2  This method  has  been applied to a  series  of soils from industries
which use PCP and the results compared with GC/MS determination of PCP via Method
8270.    These results  are  provided  in  Table 3.    These  results represent
determinations by two laboratories.


10.0 REFERENCES

1.   J.P. Mapes,  K.D. McKenzie,  L.R. McClelland, S.  Movassaghi,  R.A.  Reddy, R.L.
     Allen,   and  S.B.   Friedman,  "Rapid,   On-Site   Screening  Test   for
     Pentachlorophenol  in Soil  and Water -  PENTA-RISc™", Ensys Inc.,  Research
     Triangle Park, NC 27709
2.   J.P. Mapes, K.D. McKenzie, L.R.
     Allen,   and  S.B.  Friedman,
     Pentachlorophenol  in Soil".
     1992.
                                    McClelland,
              S. Movassaghi, R.A. Reddy,  R.L.
"PENTA-RISc1"  -  An On-Site  Immunoassay  for
Bull.  Environ. Contam. Toxicol.,  49:334-341,
3.   PENTA-RISc M  Instructions for Use, Ensys  Inc.
                                    4010-3
                                   Revision  0
                                 August  1993

-------
Table 1
Cross Reactivity for PCPa
Compound
2,6-Dichlorophenol
2,4,6-Trichlorophenol
2, 4, 5-Trichl orophenol
2,3, 4-Tr i chl orophenol
2 , 3 , 5 , 6-Tetrachl orophenol
Tetrachl orohydroqui none
Concentration { nig/Kg }
in Soil to Cause a
False Positive for PCP
at 0.5 mg/Kg
700
16
100
400
1.2
500
Concentration (/ig/L)
in Water to Cause a
False Positive for PCP
at 5 fj.g/1
600
100
500
600
7
>1500
for PENTA RISc Test Kit (EnSys, Inc.)
                             4010-4
 Revision 0
August 1993

-------
Table 2
Comparison of Immunoasssy" wtth fiC/MS
Water Matrix
Sample Type
grouri<3wster





process water


WHStewater


run-off
















!|I
Screening Results (ppm) f| Concentration measured
0.005


>



>
>



>
	
y
>






>








0.05


«



>
>

>

>
.55
>
<
>
>
>

»
>
<

>






0.1

>




<
a
>
>

<
>
€












>



0.5

<




<:
<
<,
<


c
• 	 =!
















1
>



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»



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>

' ••-''

«
<
«

c
<

>
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>
>



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5
>


>
<
<




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>







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>
>

50 J ByGC/MS
C


«








— '."
















C
3.5
0.35
*0.1
B.2
ZJ
2.9
O21
0.17
0.12
0.6
1.4
0.1
0.17
cO-1
O.OJ4
C.U96
0.064
0.086
2.1
0.073
0,026
0.006
0.169
0,239
3.190
0.114
0.3*6
1.1
13
4.3
Does screening test agree with
GC/MS determination?
rto
yes
yes
ires
yes
yes
no
yes
yes
no
yes
yes
yes
yes
yes
yes
yes
yes
no
yes
no
yes
rto
yes
no
no
yes
ye*
yes
ye*
    > * screening test Indicates that the sample concentration Is greater than tne test concentration

    < - screening test indicates that the sample concentration l& less than the test concentration

* tor PENTA BISe Test KM (EnSys. Inc.)
                                                               4010-5
  Revision  0
August  1993

-------
Table 3
Comparison of immunosssay* with SC/MS
Soil Matrix
Screening Results (opm)
0.5
>
>
<

>
>
>
>
>
>
>
>
3
>
>
>
>
>
>
>
>
>
<
<
<
>
<
>
>
*
>
>
5
>
>
<
<
>
<
>
>
<
>
<
>
<
>
>
>
>
>
>
>
>
<
>
<
t:
<
<
<
<
>
<
>
9
50
>
c
<
<
y
<
*;
<
<
>
<
<
<
<
<
<
€
>
>
>
>
<
<
c
<
<
<
<
<:
7
<
^
<

Coneentration measured fey QC/MS
HDD
se
0.31
D.T2
315
1,5
6.4
3
1.9
4E
<1
21
3.3
4
11
18
33
54
65
74
63
1.1
14.3
<1
<1
<1
3J
«1
1.4
«a

-------
TafileS
Continued
Screening Results {ppm)
0,5
>
»
>
»
»
<
<
»
5
>
>
<
>
,
<
<
«
50
»
>
<
t
>
<
<
<
Concentration measured by GC/MS
117
56
2.5
3.5
143
nd
0,02
5
Does screening test agree wttti
QC/MS determination?
yes
yes
yes
no
yes
yes
yes
yes
> - screening test Indicates that the sample concentretlon is greater tften trie test concentration

< *• screening test indicates tnst the sample concentration is less then the test concentration

* for PENTA RIS£ Test Nt (EnSys. Inc.)
                                       4010-7
  Revision  0
August  1993

-------

-------
                                 METHOD 5030A

                                PURGE-AND-TRAP
1.0   SCOPE AND APPLICATION

      1.1   This method  describes sample  preparation  and extraction  for the
analysis  of  volatile  organics  by   a  purge-and-trap  procedure.    The  gas
chromatographic determinative steps are  found  in Methods 8010, 8015, 8020, 8021
and 8030.   Although applicable to Methods 8240 and 8260,  the  purge-and-trap
procedure is already incorporated into Methods 8240 and 8260.

      1.2   Method 5030 can be used for most volatile organic compounds that have
boiling  points  below 200°C and  are  insoluble or  slightly soluble  in  water.
Volatile water-soluble compounds can be included in this analytical technique;
however, quantitation limits  (by GC or GC/MS) are approximately ten times higher
because of poor purging efficiency. The method is also limited to compounds that
elute as  sharp peaks from a  GC column packed with  graphitized  carbon  lightly
coated with  a  carbowax or  a coated capillary column.   Such compounds include low
molecular  weight  halogenated  hydrocarbons,   aromatics,   ketones,  nitriles,
acetates, acrylates, ethers,  and sulfides.

      1.3   Water samples  can be analyzed directly for volatile organic compounds
by purge-and-trap extraction  and gas chromatography.  Higher concentrations of
these analytes in water can be determined by direct  injection of the sample into
the chromatographic system.

      1.4   This method also describes the preparation of water-miscible liquids,
non-water-miscible liquids, solids, wastes,  and soils/sediments for analysis by
the purge-and-trap procedure.


2.0   SUMMARY OF METHOD

      2.1   The purge-and-trap process:   An inert  gas is  bubbled  through the
solution  at ambient  temperature,  and the volatile  components  are  efficiently
transferred from  the aqueous phase  to  the vapor phase.   The vapor is  swept
through  a sorbent  column  where the  volatile  components are adsorbed.   After
purging is completed, the sorbent column  is heated and backflushed with inert gas
to desorb the components onto a gas chromatographic column.

      2.2   If  the  sample  introduction   technique in  Section  2.1  is  not
applicable,  a portion of  the sample  is dispersed in methanol to dissolve the
volatile organic  constituents.  A portion of the methanolic  solution is combined
with water  in  a  specially designed  purging chamber.   It  is then  analyzed by
purge-and-trap GC following the normal water method.


3.0   INTERFERENCES

      3.1   Impurities in the purge gas, and from organic compounds out-gassing
from the plumbing ahead of the trap,  account for the majority of contamination
problems.   The  analytical  system  must  be  demonstrated  to  be  free  from

                                  5030A -  1                         Revision 1
                                                                     July 1992

-------
contamination under the conditions of the analysis by running laboratory reagent
blanks.  The use of non-TFE plastic  coating,  non-TFE  thread  sealants,  or flow
controllers with rubber components in the purging device should be avoided.

      3.2   Samples can  be  contaminated by  diffusion  of volatile  organics
(particularly methylene chloride and fluorocarbons) through the septum seal of
the  sample  vial during  shipment and  storage.   A trip  blank prepared  from
organic-free reagent water and carried through sampling and handling protocols
serves as a check on such contamination.

      3.3   Contamination by carryover can occur whenever high-concentration and
low-concentration  samples  are analyzed  sequentially.   Whenever  an unusually
concentrated  sample  is  analyzed,  it  should  be  followed by  an  analysis  of
organic-free reagent water  to check for cross-contamination. The trap and other
parts of the system are subject to contamination.  Therefore,  frequent bake-out
and purging of the entire system may be required.

      3.4   The  laboratory where  volatile  analysis  is  performed  should  be
completely free of solvents.


4.0   APPARATUS AND MATERIALS

      4.1   Microsyringes - 10 pL, 25 /*L,  100 /iL,  250 /*!., 500 /^L, and 1,000 j*l.
These syringes should  be  equipped with  a 20 gauge  (0.006 in ID) needle having a
length sufficient to extend from the sample inlet to  within  1  cm  of the glass
frit in the purging device.  The needle length will depend upon the dimensions
of the purging device employed.

      4.2   Syringe valve - Two-way,  with Luer  ends (three each), if applicable
to the purging device.

      4.3   Syringe -  5 ml, gas-tight with shutoff valve.

      4.4   Analytical balance - 0.0001 g.

      4.5   Top-loading balance - 0.1 g.

      4.6   Glass scintillation  vials -  20 ml,  with screw-caps and Teflon Uners
or glass culture tubes with screw-caps and Teflon liners.

      4.7   Volumetric flasks, Class A - 10 ml and 100 ml,  with  ground-glass
stoppers.

      4.8   Vials - 2 ml, for GC autosampler.

      4.9   Spatula - Stainless steel.

      4.10  Disposable pipets - Pasteur.

      4.11  Purge-and-trap device:  The purge-and-trap device consists of three
separate pieces  of equipment:  the sample purger,  the trap,  and  the desorber.
Several complete devices are commercially available.


                                  5030A - 2                         Revision 1
                                                                     July 1992

-------
      4.11.1      The recommended purging  chamber  is designed to accept 5
ml samples with a water column  at least 3 cm deep.  The gaseous headspace
between the water column  and  the trap must have  a total  volume  of less
than 15 ml.  The purge  gas must  pass  through  the  water column as finely
divided bubbles with  a diameter of less  than  3  mm at the  origin.   The
purge gas must be introduced no more than  5 mm  from the base of the water
column.  The sample purger, illustrated in  Figure 1,  meets these design
criteria.  Alternate sample purge devices may be used, provided equivalent
performance is demonstrated.

      4.11.2      The trap must be at  least  25  cm  long and have an inside
diameter of at  least  0.105  in.  Starting  from the inlet,  the trap must
contain the following  amounts of adsorbents:  1/3 of 2,6-diphenylene oxide
polymer,  1/3   of  silica  gel,   and 1/3  of  coconut   charcoal.     It  is
recommended that 1.0 cm of methyl silicone-coated packing be inserted at
the inlet to extend  the life of the trap (see Figures 2 and 3).  If it is
not necessary  to analyze for  dichlorodifluoromethane or  other  fluoro-
carbons of similar  volatility, the charcoal  can  be eliminated  and  the
polymer increased to  fill  2/3 of  the trap.    If  only  compounds  boiling
above 35°C are  to be  analyzed, both  the silica gel and  charcoal  can be
eliminated and  the  polymer increased to  fill  the entire  trap.   Before
initial  use,   the  trap  should  be conditioned  overnight  at 180°C  by
backflushing with an inert gas  flow of at  least 20 mL/min.  Vent the trap
effluent to the hood,  not to the analytical  column.  Prior to daily use,
the trap should be conditioned  for  10 min at 180°C  with backflushing.  The
trap may  be vented  to the analytical  column during daily conditioning;
however, the column must be run through the temperature program prior to
analysis of samples.

      4.11.3      The desorber should be  capable  of rapidly heating  the
trap to 180°C  for desorption.   The  polymer section of the trap should not
be heated higher than  180°C, and  the remaining sections should not exceed
220°C  during bake-out  mode.  The  desorber design illustrated in Figures 2
and 3 meet these criteria.

      4.11.4      The purge-and-trap device may be assembled as a separate
unit or  may  be coupled  to  a   gas  chromatograph,  as  shown  in  Figures 4
and 5.

      4.11.5      Trap Packing Materials

            4.11.5.1    2,6-Diphenylene  oxide  polymer  -  60/80  mesh,
      chromatographic grade (Tenax GC  or equivalent).

            4.11.5.2    Methyl    silicone   packing   -   OV-1   (3%)   on
      Chromosorb-W,  60/80 mesh or equivalent.

            4.11.5.3    Silica gel  -  35/60 mesh,  Davison, grade  15 or
      equivalent.

            4.11.5.4    Coconut charcoal  - Prepare from Barnebey  Cheney,
      CA-580-26 lot #M-2649, or  equivalent, by crushing  through  26 mesh
      screen.
                             5030A  - 3                         Revision 1
                                                               July 1992

-------
      4.12  Heater  or  heated oil  bath  -  capable  of maintaining  the purging
chamber to within 1°C,  over a temperature range from ambient to 100°C.


5.0   REAGENTS

      5.1   Organic-free reagent water - All  references  to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.2   Methanol, CH3OH - Pesticide  quality or equivalent.  Store away from
other solvents.

      5.3   Reagent Tetraglyme - Reagent tetraglyme  is defined  as tetraglyme in
which interference is not observed at the method detection limit of the compounds
of interest.

            5.3.1 Tetraglyme (tetraethylene glycol dimethyl  ether, Aldrich #17,
      240-5 or equivalent), CgH18Oc.   Purify by  treatment at  reduced pressure in
      a rotary  evaporator.   The tetraglyme should  have a  peroxide content of
      less  than  5 ppm  as  indicated by  EM Quant  Test  Strips  (available from
      Scientific Products Co., Catalog No. P1126-8 or equivalent).

            CAUTION;    Glycol  ethers  are suspected carcinogens.  All  solvent
                        handling should  be done  in a hood  while  using proper
                        protective equipment to minimize exposure to liquid and
                        vapor.

            Peroxides may be removed by  passing the  tetraglyme  through a column
      of activated  alumina.  The tetraglyme is placed in a  round  bottom flask
      equipped with a standard taper joint, and the flask is  affixed to a rotary
      evaporator. The flask is immersed  in  a water bath at 90-100°C and a vacuum
      is maintained  at  < 10  mm Hg  for at  least  two hours using  a  two stage
      mechanical pump.  The  vacuum  system is  equipped with  an all  glass trap,
      which is  maintained  in a  dry  ice/methanol bath.  Cool  the  tetraglyme to
      ambient temperature and add 100 mg/L  of 2,6-di-tert-butyl-4-methyl-phenol
      to prevent peroxide  formation. Store the tetraglyme  in a tightly sealed
      screw cap bottle  in an area that is not contaminated by  solvent vapors.

            5.3.2 In order to demonstrate that all  interfering volatiles have
      been removed from  the tetraglyme, an organic-free reagent water/tetraglyme
      blank must be analyzed.

      5.4   Polyethylene glycol, H(OCH2CH2)nOH.  Free of interferences  at the
detection limit of the  analytes.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   Refer to the introductory material to this chapter, Organic Analytes,
Section 4.1. Samples should be stored in capped bottles,  with minimum headspace,
at 4°C or less.
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7.0   PROCEDURE

      7.1   Initial calibration:  Prior to using this introduction technique for
any GC method, the system must be calibrated.  General calibration procedures are
discussed in Method 8000, while the  specific determinative  methods and Method
3500 give details on preparation of standards.

            7.1.1 Assemble a purge-and-trap device that meets the specification
      in Section 4.10.   Condition  the trap  overnight at 180°C in the purge mode
      with an inert gas  flow of at least 20  mL/min.  Prior to use, condition the
      trap daily for 10 min while backflushing at 180°C with the  column at 220°C.

            7.1.2 Connect the purge-and-trap  device to a  gas chromatograph.

            7.1.3 Prepare   the   final   solutions   containing   the   required
      concentrations of calibration  standards,  including  surrogate standards,
      directly in the  purging device.  Add  5.0 ml of organic-free reagent water
      to the purging device.   The organic-free reagent water  is  added to the
      purging device using  a 5  ml glass syringe fitted with a 15 cm  20-gauge
      needle.   The  needle  is  inserted through the  sample  inlet  shown  in
      Figure 1.  The  internal  diameter  of  the  14-gauge needle that forms the
      sample inlet will  permit insertion of the  20-gauge needle.  Next, using a
      10 /iL or  25  /xL  micro-syringe equipped  with a  long  needle (Section 4.1),
      take a volume of  the  secondary dilution solution containing appropriate
      concentrations  of  the  calibration  standards.    Add   the  aliquot  of
      calibration  solution  directly  to  the organic-free  reagent  water in the
      purging device by  inserting  the needle through the sample  inlet.   When
      discharging the  contents of the micro-syringe, be sure that the end of the
      syringe needle  is  well  beneath the  surface of  the  organic-free  reagent
      water.  Similarly,  add 10 /xL of the internal standard solution.  Close the
      2-way syringe valve at the sample inlet.

            7.1.4 Carry out the purge-and-trap  analysis  procedure using the
      specific conditions given in Table 1.

            7.1.5 Calculate  response  factors or calibration factors  for each
      analyte of interest using the procedure described in Method 8000.

            7.1.6 The average RF must  be calculated for each  compound.  A system
      performance check should be made  before this  calibration curve  is used.
      If the purge-and-trap  procedure is used with  Method  8010,  the following
      five  compounds   are  checked  for  a  minimum  average  response  factor:
      chloromethane; 1,1-dichloroethane; bromoform;  1,1,2,2-tetrachloroethane;
      and chlorobenzene.  The minimum acceptable average RF for these compounds
      should be 0.300  (0.250 for bromoform).  These compounds typically have RFs
      of 0.4-0.6,  and  are used to check compound  stability and  to check for
      degradation caused  by  contaminated lines  or active  sites in the system.
      Examples of these occurrences are:

                  7.1.6.1     Chloromethane:   This compound is  the most likely
            compound to be lost if the purge  flow is too  fast.

                  7.1.6.2     Bromoform: This compound is one  of the compounds
            most likely to be purged  very poorly if the purge flow  is too slow.

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            Cold spots and/or active sites in the transfer lines may adversely
            affect response.

                  7.1.6.3     Tetrachloroethane and 1,1-dichloroethane:   These
            compounds are degraded by contaminated transfer lines in purge-and-
            trap systems and/or active sites in trapping materials.

      7.2   On-going calibration:  Refer to Method 8000 for details on continuing
calibration.

      7.3   Sample preparation

            7.3.1 Water samples

                  7.3.1.1     Screening of the  sample  prior  to purge-and-trap
            analysis  will   provide  guidance  on  whether  sample  dilution  is
            necessary  and  will  prevent contamination  of the  purge-and-trap
            system.  Two screening techniques that can be utilized are: the use
            of an automated headspace sampler (modified Method 3810), interfaced
            to  a gas  chromatograph (GC),  equipped with  a  photo  ionization
            detector (PID),  in series with an electrolytic conductivity detector
            (HECD); and extraction  of the sample with hexadecane (Method 3820)
            and analysis of the extract on a GC with a FID and/or an ECD.

                  7.3.1.2     All samples and standard solutions must be allowed
            to warm to ambient temperature before analysis.

                  7.3.1.3     Assemble the purge-and-trap device. The operating
            conditions  for  the GC  are  given in  Section  7.0 of  the  specific
            determinative method to be employed.

                  7.3.1.4     Daily GC calibration criteria must be met (Method
            8000) before analyzing  samples.

                  7.3.1.5     Adjust  the purge gas  flow rate  (nitrogen  or
            helium)  to  that shown   in  Table 1,  on  the  purge-and-trap device.
            Optimize  the   flow  rate  to  provide  the   best   response  for
            chloromethane  and bromoform,  if  these compounds  are  analytes.
            Excessive   flow  rate   reduces   chloromethane response,   whereas
            insufficient flow reduces bromoform response.

                  7.3.1.6     Remove the plunger from a  5  ml syringe and attach
            a closed syringe valve.   Open the sample or standard bottle, which
            has been allowed to come to ambient  temperature, and carefully pour
            the  sample  into the  syringe barrel to  just  short  of overflowing.
            Replace  the syringe plunger  and compress  the sample.   Open the
            syringe valve and vent any residual air while adjusting the sample
            volume to  5.0 ml.  This process  of taking  an aliquot destroys the
            validity of the liquid  sample for  future  analysis; therefore,  if
            there is only one VOA vial, the analyst should fill  a second syringe
            at this time to protect against possible loss of sample integrity.
            This  second sample  is  maintained   only  until  such time  when the
            analyst  has determined that the first  sample has  been  analyzed
            properly.  Filling one 20 ml  syringe would allow the use of only one

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syringe.  If a second analysis  is needed from a syringe, it must be
analyzed within  24  hr.   Care  must be taken  to prevent  air  from
leaking into the syringe.

      7,3,1.7     The  following  procedure   is   appropriate   for
diluting purgeable  samples.   All  steps must  be  performed without
delays until the diluted sample is in a gas-tight syringe.

            7.3.1.7.1   Dilutions may be made in volumetric flasks
      (10 mL  to  100 ml).   Select  the volumetric flask  that  will
      allow for the  necessary dilution.  Intermediate dilutions may
      be necessary for extremely large dilutions.

            7.3.1.7.2   Calculate   the  approximate   volume   of
      organic-free reagent water to be added to the volumetric flask
      selected and add slightly less than this quantity of organic-
      free reagent water to the flask.

            7.3.1.7.3   Inject the proper  aliquot of  samples  from
      the  syringe prepared  in Section  7.3.1.5  into the  flask.
      Aliquots of less than 1  ml are  not recommended.   Dilute the
      sample to the  mark with organic-free  reagent water.  Cap the
      flask,  invert,  and  shake three  times.    Repeat the  above
      procedure for  additional  dilutions.

            7.3.1.7.4   Fill a  I ml syringe with the diluted sample
      as in Section  7.3.1.5.

      7.3.1.8     Add 10.0 pi of surrogate  spiking solution (found
in each determinative method, Section 5.0) and, if applicable, 10 /*L
of internal standard spiking solution  through the valve bore of the
syringe; then close  the valve.  The  surrogate and internal standards
may be mixed and  added as a single spiking solution.  Matrix spiking
solutions, if indicated,  should be added (10  juL)  to the sample at
this time.

      7.3.1.9     Attach the syringe-syringe valve assembly to the
syringe valve on  the  purging device.   Open the  syringe valves and
inject the sample into the purging chamber.

      7.3.1.10    Close both valves  and  purge the^sample for the
time and at the temperature specified in Table 1.

      7.3.1.11    At the  conclusion of the purge time, attach the
trap to the chromatograph, adjust the device to the desorb mode, and
begin  the gas  chromatographic temperature  program  and GC  data
acquisition.  Concurrently, introduce the trapped materials to the
gas  chromatographic  column by  rapidly  heating  the trap  to  180°C
while backflushing the trap with inert gas  between 20 and 60 mL/min
for the time specified in Table 1.

      7.3.1.12    While  the trap  is  being desorbed  into  the gas
chromatograph, empty the purging chamber.   Wash the chamber with a
minimum  of two  5 ml  flushes  of  organic-free  reagent water (or

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      methanol  followed by organic-free reagent water) to avoid carryover
      of pollutant compounds into subsequent analyses.

            7.3.1.13    After desorbing  the sample,  recondition the trap
      by returning the purge-and-trap device to the  purge mode.  Wait 15
      sec; then close the syringe valve on the purging device to begin gas
      flow through the  trap.  The trap temperature should be maintained at
      180°C for Methods 8010,  8020,  8021,  8240  and 8260 and  210°C  for
      Methods  8015 and 8030.    Trap temperatures  up  to  220°C may  be
      employed.  However, the higher temperatures will shorten the useful
      life of  the  trap.   After approximately  7  min,  turn off the trap
      heater and open  the  syringe valve  to stop the  gas flow through the
      trap.  When cool, the trap is ready for the next  sample.

            7.3.1.14    If the initial analysis of a sample or a dilution
      of  the  sample has a  concentration of  analytes  that exceeds  the
      initial calibration range, the sample must be reanalyzed at a higher
      dilution.  When  a sample is analyzed that has saturated response
      from a compound,  this  analysis must be followed by a blank organic-
      free reagent water analysis.  If the blank analysis is not free of
      interferences, the system must  be  decontaminated.  Sample analysis
      may  not  resume  until  a blank  can be  analyzed  that  is free  of
      interferences.

            7.3.1.15    All  dilutions should keep  the response of  the
      major constituents (previously saturated peaks) in the upper half of
      the  linear  range of the  curve.   Proceed to  Method 8000  and  the
      specific determinative method  for details on calculating analyte
      response.

      7.3.2 Water-miscible liquids:

            7.3.2.1     Water-miscible  liquids are  analyzed  as  water
      samples after first diluting them at least 50-fold with organic-free
      reagent water.

            7.3.2.2     Initial and serial dilutions can  be prepared by
      pipetting 2  ml  of the sample  into  a 100 ml volumetric  flask and
      diluting  to volume  with organic-free  reagent  water.    Transfer
      immediately to a 5 mL gas-tight syringe.

            7.3.2.3     Alternatively, prepare dilutions directly in a 5
      ml syringe filled with organic-free reagent water  by adding at least
      20 jut, but  not  more  than 100 juL of liquid sample.   The sample is
      ready  for  addition  of surrogate and,  if  applicable,  internal  and
      matrix spiking standards.

      7.3.3 Sediment/soil  and  waste  samples:  It is highly recommended
that all samples of this type be screened prior to the  purge-and-trap GC
analysis.   These  samples  may contain  percent quantities  of purgeable
organics  that  will contaminate  the  purge-and-trap  system,  and require
extensive  cleanup and  instrument downtime.   See  Section 7.3.1.1  for
recommended  screening  techniques.   Use  the  screening  data  to determine
whether to use the low-concentration method (0.005-1 mg/kg) or the high-

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concentration method (>1 mg/kg).

            7.3.3.1     Low-concentration method:  This  is  designed for
      samples containing individual  purgeable compounds of <1 mg/kg.  It
      is limited to sediment/soil samples and waste that is of a similar
      consistency (granular and porous).  The low-concentration method is
      based  on  purging   a  heated   sediment/soil   sample  mixed  with
      organic-free  reagent  water  containing  the  surrogate  and,  if
      applicable,  internal  and  matrix spiking  standards.    Analyze all
      reagent  blanks  and  standards  under  the   same  conditions  as  the
      samples.

                  7.3.3.1.1   Use  a   5   g   sample   if   the   expected
            concentration  is <0.1 mg/kg or a 1  g sample  for  expected
            concentrations between 0.1 and  1 mg/kg.

                  7.3.3.1.2   The GC   system  should  be  set up  as  in
            Section 7.0 of the specific determinative method. This should
            be done prior to the  preparation of the sample to avoid loss
            of volatiles  from  standards and  samples.   A  heated purge
            calibration  curve  must   be  prepared   and   used   for  the
            quantitation   of   all  samples   analyzed  with  the  low-
            concentration  method.     Follow  the   initial   and   daily
            calibration instructions,   except  for the addition  of a 40°C
            purge temperature for Methods 8010,  8020, and 8021.

                  7.3.3.1.3   Remove the plunger  from a 5  ml  Luerlock type
            syringe  equipped  with   a  syringe  valve  and  fill   until
            overflowing with organic-free   reagent water.    Replace the
            plunger and compress  the  reagent  water to vent trapped air.
            Adjust the  volume  to 5.0  ml.   Add  10 pi  each  of surrogate
            spiking solution and internal  standard solution  to the syringe
            through the valve.   (Surrogate  spiking solution and internal
            standard solution  may be  mixed together.)  Matrix spiking
            solutions,  if indicated, should be added (10 jiL)  to the sample
            at this time.

                  7.3.3.1.4   The sample  (for  volatile organics) consists
            of the entire  contents  of the sample  container.    Do not
            discard any  supernatant  liquids.   Mix the  contents  of the
            sample container with a  narrow metal  spatula.  Weigh the
            amount determined  in Section 7.3.3.1.1  into a  tared purge
            device.  Note and record the actual weight to the nearest 0.1
            9-

                  7.3.3.1.5   Determination of sample %  dry weight - In
            certain cases, sample results are  desired based  on dry weight
            basis.  When  such  data  is desired,  a  portion  of sample for
            this determination  should be  weighed out at the same time as
            the portion used for analytical  determination.

                  WARNING:    The drying oven should be contained  in a
                              hood or vented.    Significant laboratory
                              contamination may  result  from a  heavily

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                        contaminated hazardous waste sample.

                  7.3.3.1.5.1 Immediately after weighing the sample
            for extraction,  weigh  5-10 g of the sample into a tared
            crucible.   Determine the % dry weight of the sample by
            drying  overnight  at   105°C.    Allow  to  cool  in  a
            desiccator before weighing:

                  % dry weight = g of dry sample x 100
                                    g of sample

            7.3.3.1.6    Add the spiked organic-free reagent water to
      the purge device, which contains the weighed amount of sample,
      and connect the  device to the purge-and-trap system.

            NOTE: Prior to  the attachment  of  the purge  device,
                  Sections   7.3,3.1.4   and   7.3,3.1.6   must   be
                  performed  rapidly and  without  interruption  to
                  avoid loss  of volatile organics.   These  steps
                  must be  performed 1n a laboratory free of solvent
                  fumes.

            7.3.3.1.7    Heat the sample to 40°C + 1°C (Methods 8010,
      8020 and 8021) or to  85°C ±  26C (Methods~8015  and 8030}  and
      purge the sample for the time shown in Table 1.

            7.3.3.1.8    Proceed with  the  analysis as outlined in
      Sections 7.3.1.11-7.3.1.15.  Use 5 ml of  the same organic-free
      reagent water as  in  the reagent blank.   If  saturated  peaks
      occurred or would occur if  a 1 g sample  were  analyzed,  the
      high-concentration method must be followed.

            7.3.3.1.9    For    matrix    spike    analysis    of
      low-concentration sediment/soils,  add  10  nL of  the matrix
      spike solution to 5 ml of organic-free reagent water (Section
      7.3.3.1.3  ).  The concentration for  a  5 g  sample would be
      equivalent to 50 ng/kg of each matrix spike standard.

      7.3.3.2     High-concentration method:  The method  is based on
extracting the  sediment/soil with  methanol.    A waste  sample is
either  extracted  or   diluted,  depending  on  its  solubility  in
methanol.    Wastes  (i.e.  petroleum  and coke wastes)  that  are
insoluble  in  methanol  are  diluted  with  reagent tetraglyme  or
polyethylene glycol (PEG).  An aliquot of the extract is added to
organic-free reagent water  containing surrogate and, if applicable,
internal  and matrix  spiking  standards.    This  is purged at  the
temperatures indicated  in  Table 1.   All  samples with an expected
concentration of >1.0  mg/kg should be analyzed by this method.

            7.3.3.2.1    The sample (for volatile organics) consists
      of  the entire  contents of  the  sample  container.   Do  not
      discard  any  supernatant liquids.    Mix  the  contents  of  the
      sample  container  with  a   narrow  metal   spatula.     For
      sediment/soil and waste that  are insoluble in methanol, weigh

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4 g (wet weight)  of  sample into a tared 20 ml vial.   Use a
top-loading balance.  Note and record the actual weight to 0.1
gram and determine the  percent dry weight of the sample using
the procedure in Section 7.3.3.1.5.  For waste that is soluble
in methanol, tetraglyme,  or PEG, weigh 1 g (wet weight) into
a  tared scintillation  vial  or culture  tube  or  a   10  ml
volumetric flask.   (If a vial  or  tube is used,  it must  be
calibrated prior to use.   Pipet 10.0 ml of methanol  into the
vial  and  mark the  bottom  of  the meniscus.   Discard  this
solvent.)

      7.3.3.2.2   For sediment/soil or  solid waste,  quickly
add 9.0 ml  of appropriate  solvent;  then  add  1.0 ml  of the
surrogate  spiking solution  to  the  vial.   For  a  solvent
miscible  sample,   dilute  the   sample   to  10  ml  with  the
appropriate  solvent  after  adding  1.0  ml  of the  surrogate
spiking solution.   Cap and shake for 2 min.

      NOTE: Sections   7.3.3.2.1  and   7.3.3.2.2   must   be
            performed  rapidly  and  without interruption  to
            avoid loss of  volatile  organics.   These  steps
            must  be  performed  in  a  laboratory  free  from
            solvent fumes.

      7.3.3.2.3   Pipet approximately 1 ml of the extract into
a  GC  vial  for  storage,   using a  disposable  pipet.    The
remainder may be discarded.  Transfer  approximately 1  ml  of
reagent methanol  to a separate 6C vial  for use  as  the method
blank for each set of samples.   These extracts  may be stored
at 4°C in the dark,  prior to analysis.

      7.3.3.2.4   The  GC  system  should  be set  up  as  in
Section 7.0 of the specific determinative method.  This should
be  done  prior to  the  addition of  the methanol  extract  to
organic-free reagent water.

      7.3.3.2.5   Table 2 can be used to determine the volume
of methanol  extract to add to the 5 ml of organic-free reagent
water for analysis.  If  a screening  procedure  was followed,
use the estimated concentration to determine the appropriate
volume.  Otherwise,  estimate the concentration  range  of the
sample from the low-concentration  analysis to  determine the
appropriate volume.  If the sample was  submitted  as a high-
concentration sample, start with 100 juL.  All  dilutions must
keep  the  response  of  the  major  constituents  (previously
saturated peaks)  in the upper half of the linear range of the
curve.

      7.3.3,2.6   Remove  the plunger from  a  5.0 ml  Luerlock
type  syringe  equipped  with a  syringe  valve and  fill  until
overflowing with  organic-free  reagent  water.   Replace the
plunger and compress the water  to  vent  trapped  air.   Adjust
the volume  to  4.9 ml.   Pull the  plunger back to 5.0  ml  to
allow volume for  the addition  of the sample extract  and  of

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                  standards. Add 10 pL of Internal  standard solution.  Also add
                  the volume of methanol extract determined  in Section 7.3.3.2.5
                  and a volume of methanol solvent to total  100  nl (excluding
                  methanol in standards).

                        7.3.3.2.7   Attach the syringe-syringe valve assembly to
                  the syringe valve on  the  purging device.   Open  the syringe
                  valve and inject the water/methanol sample  into  the purging
                  chamber.

                        7.3.3.2.8   Proceed with the analysis as outlined in the
                  specific determinative method.  Analyze all reagent blanks on
                  the  same instrument  as that  used for  the  samples.    The
                  standards and blanks should also contain  100 juL  of methanol
                  to simulate the sample conditions.

                        7.3.3.2.9   For a matrix spike in the high-concentration
                  sediment/soil  samples,  add 8.0  ml of methanol,  1.0 ml  of
                  surrogate spike solution and  1.0 ml of matrix spike solution.
                  Add a 100 £iL  aliquot of this  extract  to 5  ml of  water for
                  purging (as per Section 7.3.3.2.6).

      7.4   Sample analysis:

            7.4.1 The samples prepared by this method may  be analyzed by Methods
      8010, 8015, 8020, 8021, 8030, 8240,  and 8260.  Refer to these methods for
      appropriate analysis conditions.


8.0   QUALITY CONTROL

      8.1   Refer to  Chapter One for specific quality control  procedures and
Method 3500 for sample preparation procedures.

      8.2   Before processing any samples,  the analyst should demonstrate through
the  analysis  of  a  calibration  blank  that  all  glassware  and  reagents  are
interference free.  Each time a set of samples is extracted,  or there is a change
in reagents, a method blank should be processed as a safeguard against chronic
laboratory contamination.   The blanks  should be carried through all  stages of
the sample preparation and measurement.

      8.3   Standard quality assurance practices should be used with this method.
Field duplicates should be collected to validate the precision of the sampling
technique.  Laboratory replicates should be  analyzed to validate the precision
of the analysis.  Spiked samples  should  be carried through all  stages of sample
preparation and measurement; they should be analyzed to validate the sensitivity
and accuracy of the  analysis.  If  the spiked  samples do not  indicate sufficient
sensitivity  to  detect  <  1 ng/g of the  analytes  in  the  sample,   then  the
sensitivity of  the  instrument should  be increased,  or  the  sample  should  be
subjected to additional cleanup.
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9.0   METHOD PERFORMANCE

      9.1   Refer to the determinative methods for performance data.


10.0  REFERENCES

1.    U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test  Procedures for the
      Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
      Final Rule and Proposed Rule," October 26, 1984.
                                  5030A - 13                        Revision  1
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                                   TABLE  1
                      PURGE-AND-TRAP OPERATING  PARAMETERS
                                           Analysis Method
                             8010
                8015
              8020/8021
                8030
Purge gas
Purge gas flow rate
 (mL/min)
Purge time (min)
Purge temperature (°C)
Desorb temperature (°C)
Backflush inert gas flow
  (mL/min)
Desorb time (min)
Nitrogen or  Nitrogen or
  Heli urn

    40
11.0 ± 0,1
  Ambient
   180

  20-60
    4
  Helium

    20
15.0 ± 0.1
  85 + 2
   180

  20-60
   1.5
Nitrogen or  Nitrogen or
  Helium       Helium
    40
11.0 ± 0.1
  Ambient
   180

  20-60
    4
    20
15.0 ± 0.1
  85 ± 2
   180

  20-60
   1.5
                                  5030A - 14
                                          Revision  1
                                           July  1992

-------
                                   TABLE 2
            QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF
                      HIGH-CONCENTRATION SOILS/SEDIMENTS

                Approximate                         Volume of
            Concentration Range                  Methanol  Extract8
              500-10,000 pg/kg                         100 pi
            1,000-20,000 pg/kg                          SO ^L
            5,000-100,000 ng/kg                         10 j*L
           25,000-500,000 ^9/kg               100 nl of 1/50 dilution b


Calculate appropriate dilution factor for concentrations exceeding this table,

aThe volume of methanol  added to 5  mL of water being purged  should be  kept
constant.  Therefore, add to the 5  mL syringe whatever volume of methanol  is
necessary to maintain a volume of 100 j*L added to the syringe.

Dilute an aliquot of the methanol  extract  and then take 100 pi for analysis.
                                  5030A - 15                        Revision 1
                                                                     July 1992

-------
                        Figure 1
                    Purging Chamber
       OPTIONAL
       FOAM TRAP
Inch O. D. Ixit
                             Into '4 Inch 0. 0.
      Inttt

2-Way Synnot V«l*
17 cm. 20 Gcuot tynng*
6 mm 0. 0. ftubbtr Stptum


  -IflmmO. D.
                                   Inltt
                                   )4 Inch 0. 0.
                      1'16lnct»0 D.
                      St*ml«u SIM:
                                                    Flow Control
   Midium N»MHV
                        5030A - 16
                                 Revision 1
                                  July 1992

-------
                              Figure 2
       Trap  Packing and Construction  for Method 8010
                  Procfdura
                           Construction
  QiMiWool  8 mm I
  Activattd
  Charcoal
    f
7.7 em
 Grada IS
 Sitic* 6*i
7.7 em
    Tw>a»    7.7 em
3%OV-1
QlauWooi
                  >
ftttiittnct
Wirt Wr §pp«d
Solid
(Ooubtt Ljytr)
    78/Foot    +•
    Rftiftanca
    Wira Wrapptd
    Solid
          Lavt r)
             • em
                           Comprwiion
                           Pining Nut
                           •nd P*rrult«
                                                   Thtrmoeouplt/
                                                   Controllfr
                                                   Sfnsor
                                             ElKtronie
                                                         Control and
                                                         Pyromtttr
                                        Tubing 25 em
                                        0 105 In. 1,0,
                                        0.125 In. 0.0
                                        St»ml«« Stni
                  Trap Inlet
                            5030A -  17
                                                          Revision  1
                                                           July  1992

-------
                                    Figure 3
        Trap Packing  and Construction  for  Methods 8020 and 8030
            Picking Procedure
                       Construction
Glau Wool   5 mm
3% OV-1   1 cm ;;

Gf«i Wool    5 mm

%
I
k
i
   Ttnax   23 cm
i
 fej
                                       Comprtsiion Pining Nut
                                       •nd Ferrule*

                                         14 Ft. 7fl/Foot Rtsittanc*
                                         Wirt WnpBtd Solid
                                                             Th«rmocoupl«/Controll«r Senior
                                                                  Eltctronic
                                                                  Temperature
                                                                  Control and
                                                                  Pyromtttr
                                                            Tubing 25 cm
                                                            0.105 In. I.D.
                                                            0,125 In. O.D.
                                                            Stiinlen Stttl
                   T«p Inltt
                                     5030A  - 18
                                                            Revision  1
                                                             July 1992

-------
                           Figure  4
                    Purge-and-Trap System
                       Purge-Sorb Mode
              For  Method 8010,  8020, and 8030
CARRIER GAS
FLOW CONTROL
PRESSURE
REGULATOR
                              OPTIONAL *PORT COLUMN
                              SELECTION VALVE
PURGE OAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
UOUIO INJECTION PORTS

      COLUMN OVEN

               CONFIRMATORY COLUMN

              TO DETECTOR
                                                ANALYTICAL COLUMN
                                       TRAP INLET
                                      22*C
                                PURGING
                                DEVICE
             NOTE
             ALL LINES BETWEEN TRAP
             AND GC SHOULD BE HEATED
             TO«0*C
                           5030A -  19
                               Revision 1
                                July  1992

-------
                            Figure  5
                     Purge-and-Trap System
                          Desorb Mode
               For  Method 8010, 8020, and 8030
CAPMERGAS
FLOW CONTROL
PRESSURE
REGULATOR
UOWO INJECTION PORTS

     COLUMN OVEN
                              OPTIONAL tPORT COLUMN
                              SELECTION VALVE
               CONFIRMATORY COLUMN


              TO DETECTOR
                                                ANALYTICAL COLUMN
PURGE OAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
                                PURGING
                                DEVICE
             NOTE
             ALL LINES BETWEEN TRAP
             AND GC SHOULD BE HEATED
             TO WC.
                           5030A  -  20
                               Revision  1
                                 July 1992

-------
          METHOD  5030A
         PURGE-AND-TRAP
     Start
 7.1  Calibrate
  CC  system.
7.1.2  Assemble
purge-and-trap
  device and
condilion trap.
 7.1.2 Connect
    t o gas
chromatograph.
 71.3 Prepare
     final
  solutions.
  7.1.4 Corry out
  purge-and- trap
    analysis.
  7.1.5 Calculate
    response or
calibration factors
 for  each analyte
  (Method 8000) .
7.1.6
Calcula te
averafe RF
for each
compound ,


             7
           5030A  -  21
                                  Revision 1
                                   July  1992

-------
                                      METHOD  5030A
                                        continued
    7.3.3.1
    Prepara
  samples  and
   set-up  CC
    system.
   7,3.3.1.4
 Heigh sample
  into tarad
    davica.
                                      7
               Low  concentration

                 Soil/sediment
            High concentrati

              Soil/sediment
   7.3.3.1.5
 Heigh anothar
  sample and
  datarmina %
  dry Height.
 7.3 3.1.6 Add
spiked raagant
water, connact
   davica to
    sys tarn .
   7,3.3.1.7
   Haat and
 purga sample
  7.3.1  Scraan
«ampla«  prior  to
 purga-and-trap
analyaia,  dilute
 •atar miicibla
    liquid*
  7.3.1 Prapara
   *ampl« and
  purg-and- trap
     davica.
     7.3.1.7
     Diluta
    purgaabla
    aamplaa .
   7.3.1.8 Add
  •urrogata and
intarnal spiking
  aolutiona (if
   indicated)
                         /
              7
                            7.3.3.2 Add
                             ntethetnol
                            eHtract to
                           reagent water
                           for ana lysis .
  7332  Set
 up CC aystem.
7.33,26  Fill
 syringe with
reagent water ,
 vent air  and
ad jua t vol ume .
 7 3326  Add
   internal
 a tandard . and
   methanol
   extract
    Analyze
 acco rding to
 determinative
    method
                     7319
                  Injact aampla
                  into chamber,
                     purge
  7 3.1.11
 Deiorb trap
  into CC.
  7.3.1  13
 Recondition
  trap and
  start  gas
    flow
7.3.1.13 Stop
gas flow and
cool trap for
next sample
   Analyze
according to
determinative
   method .
                                           5030A  -  22
                                                                Revision  1
                                                                  July  1992

-------
                                 METHOD 5040A

  ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC SAMPLING TRAIN (VOST):
                 GAS CHROMATOGRAPHV/MASS SPECTROMETRY TECHNIQUE
1.0   SCOPE AND APPLICATION

      1.1   Method 5040 was formerly Method 3720 in the Second Edition of this
manual.

      1,2   This method covers the determination of volatile principal organic
hazardous constituents  (POHCs),  collected  on  Tenax and Tenax/charcoal sorbent
cartridges  using  a volatile  organic  sampling train,  VOST  (1),    Much  of the
description for purge-and-trap GC/MS analysis is described in Method 8240 of this
chapter.  Because the majority of gas  streams  sampled  using VOST will contain a
high concentration of water,  the analytical  method  is  based on the quantitative
thermal desorption of volatile POHCs from the Tenax  and Tenax/charcoal traps and
analysis by purge-and-trap GC/MS.  For  the purposes of definition, volatile POHCs
are those POHCs with boiling points less than 100°C.

      1.3   This  method is  applicable  to  the analysis of  Tenax  and  Tenax/
charcoal cartridges used to collect volatile POHCs  from wet stack gas effluents
from hazardous waste incinerators.

      1.4   The sensitivity of the analytical  method for a particular volatile
POHC depends on the level of interferences and  the presence of detectable levels
of  volatile POHCs  in  blanks.    The  desired  target  detection  limit of  the
analytical method is  0.1 ng/L  (20  ng on a single pair  of traps) for a particular
volatile POHC  desorbed  from  either a  single  pair  of  Tenax  and  Tenax/charcoal
cartridges or  by thermal desorption of  up  to  six pairs of  traps  onto a single
pair of Tenax  and Tenax/charcoal traps.   The resulting single pair of traps is
then thermally desorbed and analyzed by purge-and-trap GC/MS.

      1.5   This  method  is   recommended  for  use  only  by  experienced  mass
spectroscopists or under the close supervision of such qualified  persons.


2.0   SUMMARY OF METHOD

      2.1   A schematic diagram of the analytical system is shown in Figure 1.
The contents of the sorbent cartridges are  spiked with  an internal standard and
thermally desorbed for 10 min at 180°C with  organic-free nitrogen or helium gas
(at a flow  rate of 40  mL/min),  bubbled through  5 ml  of  organic-free reagent
water,  and  trapped  on  an  analytical  adsorbent  trap.    After   the 10  min.
desorption,  the analytical adsorbent trap is rapidly heated to 180°C, with the
carrier gas  flow reversed so  that  the  effluent flow from the analytical trap is
directed  into  the GC/MS.   The  volatile  POHCs  are  separated by  temperature
programmed gas ehromatography and  detected by  low-resolution mass  spectrometry.
The concentrations of volatile POHCs are calculated using the internal standard
technique.
                                   5040A  -  1                         Revision 1
                                                                September 1994

-------
3.0    INTERFERENCES

       3.1   Refer to Methods 3500 and 3240.


       APPARATUS AND MATERIALS

       4,1   Thermal desorption unit:

            4.1.1 The   thermal   desorption   unit  (for   Inside/Inside  VOST
       cartridges,  use  Supelco   "clamshell"  heater;  for  Inside/Outside  VOST
       cartridges,  user-fabricated  unit  is  required)  should  be capable  of
       thermally desorbing the sorbent resin tubes.  It should also be capable of
       heating the  tubes to 180  ± 10°C  with  flow of  organic-free nitrogen or
       helium through the tubes.

       4.2   Purge-and-trap unit:

            4.2.1 The purge-and-trap unit consists of three separate pieces of
       equipment:   the sample purger,  trap,  and  the  desorber.    It  should be
       capable of meeting  all  requirements  of  Method  5030  for  analysis  of
       purgeable organic compounds from water.

      4.3   GC/MS system:  As described in Method 8240.


5.0   REAGENTS

      5.1   Organic-free reagent water.  All  references to water  in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.2   Methanol, CH3OH -  Pesticide grade,  or equivalent.

      5.3   Analytical trap reagents:

            5.3.1 2,6-Diphenylene oxide polymer:   Tenax (60/80 mesh), chrornato-
      graphic grade or equivalent.

            5.3.2 Methyl silicone packing:  3% OV-1 on  Chromosorb  W (60/80 mesh)
      or equivalent.

            5.3.3 Silica gel:    Davison Chemical  (35/00 mesh),   Grade  15,  or
      equivalent.

            5.3.4 Charcoal:  Petroleum-based  (SKC Lot 104 or equivalent).

      5.4   Stock standard solution:

            5.4.1 Stock standard solutions will be prepared from pure standard
      materials  or purchased as certified solutions.  The stock standards should
      be prepared in methanol using  assayed  liquids or gases,  as appropriate.
      Because of the toxicity of some of the organohalides, primary dilutions of
      these materials should be prepared in a  hood. A NIOSH/MESA approved toxic


                                  5040A - 2                         Revision 1
                                                                September 1994

-------
      gas respirator should be used when the analyst handles  high concentrations
      of such materials.

            5.4.2 Fresh stock  standards should be prepared weekly for volatile
      POHCs with boiling points of <35°C.   All  other standards must be replaced
      monthly, or sooner if comparison with check standards indicates a problem.

      5.5   Secondary dilution standards:

            5.5.1 Using  stock  standard   solutions,   prepare,   in  rnethanol,
      secondary  dilution  standards  that  contain  the  compounds  of  interest,
      either singly or mixed together.   The secondary dilution standards should
      be prepared at concentrations such that the desorbed  calibration standards
      will bracket the working range of the analytical  system.

      5.6   4-Bromofluorobenzene (BFB) standard:

            5.6.1 Prepare  a 25 ng/juL solution  of BFB in methanol.

      5.7   Deuterated benzene:

            5.7.1 Prepare  a 25 ng/^L solution  of benzene-d6 in methanol,


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   Refer to Method 0030, Chapter Ten.

      6.2   Sample trains  obtained from the VOST should be analyzed within 2-6
weeks of sample collection.


7.0   PROCEDURE

      7.1   Assembly of PTD device:

            7.1.1 Assemble a purge-and-trap desorption  device (PTD) that meets
      all the requirements of Method 5030 (refer to Figure 1).

            7.1.2 Connect  the thermal   desorption  device to  the  PTD  device.
      Calibrate the PTD-SC/MS system using the internal standard technique.

      7.2   Internal standard calibration procedure:

            7.2.1 This approach requires the  use of deuterated  benzene  as the
      internal standard  for  these  analyses.   Other internal  standards  may be
      proposed  for  use  in certain  situations.   The  important  criteria for
      choosing a  particular compound as an  internal  standard are that  it be
      similar in analytical behavior to the compounds  of  interest and  that it
      can be  demonstrated  that  the  measurement of the  internal  standard be
      unaffected by method or matrix  interferences.  Other internal  standards
      that have been used are ethylbenzene-d10  and, l-2-dichloroethane-d4.  One
      adds 50 ng of BFB to all sorbent  cartridges  (in  addition  to one  or more


                                   5040A -  3                        Revision 1
                                                                September 1994

-------
 internal  standards)  to  provide  continuous  monitoring  of  the  GC/MS
 performance  relative to BFB.

      7.2.2  Prepare   calibration  standards  at   a   minimum  of  three
 concentration levels for each  analyte of  interest.

      7.2.3  The  calibration standards  are  prepared  by  spiking   a  blank
 Tenax or Tenax/charcoal  trap with a methanolic solution of the calibration
 standards  (including  50  ng  of the internal  standard, such  as  deuterated
 benzene), using  the  flash  evaporation  technique.  The flash  evaporation
 technique  requires filling  the  needle  of  a  5.0 /iL  syringe with  clean
 methanol and drawing  air  into the syringe to the  1.0  ^tL mark.   This  is
 followed by  drawing  a methanolic solution  of the calibration standards
 (containing  25 M9//"L of the internal  standard)  to the 2.0 juL  mark.  The
 glass  traps should  be  attached  to  the   injection   port   of  a  gas
 chromatograph while  maintaining  the  injector temperature at  160°C.   The
 carrier  gas  flow  through  the traps  should  be  maintained  at about  50
 mL/min.

      7.2.4  After directing the gas flow through the trap, the contents  of
 the  syringe  should  be  slowly expelled  through the  gas  chromatograph
 injection port over about  15 sec.  After 25 sec have elapsed, the gas  flow
 through the  trap should  be shut off, the syringe  removed,  and the  trap
 analyzed by  the  PTD-GC/MS procedure  outlined  in  Hethod 8240,  The total
 flow of gas  through the  traps during  addition  of  calibration standards  to
 blank cartridges, or  internal  standards to sample cartridges, should  be  25
ml or less.

      7.2.5  Analyze each calibration standard for both Tenax  and Tenax/
charcoal cartridges according to  Section 7.3,  Tabulate the  area response
of the characteristic ions  of each analyte  against the concentration  of
the  internal standard  and  calculate the  response factor  (RF) for  each
compound, using  Equation 1.

      RF = ASC1S/AISCS                                                  (1)

where:

      A,.   =       Area of the  characteristic ion for the  analyte to  be
                  measured.

      AJS  =       Area  of  the  characteristic  ion  for   the  internal
                  standard.

      Cjs  =       Amount (ng)  of the  internal standard.

      Cs   =       Amount  {ng)  of  the  volatile  POHC  in  calibration
                  standard.

      If the  RF value over the working range is a  constant (<10% RSD), the
RF can be  ^  sumed to be invariant,  and the average RF  can be used for
calculations.    Alternatively,  the  results  can  be  used  to   plot  a
calibration  curve of response  ratios, As/Ais  versus  RF.


                             5040A -  4                          Revision 1
                                                          September  1994

-------
            7.2.6 The working calibration curve or RF must be verified on each
      working  day  by  the  measurement  of  one  or  more  of the  calibration
      standards.  If the response varies by more  than  ±25% for  any analyte, a
      new calibration standard must be prepared and analyzed for that analyte.

      7.3   The schematic of  the  PTD-GC/MS  system is shown  in  Figure  1.   The
sample cartridge  is placed in the  thermal  desorption apparatus  (for  Inside/
Inside VOST cartridges,  use  Supelco  "clamshell" heater; for Inside/Outside VOST
cartridges, user fabricated  unit is required)  and desorbed  in the purge-and-trap
system by heating to 180°C for 10 min at a flow rate of 40 inL/min.  The desorbed
components pass into the bottom of the water column, are purged from the water,
and collected on  the  analytical  adsorbent  trap.   After the  10  min desorption
period, the compounds are desorbed from the  analytical  adsorbent trap into the
GC/MS system according to the procedures described in Method 8240.

      7.4   Qualitative analysis

            7.4.1 The qualitative  identification of compounds  determined by this
      method is based on retention time, and  on comparison of the  sample mass
      spectrum,   after  background correction,  with characteristic  ions  in  a
      reference mass spectrum.  The reference mass  spectrum must be generated by
      the laboratory using the conditions of  this method.   The  characteristic
      ions from the  reference  mass spectrum are defined to be the three ions of
      greatest relative intensity, or any ions over  30%  relative  intensity if
      less than  three  such  ions  occur  in the reference spectrum.   Compounds
      should be identified as  present when the criteria below are  met.

                  7.4.1.1     The intensities of the characteristic  ions  of a
            compound maximize  in the same scan or within one scan of each other.
            Selection of a peak by a data system target compound search routine,
            where   the   search   is   based   on  the   presence  of   a   target
            chromatographic  peak  containing   ions  specific  for  the  target
            compound at  a compound-specific retention time, will  be accepted as
            meeting  this criterion.

                  7,4.1.2     The   RRT  of   the sample  component   is   within
            ±0.06 RRT units of  the RRT of the standard component.

                  7.4.1.3     The  relative  intensities  of the  characteristic
            ions agree within  30% of the relative  intensities of these ions in
            the reference spectrum.   (Example:  For an ion with an  abundance of
            50% in  the  reference  spectrum,  the corresponding  abundance  in  a
            sample spectrum  can  range between 20%  and 80%.)

                  7.4.1.4     Structural  isomers that produce very similar mass
            spectra  should  be  identified as  individual  isomers if  they  have
            sufficiently different GC retention times.  Sufficient GC resolution
            is achieved  if the height of the valley between two isomer peaks is
            less than 25%  of the  sum of the two peak  heights.    Otherwise,
            structural  isomers are identified as isomeric pairs.

                  7.4.1.5     Identification  is hampered when sample components
            are  not resolved  chromatographically and  produce  mass  spectra


                                  5040A  - 5                         Revision 1
                                                                September 1994

-------
      containing  ions contributed by  more  than one  analyte.   When gas
      chromatographic  peaks  obviously represent  more  than  one  sample.
      component  (i.e., a. broadened  peak with  shoulder(s)  or  a  valley
      between  two  or more  maxima),   appropriate  selection  of analyte
      spectra  and  background  spectra is  important.    Examination  of
      extracted  ion current  profiles  of appropriate ions can aid in the
      selection   of  spectra,   and  in  qualitative  identification  of
      compounds.   When analytes coelute (i.e.,  only one chromatographic
      peak is apparent), the identification  criteria can  be met, but each
      analyte spectrum will  contain extraneous  ions  contributed  by the
      coeluting compound.

      7.4.2 For  samples containing components  not associated  with the
calibration standards,  a  library search may be  made  for the purpose of
tentative  identification.    The  necessity to perform  this  type  of
identification will be determined by the type of  analyses  being conducted.
Guidelines for making  tentative  identification are:

      (1)   Relative  intensities  of major ions in the reference spectrum
(ions >  10%  of the most  abundant ion) should be  present  1n the  sample
spectrum.

      (2)   The relative intensities of the major ions should  agree within
± 20%.   (Example:   For an ion with an  abundance of 50%  in the standard
spectrum, the corresponding  sample ion abundance must be between  30 and
70%),

      (3)   Molecular  ions  present in the  reference  spectrum  should be
present in the sample  spectrum.

      (4)   Ions present in the  sample spectrum but not in the reference
spectrum  should  be  reviewed for  possible  background contamination  or
presence of coeluting  compounds.

      (5)   Ions present in the  reference spectrum but not in the sample
spectrum  should  be  reviewed  for  possible  subtraction  from  the  sample
spectrum because  of background contamination or coeluting peaks.   Data
system   library    reduction   programs   can  sometimes    create   these
discrepancies.

      Computer  generated   library  search   routines  should   not   use
normalization routines that would misrepresent  the  library  or unknown
spectra when  compared to each other.   Only after  visual comparison of the
sample  with   the  nearest  library  searches  will  the  mass  spectral
interpretation specialist assign a tentative identification.

7.5   Quantitative analysis

      7.5.1 When   an   analyte   has   been   qualitatively   identified,
quantitation  should be based on the integrated abundance from the EICP of
the  primary characteristic  ion chosen for that  analyte.   If the  sample
produces an interference for the primary characteristic ion,  a secondary
characteristic ion should be used.
                             5040A  -  6                         Revision 1
                                                          September 1994

-------
                   7.5.1.1      Using the internal standard calibration procedure,
            the  amount of analyte in the sample cartridge is calculated  using
            the response factor (RFJ  determined in Section 7.2.5 and  Equation  2,

                   Amount  of POHC  «  A8Cis/AifiRF                              (2)

            where:

                   As =  Area of the  characteristic ion for  the analyte to  be
                        measured.

                   Aj,, =  Area  for  the   characteristic  ion  of  the  internal
                        standard.

                   Cte =  Amount  (ng) of  internal standard.

                   7.5.1.2     The  choice   of  methods   for  evaluating  data
            collected  using VOST for incinerator trial burns  is a regulatory
            decision.  The procedures used extensively by  one user are outlined
            below.

                   7.5.1.3     The  total  amount  of  the  POHCs  of  interest
            collected  on a  pair of traps should be summed.

                   7.1.1.4     The observation of high concentrations of POHCs of
            interest   in   blank  cartridges   indicates   possible  residual
            contamination of the sorbent cartridges prior to shipment to  and use
            at the site.   Data that fall  in this category  (especially data
            indicating high concentrations of POHCs in  blank sorbent cartridges)
            should be qualified with regard to validity, and blank data should
            be reported separately.  The applicability of data of this type to
            the  determination of  ORE  is  a  regulatory  decision.    Continued
            observation  of  high concentrations  of  POHCs  in   blank  sorbent
            cartridges  indicates  that  procedures  for   cleanup,  monitoring,
            shipment, and storage of  sorbent cartridges by a particular user be
            investigated to  eliminate this problem.

                   7.5.1.B     If any internal standard recoveries, fall outside
            the control limits established in Section 8.4,  data for all analytes
            determined  for  that  cartridge(s)  must  be  qualified  with  the
            observation.
8,0   QUALITY CONTROL

      8.1   Refer to  Chapter  One for specific quality  control  procedures and
Method 0030 for sample preparation procedures.

      8.2   Each laboratory that  uses this method  is required to operate a formal
quality control  program.  The minimum requirements of this program consist of an
initial demonstration of laboratory capability and the analysis of blank Tenax
and  Tenax/charcoal  cartridges  spiked with  the  analytes  of  interest.    The
laboratory is required to maintain performance records to define the quality of


                                   5040A  -  7                         Revision I
                                                                September 1994

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data  that are generated.   Ongoing performance  checks  must  be  compared with
established performance criteria to determine if results are within the expected
precision and accuracy limits of the method.

            8.2,1 Before performing any analyses, the analyst must demonstrate
      the  ability to  generate  acceptable  precision and  accuracy  with this
      method.  This ability is established as described in Section 7.2.

            8.2.2 The  laboratory  must  spike   all   Tenax   and  Tenax/charcoal
      cartridges with the internal  standard(s) to monitor continuing laboratory
      performance.  This procedure is described in Section 7.2,

      8.3   To  establish  the  ability  to  generate  acceptable  accuracy  and
precision, the analyst  must spike blank Tenax and Tenax/charcoal cartridges with
the analytes of interest at two concentrations in the working range.

            8,3.1 The average response factor (RF)  and  the standard deviation
      (s) for each must be calculated.

            8.3.2 The average recovery and standard deviation must fall within
      the expected range for determination of volatile POHCs using this method.
      The expected range for recovery of volatile POHCs using this method  is 50-
      150%.

      8.4   The  analyst  must  calculate  method performance criteria  for  the
internal  standard(s).

            8.4.1 Calculate  upper   and   lower   control   limits   for  method
      performances  using   the  average  area   response   (A)   and   standard
      deviation(s) for internal standard:

            Upper Control  Limit (UCL) = A + 3s
            Lower Control  Limit (LCL) - A - 3s

            The UCL and  LCL  can  be used to construct control  charts that  are
      useful in observing  trends  in  performance.   The  control  limits  must be
      replaced by method performance  criteria as they become available from the
      U.S. EPA.

      8.5   The laboratory is required to spike all  sample cartridges  (Tenax and
Tenax/charcoal) with internal standard,

      8.6   Each day,  the  analyst  must demonstrate  through analysis  of blank
Tenax  and  Tenax/charcoal   cartridges  and  organic-free  reagent  water  that
interferences from the analytical system are under control.

      8.7   The daily  GC/MS performance  tests  required  for  this method  are
described in Method 8240.
9.0   METHOD PERFORMANCE

      9.1   Refer to the determinative methods for performance data.


                                   5040A  - 8                         Revision 1
                                                                September 1994

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10.0  REFERENCES

1.    Protocol   for  Collection  and  Analysis  of Volatile  POHC's  Using  VOST,
      EPA/600/8-84-007, March 1984.

2.    Validation  of the  Volatile  Organic  Sampling   Train  (VOST)  Protocol.
      Volumes I  and II.  EPA/600/4-86-014a, January 1986.
                                  5040A - 9                         Revision 1
                                                                September 1994

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                         [ Flow During     J

D
^\

N2 1/1}
m^ <•• «^M
Thermal
Desorption
tnomoer
Flov
GC
CH
D-i
Deiorptlon
t to
/MS
•* Flaw During ^
1 Adiorption I
j L>^JxIpxI|!>.
Frit ^fy r.T\ w
W T«""
1 T
/
Heated
Line
i (7.7cm)
[ @ Silica Gel (7.7cm)
(4J Charcoal (7.7cm)
Figure 1. Schematic diagram of trap desorpikin/analysis system.

               5040A  -  10
                                                                    Revision 1
                                                                September  1994

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                                          METHOD 5040A
ANALYSIS  OF  SORBENT  CARTRIDGES FROM VOLATILE  ORGANIC  SAMPLING  TRAIN  (VOST)
                   GAS  CHROMATOGRAPHY/MASS SPECTROMETRY  TECHNIQUE
     Start
 7,1,1 Assemble
 purge and trap
   deaorption
    device.
  7.1.2 Connect
     thermal
    deaorption
     device;
  calib. system.
  7.2.1 Select
    internal
    standard.
   7.2.3 Prepare
    calibration
  standards uaing
  flash evaporat,
    technique.
   7.2.4 Diraci
     g*a flow
  through traps.
   7.2.4 Expel
   contanta of
 •yringe through
   GC injection
     port.
 7.2.4 Analyze
 trap by P-T-0
    GC/MS
   procedure.
  7.2.S Analyze
   each ealib.
  etandard for
 both cartridges
    (eee 7.3),
 7.2.5 Tabulate
 area response
 and calculate
response factor.
   7.2.8 Verify
    response
   factor each
      day.
    7.3 Place
     sample
   cartridge in
desorp. apparatus;
  dvtorfa in P-T.
    7.3 Deaorb
    into GC/MS
     ayatara.
       7.4.1
    Quantatively
      identrfy
  volatile POHCa.
      7.5.1 lie*
       primary
    characteristic
       ion for
     quant itation.
       7.6.1.1
      Calculate
  •mount of analyte
      in aarnpla.
  7.5; 1.3 Sym
amount of POHCt
  of intareit for
  each pair of
     trapa.
 7.S.1.4 Examine
 blank* data for
 aigni of raaidual
 contamination.
 7.6.1.S Compare
     int. atd.
   recoveries to
   Section 8.4
   control limit*.
                                                                                     Stop
                                           5040A  -  11
                                                              Revision  1
                                                         September 1994

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\

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                                  METHOD  5041

       PROTOCOL  FOR ANALYSIS  OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC
          SAMPLING TRAIN  fVOST]; WIDE-BORE CAPILLARY  COLUMN TECHNIQUE
1.0   SCOPE AND APPLICATION

      1.1   This method describes  the  analysis of volatile  principal  organic
hazardous  constituents  (POHCs)  collected  from  the  stack  gas  effluents  of
hazardous waste incinerators using the VOST methodology (1). For a comprehensive
description of  the VOST  sampling  methodology see Method  0030.   The  following
compounds may be determined by this lethod:
      Compound Name
CAS No."
Acetone
Acrylonitrile
Benzene
Bromodichloromethane
Bromoformb
Bromomethane0
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chi orod i bromomethane
Chloroethane0
Chloroform
Chloromethane0
Di bromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-1 , 3-Dichl oropropene
Ethyl benzene"
lodomethane
Methyl ene chloride
Styreneb
1,1,2, 2 -Tetrachl oroethaneb
Tetrachl oroethene
Toluene
67-64-1
107-13-1
71-43-2
75-27-4
75-25-2
74-83-9
75-15-0
56-23-5
108-90-7
124-48-1
75-00-3
67-66-3
74-87-3
74-95-3
75-35-3
107-06-2
75-35-4
156-60-5
78-87-5
10061-01-5
10061-02-6
100-41-4
74-88-4
75-09-2
100-42-5
79-34-5
127-18-4
108-88-3
                                                                   (continued)
                                   5041  -  1
                 Revision  0
             September  1994

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      Compound Name                                 CAS No.a


      1,1,1-Trichloroethane                         71-55-6
      1,1,2-Trichloroethane                         79-00-5
      Trichloroethene                               79-01-6
      Trichlorofluoromethane                        75-69-4
      l,2,3-Trichloropropaneb                       96-18-4
      Vinyl chloride0                               75-01-4
      Xylenesb


      *   Chemical  Abstract Services Registry Number.

      b   Boiling  point  of this compound  is above  132°C,  Hethod  0030 is not
appropriate for quantitative sampling of this analyte.

      c   Boiling point of  this compound is below  30°C.  Special precautions must
be taken when sampling  for this analyte  by  Method 0030. Refer to Sec. 1.3 for
discussion.

      1.2   This method  is most successfully  applied to the analysis  of non-polar
organic compounds with boiling points between 30"C and  100°C,  Data are applied
to the calculation of destruction and removal efficiency (ORE), with limitations
discussed below.

      1.3   This method  may be applied to analysis of many  compounds which boil
above 1QO°C, but Method  0030 is always inappropriate for collection of compounds
with boiling points above  132°C.  All  target analytes with boiling points greater
than 132°C  are so  noted  in the target analyte list presented in Sec. 1.1.  Use
of Method 0030 for collection  of  compounds  boiling between 100°C and  132°C is
often possible,   and  must be  decided based on  case   by  case  inspection  of
information such  as  sampling  method collection efficiency,  tube  desorption
efficiency, and analytical method  precision  and  bias.   An organic compound with
a boiling point below 30°C may break through the sorbent under the conditions
used for sample collection.   Quantitative  values  obtained for compounds with
boiling  points below  30°C must be qualified,  since the value obtained represents
a minimum value for the compound if breakthrough has occurred.  In certain cases,
additional  QC  measures may have been taken during sampling very  low boilers with
Method  0030.      This   information   should   be   considered  during  the  data
interpretation stage.

      When  Method  5041 is  used for survey  analyses, values for compounds boiling
above 132°C may be reported and qualified  since the quantity obtained represents
a minimum value for the  compound.   These  minimum values  should not be used for
trial burn  ORE calculations or to  prove  insignificant risk.

      1.4   The VOST analytical  methodology  can be used  to quantitate volatile
organic   compounds that  are  insoluble or  slightly  soluble  in  water.   When
volatile, water soluble compounds are included  in the  VOST  organic  compound
analyte  list,  quantitation limits  can be  expected to be  approximately ten times

                                   5041  - 2                          Revision 0
                                                                September 1994

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higher than quantitation limits for water insoluble  compounds  (if the compounds
can be recovered at all) because the purging efficiency from water (and possibly
from Tenax-GC®)  is  poor.

      1.5   Overall sensitivity  of the method is dependent  upon  the level of
interferences  encountered  in  the  sample  and   the   presence  of  detectable
concentrations of volatile POHCs in blanks.  The  target detection limit of this
method is 0.1 pg/m3 (ng/L) of flue gas, to permit calculation  of a ORE equal to
or greater  than 99.99% for volatile  POHCs which may  be present  in  the waste
stream at 100 ppm.  The upper end of the range of applicability of this method
is limited by the dynamic range of the analytical instrumentation,  the overall
loading  of  organic compounds  on  the  exposed  tubes,  and  breakthrough  of the
volatile POHCs on the sorbent traps used to collect the sample. Table  1 presents
retention times  and characteristic ions  for volatile compounds which  can be
determined by this method.  Table 2 presents method detection  limits for a range
of volatile compounds analyzed by the wide-bore VOST methodology.

      1.6   The wide-bore VOST analytical methodology  is restricted to use by,
or under the supervision of, analysts experienced in the use of sorbent media,
purge-and-trap systems,  and gas chromatograph/mass spectrometers, and skilled in
the interpretation of mass spectra and their use as  a quantitative tool.


2.0  SUMMARY OF METHOD

      2.1   The sorbent tubes  are thermally desorbed  by heating and purging with
organic-free helium.   The gaseous effluent from the  tubes is bubbled through
pre-purged organic-free reagent water  and trapped on an analytical  sorbent trap
in a purge-and-trap unit (Figure 2).  After desorption, the analytical sorbent
trap is heated rapidly  and the gas  flow from the  analytical trap is directed to
the head  of a wide-bore  column  under subambient conditions.  The volatile organic
compounds desorbed from  the  analytical   trap  are   separated by  temperature
programmed  high  resolution gas  chromatography  and  detected by  continuously
scanning low resolution mass spectrometry (Figure  3).  Concentrations of volatile
organic compounds are calculated from a multi-point calibration curve, using the
method of response factors.


3.0   INTERFERENCES

      3.1   Sorbent tubes which are to  be analyzed for volatile  organic compounds
can be contaminated by diffusion of  volatile  organic compounds  (particularly
Freon® refrigerants and common organic solvents)  through the external  container
(even through a Teflon® lined  screw cap on  a glass container) and the  Swagelok®
sorbent tube caps during shipment  and  storage.   The  sorbent  tubes  can also be
contaminated if organic solvents  are present  in the analytical laboratory.  The
use of blanks  is  essential  to assess  the extent of any  contamination.   Field
blanks must be prepared and taken to the field.  The end caps of the  tubes are
removed for the period of time required  to exchange two  pairs of  traps on the
VOST sampling apparatus.  The tubes are recapped and  shipped and handled exactly
as the actual  field samples are shipped and handled.  At least  one pair of field
blanks is included with each six pairs of sample cartridges collected.
                                   5041 - 3                         Revision 0
                                                                September 1994

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       3.2    At   least   one   pair  of   blank  cartridges  (one  Tenax-GC®,   one
 Tenax-GC®/charcoal)  shall be included with  shipment of cartridges to a hazardous
 waste  incinerator site  as trip  blanks.  These trip blanks will be  treated  like
 field  blanks except  that the end caps will  not  be removed during  storage  at the
 site.   This  pair of traps will  be analyzed to monitor potential contamination
 which  may occur  during  storage  and shipment,

       3.3    Analytical   system   blanks  are  required   to   demonstrate   that
 contamination  of the  purge-and-trap  unit  and the  gas  chromatograph/mass
 spectrometer has  not occurred or that,  in the event of analysis  of sorbent tubes
 with  very  high  concentrations of organic  compounds,,  no  compound carryover is
 occurring.  Tenax® from the same preparation batch as the Tenax®  used for field
 sampling should  be used in  the  preparation of the method (laboratory) blanks.
 A  sufficient number  of cleaned  Tenax® tubes from the  same  batch as the field
 samples should be reserved  in the laboratory for  use as  blanks.

       3.4    Cross contamination  can occur whenever low-concentration samples are
 analyzed after  high-concentration  samples, or when  several  high-concentration
 samples are  analyzed sequentially.   When  an unusually concentrated sample is
 analyzed, this analysis should  be followed by a method blank to establish  that
 the  analytical   system  is  free of  contamination.    If analysis  of  a  blank
 demonstrates that the system is  contaminated, an additional bake cycle should be
 used.   If the analytical system is still contaminated after additional baking,
 routine system maintenance  should  be  performed:  the  analytical trap should be
 changed and  conditioned,  routine column  maintenance should be  performed   (or
 replacement of the column  and conditioning  of the new  column, if necessary),  and
 bakeout of the ion source  (or cleaning of the ion source and rods, if  required).
 After  system maintenance has been  performed,  analysis of  a blank  is required to
 demonstrate  that  the cleanliness of the system is acceptable.

       3.5    Impurities  in the purge gas and from  organic compounds out-gassing
 in tubing account for  the majority  of contamination  problems.   The  analytical
 system must  be demonstrated to be free from contamination under the  conditions
 of the analysis  by analyzing two  sets of clean, blank sorbent tubes with organic-
 free reagent purge water as  system blanks.  The analytical system is  acceptably
 clean  when these  two sets of blank tubes show values for  the analytes which  are
 within  one  standard deviation  of the normal  system  blank.   Use  of  plastic
 coatings,   non-Teflon®  thread  sealants,  or  flow  controllers  with  rubber
 components should be avoided.

       3,6   VOST  tubes are handled in the  laboratory to spike standards and to
 position the tubes within the  desorption  apparatus.   When sorbent  media   are
 handled in the  laboratory atmosphere,  contamination is  possible  if there   are
 organic solvents  in  use anywhere in the laboratory.   It  is  therefore necessary
 to make daily use of  system blanks  to monitor the cleanliness  of  the sorbents  and
 the absence of contamination from the analytical  system.  A single set of system
 blank  tubes  shall be  exposed  to  normal   laboratory  handling  procedures   and
 analyzed as  a sample.   This  sample  should  be within  one  standard deviation of
normal VOST  tube blanks to  demonstrate  lack  of  contamination of  the  sorbent
media.

      3.7    If the emission source has  a high concentration of non-target organic
compounds  (for example,  hydrocarbons at concentrations  of hundreds of ppm),   the


                                   5041 - 4                         Revision 0
                                                                September  1994

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 presence of these non-target compounds will interfere with the performance of the
 VOST  analytical  methodology.   If  one  or more  of the compounds  of  interest
 saturates  the  chromatographic  and  mass  spectrometric   instrumentation,  no
 quantitative calculations can be made and the tubes which have been sampled under
 the same conditions will yield no valid data for any of the  saturated compounds.
 In the presence of a very high organic loading,  even  if the compounds of  interest
 are not saturated, the instrumentation is  so saturated that  the linear range has
 been surpassed.  When  instrument saturation occurs,  it is possible that compounds
 of  interest  cannot  even  be  identified  correctly because  a  saturated mass
 spectrometer  may mis-assign  masses.    Even  if  compounds  of  interest  can be
 identified,  accurate  quantitative  calculations are  impossible at  detector
 saturation.   No  determination can  be made at detector saturation,  even  if the
 target compound itself is not saturated. At detector saturation, a negative bias
 will be encountered in  analytical measurements and  no accurate calculation can
 be made for the Destruction and Removal Efficiency  if analytical values may be
 biased negatively.

      3.8   The recoveries of  the surrogate compounds, which are spiked on the
 VOST tubes  immediately before analysis,  should  be monitored  carefully  as an
 overall indicator  of  the performance  of the  methodology.   Since the  matrix of
 stack emissions is so  variable, only a general  guideline for recovery of 50-150%
 can be used for surrogates.  The  analyst cannot use  the surrogate recoveries as
 a guide for correction of compound recoveries.  The  surrogates  are valuable only
 as a general  indicator  of correct operation of the methodology.  If surrogates
 are not observed or if recovery of  one or  more  of the surrogates is outside the
 50-150% range, the VOST methodology is not  operating  correctly.  The cause  of the
 failure  in  the methodology  is not  obvious.   The  matrix  of  stack  emissions
 contains large amounts of  water,  may be  highly  acidic, and  may contain large
 amounts  of  target  and non-target  organic compounds.   Chemical and  surface
 interactions may be occurring on the tubes. If recoveries of surrogate compounds
 are extremely low or surrogate  compounds  cannot   even be identified  in  the
 analytical  process, then failure to  observe an analyte may or may not imply that
 the compound of interest has  been removed  from  the emissions with a high degree
 of efficiency (that is, the Destruction  and Removal  Efficiency for that analyte
 is high).


 4,0   APPARATUS AND MATERIALS

      4.1   Tube desorption apparatus:  Acceptable performance of the methodology
 requires:   1)  temperature regulation  to  ensure  that  tube temperature during
desorption  is regulated to 180°C  ± 10°;  2) good  contact between tubes and the
heating apparatus  to  ensure  that  the sorbent  bed  is  thoroughly  and  uniformly
heated  to  facilitate  desorption  of  organic  compounds;     and  3)  gas-tight
connections to the  ends  of the tubes to ensure flow of desorption gas through the
tubes  without leakage  during the heating/desorption  process,  A simple clamshell
heater which  will  hold tubes  which are  3/4"  in outer diameter will  perform
acceptably  as a desorption apparatus.

      4.2   Purge-and-trap device:   The purge-and-trap  device consists of three
separate pieces of equipment:   a sample purge vessel, an analytical  trap, and a
desorber. Complete devices are commercially available from a variety of sources,
or the separate components may be assembled.   The cartridge thermal  desorption


                                   5041 -  5                         Revision 0
                                                                September 1994

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apparatus Is  connected to  the  sample  purge  vessel  by  1/8"  Teflon®  tubing
(unheated transfer line).   The tubing which connects the desorption chamber to
the sample purge vessel should be as short as is practical.

            4.2.1 The sample purge vessel  is required to hold 5 ml of organic-
      free reagent water, through which the gaseous effluent from the VOST tubes
      is routed.  The water column should be at least 3  cm deep.   The gaseous
      headspace between the water  column  and the analytical  trap  must  have a
      total  volume of  less  than  15 ml.   The purge  gas  roust pass  through  the
      water column as finely divided bubbles with a  diameter  of less than 3 mm
      at  the  origin.   The  sample  purger  shown   in   Figure  4  meets  these
      requirements.   Alternate sample purging vessels may be used if equivalent
      performance is  demonstrated.

            4.2.2 The  analytical  trap must  be at  least 25 cm  and have  an
      internal  diameter of  at  least 0.105  in.  The analytical  trap must contain
      the following components:

            2,6-diphenylene oxide polymer:      60/80 mesh, chromatograph grade
                                                (Tenax-GC®,  or equivalent)

            methyl  silicone packing:             OV-1  (3%) on Chromosorb-W 60/80
                                                mesh, or equivalent

            silica gel:                         35/60 mesh, Davison grade 15 or
                                                equivalent

            coconut charcoal:                    prepare   from  Barneby  Cheney,
                                                CA-580-26,  or  equivalent,  by
                                                crushing  through   26   mesh
                                                screen.

            The  proportions  are:  1/3 Tenax-GC®,   1/3   silica  gel,  and  1/3
      charcoal,  with  approximately 1.0  cm  of  methyl   silicone  packing.  The
      analytical  trap should be conditioned for four hours at 180°C with gas flow
      (10 mL/min) prior to  use in  sample  analysis.   During  conditioning,  the
      effluent  of the trap  should not  be vented  to the analytical  column.   The
      thermal desorption apparatus  is  connected  to the injection  system of the
      mass spectrometer by  a transfer  line which is  heated to 100°C.

            4.2.3 The desorber must be capable of rapidly heating the analytical
      trap to.!80°C for desorption.  The polymer section  of the trap should  not
      exceed 180°C, and the  remaining  sections  should not exceed 220°C,  during
      bake-out  mode.

      4.3   Gas  chromatograph/mass  spectrometer/data  system:

            4.3.1  Gas chromatograph:   An analytical  system  complete with  a
      temperature programmable oven with  sub-ambient temperature  capabilities
      and all required  accessories, including syringes, analytical  columns,  and
      gases.
                                   5041  -  6                          Revision  0
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            4.3.2 Chromatographic  column:  30 m  x  0.53 mm  ID  wide-bore fused
      silica capillary column, 3 IM film thickness, DB-524  or equivalent.

            4.3.3 Mass spectrometer:  capable of scanning from 35-260 amu every
      second or  less,  using 70 eV (nominal) electron energy  in  the electron
      ionization  mode  and  producing  a mass spectrum that  meets all  of the
      criteria in Table 3 when 50 ng of 4-brontofluorobenzene (BFB) is injected
      into the water in the purge vessel.

            4.3.4 Gas  chromatograph/mass   spectrometer  interface:   Any  gas
      chromatograph  to  mass  spectrometer  interface  that  gives  acceptable
      calibration points at 50  ng or less per injection of each of the analytes,
      and achieves the performance  criteria for 4-bromofluorobenzene shown in
      Table 3,  may be used.   If a glass jet separator is used with the wide-bore
      column, a helium  make-up  flow of approximately 15 ml, introduced after the
      end of the column  and  prior  to the  entrance  of the effluent  to  the
      separator, will be required for optimum performance.

            4.3.5 Data system:  A  computer  system that allows  the  continuous
      acquisition and  storage  on  machine  readable  media  of all  mass  spectra
      obtained throughout the  duration of  the Chromatographic  program must be
      interfaced to the mass  spectrometer.  The computer must  have software that
      allows searching  any gas  chromatographic/mass spectrometric data file for
      ions of a specified mass and  plotting such ion abundances versus time or
      scan number.   This  type  of  plot is defined as  an Extracted Ion Current
      Profile  (EICP).     Software  must  also  be available  that  allows  the
      integration of the  ion abundances in  any  EICP between specified time or
      scan number limits.  The most recent version of the EPA/NIST Mass Spectral
      Library should also be available.

      4.4   Wrenches:  9/16", 1/2", 7/16",  and 5/16".

      4.5   Teflon® tubing:  1/8" diameter.

      4.6   Syringes: 25 /iiL syringes (2), 10 ^L  syringes (2).

      4.7   Fittings:  1/4" nuts, 1/8"  nuts,  1/16" nuts, 1/4"  to 1/8" union, 1/4"
to 1/4" union,  1/4" to  1/16" union.

      4.8   Adjustable  stand  to  raise the  level of  the  desorption  unit,  if
required.

      4.9   Volumetric  flasks:   5 ml,  class A with  ground glass stopper.

      4.10  Injector port or equivalent,  heated to 180°C for loading standards
onto VOST tubes prior to analysis.

      4.11  Vials:  2 mL,  with Teflon® lined screw caps or  crimp tops.

      4.12  Syringe:   5 ml, gas-tight  with shutoff  valve.
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5.0   REAGENTS

      5.1   Reagent grade chemicals  shall be used In all  tests.  Unless otherwise
Indicated, it is intended that all reagents  shall conform to the specifications
of the Committee on Analytical Reagents  of the American  Chemical Society, where
such specifications are available. Other grades may  be used, provided it  is first
ascertained that the reagent  is  of  sufficiently high  purity to permit its use
without lessening the accuracy of the determination,

      5.2   Organic-free reagent water - All  references  to water in this method
refer to organic-free reagent water, as defined in Chapter One.

            5.2.1 It is  advisable to maintain the stock  of organic-free reagent
      water generated for use in  the purge-and-trap apparatus with a continuous
      stream of inert gas bubbled through the water. Continuous bubbling of the
      inert gas maintains a positive pressure of inert gas above the water as a
      safeguard against contamination.

      5.3   Methanol, CH3OH.    Pesticide quality  or  equivalent.   To  avoid
contamination with  other  laboratory solvents,  it  is  advisable to  maintain  a
separate stock of methanol for the preparation of standards for VOST analysis and
to regulate the use of this methanol very carefully.

      5.4   Stock  standard solutions  - Can  be prepared  from pure  standard
materials or can be purchased as  certified solutions.  Stock standard solutions
must be prepared in high purity methanol.  All preparation of standards should
take place in a hood, both  to avoid contamination  and  to  ensure  safety of the
analyst preparing the standards.

            5.4.1 Place  about 4 ml of high purity methanol in a 5 ml volumetric
      flask.   Allow the  flask to  stand,  unstoppered, for about  10 min, or until
      all  alcohol  wetted surfaces have dried.

                  5.4.1.1     Add appropriate volumes  of neat liquid chemicals
            or certified solutions,  using a syringe of the appropriate volume.
            Liquid which is  added to the volumetric flask  must  fall  directly
            into the alcohol without contacting  the neck of the flask.  Gaseous
            standards can   be  purchased as  methanol   solutions  from  several
            commercial  vendors.

                  5.4.1.2     Dilute  to volume with   high  purity  methanol,
            stopper, and then mix by inverting the  flask several times.  Calcu-
            late concentration by the dilution  of  certified  solutions  or neat
            chemicals.

            5.4.2 Transfer the stock  standard  solution into a Teflon® sealed
      screw cap  bottle.    An  amber   bottle  may  be  used.  Store,   with  minimal
      headspace, at -10°C to -20°C,  and  protect  from light.

            5.4.3 Prepare fresh standards every two months for gases.  Reactive
      compounds such as  styrene may need to  be  prepared more  frequently.   All
      other standards must  be  replaced after six  months,  or sooner if comparison
      with check standards  indicates a problem.


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       5.5   Secondary  dilution  standards:    Using  stock  standard solutions,
 prepare, in high purity methanol,  secondary dilution standards containing the
 compounds  of  interest, either  singly  or mixed  together.   Secondary dilution
 standards must be stored with minimal headspace and should be checked frequently
 for  signs  of degradation  or  evaporation,  especially just  prior  to preparing
 calibration standards  from them.

       5.6   Surrogate  standards:  The  recommended  surrogates are toluene~ds,
 4-bromofluorobenzene,  and l»2-dichloroethane-d4.  Other compounds may be used as
 surrogate compounds, depending upon the requirements of the analysis.  Surrogate
 compounds are selected  to span the elution range of the compounds of interest.
 Isotopically labeled compounds are selected to preclude the observation of the
 same compounds in the stack emissions.   More  than one  surrogate is  used so that
 surrogate measurements  can still be made even if analytical interferences with
 one or more of the surrogate compounds are encountered.  However, at least three
 surrogate compounds should be used to monitor the performance of the methodology.
 A stock surrogate compound solution in high purity methanol should be prepared
 as described  in  Sec. 5.4,  and  a surrogate  standard  spiking solution should be
 prepared from the  stock  at  a  concentration  of  250  jLtg/10 ml in  high  purity
 methanol.  Each  pair of VOST tubes (or each individual VOST tube,  if the tubes
 are  analyzed  separately)  must be  spiked with  10 pi  of  the surrogate spiking
 solution prior to GC/MS analysis.

       5.7   Internal   standards:    The  recommended  internal  standards  are
 bromochloromethane, 1,4-difluorobenzene, and chlorobenzene-ds.  Other compounds
 may be used as internal standards as long as they have retention times similar
 to the compounds being analyzed by GC/MS.   The internal  standards  should be
 distributed through the chromatographic elution range.  Prepare  internal standard
 stock  and  secondary  dilution  standards  in  high  purity  methanol using  the
 procedures described  in Sees.  5.2 and  5.3.   The secondary dilution  standard
 should be prepared at a concentration of 25 mg/L of each of the  internal standard
 compounds.   Addition of 10 pi  of this  internal  standard solution  to each pair
 of VOST tubes  (or to each VOST  tube, if  the tubes are  analyzed individually) is
 the equivalent of 250 ng total.

      5.8   4-Bromofluorobenzene (BFB) standard;  A standard  solution containing
 25 ng/juL of BFB  in  high purity methanol should be prepared for use as a tuning
 standard.

      5.9   Calibration standards:  Calibration standards at a minimum of five
 concentrations will be required from the secondary dilution of stock standards
 (see Sees.  5.2  and 5,3).   A range of  concentrations for  calibration can be
 obtained by use  of different  volumes  of a 50 mg/L  methanol  solution of  the
 calibration  standards.   One  of  the  concentrations  used  should  be  at  a
 concentration  near, but above,  the method  detection  limit.   The  remaining
 concentrations should correspond to the expected  range of concentrations  found
 in field samples  but should not exceed the linear range of the GC/MS analytical
 system {a typical range for a calibration would be 10,  50,  100, 350, and 500 ng,
 for  example).    Each  calibration  standard  should  contain each   analyte  for
detection by this method.  Store calibration standards  for  one week  only in a
 vial  with no headspace.
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      5.10  Great care must be taken to maintain the integrity of all standard
solutions.  All  standards  of  volatile  compounds in methanol  must be stored at
-10° to -20°C  in  amber  bottles with Teflon®  lined screw caps or crimp tops.  In
addition, careful attention must be paid to the use of syringes designated for
a specific purpose or  for  use with only a single standard solution since cross
contamination of volatile  organic standards can occurs very readily.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See Method 0030 for the VOST Sampling Methodology,

      6.2   VOST samples are collected on paired cartridges.   The first of the
pair  of sorbent cartridges  is  packed with approximately  1,6 g  of  Tenax-GC®
resin.  The second cartridge of  the pair is packed with Tenax-GC® and petroleum
based charcoal  (3:1  by volume;  approximately 1 g of each).   In  sampling,  the
emissions gas stream passes through the Tenax-GC® layer first and then through
the charcoal  layer.   The Tenax-GC® is cleaned and reused;  charcoal  is not reused
when tubes are prepared.  Sorbent is cleaned  and the tubes are packed.  The tubes
are desorbed and subjected to a blank  check prior  to  being  sent  to the field.
When the tubes are used for sampling (see Figure 5 for a schematic diagram of the
Volatile  Organic  Sampling  Train (VOST)), cooling  water is circulated  to  the
condensers and the temperature of the cooling water is maintained  near 0°C.  The
end caps  of the  sorbent  cartridges are placed  in  a clean,  screw capped glass
container during sample collection.

      6,3   After  the  apparatus  is  leak  checked,   sample  collection   is
accomplished by opening the valve to the first condenser, turning on the pump,
and sampling at a rate  of  1 liter/min for 20 minutes.  The volume of sample for
any pair of traps  should not exceed 20 liters.  An alternative set of conditions
for sample collection requires sampling at a reduced flow rate,  where the overall
volume of sample collected is 5 liters at a rate of 0.25 L/min for 20 minutes.
The 20 minute period is required for collecting an integrated  sample.

      6.4   Following  collection  of  ZO liters  of sample,  the  train  is  leak
checked a second  time at the highest pressure drop encountered  during the run to
minimize the chance of vacuum desorption of organics from the  Tenax®.

      6.5   The train  is returned to atmospheric pressure and the two sorbent
cartridges are removed. The end caps  are  replaced and the cartridges are placed
in a sir "ible  environment  for  storage and transport until analysis.  The sample
is cons  ared  invalid if the leak test does not meet specifications.

      6.6   A new pair of  cartridges  is  placed in the VOST,  the  VOST is  leak
checked, and the  sample collection  process is repeated until six pairs of traps
have been exposed.
      6
exposure
stored
."*   All  sample  cartridges are  kept  in  coolers on  cold packs  after
e and during shipment.  Upon receipt at the laboratory, the cartridges are
in a refrigerator at 4°C  until  analysis.
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 7.0    PROCEDURE

       7.1    Recommended   operating   conditions   for   cartridge   desorber,
 purge-and-trap unit, and gas chromatograph/mass spectrometer using the wide-bore
 column are:
      Cartridge  Desorption Oven
      Disorb Temperature
      Desorb Time
      Desorption Gas  Flow
      Desorption/Carrier Gas

      Purge-and-Trap  Concentrator
      Analytical Trap Desorption Flow
      Purge Temperature
      Purge Time
      Analytical Trap Desorb Temperature
      Analytical Trap Desorb Time

      Gas Chromatpgraph
      Column
      Carrier Gas Flow
      Makeup Gas Flow
      Injector Temperature
      Transfer Oven Temperature
      Initial Temperature
      Initial Hold Time
      Program Rate
      Final Temperature
      Final Hold Time

      Mass Spectrometer
      Manifold Temperature
      Scan Rate
      Mass Range
      Electron Energy
      Source Temperature
180°C
11 minutes
40 mL/min
Helium, Grade 5.0
2.5 mL/min helium
Ambient
11 minutes
180°C
5 minutes
DB-624,  0.53  mm  ID x  30 m  thick
film (3 ^m) fused silica capillary,
or equivalent
15 mL/min
15 mL/min
200°C
240°C
5°C
2 minutes
6°C/min
240°C
1 minute, or until  elution  ceases
105°C
1 sec/cycle
35-260 amu
70 eV (nominal)
According    to
specifications
manufacturer's
      7.2   Each GC/MS  system  must  be hardware tuned to meet  the criteria in
Table 3 for a  50  ng injection of 4-bromofluorobenzene (2  fj.1  injection of the BFB
standard solution  into  the water of the purge  vessel).   No  analyses  may be
initiated until the criteria presented in Table 3 are met.

      7.3   Assemble a  purge-and-trap device  that  meets the specifications in
Method 5030.  Condition  the analytical trap overnight at  180°C in the purge mode,
with an inert  gas flow of at  least 20 mL/min.  Prior  to  use each day, condition
the trap for 10 minutes by backf lush ing at  18Q°C, with the  column  at  220°C.

      7.4   Connect the purge-and-trap device to a gas chromatograph.
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       7.5   Assemble   a   VOST  tube  desorption  apparatus  which  meets   the
 requirements  of  Sec. 4.1.

       7.6   Connect  the  VOST tube  desorption  apparatus  to the purge-and-trap
 unit.

       7.7   Calibrate the instrument using the internal standard procedure, with
 standards  and  calibration  compounds  spiked  onto  cleaned   VOST  tubes   for
 calibration.

            7.7.1 Compounds  in  methanolic  solution  are spiked onto VOST tubes
       using the flash evaporation technique.   To perform  flash  evaporation,  the
       injector of  a  gas  chromatograph or an  equivalent  piece of equipment is
       required.

                  7.7.1.1     Prepare a syringe with the appropriate volume of
            methanolic standard solution (either surrogates, internal standards,
            or calibration compounds).

                  7.7.1.2     With  the injector port heated to 180°C,  and with
            an inert gas  flow of 10 mL/min  through  the injector port,  connect
            the  paired VOST  tubes  (connected  as in  Figure  1,  with gas  flow in
            the  same direction  as the sampling gas flow) to the injector port;
            tighten  with  a  wrench  so that there  is no leakage  of gas.   If
            separate , tubes  are  being  analyzed,  an  individual  Tenax®  or
            Tenax®/charcoal  tube  is connected to the injector.

                  7.7.1.3     After directing  the  gas  flow through the VOST
            tubes, slowly inject the first standard solution over a period of 25
            seconds.   Wait  for 5 sec before withdrawing the  syringe  from the
            injector port.

                  7.7.1.4     Inject  a  second  standard  (if required)  over a
            period of  25 seconds  and wait for  5 sec before  withdrawing  the
            syringe from the injector port.

                  7.7.1.5     Repeat the sequence  above as required until  all of
            the necessary compounds are spiked onto the VOST tubes.

                  7.7.1.6     Wait for 30 seconds, with gas  flow, after the last
            spike before disconnecting the  tubes.  The total time the tubes are
            connected to the injector port  with gas flow should not exceed 2.5
            minutes.   Total  gas  flow through  the  tubes  during the  spiking
            process should not exceed  25 ml  to  prevent break through of adsorbed
            compounds  during the  spiking  process.    To allow more time  for
            connecting and disconnecting tubes, an on/off valve may be installed
            in the gas  line to the  injector  port so that gas  is  not  flowing
            through the tubes during the connection/disconnection process.

      7.8   Prepare the purge-and-trap unit with  5  ml  of organic-free  reagent
water in the purge vessel.
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      7.9   Connect the paired VOST tubes to the gas lines in the tube desorption
unit.  The tubes must be connected so that the  gas flow during desorption will
be opposite to  the  flow of gas during sampling: i.e., the tube desorption gas
passes through  the charcoal portion of the tube first.  An on/off valve may be
installed in the gas line leading to the tube desorption unit in order to prevent
flow of gas through the tubes during the connection process,

      7.10  Initiate tube desorption/purge and heating of  the  VOST tubes in the
desorption apparatus.

      7.11  Set the oven of the gas  chromatograph to subambient temperatures by
cooling with liquid nitrogen.

      7.12  Prepare the GC/MS system for data acquisition.

      7.13  At the conclusion of the tube/water purge time,  attach the analytical
trap to the gas chromatograph,  adjust the  purge-and-trap  device to the desorb
mode,  and  initiate  the  gas  chromatographic  program   and  the  GC/MS  data
acquisition.  Concurrently,   introduce  the   trapped   materials  to   the  gas
chromatographic  column  by  rapidly heating the  analytical  trap  to 180°C while
backflushing the  trap  with inert gas at 2.5  mL/min  for 5 min.   Initiate the
program for the gas chromatograph and simultaneously initiate data acquisition
on the GC/MS system.

      7.14  While  the  analytical  trap   is   being   desorbed  into   the  gas
chromatograph, empty the purging  vessel.  Wash the purging  vessel with a minimum
of two  5 mL flushes  of organic-free reagent  water  (or methanol  followed  by
organic-free reagent  water)  to  avoid carryover of  analytes  into  subsequent
analyses.

      7.15  After the sample has  been desorbed,  recondition the analytical trap
by employing a bake cycle on the purge-and-trap unit.   The analytical  trap may
be  baked  at  temperatures  up  to  220°C,    However,   extensive use  of  high
temperatures to recondition  the trap will   shorten  the   useful  life  of  the
analytical trap.  After approximately 11 minutes, terminate  the trap  bake and
cool  the trap to ambient temperatures  in preparation for the next sample.  This
procedure is a convention for reasonable  samples and should be adequate if the
concentration of contamination does  not saturate the analytical system.  If the
organic compound concentration is so high that the analytical system is saturated
beyond the point where even extended system bakeout  is not sufficient  to clean
the system, a more extensive system maintenance must  be performed.   To perform
extensive system maintenance,  the analytical  trap is  replaced and the  new trap
is conditioned.   Maintenance is  performed on the GC column  by removing at least
one foot  from  the front end  of  the column.   If  the  chromatography  does  not
recover after column maintenance, the chromatographic  column must be  replaced.
The ion source  should  be baked  out and,  if  the bakeout  is not  sufficient  to
restore mass spectrometric  peak  shape and  sensitivity,  the ion  source and the
quadrupole rods must be cleaned.

      7.16  Initial calibration for  the analysis of VOST tubes; It is  essential
that  calibration be performed in the mode  in which  analysis will be performed.
If tubes are being analyzed as pairs,  calibration  standards should be  prepared
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on paired tubes.  If tubes are being analyzed individually, a calibration should
be performed on individual  Tenax® only tubes and Tenax®/charcoal tubes.

            7.16.1       Prepare the calibration standards by spiking VOST tubes
      using the procedure  described in Sec. 7.7.1.   Spike  each pair  of VOST
      tubes  (or  each of the individual  tubes)  immediately before  analysis.
      Perform the calibration analyses in order  from low concentration  to high
      to minimize the compound carryover.  Add 5.0  ml  of organic-free  reagent
      water to the  purging  vessel.   Initiate tube desorb/purge according to the
      procedure described above.

            7.16.2       Tabulate the area response of the characteristic  primary
      ions  (Table  1} against  concentration for each  target  compound,  each
      surrogate compound,  and each internal  standard.   The first  criterion for
      quantitative  analysis  is  correct  identification of  compounds.    The
      compounds must  elute within ± 0.06 retention  time units of  the  elution
      time of the standard  analyzed  on the same analytical system on the day of
      the analysis.   The analytes  should be quantitated relative to the  closest
      eluting  internal  standard,  according to the  scheme shown  in Table  4.
      Calculate response factors (RF) for each compound relative to the internal
      standard shown  in Table  4.   The  internal  standard   selected for  the
      calculation  of  RF  is the internal  standard  that  has  a retention  time
      closest to the  compound being measured.  The RF is calculated as follows:
      where:

           Ax  =  area   of  the  characteristic  ion  for  the  compound   being
                  measured.

           Ajs  =   area  of  the characteristic  ion  for  the  specific  internal
                  standard.

           Cis  =   concentration  of the specific  internal  standard.

           C,,  =  concentration  of the compound  being measured.

           7.16.3      The average RF must  be  calculated  for each  compound. A
      system  performance check should be made before the calibration  curve  is
      used.   Five  compounds (the System Performance Check  Compounds, or  SPCCs)
      are  checked  for a minimum average response factor.  These compounds are
      chloromethane,  1,1-dichloroethane,  bromoform, 1,1,2,2-tetrachloroethane,
      and  chlorobenzene.  The minimum acceptable average RF for  these compounds
      should  be 0.300 (0.250 for bromoform}.  These compounds typically  have RFs
      of 0.4  -  0.6,  and are used  to check compound instability and check for
      degradation  caused by contaminated lines  or active sites in  the system.
      Examples  of  these occurrences are:

                  7.16.3.1     Chloromethane:  This compound  is  the  most  likely
           compound  to be lost  if the purge flow is too fast.
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             7.16.3,2    Bromoform:  This compound is  one of the compounds
      most likely to be purged very poorly if the purge flow  is too slow.
      Cold  spots and/or  active  sites  in  transfer  lines  may adversely
      affect response.  Response of the primary quantitation ion (m/z 173)
      is directly affected by the tuning for 4-bromofluorobenzene at the
      ions of masses 174 and  176, Increasing the ratio of ions 174 and 176
      to   mass   95   (the   base   peak  of   the   mass   spectrum   of
      bromofluorobenzene) may improve bromoform response.

             7.16.3.3    1,1,2,2-Tetrachloroethane and 1,1-dichloroethane:
      These  compounds are degraded  by  contaminated transfer lines  in
      purge-and-trap systems and/or active sites in trapping materials.

      7,16.4      Using the response factors from the  initial calibration,
calculate  the   percent  relative  standard  deviation  (%RSD)  for  the
Calibration Check Compounds  (CCCs).
      %RSD  =  (SD/X) x 100
where:
      %RSD

      RF,

      RF


      SD
percent relative standard deviation

individual  RF measurement

mean of 5 initial RFs for a compound (the 5  points
over the calibration range)

standard deviation of average RFs for a compound,
where SD is calculated:
       SD =
      The %RSD  for  each  individual  CCC should be less  than  30 percent.
This criterion must be met in order for the individual  calibration to be
valid. The CCCs are: 1,1-dichloroethene, chloroform, 1,2-dichloropropane,
toluene,  ethylbenzene, and vinyl chloride.

7.17  Daily EC/MS Calibration

      7.17.1   Prior  to  the  analysis  of  samples,  purge 50  ng of  the
4-bromofluorobenzene standard.  The resultant mass  spectrum  for the  BFB
must meet  all  of the criteria  given  in  Table 3 before  sample analysis
begins.   These  criteria must  be demonstrated  every  twelve  hours  of
operation.

      7.17.2   The initial calibration curve (Sec. 7.16)  for each compound
of  interest  must be  checked and  verified once every  twelve  hours  of
analysis   time.    This   verification  is   accomplished  by  analyzing  a
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calibration  standard  that  is   at  a  concentration  near the  midpoint
concentration  for  the  working range of the  GC/MS  and checking the SPCC
(Sec. 7.16.3}  and CCC  (Sec. 7.16.4).

      7.17.3    System  Performance  Check  Compounds  (SPCCs):    A  system
performance check must be made each twelve hours  of analysis.  If the SPCC
criteria  are  met,  a  comparison of response  factors  is made for  all
compounds.   This is the  same  check that  is applied  during  the initial
calibration.  If the minimum response factors are not achieved, the system
must be evaluated, and corrective action must be  taken before  analysis is
allowed to begin.  The  minimum response factor for volatile SPCCs is 0.300
(0,250  for  bromoform) .    If  these minimum response  factors are  not
achieved,  some  possible  problems  may  be degradation  of the  standard
mixture, contamination of the  injector port, contamination at the front
end  of  the  analytical   column,  and  active  sites  in  the  column  or
chromatographic  system.   If the  problem is active sites at the front end
of the analytical column, column maintenance (removal of  approximately 1
foot from the front end of the column)  may remedy the problem.

      7.17.4    Calibration Check Compounds:  After  the system performance
check has  been met, CCCs  listed in Sec.   7.16.4 are used to  check  the
validity of the initial  calibration.  Calculate the  percent  difference
using the following equation:
                            -  RFJ  x 100
      % Difference =
where:

      RFj *     average response factor from initial calibration

      RFC  =     response factor from current calibration check standard.

      If the percent difference for any compound is greater than 20, the
laboratory should consider  this  a warning limit.  Benzene,  toluene, and
styrene will  have problems with response factors if Tenax® decomposition
occurs  (either  as  a  result  of  sampling   exposure  or  temperature
degradation), since  these  compounds are decomposition products of Tenax®.
If the  percent difference  for each  CCC  is less  than 25%,  the initial
calibration  is  assumed  to  be valid.    If  the   criterion  of  percent
difference less  than 25%  is not  met for  any  one  CCC,  corrective action
MUST be taken.   Problems similar to those  listed under SPCCs could affect
this criterion.   If a  source of the problem  cannot  be determined after
corrective action is taken,  a new five-point calibration  curve MUST be
generated.    The  criteria  for the  CCCs  MUST be met  before quantitative
analysis can begin.

      7.17.5      Internal standard responses  and retention times in the
check calibration standard must be evaluated immediately after or during
data acquisition. If the retention time for any  internal standard changes
by more than 30 seconds  from the last  check calibration (12  hr),  thi
chroraatographic system  must  be inspected for malfunctions and corrections


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must  be  made,  as required.  A  factor which may influence the retention
times of the  internal  standards on  sample tubes is the level of overall
organic  compound  loading  on  the VOST  tubes.  If the VOST tubes are very
highly  loaded with  either a single  compound or  with  multiple organic
compounds, retention times for standards and compounds of interest will be
affected.   If  the  area  for the  primary  ion  of  any  of  the  internal
standards changes by a factor of two (-50%  to +100%) from the last daily
calibration check, the gas chromatograph and mass  spectrometer should be
inspected for malfunctions and  corrections must be made, as appropriate.
If the level of organic loading  of samples  is  high,  areas for the primary
ions  of  both  compounds  of  interest  and  standards  will   be  adversely
affected.  Calibration  check  standards should not be subject to variation,
since the concentrations of organic  compounds  on these samples are set to
be  within  the  linear  range of the  instrumentation.    If  instrument
malfunction has occurred, analyses of samples performed under conditions
of malfunction may be invalidated.

7.18  GC/MS Analysis of Samples

      7.18.1      Set  up  the cartridge desorption unit,  purge-and-trap
unit, and GC/MS as described above.

      7.18,2      BFB tuning criteria and  daily GC/MS calibration check
criteria must be met before analyzing samples.

      7.18.3      Adjust  the helium purge gas flow  rate  (through  the
cartridges  and  purge vessel) to approximately  40  mL/rrnn.   Optimize  the
flow rate to provide  the best response for  chloromethane  and bromoform, if
these compounds are  analytes. A flow rate  which is too  high reduces  the
recovery of chloromethane, and  an insufficient gas flow rate reduces  the
recovery of bromoform.

      7.18.4      The first analysis performed after the tuning check and
the calibration or daily calibration check is  a  method blank.  The method
blank consists of clean VOST tubes (both Tenax® and Tenax«/charcoal) which
are spiked with surrogate  compounds and internal  standards  according to
the procedure described in Sec.  7.7.1.   The tubes which are used for  the
method blanks  should  be  from  the same batch of  sorbent  as the sorbent used
for the  field samples.   After  the  tubes  are cleaned  and  prepared  for
shipment to the field,  sufficient pairs of tubes should be retained from
the same batch  in the  laboratory  to provide method blanks during  the
analysis.

      7.18.5      The organic-free reagent water for the purge vessel  for
the analysis  of each of  the VOST  samples  should  be supplied  from  the
laboratory inventory which is maintained with constant bubbling  of inert
gas to avoid contamination.

      7.18.6      If  the  analysis  of  a   pair of VOST  tubes  has  a
concentration  of analytes that exceeds the initial  calibration  range, no
reanalysis of  desorbed  VOST tubes is possible.  An additional calibration
point can be added to bracket the higher concentration encountered in  the
samples so that the calibration  database encompasses six or more points.
                             5041  - 17                         Revision 0
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Alternatively,  the  data may be  flagged in the  report  as "extrapolated
beyond the upper range of the calibration."  The use of the secondary ions
shown in Table 1 is  permissible only in  the  case  of interference with the
primary quantitation  ion.   Use of  secondary  ions  to  calculate compound
concentration  in  the case  of  saturation of  the primary ion  is  not  an
acceptable procedure, since a negative bias  of an unpredictable magnitude
is  introduced  into  the  quantitative data  when  saturation  of  the  mass
spectrum of a compound is encountered,   If high organic loadings, either
of  a  single compound or of multiple compounds,  are encountered,  it  is
vital that  a  method blank be analyzed  prior  to  the analysis  of another
sample  to demonstrate  that no  compound  carryover  is  occurring.    If
concentrations of organic compounds are sufficiently high that carryover
problems are profound, extensive bakeout of the purge-and-trap unit will
be required.   Complete  replacement  of the contaminated  analytical trap,
with the associated  requirement for  conditioning the new  trap, nay also be
required for VOST samples which show excessive concentrations of organic
compounds.  Other measures  which might be required for decontamination  of
the  analytical   system  include  bakeout   of the mass  spectrometer,
replacement of the filament of  the mass  spectrometer, cleaning of the ion
source of the mass  spectrometer, and/or (depending on the nature of the
contamination) maintenance  of the chromatographic  column  or replacement of
the  chromatographic   column,   with  the   associated   requirement   for
conditioning the new chromatographic column.

7.19  Data Interpretation

      7.19.1      Qualitative analysis:

            7.19.1.1    The  qualitative   identification  of   compounds
      determined  by this  method  is  based on  retention time,  and  on
      comparison of  the sample mass spectrum, after background correction,
      with  characteristic   ions  in  a  reference  mass   spectrum.   The
      reference mass spectrum must  be generated  by the  laboratory using
      the conditions of  this method.   The  characteristic ions  from the
      reference mass spectrum are defined to be the three ions of greatest
      relative intensity, or any ions  over 30% relative  intensity if less
      than three  such  ions occur  in the reference spectrum.   Compounds
      should be identified as present when the criteria  below are met.

                  7.19.1.1.1  The intensities  of  the characteristic  ions
            of a compound maximize  in  the same scan or within one scan  of
            each  other.   Selection of  a peak by  a  data system  target
            compound search  routine where  the  search  is  based on  the
            presence of  a  target  chromatographic  peak  containing  ions
            specific  for the  target compound  at a  compound  specific
            retention time will be accepted as meeting  this  criterion.

                  7.19.1.1.2  The RRT of the  sample component  is  +  0.06
            RRT units of the RRT of the  standard  component.
                  7.19.1.1.3  The    relative     intensities    of    the
            characteristic  ions  agree  within  30%  of the   relative
            intensities  of  these  ions   in  the   reference   spectrum.
            (Example:   For  an ion with  an  abundance of  50% in  the
                            5041  -  18                         Revision  0
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      reference  spectrum,  the  corresponding abundance in a sample
      spectrum can range between 20% and 80%.}

            7.19.1,1,4  Structural isomers  that produce very similar
      mass  spectra  should  be identified as individual  isomers if
      they   have  sufficiently  different   GC   retention  times.
      Sufficient  GC  resolution is  achieved if the  height  of the
      valley between two isomer peaks is less than 25% of  the sum of
      the  two peak  heights.    Otherwise,   structural  isomers are
      identified as isomeric pairs.

            7.19.1.1.5  Identification  is  hampered  when  sample
      components  are  not resolved  chromatographically and produce
      mass  spectra  containing   ions contributed  by more  than one
      analyte.  When gas chromatographic peaks obviously represent
      more  than  one  sample component  (i.e., a broadened  peak with
      shoulder(s)  or  a   valley  between   two  or  more  maxima),
      appropriate  selection of analyte   spectra  and  background
      spectra is  important.  Examination of extracted ion current
      profiles of appropriate   ions  can aid  in  the  selection  of
      spectra, and in  qualitative identification of compounds.  When
      analytes coelute  (i.e.,   only one  chromatographic peak  is
      apparent),  the  identification criteria  can  be  met,  but  each
      analyte spectrum will contain extraneous ions contributed by
      the coeluting compound.

      7.19.1.2    For samples containing components not associated
with the calibration  standards,  a library search may be made for the
purpose of tentative  identification.  The necessity to perform this
type of  identification will be  determined  by the  type of analyses
being conducted.   Guidelines for making tentative identification
are:

      (1)   Relative  intensities  of major  ions  in  the  reference
spectrum (ions >  10%  of  the most abundant ion) should be present in
the sample  spectrum.

      (2)   The relative intensities of  the  major ions should agree
within + 20%.   (Example:  For an ion with an abundance  of 50% in the
standard spectrum, the corresponding sample ion  abundance must be
between 30 and 70%).

      (3)   Molecular ions  present  in the reference spectrum should
be present  in the sample spectrum.

      (4)   Ions   present  in the  sample spectrum  but not in the
reference  spectrum  should be  reviewed for possible  background
contamination or presence of coeluting compounds.

      (5)   Ions  present in the reference  spectrum but not  in the
sample spectrum should be reviewed for possible subtraction from the
sample spectrum  because  of background contamination  or  coeluting
peaks.  Data system library reduction programs can sometimes create
these discrepancies.

                      5041 - 19                        Revision 0
                                                    September 1994

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      Computer  generated  library  search  routines  should  not use
normalization  routines that  would  misrepresent  the  library or
unknown  spectra when compared to  each other.   Only after visual
comparison of sample with the nearest library searches will the  mass
spectral    interpretation    specialist    assign    a   tentative
identification.

7.19.2      Quantitative analysis:

      7.19,2,1    When  a   compound  has   been   identified,   the
quantitative  analysis  of   that  compound  will  be  based  on  the
integrated abundance from the extracted ion current profile of the
primary  characteristic  ion  for that  compound (Table 1).   In the
event  that  there  is interference  with  the  primary ion  so  that
quantitative measurements cannot  be made, a  secondary  ion  may be
used.

      NOTE: Use  of  a  secondary   ion  to  perform  quantitative
            calculations in the  event of  the saturation  of the
            primary  ion is  not an  acceptable  procedure because of
            the unpredictable extent of the negative bias which is
            introduced.   Quantitative calculations  are performed
            using the  internal  standard  technique.   The internal
            standard used to perform quantitative calculations shall
            be the internal  standard nearest the retention time of
            a given analyte (see Table 4).

      7.19.2.2    Calculate the amount of each identified analyte
from the VOST tubes as follows:

      Amount (ng)  =  (AECis)/(AisRF)

where:

      A,.  =  area of  the characteristic ion for the  analyte  to be
            measured.

      Ais =  area of the characteristic ion of the internal standard,

      Cjs =  amount (ng} of the internal standard.

      7,19.2.3    The  choice  of   methods   for   evaluating  data
collected using the VOST methodology for incinerator trial burns is
a  regulatory  decision.   Various  procedures   are  used  to  decide
whether  blank  correction   should  be  performed  and  how  blank
correction should be performed.  Regulatory agencies to which VOST
data are submitted also vary in their preferences  for data which are
or which are not blank corrected.

      7.19.2.4    The  total  amount  of   the  PQHCs  of  interest
collected on a pair of traps should be summed.
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                  7.19,2,5    The occurrence of high concentrations  of analytes
            on method blank cartridges indicates possible residual contamination
            of  sorbent cartridges prior  to  shipment and use  at  the sampling
            site.  Data with high  associated blank values must be qualified with
            respect  to  validity,  and  all   blank  data should  be  reported
            separately.   No  blank  corrections should  be made in  this case.
            Whether or not data of this type can be applied to the determination
            of  destruction and removal  efficiency is  a regulatory decision.
            Continued  observation of  high concentrations of analytes on blank
            sorbent cartridges indicates  that procedures for  cleanup  and quality
            control for  the sampling  tubes are inadequate.   Corrective action
            MUST  be  applied to tube preparation  and  monitoring  procedures to
            maintain  method blank concentrations  below  detection  limits  for
            analytes.

                  7.19.2.6    Where applicable, an estimate of concentration for
            noncalibrated components in  the  sample may  be made.   The formulae
            for quantitative  calculations presented above should  be used with
            the following modifications:   The  areas  A,, and Ais should  be from the
            total  ion   chromatograms,   and  the   Response   Factor  for  the
            noncalibrated  compound  should be  assumed to be 1.   The  nearest
            eluting internal standard free from interferences in the total  ion
            chromatogram should be  used  to determine the concentration.   The
            concentration which is obtained should  be  reported indicating:  (1)
            that the value  is an estimate; and (2) which  internal  standard was
            used.

                  7.19.2.7    If any internal standard recoveries fall  outside
            the control  limits established in  Sec.  8.4,  data for  all analytes
            determined  for  that  cartridge(s)  must  be qualified  .with  the
            observation.    Report  results  without  correction  for  surrogate
            compound recovery data.  When duplicates  are analyzed,  report  the
            data obtained with the sample results.


8.0   QUALITY CONTROL

      8.1   Each laboratory that  uses  these methods  is  required to operate a
formal quality control program.   The minimum quality control requirements are
specified in Chapter One.  In addition, this program should consist of an initial
demonstration of laboratory capability  and an ongoing  analysis of check samples
to evaluate and document data quality.  The laboratory must maintain records to
document the quality  of  the data  generated.  Ongoing data  quality  checks  are
compared with established performance criteria  to  determine if the  results of
analyses meet  the performance  characteristics of the  method.   When  sample
analyses indicate atypical  method  performance,  a quality  control check standard
(spiked method blank)  must  be analyzed to confirm  that  the measurements were
performed in an in-control  mode of instrument operation.

      8.2   Before processing  any  samples,  the  analyst should  demonstrate,
through the analysis  of a method blank  (laboratory blank  sorbent tubes,  reagent
water purge) that interferences from the analytical system,  glassware,  sorbent
tube preparation, and  reagents  are  under  control.   Each time a new batch of


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sorbent tubes  is  analyzed,  a method blank should be  processed as a safeguard
against chronic laboratory contamination.  Blank tubes which have been carried
through all the stages  of sorbent preparation and handling should be  used in the
analysis.

      8.3   The experience  of  the  analyst performing  the GC/MS analyses  is
invaluable to the  success of the analytical methods.   Each day that the analysis
is  performed,  the  daily  calibration  check  standard  should  be  evaluated  to
determine  if the  chromatographic  and  tube  desorption  systems  are operating
properly.  Questions that should be asked are:  Do the peaks look normal?  Is the
system response obtained comparable  to  the response from  previous calibrations?
Careful examination  of  the chromatogram of the calibration standard can indicate
whether column maintenance is  required or whether the column  is still  usable,
whether there  are leaks in the  system,  whether the  injector  septum requires
replacing, etc. If  changes are made to the system (such as change of a column),
a calibration check  must be carried out and a  new multipoint calibration must be
generated.

      8.4   Required instrument quality  control  is  found  in the  following
sections:

            8.4.1  The mass spectrometer must be tuned  to meet the specifications
      for 4-bromofluorobenzene in Sec.  7.2 {Table 3).

            8J4.2  An initial  calibration  of the tube  desorption/purge-and-trap/
      GC/MS must be  performed as specified in Sec. 7.7.

            8.4.3  The GC/MS system must meet the SPCC  criteria specified in Sec.
      7.16.3 and the CCC criteria in Sec.  7.16.4  each  twelve hours of instrument
      operation.

      8.5   To  establish  the  ability  to generate   acceptable  accuracy  and
precision, the analyst  must  perform the following operations.

            8.5.1  A  quality control  (QC) check  sample concentrate  is required
      containing each  analyte  at a  concentration  of  10 mg/L  in high  purity
      methanol.   The QC check  sample  concentrate may  be prepared  from  pure
      standard materials or  purchased as certified solutions.   If the QC check
      sample concentrate is  prepared by the  laboratory, the QC  check  sample
      concentrate  must  be prepared using stock standards prepared independently
      from the stock standards  used for calibration.

            8.5.2  Spike four pairs of cleaned,  prepared  VOST tubes  with  10  /uL
      of the QC check  sample  concentrate and analyze these spiked  VOST tubes
      according to the  mathod beginning in Sec.  7.0.

            8.5.3  Calculate  the  average  recovery (X)  in ng and  the standard
      deviation of the  recovery (s)  in  ng for each analyte using the results of
      the four analyses.

            8.5.4  The average recovery  and standard  deviation must fall  within
      the expected range for determination of volatile organic  compounds using
      the VOST  analytical  methodology.   The expected  range  for recovery  of


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                                                                September 1994

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      volatile  organic compounds  using  this method  is  50-150%.    Standard
      deviation will be compound dependent, but should, in general, range from
      15 to 30 ng.   More detailed method performance criteria must be generated
      from historical  records in the laboratory or from interlaboratory studies
      coordinated by the  Environmental  Protection Agency.  Since the additional
      steps of  sorbent tube  spiking  and desorption are  superimposed  upon the
      methodology of Method 8260,  direct transposition of Method 8260 criteria
      is questionable.  If the recovery and standard deviation for all  analytes
      meet the acceptance  criteria, the system performance is acceptable and the
      analysis of field samples may begin.   If any individual standard deviation
      exceeds the precision limit  or any individual  recovery falls outside the
      range for accuracy, then the system performance is unacceptable for that
      analyte.

            NOTE: The large  number  of analytes listed  in Table  1  presents  a
                  substantial probability that one or more will  fail  at  least
                  one of  the acceptance criteria when  all  analytes  for this
                  method  are  determined.

            8,5.5 When one or more of  the analytes tested  fails at least one of
      the acceptance criteria, the analyst must proceed according to one of the
      alternatives below.

                  8.5.5.1     Locate and correct the source of any problem with
            the methodology and  repeat the test for  all  the analytes beginning
            with Sec.  8.5.2.

                  8.5.5.2     Beginning with Sec.  8.5.2,  repeat  the test only
            for those analytes that  have  failed to meet  acceptance criteria.
            Repeated failure, however, will  confirm a general  problem  either
            with  the  measurement  system  or with  the  applicability  of  the
            methodology to the particular analyte (especially if the analyte in
            question is not listed in Table 1).  If the problem is identified as
            originating in the measurement system,  locate  and correct the source
            of the problem and repeat the  test for all  compounds  of  interest
            beginning with Sec.  8.5.2.

      8.6   To determine  acceptable accuracy  and precision limits for surrogate
standards,  the following  procedure  should  be performed.

            8.6.1 For each sample analyzed,  calculate the percent recovery of
      each surrogate compound in the sample.

            8.6.2 Once a minimum of thirty samples has been analyzed, calculate
      the average percent  recovery (p) and  the standard deviation of the percent
      recovery (s)  for each of the  surrogate compounds.

            8.6.3 Calculate  the  upper  and   lower  control limits  for  method
      performance for  each surrogate standard.  This calculation  is performed as
      follows:

            Upper Control  Limit  (UCL)  = p  4- 3s
            Lower Control  Limit  (LCL)  = p  -  3s


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                                                                September 1994

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            For  reference,  the comparable control  limits  for recovery of the
      surrogate  compounds from water  and  soil  in Method 8240  are:

            4-Bromofluorobenzene   Water:  86-115%     Soil:  74-121%
            I,2-Dichloroethane-d4  Water:  76-114%     Soil:  70-121%
            Toluene-dg             Water:  88-110%     Soil:  81-117%

            The  control limits for the VOST methodology would  be expected to be
      similar, but exact data are not presently available.  Individual laboratory
      control limits can be  established by the analysis of  replicate samples.

            8.6.4  If surrogate recovery is not within  the  limits established by
      the  laboratory,  the  following procedures are required:  (1)  Verify that
      there are  no errors  in calculations,   preparation  of surrogate spiking
      solutions, and preparation of internal  standard  spiking  solutions.  Also,
      verify that instrument performance criteria have been met, (2) Recalculate
      the data and/or analyze  a replicate sample, if replicates are available.
      (3)  If  all  instrument  performance criteria  are  met  and  recovery  of
      surrogates from spiked blank  VOST  tubes (analysis  of a method blank)  is
      acceptable,  the problem  is due  to  the  matrix.   Emissions samples may  be
      highly acidic and may be highly  loaded  with target and non target organic
      compounds.   Both  of these  conditions  will- affect the ability to recover
      surrogate compounds which are spiked on the field samples.  The surrogate
      compound recovery is   thus a  valuable  indicator of  the interactions  of
      sampled compounds with  the  matrix.   If surrogates  spiked  immediately
      before  analysis  cannot  be  observed  with  acceptable  recovery,  the
      implications for  target  organic  analytes which  have been sampled in the
      field must be assessed very carefully.   If chemical or other interactions
      are occurring on the exposed tubes,  the failure  to observe an analyte may
      not necessarily imply  that the Destruction and Removal  Efficiency for that
      analyte is high.

      8.7   It  is  recommended  that  the  laboratory adopt  additional  quality
assurance practices for use  with this method.  The specific practices that are
most productive  depend  upon  the  needs  of the laboratory  and the  nature of the
samples analyzed.  Field duplicates may be analyzed to assess the precision  of
the environmental measurements.  When  doubt exists over the  identification of a
peak on  the chromatogram, confirmatory  techniques such as gas chromatography with
a dissimilar column or a different ionization mode using a mass spectrometer may
be used, if replicate samples showing the same compound are  available.  Whenever
possible,  the laboratory   should  analyze  standard  reference  materials  and
participate in relevant performance evaluation studies.


9.0  METHOD PERFORMANCE

      9.1   The method detection  limit  (MDL)  is defined in Chapter One.  The MDL
concentrations listed in Table 2  were  obtained using cleaned blanked VOST tubes
and reagent water.   Similar  results  have  been achieved  with field samples.  The
MDL actually achieved in a  given  analysis will vary depending upon instrument
sensitivity and the effects  of  the matrix.  Preliminary spiking studies indicate
that under these  conditions, the  method detection limit for  spiked compounds 1n
extremely complex matrices may be larger by a factor of 500-1000.


                                  5041 -  24                         Revision 0
                                                                September 1994

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10.0  REFERENCES

1.    Protocol  for Collection  and  Analysis  of  Volatile  POHCs  Using  VOST.
      EPA/600/8-84-007, March, 1984.

2.    Validation  of the  Volatile  Organic Sampling  Train  (VOST)  Protocol,
      Volumes I and II.  EPA/600/4-86-014A, January,  1986.

3,    U. S. EPA 40  CFR  Part  136,  "Guidelines  Establishing Test  Procedures for
      Analysis of Pollutants  Under the Clean Water  Act, Method 624," October 26,
      1984.

4.    Bellar, T. A., and J. J. Lichtenberg,  J.  Amer. Water Works Assoc., 66(12),
      739-744, 1974.

5.    Bellar, T. A., and J.  J. Lichtenberg, "Semi-Automated Headspace Analysis
      of Drinking Waters and  Industrial Waters  for Purgeable  Volatile Organic
      Compounds," in Van Hall, ed.,  Measurement  of Organic Pollutants in Hater
      and Wastewater,  ASTM STP 686,  pp 108-129,  1979.
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                                                                September 1994

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                                   TABLE 1.
        RETENTION TIMES AND CHARACTERISTIC  IONS FOR VOLATILE COMPOUNDS
                     WHICH CAN BE ANALYZED BY METHOD 5041
Retention
Compound Time (min)
Acetone
Acrylonitrile
Benzene
Bromochl oromethane
Bromodi chl oromethane
4-Bromofluorobenzene
Bromoform
Bromomethane
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chlorodibromomethane
Chloroethane
Chloroform
Chloromethane
Dibromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans -1,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans- 1 , 3 -Di chl oropropene
1 ,4-Difluorobenzene
Ethyl benzene
lodomethane
Methyl ene chloride
Styrene
1,1,2. V -Tetrachl oroethane
Tetrat oroet^rne
Toluer
1,1,1 chloroethane
1,1,2- ? i chl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
1 ,2,3-Trichloropropane
Vinyl chloride
Xylenes*
7.1
8.6
13.3
12.0
16.0
23.4
22.5
4.1
7.1
12.6
20.5
19.3
4.2
12.2
3.0
15.4
10,0
13.3
6.4
8.6
15.2
17.0
18.2
14.2
21.1
7.0
8.1
22.3
24.0
18.6
17.4
12.4
18.4
14.5
5.1
24.0
3.2
22.2
Primary Ion
Mass
43
53
78
128
83
95
173
94
76
117
112
129
64
83
50
93
63
62
96
96
63
75
75
114
106
142
84
104
83
164
92
97
97
130
101
75
62
106
Secondary Ion(s)
Mass(es)
58
52, 51
52, 77
49, 130, 51
85, 129
174, 176
171, 175, 252
96, 79
78
119, 121
114, 77
208, 206
66, 49
85, 47
52, 49
174, 95
65, 83
64, 98
61, 98
61, 98
62, 41
77, 39
77, 39
63, 88
91
127, 141
49, 51, 86
78, 103
85, 131, 133
129, 131, 166
91, 65
99, 117
83, 85, 99
95, 97, 132
103, 66
110, 77, 61
64, 61
91
The retention time given  is  for m-  and p-xylene, which coelute  on  the wide-bore
column.  o-Xylene elutes approximately 50 seconds later.
                                  5041  - 26
    Revision 0
September 1994

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                                      TABLE 2.
               PRELIMINARY METHOD DETECTION LIMITS AND BOILING POINTS
                   FOR VOLATILE ORGANICS ANALYZED BY METHOD 5041*
Compound
Chloromethane
Bromomethane
Vinyl chloride
Chloroethane
Methylene chloride
Acetone
Carbon disulfide
1,1-Dichloroethene
1,1-Dichloroethane
trans-l,2-Dichloroethene
Chloroform
1,2-Dichloroethane
1,1,1-Tri chloroethane
Carbon tetrachloride
Bromodichloromethane
1,1,2,2-Tetrachloroethane"
1,2-Dichloropropane
trans- 1 , 3 -Di chl oropropene
Trichloroethene
Dibromochloromethane
1,1,2-Trichloroethane
Benzene
cis-1 , 3-Dichl oropropene
Bromoform""
Tetrachl oroethene
Toluene
Chlorobenzene^
Ethyl benzene"
Styrene"
Trichlorofl uoromethane
lodomethane
Acryloni trile
Dibromomethane
1,2,3-Trichloropropane**
total Xylenes"
CAS Number
74-87-3
74-83-9
75-01-4
75-00-3
75-09-2
67-64-1
75-15-0
75-35-4
75-35-3
156-60-5
67-66-3
107-06-2
71-55-6
56-23-5
75-27-4
79-34-5
78-87-5
10061-02-6
79-01-6
124-48-1
79-00-5
71-43-2
10061-01-5
75-25-2
127-18-4
108-88-3
108-90-7
100-41-4
100-42-5
75-69-4
74-88-4
107-13-1
74-95-3
96-18-4

Detection
Limit, ng
58
26
14
21
9
35
11
14
12
11
11
13
8
8
11
23
12
17
11
21
26
26
27
26
11
15
15
21
46
17
9
13
14
37
22
Boiling
Point, °t
-24
4
-13
13
40
56
46
32
57
48
62
83
74
77
88
146
95
112
87
122
114
80
112
150
121
111
132
136
145
24
43
78
97
157
138-144
*  The method  detection  limit (HDL)  is  defined as the  minimum concentration of  a
   substance that can be measured and reported  with 99%  confidence  that the analyte
   concentration is greater than  zero and is determined from analysis of a sample in
   a given  matrix  containing the analyte.   The detection  limits cited  above  were
   determined according  to  Title  40  CFR,  Part 136, Appendix B, using standards spiked
   onto clean VOST tubes.  Since clean VOST tubes were used,  the  values cited above
   represent the best that  the methodology can achieve.  The presence of an emissions
   matrix will  affect the ability of the  methodology to perform at its optimum level.
** Not appropriate for quantitative  sampling by  Method 0030.
                                     5041 - 27
    Revision 0
September 1994

-------
                                   TABLE 3.
              KEY ION  ABUNDANCE CRITERIA FOR  4-BROMQFLUOROBENZENE
Mass                           Ion Abundance Criteria
 50                            15 to 40% of mass 95
 75                            30 to 60% of mass 95
 95                            base peak,  100% relative  abundance
 96                            5 to 9% of mass 95
173                            less than 2% of mass 174
174                            greater than 50% of mass  95
175                            5 to 9% of mass 174
176                            greater than 95%, but  less  than  101% of  mass  174
177                            5 to 9% of mass 176
                                  5041 - 28                         Revision 0
                                                                September 1994

-------
                                   TABLE  4.
           VOLATILE  INTERNAL  STANDARDS  WITH  CORRESPONDING  ANALYTES
                           ASSIGNED FOR QUANT RATION
Bromochlpromethane

Acetone
Acrylonitrile
Bromomethane
Carbon distil fide
Chloroethane
Chloroform
Chloromethane
1,1-Dichloroethane
1,2-Dichloroethane
l,2-Dichloroethane-d4 (surrogate)
1,1-Dichloroethene
Trichloroethene
trans-1,2-Dichloroethene
lodomethane
Methylene chloride
Tri chlorof1uoromethane
Vinyl chloride
1,4-Di f1uorobenzene

Benzene
Bromodi chloromethane
Brotnoform
Carbon tetrachloride
Chlorodibromomethane
Dibromomethane
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-1,3-Dichlcropropene
1,1,1-Tri chloroethane
1,1,2-Tr1chloroethane
                               Ch1orobenzene-d5
                               4-Bromofluorobenzene (surrogate)
                               Chlorobenzene
                               Ethyl benzene
                               Styrene
                               1,1,2,2-Tetrach1oroethane
                               Tetrachloroethene
                               Toluene
                               Toluene-d8 (surrogate)
                               1,2,3-Tri chloropropane
                               Xylenes
                                   5041  -  29
                    Revision 0
                September 1994

-------
                                Ol
                              een
                              o •-«
                              O)
                             oe
                                 o.
                                 01
                    o
                    o
 s-
 o

o

 en
                            a
                            en
                            o
                            in
                    OJ
                    s_
 i    i
©  0

-------
Cartridge Oesorplion Unit
1/8" Teflon Tubing
                                                         Stand to Raise
                                                        Clam Shell Oven
      Figure 2.   Cartridge  Desorption  Unit with  Purge and Trap Unit
                                  5041  -  31
    Revision 0
September 1994

-------
Tube
Desorption
Unit


Purge and Trap
Apparatus


Gas
Chromalograph
                                                       Interface
Mass
Spectrometer
i

                                                                      | Polo System  j


Storage Media
lor Archive
Figure 3.  Schematic Diagram  of  Overall  Analytical  System
                         5041  -  32
    Revision 0
September 1994

-------
       Water nil Line
Sin»«red Class frit


     Gas Flow
                          Figure 4.   Sample Purge  Vessel
                                     5041  - 33
    Revision  0
September  1994

-------
    Slack
(or l«il system)
                          Condenialt
                            Trap
                          Impingcr
                                                               Silica Gel
                                                                              Vacuum
                                                                              .Indicator
                                                                                                 Cxhauil
      Figure  5.   Schematic of Volatile Organic Sampling Train (VOST)
                                    5041  -  34
     Revision  0
September  1994

-------
                           METHOD 5041
PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC
       SAMPLING TRAIN: WIDE-BORE CAPILLARY COLUMN TECHNIQUE



( Start J
1
r
7.1 Condition* for
cartridge
deeorption oven,
purge-and-trap
concentrator, GC,
•nd MS.
1
7.2 Daily, tuna
the GC/MS with
BFB and check
calibration curve
(a*e Section 7.17).
^
i
7.3 - 7.6
Assemble the
ayatem.
1
r
7.7.1 Calibrate the
instrument eyatem
Ljiing th* internal ltd.
procedure. Std». and
calibration compound*
are epiked into cleaned
VOST tube* uaing th*
flaah evaporation
technique.
1
f
7.8 Prep th*
purge-and-trap
unit with 6 ml
organic-free
reagent water.
1
7.9 C<
paired
tubee
gai Mr
a»*or
f
Miiiaet
VOST
to the
ea lor
ition.







	 . fc



7.10 Initiate
tube deaorption/
purge and
heating.
,
.
7.11 Sat th* GC
oven to »ubambient
temperature
with liquid
nitroflsn.
^
T
7.12 Prep the
GC/MS ayitem
for date
aquieition.
J
f
7.13 After the tube/
water purge time,
attach the
analytical trap to
the GC/MS for
daaorpttort.
^
r
7.14 Waah purging
veaiel with two
S mi flua hea of
organic-free
reagent water.
1
r

7. IE Recondition th*
enalytical trap by
making it cut ml
tempi up to 220 C for
11 min. Trap replacement
may be naceeaory
if th* analytical trap
i* aatu rated beyond
cleanup.
1
r
7.18.1 Prep
calibration atde.
at in 7.7.1. Add
water to veeiel
and deaorb.



, 	 ,. 	 fr

7.16.2
Tabulate the
area re»pon»e
of ell compounds
of interest.
V


7.16.3
Calculate the
average RF for
each compound
of intereet.
1 r
7.16.4 Calculate
the %RSD
for the CCC*.
The %RSO must
be <30%.
v
7.18 GC/MS
anelyei« of
aemplea.
ir
7.13.1 Qualitative
anelyai* of data
and ident. guideline*
of compounds.
i r
7.19.2 Quantitative
anelyei* of data for
the compound* of
interest.
1 r
/ Stop J

                             5041  -  35
    Revision 0
September 1994

-------

-------
                                  METHOD 5050

                    BOMB PREPARATION METHOD FOR SOLID WASTE
1.0   SCOPE AND APPLICATION

      1.1    This  method describes the sample  preparation  steps necessary to
determine total  chlorine in solid waste  and virgin and  used  oils,  fuels and
related materials,  including:  crankcase, hydraulic, diesel, lubricating and fuel
oils,  and  kerosene  by  bomb  oxidation and  titration  or  ion  chromatography.
Depending on the  analytical  finish chosen, other halogens  (bromine and fluorine)
and other elements (sulfur  and nitrogen) may also be determined.

      1.2    The  applicable  range  of  this method  varies  depending  on the
analytical  finish chosen.  In general, levels as low as  500 jug/g chlorine in the
original oil  sample  can be determined.  The  upper  range can  be extended to
percentage levels by dilution of the combustate.

      1.3    This  standard may  involve hazardous materials,  operations, and
equipment.   This  standard does not purport to address  all  of the safety problems
associated with its use.  It is  the responsibility of the  user  of this standard
to  establish  appropriate  safety and health   practices and   determine the
applicability of  regulatory  limitations prior to  use.  Specific safety statements
are given in Section 3.0.

2.0   SUMMARY OF METHOD

      2.1    The sample  is  oxidized  by combustion in  a bomb containing oxygen
under pressure.   The  liberated halogen  compounds  are  absorbed in  a sodium
carbonate/sodium bicarbonate  solution.   Approximately 30  to  40 minutes are
required to prepare a sample by  this  method.  Samples with a  high water content
(> 25%)  may not combust efficiently and may require the addition  of a mineral oil
to facilitate combustion.  Complete combustion  is still not guaranteed for such
samples.

      2.2    The bomb combustate solution can then be analyzed for the following
elements as their anion  species by one or more of the following methods:
      Method          Title
      9252            Chloride  (Titrimetric,  Mercuric  Nitrate)
      9253            Chloride  (Titrimetric,  Silver Nitrate)
      9056            Inorganic Anions by Ion Chromatography (Chloride, Sulfate,
                      Nitrate,  Phosphate,  Fluoride,  Bromide)
                                   5050 - 1                       Revision 0
                                                                  September 1994

-------
      NOTE:  Strict  adherence to all of  the  provisions  prescribed hereinafter
      ensures against explosive rupture of the bomb,  or a blowout, provided the
      bomb  is  of  proper design  and  construction  and   in  good  mechanical
      condition.   It is  desirable,  however, that the  bomb be  enclosed  in a
      shield  of  steel  plate at  least  1/2 in. (12.7 mm) thick,  or equivalent
      protection be provided against unforeseeable contingencies.

3.0   INTERFERENCES

      3.1     Samples  with very  high water  content  (> 25%)  may  not  combust
efficiently  and may  require  the  addition  of  a  mineral   oil   to  facilitate
combustion.

      3.2     To  determine total  nitrogen in  samples, the  bombs  must  first be
purged of ambient air.  Otherwise,  nitrogen results will  be biased high.

4.0   APPARATUS AND MATERIALS

      4.1     Bomb,  having a  capacity of not  less than 300  ml,  so constructed
that it will  not  leak during the test,  and  that quantitative  recovery of the
liquids from the bomb may  be readily achieved.  The inner surface of the  bomb may
be made of stainless steel or any other material that will not be affected by the
combustion process or products.  Materials used in the bomb assembly, such as the
head gasket and lead-wire insulation,  shall  be resistant to heat and  chemical
action and shall not undergo  any reaction that will affect the chlorine content
of the sample in the bomb.

      4.2     Sample cup,  platinum or stainless steel, 24 mm  in outside diameter
at the bottom,  27 mm in outside diameter at the top, 12 mm in  height outside, and
weighing 10 to 11 g.

      4.3     Firing wire,  platinum or  stainless  steel,  approximately  No.  26 B
& S gage.

      4.4     Ignition circuit, capable of supplying sufficient current to ignite
the nylon thread or cotton wicking  without melting the wire.

      NOTE: The switch in  the ignition circuit shall  be of the type that remains
      open, except when held in closed position by the operator.

      4.5    Nylon sewing thread, or Cotton Wicking, white.

      4.6     Funnel, to fit  a 100-mL volumetric flask.

      4.7    Class A volumetric  flasks,  100-mL, one per sample.

      4.8    Syringe, 5-  or  10-mL disposable  plastic or glass.

      4.9    Apparatus for specific analysis  methods are given in the methods.

      4.10   Analytical balance:  capable of  weighing to 0.0001 g.
                                   5050 - 2                       Revision 0
                                                                  September 1994

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5.0    REAGENTS

       5.1     Purity of reagents.  Reagent-grade chemicals shall be used  in all
tests.   Unless  otherwise  indicated,  it  is  intended that  all  reagents shall
conform  to  the  specifications of the Committee on  Analytical  Reagents of the
American Chemical Society, where such specifications  are available. Other grades
may be used, provided it is first ascertained that the reagent is  of sufficiently
high   purity  to  permit  its  use  without  lessening  the  accuracy   of  the
determination.

       5,2     Reagent water.   All references to water  in  this  method refer to
reagent water, as defined in Chapter One.

       5.3     Oxygen.    Free  of  combustible material  and  halogen  compounds,
available at  a pressure of 40 atra.

       WARNING: Oxygen  vigorously accelerates combustion (see Appendix Al.l)

       5.4     Sodium bicarbonate/sodium  carbonate  solution.   Dissolve 2.5200 g
NaHC03 and 2.5440 g Na2C03 in  reagent water  and dilute to  1  L.

       5.5     White  oil.  Refined.

       5.6     Reagents'and materials for specific analysis methods are given in
the methods.

6.0    SAMPLE  COLLECTION, PRESERVATION,  AND HANDLING

       6.1     All samples must be collected using a sampling  plan that addresses
the considerations discussed in Chapter Nine.

      6.2     Ensure  that the portion of the sample used for the test is repre-
sentative of  the sample.

      6.3     To  minimize  losses  of volatile halogenated  solvents that may be
present in the sample,  keep the field and laboratory samples as free of headspace
as possible.

      6.4     Because used oils may contain toxic and/or carcinogenic substances
appropriate field and  laboratory safety procedures should be followed.

7.0   PROCEDURE

      7.1     Sample Preparation

              7.1.1  Preparation of bomb and sample.  Cut a piece of firing wire
      approximately 100 mm in  length and attach the  free ends to the terminals.
      Arrange the wire so that it will  be just  above  and not touching the sample
      cup.  Loop a  cotton thread  around the wire  so that  the ends  will extend
      into the sampling cup.   Pipet  10 mL of the NaHCO.j/Na2C03 solution into the
      bomb,  wetting the sides.  Take an aliquot of  the  oil  sample  of approxi-
      mately 0.5 g using a 5-  or  10-mL disposable plastic syringe, and place in
      the sample cup.  The actual  sample weight is determined by the difference


                                   5050 -  3                       Revision 0
                                                                  September  1994

-------
      between the weight of the empty and  filled  syringe.   Do  not use more than
      1 g of sample.

               NOTE:  After repeated use of the bomb  for chlorine determination,
               a  film may be noticed on the inner  surface.   This dullness should
               be removed by periodic  polishing  of the bomb.   A satisfactory
               method  for doing this  is to rotate the bomb in a lathe at about
               300  rpm  and  polish the inside surface  with  Grit  No.  2/0  or
               equivalent paper1 coated with  a  light  machine oil  to prevent
               cutting,  and  then with  a paste  of grit-free chromic oxide2 and
               water.  This procedure will  remove  all but very  deep pits and put
               a  high  polish  on the surface.   Before using the bomb, it should
               be washed with soap and water to remove oil  or paste left from the
               polishing  operation.  Bombs  with porous or pitted surfaces should
               never  be  used because  of the  tendency to  retain  chlorine from
               sample  to  sample.

               NOTE:     If  the  sample  is  not   readily  combustible,  other
               nonvolatile, chlorine-free combustible diluents such as white oil
               may  be employed.   However, the combined  weight of  sample  and
               nonvolatile diluent  shall not  exceed  1 g.   Some solid additives
               are  relatively insoluble but may  be  satisfactorily  burned when
               covered with a layer of  white oil.

               NOTE:   The practice  of alternately running  samples high and low
               in chlorine content  should  be  avoided whenever possible.   It is
               difficult  to rinse the last traces of chlorine  from the walls of
               the  bomb,  and  the tendency  for residual chlorine  to  carry over
               from  sample  to  sample  has  been  observed   in  a  number  of
               laboratories.  When a sample high in chlorine has preceded one low
               in chlorine content, the test  on the  low-chlorine sample should
               be repeated,  and one  or both  of  the low  values  thus  obtained
               should  be considered  suspect  if they do  not  agree  within  the
               limits  of  repeatability  of  this method.

               NOTE:  Do  not use more than 1 g total of sample and white oil  or
               other chlorine-free  combustible material.  Use  of excess amounts
               of these  materials  could  cause a  buildup   of  dangerously  high
               pressure and possible  rupture of the  bomb.

               7.1.2     Addition of oxygen.   Place  the sample cup  in  position
      and arrange the  thread  so  that the end dips  into the  sample.  Assemble the
      bomb and  tighten   the  cover  securely.    Admit oxygen  slowly (to  avoid
      blowing the oil  from the  cup) until  a pressure  is reached as indicated in
      Table 1.

              NOTE:  Do  not  add oxygen  or  ignite the sample if  the bomb has been
              jarred, dropped,  or  tiled.
     "'Emery Polishing  Paper grit No. 2/0 may be purchased from the Behr-Manning
Co., Troy, NY.

     2Chromic  oxide  may  be purchased  from  J.T.  Baker & Co.,  PhiTiipsburg,  NJ.

                                   5050 -  4                       Revision 0
                                                                  September 1994

-------
               7,1.3    Combustion.   Immerse the  bomb in a  cold water  bath.
      Connect  the terminals to the open electrical circuit.   Close the circuit
      to  ignite the sample.  Remove the bomb from the  bath after  immersion for
      at  least  10 minutes.   Release  the pressure at a slow,  uniform rate such
      that the operation requires at  least  1 min.  Open the bomb and examine the
      contents.  If traces of unburned oil  or sooty  deposits are found, discard
      the determination, and thoroughly clean the bomb before using it again.

               7.1.4    Collection of halogen solution.  Using reagent water and
      a funnel, thoroughly rinse the  interior of the bomb, the sample cup, the
      terminals,  and  the  inner  surface  of the  bomb  cover  into  a   IQQ-mL
      volumetric flask.  Dilute to the mark with reagent water.

               7.1.5    Cleaning procedure for bomb and sample cup.  Remove any
      residual fuse wire from the terminals and the cup.  Using hot water,  rinse
      the interior  of  the  bomb,  the  sample cup, the  terminals,  and  the  inner
      surface of the bomb cover.   (If any  residue remains,  first scrub the bomb
      with Alconox  solution).   Copiously rinse the bomb,  cover,  and  cup with
      reagent water.

      7.2      Sample Analysis.   Analyze the  combustate  for  chlorine  or  other
halogens using the methods listed in Step 2.2.  It may be necessary  to dilute the
samples so that the concentration will fall within the range  of standards.

      7.3      Calculations.    Calculate  the  concentrations  of  each  element
detected in the sample according to the following equation:

                             Ccom * Vcom x DF                   (1)
                    C,
                     o
      where:

          C0      =  concentration of element in the sample,
          CCom     =  concentration of element in the combustate,
          Vcom     =  total volume of combustate, ml
          DF      =  dilution factor
          W0      =  weight of sample combusted, g.

      Report the  concentration  of  each  element  detected in  the  sample  in
micrograms per gram.
                                   5050 - 5                       Revision 0
                                                                  September 1994

-------
       Example:  A 0.5-g oil sample was combusted,  yielding 10 ml  of combustate.
 The  combustate  was  diluted to  100 ml  total  volume and analyzed for chloride,
 which was measured to be 5 ^g/ml.  The concentration of chlorine in the original
 sample  is then  calculated as  shown below:

                                5 ug   x  (10 ml)  x (10)
                     C0  =        ml                              (2)
                                         0.5 g
                    C0  =       1,000 M                         (3)
                                       g


8.0   QUALITY CONTROL

      8,1   Refer to Chapter One for specific quality control procedures.

      8.2   One sample in ten should be bombed twice.  The results should agree
to within 10%, expressed as the relative percent difference of the results.

      8.3   Analyze matrix spike and matrix spike duplicates - spike samples with
the  elements  of  interest  at  a  level  commensurate  with  the  levels  being
determined.   The  spiked compounds should be  similar  to  those expected in the
sample.  Any  sample suspected  of  containing > 25% water should also be spiked
with organic chlorine.

      8.4   For  higher   levels   (e.g.,   percent   levels),   spiking   may  be
inappropriate.   For  these  cases,  samples  of known  composition  should  be
combusted.  The results should agree to within  10% of the expected result.

      8.5   Quality control  for  the analytical method(s) of  choice  should be
followed.


9.0   PERFORMANCE

      See analytical methods referenced in Step 2.2.


10.0 REFERENCES

1.    ASTH Method D 808-81,  Standard Test  Method  for  Chlorine in New and Used
Petroleum Products (Bomb Method).  1988 Annual  Book of ASTM Standards.  Volume
05.01 Petroleum Products and Lubricants.

2.    Gaskill, A.;  Estes, E. D.; Hardison, D. L.; and Myers, L. E.   Validation
of Methods for Determining  Chlorine  in Used Oils  and  Oil  Fuels.   Prepared for
U.S. Environmental  Protection Agency, Office of Solid Waste.  EPA Contract No.
58-01-7075,  WA 80.   July 1988.
                                   5050 - 6                       Revision 0
                                                                  September 1994

-------
                                   TABLE 1.
                                GAGE PRESSURES
Capacity of bomb, ml
Minimum
gage
pressure8,  atm
Maximum
gage
pressure8
atm
      300 to 350
      350 to 400
      400 to 450
      450 to 500
   38
   35
   30
   27
    40
    37
    32
    29
"The minimum pressures are specified to provide sufficient oxygen for complete
combustion, and the maximum pressures represent a  safety  requirement.  Refer to
manufacturers' specifications for appropriate gage pressure, which may be lower
than those listed here.
                                   5050 - 7
                                Revision 0
                                September 1994

-------
                                   APPENDIX

                         Al.   PRECAUTIONARY STATEMENTS

Al.'l  Oxygen

      Warning—Oxygen vigorously accelerates combustion.

      Keep oil and grease away.   Do not use oil  or  grease  on  regulators, gages,
or control equipment.

      Use only with equipment conditioned for oxygen service by careful cleaning
to remove oil, grease, and other combustibles.

      Keep combustibles away from oxygen and eliminate ignition sources.

      Keep surfaces clean to  prevent ignition  or explosion,  or both,  on contact
with oxygen.

      Always use a pressure regulator.  Release regulator tension before opening
cylinder valve.

      All equipment  and  containers used must be suitable and recommended  for
oxygen service.

      Never attempt to transfer  oxygen from cylinder in which it is received to
any other cylinder.  Do not mix gases in cylinders.

      Do not drop cylinder.  Make sure cylinder is secured at  all times.

      Keep cylinder valve closed when not in use.

      Stand away from outlet  when opening cylinder valve.

      For technical use only.  Do not use for inhalation purposes.

      Keep cylinder out of sun and away from heat.

      Keep cylinders from corrosive environment.

      Do not use cylinder without label.

      Do not use dented or damaged cylinders.

      See Compressed Gas Association booklets  G-4 and G4.1 for details of safe
practice in the use of oxygen.
                                   5050 - 8                       Revision 0
                                                                  September 1994

-------
              METHOD  5050
BOMB PREPARATION METHOD FOR SOLID WASTE
        START
1
? 1 I Prepare bcmb
and sample
I
71.2 Slowly add
oxygen to aampie
CUJ3
I
7 1.3 Ifnttterse bomb
in cold wa LET ;
ignite sample ;
remove bomb f r om
*ta ter ; release
pressure, open bocnb
1
1 1 4 Hir.a e bomb ,
sample cup,
terminals . and bomb
covet **ith water




1 . 1 . S Hinate bomb .
sample cup ,
terminals , and bomb
cover with ha I
wa ter
1
7 2 Analyze
cstfibuj ta t«
1
? 3 Calculate
can cert tra lion of
each element
detected
1
C - )

                5050  -  9
Revision 0
September 1994

-------

-------
                                  METHOD 6020

                 INDUCTIVELY  COUPLED  PLASMA  - MASS SPECTROMETRY
 1.0  SCOPE AND APPLICATION

       1.1  Inductively  coupled plasma-mass  spectrometry  (ICP-MS)  is  applicable
 to the determination of sub-^g/L concentrations of a large number of elements  in
 water  samples  and  in  waste extracts  or  digests  [1,2].    When  dissolved
 constituents are required, samples must be filtered  and  acid-preserved  prior  to
 analysis.  No  digestion is  required prior to analysis for dissolved elements  in
 water  samples.  Acid digestion prior to filtration and analysis  is required for
 groundwater, aqueous samples, industrial  wastes,  soils,  sludges,  sediments, and
 other  solid wastes for  which  total  (acid-leachable) elements are  required.

       1.2  ICP-MS has been  applied to the determination of  over 60 elements  in
 various matrices.  Analytes for which EPA has  demonstrated the acceptability  of
 Hethod 6020 in a multi-laboratory study on solid wastes are listed in  Table  1.
 Acceptability of the method for an element was based  upon the multi-laboratory
 performance compared with that of  either  furnace  atomic absorption spectroscopy
 or inductively coupled plasma-atomic emission  spectroscopy.   It  should  be noted
 that  the multi-laboratory  study  was conducted in  1986.    Multi-laboratory
 performance data for the listed elements  (and others) are provided in  Section  9.
 Instrument detection limits, sensitivities, and linear ranges will vary  with the
 matrices,  instrumentation,  and operating conditions.    In relatively simple
 matrices, detection limits will generally be below 0.02//g/L.

       1.3  If Method 6020 is  used to determine any analyte  not listed  in Table
 1,  it  is the  responsibility  of  the  analyst  to  demonstrate the  accuracy and
 precision of  the  Method in the waste  to be analyzed.   The analyst  is always
 required to  monitor potential sources  of interferences  and  take appropriate
 action to ensure data of known quality (see Section 8.4).

       1.4   Use  of  this  method   is  restricted  to  spectroscopists  who  are
 knowledgeable in the recognition and in the correction of spectral,  chemical, and
physical interferences  in ICP-MS.

       1.5   An  appropriate  internal  standard is  required for  each  analyte
determined by ICP-MS.   Recommended internal standards are 6Li,  45Sc,  89Y,  103Rh,
 mln,  159Tb,  165Ho,  and 209Bi.  The  lithium  internal  standard  should  have  an
enriched abundance of 6Li, so that  interference from lithium native to  the sample
 is minimized.   Other  elements may need to be used  as internal  standards when
samples contain significant amounts of the recommended internal standards.

2.0  SUMMARY OF METHOD

      2.1 Prior  to analysis,  samples which  require  total  ("acid-leachable")
values must be digested using appropriate sample preparation methods (such   as
Methods 3005 - 3051).


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      2,2  Method 6020 describes the multi-elemental determination  of analytes
by ICP-MS.  The method measures ions produced by a radio-frequency  inductively
coupled plasma.  Analyte species originating in a liquid are nebulized and the
resulting  aerosol  transported by argon gas  into  the plasma torch.   The ions
produced  are entrained  in  the  plasma gas  and  introduced,  by  means  of  an
interface, into a mass spectrometer.  The ions produced in the plasma are sorted
according to their mass-to-charge ratios and  quantified with  a  channel electron
multiplier.  Interferences  must be assessed and valid corrections applied or the
data  flagged to  indicate  problems.    Interference  correction  must  include
compensation for background  ions contributed  by the plasma gas, reagents, and
constituents of the sample matrix.

3.0  INTERFERENCES

      3.1  Isobaric elemental interferences  in  ICP-MS  are caused by  isotopes of
different elements forming  atomic ions with the same nominal mass-to-charge ratio
(m/z). A  data  system must be  used  to  correct for these  interferences.   This
involves determining the signal for another isotope of the interfering element
and subtracting the appropriate signal  from the analyte isotope signal.  Since
commercial ICP-MS  instruments  nominally provide unit  resolution at 10% of the
peak height,  very high ion currents at adjacent masses can also contribute to ion
signals at the mass of.interest. Although this type of interference is uncommon,
it is not  easily corrected, and samples exhibiting a significant problem of this
type could require resolution improvement, matrix separation, or analysis using
another verified and documented isoptope,  or use of another method.

      3.2  Isobaric molecular and doubly-charged ion interferences  in ICP-MS are
caused by ions consisting of more than one atom or charge,  respectively.   Most
isobaric  interferences that  could  affect  ICP-MS determinations  have  been
identified in the  literature [3,4].   Examples  include ArCl* ions on the 7SAs
signal  and MoO*  ions  on  the  cadmium  isotopes.    While  the approach  used  to
correct for molecular  isobaric interferences is demonstrated  below using the
natural isotope abundances from the literature [5], the most precise coefficients
for an instrument can be determined from the ratio of the  net  isotope signals
observed  for  a  standard solution  at a concentration providing  suitable (<1
percent)   counting  statistics.   Because the 35C1  natural  abundance of  75.77
percent  is 3.13  times the  37C1  abundance  of  24.23 percent,   the  chloride
correction for arsenic can  be calculated (approximately)  as follows (where the
^Ar37^*  contribution at m/z 75  is  a negligible 0.06 percent  of  the *°Ar35Cl +
signal):

      corrected   arsenic   signal   (using   natural   isotopes   abundances   for
      coefficient approximations)  =

      (m/z 75 signal)  - (3.13) (m/z 77  signal)  4 (2.73)  (m/z 82 signal),
      (where  the  final  term adjusts  for any selenium contribution  at 77 m/z),

      NOTE: Arsenic values  can be biased high by this type of equation when the
      net  signal at m/z 82 is caused  by  ions other than  Se+,  (e.g.,  81BrH+' from
      bromine wastes [6]).


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Similarly,

      corrected   cadmium   signal   (using  natural   isotopes  abundances  for
      coefficient approximations) =

      (m/z 114 signal) - (O.OZ7)(m/z 118 signal) - (1.63)(m/z 108 signal),
      (where last 2 terms adjust for any tin or MoO+  contributions at m/z 114).

      NOTE: Cadmium  values will be  biased low  by this type  of equation when
      8ZZrO*  ions contribute  at m/z 108,  but use of  m/z  111  for  Cd  is even
      subject to  direct  (94ZrOH4) and indirect (BOZrQ*) additive interferences
      when Zr is  present.

      NOTE: As  for  the  arsenic equation  above,  the  coefficients  in  the  Cd
      equation are ONLY illustrative. The most appropriate coefficients for an
      instrument  can  be  determined  from the  ratio of  the  net isotope  signals
      observed for a  standard solution at a  concentration providing suitable (<1
      percent) counting precision.

The^accuracy  of  these types of equations  is  based upon the  constancy  of the
OBSERVED isotopic ratios for the interfering species.  Corrections that presume
a constant fraction of a molecular ion relative to the "parent" ion have not been
found [7] to be reliable, e.g., oxide levels  can vary.   If a correction for an
oxide ion  is  based  upon  the  ratio of  parent-to-oxide  ion  intensities,  the
correction must be adjusted for the degree of oxide formation by the use of an
appropriate oxide internal  standard  previously demonstrated  to  form a  similar
level  of oxide as  the interferant.  This type of correction  has been reported [7]
for oxide-ion corrections  using ThO+/Th+ for the  determination of  rare earth
elements.  The use of aerosol desolvation and/or mixed plasmas have been shown
to greatly reduce molecular interferences  [8].   These techniques can  be used
provided that  method  detection  limits, accuracy, and precision requirements for
analysis of the samples can be met.

      3.3  Physical interferences are associated with the sample nebulization and
transport processes as well as with  ion-transmission efficiencies.  Nebulization
and transport  processes can be affected if a matrix component  causes  a change in
surface   tension   or   viscosity.    Changes  in matrix  composition  can  cause
significant signal suppression or enhancement [9].   Dissolved  solids  can deposit
on the  nebulizer  tip of a  pneumatic nebulizer  and on the  interface  skimmers
(reducing the  orifice size  and  the instrument  performance).  Total solid levels
below 0.2% (2,000 mg/L) have been currently recommended [10]  to minimize solid
deposition.   An   internal  standard  can  be   used  to correct for  physical
interferences, if it  is carefully matched to the analyte so  that the two elements
are similarly  affected by matrix changes [11].  When the intensity level of an
internal standard is  less  than  30  percent or greater  than 120  percent  of the
intensity  of  the  first standard used during  calibration,  the  sample  must  be
reanalyzed after a fivefold (1+4) or greater  dilution has  been performed.

      3.4   Memory interferences can occur when there  are large concentration
differences between samples or standards  which  are analyzed  sequentially.  Sample


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deposition on the sampler and skimmer cones, spray chamber design,  and the  type
of nebulizer affect the extent  of the memory  interferences which are  observed.
The rinse period  between  samples must be long enough to eliminate  significant
memory interference.

4,0  APPARATUS AND MATERIALS

      4.1  Inductively coupled  plasma-mass  spectrometer:

            4.1.1   A system  capable  of providing  resolution,  better than or
      equal to amu at 10% peak height is required.  The  system must  have a  mass
      range from at least  6  to 240 amu and a data system  that allows  corrections
      for isobaric  interferences and  the application of the  internal  standard
      technique.  Use of  a  mass-flow  controller for the nebulizer  argon and a
      peristaltic pump for the  sample solution are  recommended.

            4.1.2  Argon gas  supply:  high-purity grade (99.99%).

i.O  REAGENTS

      5.1  Acids used in the preparation of standards and for  sample processing
must be of high purity.  Redistilled acids  are recommended because  of  the  high
sensitivity of ICP-MS.  Nitric acid at less than 2 per cent (v/v) is required for
ICP-MS to minimize damage to the  interface and to minimize isobaric molecular-ion
interferences with  the analytes.   Many more molecular-ion  interferences  are
observed on the analytes  when hydrochloric and  sulfuric acids are  used [3,4].
Concentrations of antimony and  silver between 50-500 //g/L require 1%  (v/v) HC1
for stability;  for  concentrations above  500  //g/L Ag,  additional HC1  will be
needed.

      5.2 Reagent water:  All references to water  in the method refer to reagent
water unless otherwise  specified.   Refer  to  Chapter One for a definition of
reagent water.

      5.3 Standard  stock  solutions may be purchased or prepared from ultra-high
purit1  grade chemicals  or  metals (99.99  or greater purity }.   See Method 6010A,
Sect     5.3,  for instructions on preparing  standard solutions  from  solids.

            5.3.1   Bismuth internal  standard solution, stock,  1 ml = 100 /jg Bi:
      Dissolve 0.1115 g Bi203 in a  minimum amount of dilute  HN03.   Add  10 ml
      cone.  HN03 and dilute  to 1,000 mi.  with reagent water.

            5.3.2   Holmium internal  standard solution, stock,  1 ml = 100//g Ho:
      uissolve 0.1757 g Ho2(C03)2-5H20  in 10 ml reagent water and   10 ml HN03.
      After dissolution is  complete,  warm  the  solution to degas.   Add  10 ml
      cone.  HN03 and dilute  to 1,000 ml  with reagent water.

            5.3.3   Indium  internal standard solution, stock,  1 ml = 100 //g In:
      Dissolve 0.1000 g indium  metal  in  10 ml cone. HN03.   Dilute  to  1,000 ml
      with  reagent water.


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             5.3.4  Lithium internal standard solution, stock,  1  ml  =  100 fjg 6Li:
      Dissolve 0.6312 g 95-atom-% 6Li,  Li2COa in 10 ml of reagent water and 10 ml
      HN03.   After  dissolution is complete, warm the solution to degas.   Add
      10 ml  cone. HN03 and dilute  to 1,000 ml  with reagent water.

             5.3.5  Rhodium internal standard solution, stock, 1 ml = 100 //g Rh:
      Dissolve  0.3593  g  ammonium  hexachlororhodate  (II!)  {NH4)3RhCl6  in  10 mL
      reagent water.  Add  100  ml  cone.  HC1  and dilute to  1,000  ml  with reagent
      water.

             5.3.6  Scandium internal  standard solution, stock, 1 raL = 100//g Sc:
      Dissolve 0.15343 g Scz03 in  10 ml (1+1)  hot  HN03.  Add 5 ml cone.  HN03 and
      dilute to  1,000 ml with  reagent  water.

             5.3.7  Terbium internal standard solution, stock, 1  ml = 100 //g Tb:
      Dissolve 0.1828 g Tb2(C03)3-5H20 in 10  ml (1+1)  HN03.  After dissolution is
      complete,  warm the solution  to degas.   Add  5 ml cone.  HN03 and dilute to
      1,000.ml with reagent water.

             5.3.8  Yttrium internal standard  solution, stock, 1 ml  = 100 f/q Y:
      Dissolve 0.2316 g Y2(C03)3.3H20  in 10  ml (1+1)  HN03.  Add  5 ml  cone.  HN03
      and dilute to 1,000 ml with  reagent water.

             5.3.9  Titanium solution,  stock,  1  mL  = 100 ^g T1:  Dissolve  0.4133 g
      (NH4)2TiFe  in  reagent water.  Add 2 drops cone.  HF and dilute to  1,000 ml
      with reagent water.

             5.3.10   Molybdenum solution, stock,  1 mL =  100  fjg  Mo:    Dissolve
      0.2043 g  (NH4)2Mo04 in reagent water.    Dilute  to  1,000 mL with  reagent
      water.

      5.4  Mixed calibration  standard  solutions are prepared by diluting   the
stock-standard solutions to levels in  the linear  range for the  instrument  in a
solvent consisting of  1  percent (v/v)  HN03  in reagent water.  The calibration
standard solutions  must contain  a suitable  concentration of  an appropriate
internal standard for each analyte.  Internal  standards may be added  on-line at
the time of analysis using  a second  channel  of the  peristaltic  pump and  an
appropriate mixing manifold.)   Generally, an internal standard should be no  more
than 50 amu  removed  from the  analyte.   Recommended  internal   standards  include
eLi, 45Sc, 89Y, 103Rh, 115In, 159Tb,  ^Ho, and  209Bi.   Prior  to preparing the mixed
standards,  each stock solution  must be analyzed separately to determine  possible
spectral interferences or the  presence  of impurities.  Care must be  taken  when
preparing  the mixed standards that  the elements are compatible  and  stable.
Transfer the mixed standard solutions  to freshly  acid-cleaned FEP  fluorocarbon
bottles for storage.  Fresh mixed standards  must be prepared  as  needed  with the
realization that concentrations can change on aging.  Calibration standards  must
be  initially verified  using  a quality  control  standard  (see Section  5.7)  and
monitored weekly for stability.
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      5.5   Blanks:  Three types of blanks are  required  for the analysis.  The
calibration  blank  is  used  in  establishing   the   calibration  curve.    The
preparation  blank is  used to monitor for possible contamination resulting from
the sample preparation procedure.  The rinse blank is used to flush the  system
between all  samples and standards.

             5.5,1  The calibration blank consists of the same concentration(s)
      of the same acid(s) used to prepare the final dilution of  the calibrating
      solutions of  the  analytes [often  1 percent HN03 (v/v)  in reagent water]
      along  with  the  selected concentrations  of  internal  standards  such that
      there  is  an  appropriate  internal  standard  element  for  each of  the
      analytes.  Use  of HC1 for antimony and silver is cited in Section 5.1

             5.5.2  The preparation  (or  reagent)  blank must be carried through
      the  complete preparation procedure  and contain  the  same volumes  of
      reagents as the sample solutions.

             5.5.3   The  rinse blank consists of  1 to 2  percent HN03  (v/v)  in
      reagent water.  Prepare a sufficient  quantity to flush the system between
      standards and samples.

            NOTE:  The  ICS  solutions  in Table  2  are  intended  to  evaluate
            corrections for known  interferences on only the analytes in Table 1.
             If Method 6020 is used to determine an element not listed in Table
             1,  it  is  the responsibility  of  the  analyst to  modify the  ICS
            solutions, or prepare  an alternative ICS  solution, to allow adequate
            verification of correction  of interferences on the unlisted element
             (see section 8.4).

      5.6  The interference check solution  (ICS)  is  prepared  to contain known
concentrations of interfering  elements that will  demonstrate  the magnitude of
interferences and provide an adequate test of any corrections.  Chloride in the
ICS provides a means to evaluate  software  corrections  for  chloride-related
interferences such as 35C1160*  on  51V+ and 40Ar35Cl +  on 75As*.   Iron  is used to
demonstrate  adequate  resolution  of  the spectrometer for  the  determination  of
manganese. Holybdenum serves to indicate  oxide  effects on cadmium isotopes.  The
other components are present to evaluate the ability of the measurement system
to correct for various molecular-ion isobaric interferences. The ICS is used to
verify that  the  interference levels are  corrected  by the data  system  within
quality control limits.

            5.6.1  These solutions must  be  prepared  from ultra-pure reagents.
      They can be obtained commercially or prepared by the following procedure.

                  5.6.1.1   Mixed ICS  solution I  may be  prepared by  adding
            13.903 g A1(N03)3-9H20S  2.498 g CaC03 (dried at 180  C for 1 h before
            weighing), 1.000 g Fe, 1.658 g MgO,  2.305 g Na2C03,  and 1.767  g K2C03
            to 25 ml of reagent water.   Slowly add 40 ml of (1+1) HN03.   After
            dissolution is  complete,  warm the solution to degas.    Cool  and
            dilute to  1,000 ml with  reagent water.


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                  5.6.1.2   Mixed  ICS solution  II  may be  prepared by  slowly
            adding 7.444 g 85 % H3P04, 6.373 g 96% H2S04,  40.024  g  37%  HC1,  and
            10.664 g citric  acid  C607Ha to 100 ml of reagent water.  Dilute to
            1,000 ml with reagent water.

                  5.6.1.3   Mixed ICS  solution  III may be  prepared by  adding
            1.00 ml  each  of  IDO-jug/mL  arsenic,  cadmium,   chromium,  cobalt,
            copper, manganese, nickel, silver, and zinc stock solutions  to about
            50 ml  reagent  water.  Add  2.0 ml  concentrated HN03,  and dilute  to
            100.0 ml with reagent water.

                  5.6.1.4  Working  ICS Solutions

                        5.6.1.4.1   ICS-A  may  be prepared  by adding 10.0 ml  of
                  mixed  ICS  solution  I   (5.7.1.1),  2.0 ml each of IQO-fjg/ml
                  titanium stock solution (5.3.9) and molybdenum  stock  solution
                  (5.3.10),  and  5.0 ml  of  mixed  ICS  solution  II (5.7.1.2).
                  Dilute to  100 ml with reagent water.  ICS solution A must  be
                  prepared fresh weekly.

                        5.6.1.4.2   ICS-AB may be prepared by adding 10.0 ml  of
                  mixed  ICS  solution  I  (5.7.1.1),  2.0 ml each of 100-#g/iL
                  titanium stock solution (5.3.9) and molybdenum  stock  solution
                  (5.3.10),  5.0 ml  of mixed  ICS  solution  II  (5.7.1.2),  and
                  2.0 ml of Mixed ICS solution III  (5.7.1.3).   Dilute to  100  mL
                  with  reagent water.  Although  the  ICS solution  AB  must  be
                  prepared fresh weekly,  the  analyst  should be aware  that  the
                  solution may precipitate silver more quickly.

      5.7  The quality control  standard is the initial calibration verification
solution (ICV), which must be prepared in the same acid matrix as the calibration
standards.  This solution must be an independent standard near the midpoint  of
the  linear range  at  a concentration  other than that  used for instrument
calibration.  An independent standard is defined as a standard composed of  the
analytes from a source different from those used in the  standards  for instrument
calibration.

      5.8  Mass spectrometer tuning solution,   A solution containing  elements
representing all of the mass regions of interest  (for example, 10//g/L of Li,  Co,
In, and Tl) must be  prepared  to verify that the  resolution and mass calibration
of the instrument are within the required specifications (see Section 7.5). This
solution is also used to verify that  the instrument has reached thermal stability
(See Section 7.4).

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   Sample  collection procedures  should  address  the  considerations
described in Chapter Nine of this Manual.
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      6.2  See the introductory material in Chapter Three, Inorganic Analytes,
Sections  3.1,3 for  information  on  sample handling  and preservation.   Only
polyethylene or fluorocarbon {TFE or PFA)  containers  are  recommended for use in
Method 6020.

7.0   PROCEDURE

      7.1  Solubilization and digestion procedures are presented in the Sample
Preparation Methods  (e.g., Methods 3005 - 3051).

      7.2   Initiate  appropriate operating  configuration of  the  instruments
computer according to the instrument manufacturer's instructions.

      7.3  Set up the instrument  with the proper operating parameters according
to the instrument manufacturer's instructions.

      7,4  Operating conditions:   The analyst  should  follow the instructions
provided by the  instrument manufacturer.   Allow  at  least 30  minutes  for the
instrument to equilibrate before analyzing any samples.  This must be verified
by analyzing a tuning solution (Section 5.8)  at least four times with relative
standard deviations of < 5% for the analytes contained in the tuning solution.

            NOTE:  Precautions must  be taken to  protect  the channel  electron
            multiplier from high  ion  currents.  The channel electron multiplier
            suffers from fatigue  after being exposed to high  ion currents.  This
            fatigue  can  last  from several seconds  to hours depending  on the
            extent of exposure.  During this time period, response factors are
            constantly changing, which invalidates the calibration curve, causes
            instability, and invalidates sample analyses.

      7.5  Conduct mass calibration and resolution checks  in the mass regions of
interest.  The mass calibration and resolution parameters are required criteria
which must be  met prior to any  samples being analyzed.  If the mass calibration
differs more than 0.1 amu  from the true value,  then the mass calibration must be
adjusted to the correct value.  The resolution must also be verified to be less
than 0.9 amu full width at 10 percent peak height,

      7.6  Calibrate  the  instrument  for the  analytes of  interest (recommended
isotopes for  the analytes  in  Table  1  are  provided in  Table  3), using the
calibration blank and at least  a single initial  calibration  standard according
to the instrument manufacturer's  procedure.  Flush  the  system with the rinse
blank (5.5.3)  between each standard solution.  Use the average of at leastthree
integrations for both calibration and sample analyses.

      7.7  All masses which  could affect data quality should  be  monitored to
determine potential  effects from matrix components on  the analyte  peaks.   The
recommended isotopes  to be monitored are liste in Table 3.

      7.8   Immediately  after  the  calibration  has  been  established,   the
calibration must  be verified and documented for every  analyte  by the analysis of
the calibration verification solution (Section 5.7).   When measurements exceed

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±, 10% of  the  accepted value,  the analyses  must  be  terminated,  the problem
corrected, the instrument  recalibrated, and the new calibration verified.  Any
samples analyzed under an out-of-control calibration must be reanalyzed.  During
the course of an analytical run, the instrument may be "resloped" or  recalibrated
to  correct  for  instrument  drift.   A  recalibration must  then  be followed
immediately by a new analysis of a CCV and CCB before any  further samples may be
analyzed.

      7.9   Flush  the system  with the rinse  blank solution  (5.5.3)  until the
signal levels return  to the method's  levels of quantitation (usually about 30
seconds) before the analysis  of  each sample (see Section 7.7).   Nebulize each
sample until a steady-state signal is achieved (usually about 30 seconds) prior
to collecting data. Analyze the calibration verification  solution (Section 5.6)
and the calibration blank (Section 5.5.1)  at a frequency  of at  least  once every
10 analytical samples.  Flow-injection systems may be used as  long as they can
meet the performance criteria of  this method.

      7.10   Dilute and reanalyze  samples that are more  concentrated than the
linear range for an analyte (or  species needed for a correction) or measure an
alternate  less-abundant isotope.   The  linearity  at  the alternate  mass must be
confirmed by appropriate calibration (see Sec. 7.6 and 7.8).

      7.11   Calculations:    The  quantitative values  shall   be   reported  in
appropriate units, such as micrograms per liter U/g/L) for aqueous samples and
milligrams per  kilogram (mg/kg) for solid samples.  If  dilutions were performed,
the appropriate corrections must  be applied to the sample values.

            7.11.1  If appropriate, or required, calculate results for solids on
      a dry-weight basis as follows:

                   (1)   A  separate determination of   percent  solids must  be
                        performed.

                   (2)   The concentrations determined  in  the  digest  are to be
                        reported  on the basis of the dry weight of the sample.

                  Concentration  (dry weight)(mg/kg)  =  §-^-f
                                                       W A, «9

                        Where,

                  C = Digest Concentration (mg/L)
                  V = Final volume in liters after sample preparation
                  W = Weight in kg of wet sample

                    =  % Solids
                          100

      Calculations  should  include  appropriate  interference  corrections  (see
      Section 3.2   for  examples),  internal-standard   normalization,  and  the


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      summation of signals at 206, 207,  and 208 m/z for lead  (to compensate for
      any differences  in  the abundances of these isotopes between samples and
      standards),

8.0  QUALITY CONTROL

      8.1  All quality control  data  should be maintained and be available for
easy reference or inspection.

      8.2   Instrument  Detection  Limits  (IDLs)  in #g/L  can be  estimated  by
calculating the average of  the  standard deviations of the three runs on three
non-consecutive days from the analysis  of a reagent blank solution with seven
consecutive measurements per day.   Each  measurement must be performed as though
it were a separate analytical sample (i.e., each measurement must be followed by
a rinse  and/or any other  procedure normally performed between the analysis of
separate samples).   IDLs must be determined at least every three months and kept
with the instrument log book.  Refer to Chapter One for additional guidance.

      8.3  The intensities of all internal standards must be monitored for every
analysis.  When the  intensity of any  internal  standard  fails  to fall between 30
and  120  percent of  the intensity of  that  internal  standard in  the  initial
calibration standard, the following procedure is followed.  The sample must be
diluted fivefold (1+4) and reanalyzed with the addition of appropriate amounts
of  internal  standards.  This procedure must be repeated  until  the internal -
standard intensities  fall within the prescribed window.  The intensity levels of
the internal  standards for the calibration blank  {Section 5.5.1) and instrument
check standard (Section 5.6) must agree within ±  20  percent of  the intensity
level of the  internal standard of the original calibration solution.  If they do
not agree,  terminate  the analysis, correct the problem,  recalibrate, verify the
new calibration,  and reanalyze the affected samples.

      8.4  To obtain analyte data of known quality, it  is necessary to measure
more than the  analytes  of interest in order to apply corrections or to determine
whether  interference  corrections  are   necessary.   If the  concentrations  of
interference sources  (such as C, Cl, Mo,  Zr, W) are  such that,  at the correction
factor,   the  analyte  is  less  than  the  limit  of   quantification  and  the
concentration  of  interferents  are   insignificant,  then  the  data  may  go
uncorrected.   Note that monitoring the interference  sources does not necessarily
require monitoring  the interferant itself, but that a molecular species may be
monitored to  indicate  the   presence  of  the interferent.    When  correcttion
equations are  used,   all  QC  criteria  must  also be  met.    Extensive QC  for
interference corrections are required at all times.  The monitored masses must
include those elements  whose hydrogen,  oxygen,  hydroxyl,  chlorine,  nitrogen,
carbon  and  sulfur  molecular  ions  could  impact  the  analytes  of  interest.
Unsuspected interferences may be detected by adding  pure major matrix components
to a sample  to observe  any impact  on the analyte signals.  When an interference
source is present, the  sample elements impacted must be flagged to indicate (a)
the percentage interference  correction applied to the data or  (b) an uncorrected
interference by virtue  of the  elemental equation used  for quantitation.   The
isotope proportions for an element or molecular-ion cluster provide information
useful  for quality  assurance.

                                   6020-10                       Revision  0
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      NOTE:  Only isobaric elemental, molecular, and doubly charged Interference
      corrections which use the observed isotopic-response ratios or parent-to-
      oxide ratios (provided an oxide internal  standard  is used as described in
      Section 3.2) for each  instrument system are acceptable  corrections for use
      in Method 6020.

      8.5  Dilution  Test:   If the analyte concentration  is within the linear
dynamic range of the  instrument and sufficiently high (minimally,  a  factor of at
least 100 times greater than  the  concentration in  the reagent blank, refer to
Section 5,5.2), an analysis  of a fivefold (1+4}  dilution  must agree within ± 10%
of the original determination.  If not, an interference effect must be suspected.
One dilution test  must be  included for each twenty  samples  (or  less) of each
matrix in a batch.

      8.6  Post-Digestion Spike Addition:  An analyte spike added to a portion
of a prepared sample, or its dilution, should be recovered to within 75 to 125
percent of the  known  value or within the  laboratory derived acceptance criteria.
The spike  addition  should  be based on  the  indigenous  concentration  of  each
element of interest  in the  sample.   If the spike  is  not  recovered within the
specified limits,  the sample must be diluted and reanalyzed to compensate for the
matrix effect.   Results must agree to within 10% of the original determination.
The use of a standard-addition analysis procedure  may also be used to compensate
for this effect (Refer to Method 7000).

      8.7  A  Laboratory Control Sample (LCS)  should  be analyzed for each analyte
using the  same sample preparations,  analytical  methods  and  QA/QC  procedures
employed for  the test samples. One LCS should be prepared  and analyzed for each
sample batch  at a frequency of one LCS for each 20  samples or less.

      8.8  Check  the instrument calibration by analyzing appropriate quality
control  solutions as follows:

            8.8.1  Check  instrument  calibration  using   a  calibration  blank
      (Section  5.5.1)   and  the  initial  calibration  verification  solution
      (Sections 5.7 and 7.9).

           8.8.2  Verify  calibration at a  frequency of every  10  analytical
      samples  with  the  instrument  check  standard  (Section  5.6)  and  the
      calibration blank (Section  5.5.1).  These solutions must also be analyzed
      for each  analyte at  the  beginning of the analysis and after  the  last
      sample.

           8,8.3  The  results of  the initial calibration verification solution
      and the instrument check standard  must agree within ± 10% of the expected
      value.     If  not,  terminate  the   analysis,   correct  the  problem,   and
      recalibrate the instrument.   Any sample analyzed under an out-of-control
      calibration must  be  reanalyzed .                                     '

           8.8.4  The  results  of the calibration  blank  must be less than  3
      times the current IOL  for each element.    If  this is  not the  case,  the
      reason  for the  out-of-control  condition must  be found  and corrected,  and

                                   6020-11                        Revision 0
                                                                  September 1994

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      affected samples must be reanalyzed.  If the laboratory consistently has
      concentrations greater than 3 times the IDL,  the IDL may be  indicative of
      an estimated  IDL and should be re-evaluated.

      8.9    Verify  the  magnitude  of  elemental  and  molecular-ion  isobaric
interferences  and  the  adequacy of  any  corrections  at the  beginning  of  an
analytical run or once every 12 hours, whichever is more frequent.  Do this by
analyzing the interference  check solutions A and AB.  The analyst  should be aware
that precipitation  from solution AB may occur with some elements, specifically
silver. Refer to  Section 3.0  for  a discussion on interferences and  potential
solutions to those  interferences if additional guidance is needed.

      8.10   Analyze one duplicate sample  for  every matrix  in a batch  at  a
frequency of one matrix duplicate for every 20 samples.

            8.10,1   The relative  percent difference  (RPD)  between  duplicate
      determinations must be calculated as follows:

                                ID, -  D2 I
                    RPD =      	     x 100
                               (0,  + D2)/2

            where:

            RPD = relative percent difference.
            D,  « first  sample value.
            D2 = second sample value (duplicate)

      A control  limit  of  20%  RPD  should not  be exceeded for  analyte  values
      greater than 100  times the instrumental detection limit.  If  this limit is
      exceeded, the reason for the  out-of-control  situation  must  be  found and
      corrected, and any samples analyzed during the out-of-control  condition
      must be reanalyzed.

9.0  METHOD PERFORMANCE

      9.1  In an EPA multi-laboratory study, 10 laboratories applied the
IC.-'-MS technique  to both aqueous and  solid  samples.   TABLE 4  summarizes the
method performance data for aqueous samples.   Performance data for  solid samples
is provided in TABLE 5.

10.0  REFERENCES

1. Horlick, 6., et  al., Spectrochim. Acta 40B, 1555 (1985).

2. Gray, A.L., Spectrochim. Acta 40B, 1525 (1985); 41B, 151 (1986).

3. Tan, S.H., and Horlick,  G., Appl. Spectrosc. 40, 445 (1986).

4. Vaughan, M.A., and Horlick, G., Appl. Spectrosc. 40, 434 (1986).


                                   6020-12                        Revision 0
                                                                  September 1994

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5. Holden, N.E.,  "Table of the Isotopes," in Lide, O.R,? Ed.,  CRC Handbook of
Chemistry and Physics,  74th  Ed.,  CRC  Press,  Boca  Raton,  FL,  1993.
6. Hinners, T.A., Heithmar,  E., Rissmann,  E., and Smith,  0.,  Winter Conference
on Plasma Spectrochemistry,  Abstract  THP18;  p.  237, San  Diego,  CA  (1994).
7. Lichte, F.E., et al., Anal. Chem.  59,  1150 (1987).
8. Evans E.H., and Ebdon,  1., J.  Anal. At. Spectrom. 4,  299  (1989).
9. Beauchemin, D., et al., Spectrochim. Acta 42B,  467  (1987).
10. Houk, R.S., Anal. Chem.  58, 97A (1986).
11. Thompson, O.J., and Houk, R.S., Appl.  Spectrosc. 41,  801  (1987).
                                    6020-13                       Revision  0
                                                                  Septaiter 1994

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TABLE 1.  ELEMENTS APPROVED FOR ICP-MS DETERMINATION
            Element                      CAS* #
            Aluminum                   7429-90-5
            Antimony                   7440-36-0
            Arsenic                    7440-38-2
            Barium                     7440-39-3
            Beryllium                  7440-41-7
            Cadmium                    7440-43-9
            Chromium                   7440-47-3
            Cobalt                     7440-48-4
            Copper                     7440-50-8
            Lead                       7439-92-1
            Manganese                  7439-96-5
            Nickel                     7440-02-0
            Silver                     7440-22-4
            Thallium                   7440-28-0
            Zinc                       7440-66-6
                                   6020-14                        Revision 0
                                                                  September 1994

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TABLE 2.  RECOMMENDED INTERFERENCE CHECK SAMPLE COMPONENTS AND CONCENTRATIONS
Solution
component
Al
Ca
Fe
Mg
Na
P
K
S
C
Cl
Mo
Ti
As
Cd
Cr
Co
Cu
Nn
N1
Ag
Zn
Solution A
Concentration (mg/L)
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
200.0
1000.0
2.0
2.0
0.0
0.0
0,0
0.0
0.0
0.0
0.0
0.0
0.0
Solution AB
Concentration (mg/L)
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
200.0
1000.0
2.0
2.0
0.0200
0.0200
0.0200
0.0200
0.0200
0.0200
0.0200
0.0200
0.0200
                                   6020-15                        Revision  0
                                                                  Septenter 1994

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 TABLE 3.   RECOMMENDED  ISOTOPES FOR SELECTED ELEMENTS
Mass                                            Element  of interest


27                                                   AT umi num
121,  123                                             Antimony
75                                                   Arsenic
138,  137, 136, 135,  134                              Barium
9                                                    Beryl 1i urn
209                                                  Bismuth  (IS)
114.  112, 111. 110,  113,  116,  106                    Cadmium
42, 43, 44. 46, 48                                   Calcium  (I)
35, 37, (77, 82)a                                    Chlorine (I)
52, 53. 50, 54                                       Chromium
59                                                   Cobalt
63, 65                                               Copper
165                                                  Hoi mi urn  (IS)
115,  113                                             Indium (IS)
56, 14, 57, 58                                       Iron  (I)
139                                                  Lanthanum  (I)
208, 207, 206, 204                                   Lead
6*77                                                Lithium  (IS)
24, 25, 26                                           Magnesium  (I)
55                                                   Manganese
98, 96, 92, 97, 94,  (108)a                           Molybdenum  (I)
58, 60, 62, 6J.> 64                                   Nickel
38                                                   Potassium  (I)
103                                                  Rhodium  (IS)
45                                                   Scandium (IS)
107, 109                                             Silver
23                                                   Sodium (I)
159                                                  Terbium  (IS)
205. 203                                             Thallium
120, 118                                             Tin (I)
89                                                   Yttrium  (IS)
64, 66, !l> !Z» 70                                   Zinc

      NOTE:  Method 6020 is recommended for only those analytes  listed in Table
1.    Other  elements  are  included  in  this table  because they  are  potential
interferents (labeled I) in the determination of recommended analytes, or because
they are commonly used internal standards (labeled IS).   Isotopes are listed  in
descending order of natural abundance.  The most generally useful  isotopes are
underlined and in  boldface,  although certain matrices  may require the use  of
alternative isotopes. a These masses are also useful  for  interference correction
(Section 3.2).  b Internal standard must be enriched in the 6Li  isotope.  This
minimizes interference from indigenous lithium.
                                    6020-16                        Revision  0
                                                                   September 1994

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TABLE  4,
SOLUTIONS
ICP-MS MULTI-LABORATORY  PRECISION AND  ACCURACY DATA  FOR AQUEOUS
Element
Comparability8
Range
%RSD
Range
Nb Sc
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
        95  -  100
           d
        97  -  114
        91  -  99
       103  -  107
        98  -  102
        99  -  107
        95  -  105
       101  -  104
        85  -  101
        91  -  900
        71  -  137
        98  -  102
        95  -  101
        98  -  101
       101  -  114
       102  -  107
       104  -  105
        82  -  104
        88  -  97
       107  -  142
        93  -  102
 11 - 14
5.0 - 7.6
7.1 - 48
4.3 - 9.0
8,6 - 14
4.6 - 7.2
5.7 - 23
 13 - 27
8.2 - 8.5
6.1 - 27
 11 - 150
 11
 10
8.8
6.1
23
15
15
6.7
9.9 - 19
 15 - 25
5.2 - 7.7
 24 - 43
9.7 - 12
 23 - 68
6.8 - 17
14 - 14
16 - 16
12 - 14
16 - 16
13 - 14
18 - 20
17 - 18
16 - 18
18 - 18
17 - 18
10 - 12
17 - 18
16 - 16
18 - 18
18 - 18
11 - 12
12 - 12
13 - 16
 9 - 10
18 - 18
 8 - 13
16 - 18
4
3
4
5
3
3
5
4
3
5
5
6
5
4
2
5
3
2
5
3
3
a Comparability refers to the percent agreement of mean ICP-MS values to those
of  the reference  technique.   b  N  is  the  range of  the  number  of  ICP-MS
measurements where the analyte values  exceed the limit of quantitation  (3.3 times
the average IOL value).      c S is the number of samples with results greater
than the  limit of quantitation.   d  No comparability values  are  provided for
antimony  because  of evidence  that  the reference  data  is  affected  by  an
interference.
                                   6020-17
                                                      Revision  0
                                                      September 1994

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TABLE 5.  ICP-MS HULTI-LABORATORY  PRECISION AND ACCURACY DATA FOR SOLID MATRICES
Element
Comparability3
Range
%RSD
Range Nb
Sc
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thai1i urn
Vanadium
Zinc
 83 - 101
    d
 79 - 102
100 - 102
 50 - 87
 93 - 100
 95 - 109
 77 - 98
 43 - 102
 90 - 109
 87 - 99
 90 - 104
 89 - 111
 80 - 108
 87 - 117
 97 - 137
   81
 43 - 112
100 - 146
   91
 83 - 147
 84 - 124
 11 - 39
 12 - 21
 12 - 23
4.3 - 17
 19 - 34
6.2 - 25
4.1 - 27
 11 - 32
 15 - 30
9.0 - 25
6.7 - 21
5.9 - 28
7.6 - 37
 11 - 40
9.2 - 29
 11 - 62
   39
 12 - 33
 14 - 77
   33
 20 - 70
 14 - 42
13 - 14
15 - 16
16 - 16
15 - 16
12 - 14
19 - 20
15 - 17
17 - 18
17 - 18
18 - 18
12 - 12
15 - 18
15 - 16
16 - 18
16 - 18
10 - 12
  12
15 - 15
 8 - 10
  18
 6 - 14
18 - 18
7
2
7
7
5
5
7
7
6
7
7
7
7
7
7
5
1
3
5
1
7
7
a Comparability refers to the percent agreement of mean ICP-MS values to those
of  the reference  technique.      N  is  the  range of  the  number  of  ICP-MS
measurements where the analyte values exceed the limit of quantitation (3,3 times
the average IDL value).      c S is the number of samples with results greater
than the  limit  of quantitation.   d No comparability values  are  provided for
antimony  because  of  evidence  that  the  reference  data  is  affected  by  an
interference.
                                    6020-18
                                               Revision  0
                                               September 1994

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                  HETHOD 6020
INDUCTIVELY COUPLED PLASMA  - HASS  SPECTROMETRY
7,1 Ainlyi.
by M*tko«
Method 6010,
«ll,_ni

7.1 Un
M«iwd aoto.
                   6020-19
Revision  0
September 1994

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                                 METHOD 7060A

                ARSENIC  (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
 1.0  SCOPE AND APPLICATION

      1.1   Method  7060  Is  an  atomic  absorption  procedure  approved  for
 determining the concentration of arsenic in wastes,  mobility procedure extracts,
 soils,  and  ground  water.   All  samples  must  be  subjected to  an appropriate
 dissolution step prior to analysis.

 2.0  SUMMARY OF METHOD

      2.1   Prior to analysis by Method 7060,  samples must  be prepared  in order
 to  convert  organic forms of  arsenic  to  inorganic forms,  to  minimize organic
 interferences, and  to convert the  sample  to  a suitable solution for analysis.
 The sample preparation procedure varies depending on the sample matrix.  Aqueous
 samples are subjected to the acid digestion procedure described  in this method.
 Sludge samples are  prepared using the procedure described  in Method 3050.

      2.2  Following the appropriate dissolution of the sample, a representative
 aliquot of the digestate is  spiked  with a nickel nitrate solution and is placed
manually or by means of  an automatic sampler  into a graphite tube furnace.  The
 sample  aliquot  is  then  slowly evaporated  to dryness,  charred  (ashed),  and
 atomized.  The absorption of hollow cathode or  EDL radiation during atomization
will be proportional to  the  arsenic concentration.  Other modifiers may be used
 in  place  of  nickel  nitrate  if   the analyst  documents the  chemical  and
concentration used.

      2.3   The typical  detection limit for water samples using this method is
 1 ug/L.  This detection limit may not be achievable when  analyzing waste samples.

3.0  INTERFERENCES

      3.1   Elemental  arsenic and many of its  compounds  are  volatile; therefore,
samples may be subject to losses of arsenic  during  sample  preparation.  Spike
samples  and  relevant  standard  reference  materials  should  be processed  to
determine if the chosen  dissolution method is appropriate.

      3.2   Likewise,   caution  must  be   employed  during  the  selection  of
temperature and times  for the  dry and char (ash) cycles.  A  matrix modifier such
as nickel  nitrate  must be added to all  digestates prior to  analysis to minimize
volatilization losses during drying and ashing.

      3.3   In addition  to the normal interferences experienced during graphite
furnace analysis, arsenic analysis can suffer  from severe nonspecific absorption
and light scattering caused by  matrix  components during  atomization.   Arsenic
analysis  is  particularly susceptible  to these  problems  because  of  its  low
analytical wavelength (193.7  nm).   Simultaneous background correction must be
employed to  avoid  erroneously  high results.   Aluminum  is a  severe  positive
interferent in  the analysis  of arsenic, especially  using D2  arc  background


                                   7060A  - 1                       Revision 1
                                                                  September 1994
                                      \

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 correction.   Although  Zeeman background  correction  is  very useful  in this
 situation, use of any appropriate background correction technique  is  acceptable.

      3.4    If the  analyte  is not  completely volatilized and removed from  the
 furnace during  atomization,  memory effects will occur.   If this situation  is
 detected by  means of blank  burns,  the tube should be cleaned by operating  the
 furnace at full power at regular intervals in the analytical scheme.

 4.0  APPARATUS AND  MATERIALS

      4.1    Griffin  beaker or equivalent:  250 ml.

      4.2    Class A  Volumetric flasks:  10-mL.

      4.3    Atomic absorption spectrophotometer:  Single or dual channel, single-
 or  double-beam instrument  having  a  grating monochromator,  photo-multiplier
 detector, adjustable slits,  a wavelength range of 190 to 800 nm, and provisions
 for simultaneous background correction and interfacing with a suitable recording
 device.

      4,4    Arsenic hollow cathode lamp, or electrodeless discharge  lamp  (EDL):
 EDLs provide better  sensitivity for arsenic analysis.

      4.5    Graphite furnace:  Any  graphite furnace device with the appropriate
 temperature  and timing controls.

      4.6   Data  systems  recorder:   A recorder  is   strongly recommended for
 furnace work so that there will be a permanent record and so that any problems
with the analysis  such as drift, incomplete atomization, losses during charring,
 changes in sensitivity, etc., can easily be recognized.

      4.7    Pipets:   Microliter with disposable tips.  Sizes can range from
 5 to 1,000 uL, as required.

 5.0  REAGENTS

      5.1   Reagent water:   Water should be monitored for impurities.
All references to water will refer to reagent water.

      5.2   Concentrated nitric acid: Acid should be analyzed to determine levels
of impurities.  If a method  blank using  the acid is 
-------
      5.5   Nickel nitrate solution (5%):  Dissolve 24.780 g of ACS reagent grade
Ni(N03)2"6H20 or equivalent in reagent water and dilute to 100 ml.

      5.6   Nickel nitrate solution (1%):   Dilute 20 ml of the 5% nickel nitrate
to 100 ml with reagent water.

      5.7   Arsenic working standards:  Prepare dilutions of  the stock solution
to be  used as calibration  standards at the  time  of the  analysis.   Withdraw
appropriate aliquots of the stock solution, add concentrated  HN03, 30% H202, and
5% nickel nitrate solution or other appropriate matrix modifier.  Amounts added
should be representative of the concentrations found  in  the samples.  Dilute to
100 ml with reagent water.

6.0  SAMPLE COLLECTION, PRESERVATION, AND  HANDLING

      6.1   All  samples  must have  been  collected  using a sampling  plan that
addresses the considerations discussed in  Chapter Nine of this manual.

      6.2   All sample containers must be prewashed with  detergents, acids, and
reagent water.  Plastic and glass containers are both suitable.

      6.3   Special  containers   (e.g.,  containers  used  for  volatile  organic
analysis) may  have to be  used  if  very volatile  arsenic compounds are  to  be
analyzed.

      6.4   Aqueous samples must be acidified to a pH of <2 with nitric acid and
refrigerated prior to analysis.

      6.5   Although waste samples do not need to be refrigerated sample handling
and storage must comply with the  minimum requirements established in Chapter One.

7.0  PROCEDURE

      7.1   Sample preparation:  Aqueous samples should be prepared in the manner
described in  Paragraphs  7.1.1-7.1.3.   Sludge-type samples should  be  prepared
according to  Method 3050A.   The  applicability of a sample-preparation technique
to a new matrix  type must be demonstrated  by  analyzing  spiked samples  and/or
relevant standard reference materials.

            7.1.1    Transfer a  known volume of well-mixed sample  to  a  250-mL
      Griffin  beaker or  equivalent;  add   2  mL  of  30% H202  and  sufficient
      concentrated HN03 to result in an acid concentration of 1% (v/v).   Heat,
      until  digestion is complete,  at 95°C  or until the volume is slightly less
      than 50 mL.

            7.1.2   Cool, transfer to a volumetric flask, and bring back to  50
      mL with reagent water.

            7.1.3   Pipet 5 mL of this digested solution  into  a 10-mL volumetric
      flask,  add 1 mL  of the 1% nickel nitrate solution or  other appropriate
      matrix  modifier, and dilute to  10 mL with reagent  water.   The  sample  is
      now ready for injection into the furnace.


                                   7060A -  3                      Revision 1
                                                                  September 1994

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      7.2   The 193.7-nm wavelength line and a background correction  system are
required.  Follow the manufacturer's suggestions for all other spectrophotoraeter
parameters.

      7.3   Furnace  parameters suggested by the manufacturer should be employed
as  guidelines.     Because  temperature-sensing  mechanisms  and  temperature
controllers can  vary between  instruments or  with  time, the validity  of the
furnace parameters must  be  periodically confirmed by systematically altering the
furnace parameters while analyzing a standard.  In this manner,  losses  of analyte
due to overly  high temperature settings or losses in sensitivity due to less than
optimum settings  can be minimized.  Similar verification of furnace  parameters
may be required for  complex sample matrices.

      7.4   Inject a measured microliter aliquot of sample into the furnace and
atomize.  If the  concentration found is greater than the highest  standard, the
sample should  be  diluted in the same acid matrix  and reanalyzed.  The use of
multiple  injections  can  improve  accuracy and help detect furnace  pipetting
errors.

8.0  QUALITY CONTROL

      8.1  Refer to  section 8.0 of Method 7000.

9.0  METHOD PERFORMANCE

      9.1   Precision and accuracy data are available in Method 206.2  of Methods
for Cnemical Analysis of Water and Wastes.

      9.2  The optimal  concentration range for aqueous samples using this method
is 5-100  ug/L.   Concentration ranges  for non-aqueous samples will  vary with
matrix type.

      9.3   The data shown  in Table  1 were  obtained  from records of state and
contractor laboratories.   The  data  are intended to  show the  precision  of the
combined sample preparation and analysis method.

10.0  REFERENCES

1.    Methods   for Chemical Analysis  of  Water and  Wastes,  EPA-600/4-82-055,
December 1982, Method 206.2.

2.    Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2,  EPA Contract No.  68-01-7075, September  1986.
                                   7060A  - 4                       Revision 1
                                                                  September 1994
                                                        \

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                       TABLE  1. METHOD  PERFORMANCE  DATA
Sample                      Preparation                 Laboratory
Matrix                        Method                    Replicates
Contaminated soil               3050                  2.0,  1.8  ug/g

Oily soil                       3050                  3.3,  3.8  ug/g

NBS SRM 1646 Estuarine sediment 3050                  8.1,  8.33 ug/ga

Emission control dust           3050                  430,  350  ug/g


aBias of -30 and -28% from expected, respectively.
                                  7060A  - 5                       Revision  1
                                                                  Septenfcer 1994

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                          METHOD 7060A
       ARSENIC (ATOMIC ABSORPTION,  FURNACE  TECHNIQUE)
7.1.1 Tran.f.r
   • upli to
baakic.arfd H«0,
mat ease. HHO.,
 7 . 1 Pr«pmr<
accord ing te
M*thod 3050
                            7060A  -  6
                             Revision  1
                             Septenter 1994

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                                 METHOD 7062

       ANTIMONY AND ARSENIC  (ATOMIC ABSORPTION.  BOROHYDRIDE REDUCTION)


 1,0  SCOPE AND APPLICATION

      1,1  Method 7062 1s an atomic absorption procedure for determining  1
 to 400//g/L concentrations of antimony and arsenic in  wastes, mobility procedure
 extracts, soils, and ground water.   Method 7062 is  approved  for sample matrices
 that contain up to  a total of 4000 mg/L concentrations of cobalt, copper, iron,
 mercury, or  nickel.   A  solid  sample can  contain  up to 40% by  weight  of the
 interferents  before  exceeding 4000  mg/L  in  a digested sample.   All  samples
 including aqueous matrices must be  subjected to an  appropriate dissolution step
 prior to analysis. Spiked samples and relevant standard reference materials are
 used to determine the applicability of the method  to a given waste.

 2.0  SUMMARY OF METHOD

      2.1  Samples are prepared according to the nitric add  digestion procedure
 described  in   Method   3010  for   aqueous   and  extract  samples   and  the
 nitric/peroxide/hydrochloric acid digestion procedure described in Method 3050
 (furnace AA  option) for sediments,  soils,  and  sludges.   Excess  peroxide  is
 removed by evaporating   samples to  near dryness at  the end of  the digestion
 followed by degassing the  samples  upon addition of  urea.   L-cysteine is then
 added as a masking  agent.    Next,  the  antimony and arsenic in  the digest are
 reduced to the trivalent  forms with  potassium iodide.  The trivalent  antimony and
 arsenic are then converted to volatile hydrides using  hydrogen produced from the
 reaction of the acidified sample with  sodium borohydride in a continuous-flow
 hydride generator.

      2.2  The  volatile  hydrides are  swept into,  and decompose in,  a  heated
 quartz  cell   located   in   the   optical   path   of  an   atomic   absorption
 spectrophotometer.    The  resulting  absorption  of  the  lamp  radiation  is
proportional  to the arsenic or antimony concentration.

      2.3  The typical  detection limit for this method is 1.0 fjg/L.

3.0  INTERFERENCES

      3.1    Very  high  (>4000 mg/L)  concentrations  of cobalt,   copper,  iron,
mercury, and  nickel  can cause analytical interferences through precipitation as
reduced metals and associated blockage of transfer lines and fittings.

      3.2   Traces of peroxides left following the sample work-up can result in
analytical  interferences. Peroxides must  be removed by evaporating each sample
to near dryness  followed  by  reaction with  urea  and  allowing sufficient time for
degassing  before analysis (see Sections 7.1 and 7.2).
                                    7062-1                        Revision 0
                                                                  September 1994

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      3.3   Even after  acid  digestion,  organic compounds  will  remain  in  the
sap  "•.    These  flame  gases  and  these organic  compounds can  absorb  at  the
ant   ical wavelengths and background correction must be used.

4.0  APPARATUS AND MATERIALS

      4.1  Electric  hot  plate:   Large enough to hold at least  several  100 mL
Pyrex digestion beakers.

      4.2   A  continuous-flow hydride  generator:    A commercially  available
continuous-flow  sodium  borohydride/HCl  hydride   generator   or  a  generator
constructed similarly to that shown in  Figure 1 (P. S. Analytical or equivalent).

            4.2,1  Peristaltic Pump: A four-channel, variable-speed peristaltic
      pump to permit regulation of liquid-stream flow rates (Ismatec Reglo-100
      or equivalent).   Pump  speed and tubing diameters should  be  adjusted to
      provide  the  following  flow rates:    sample/blank  flow  =  4.2  ml/min;
      borohydride flow =2.1 mL/min;  and potassium  iodide  flow = 0.5 mL/min.

            4.2.2  Sampling Valve  (optional):    A sampling valve (found in  the
      P. S.  Analytical  Hydride Generation System  or equivalent) that  allows
      switching between  samples and blanks  (rinse solution) without introduction
      of air into the system will  provide  more signal  stability.

            4.2.3  Transfer Tubing and Connectors:   Transfer tubing (1 mm I.D.),
      mixing T's, and connectors are made of a  fluorocarbon (PFA or TFM) and  are
      of compatible  sizes  to form  tight,  leak-proof  connections  (Latchat,
      Technicon, etc. flow injection  apparatus accessories  or equivalent).

            4.2.4  Mixing Coil:  A 20-turn  coil made by wrapping transfer tubing
      around a 1-cm diameter by 5-cm  long  plastic or  glass  rod (see Figure  1).

            4.2.5  Mixing  Coil  Heater,  if appropriate:   A  250-mL  Erlenmeyer
      flask containing 100 ml of  water  heated to  boiling on a  dedicatee one-
      beaker hotplate (Corning PC-35 or  equivalent).   The mixing coil  in 4.2.4
      is immersed in  the boiling water to speed kinetics of the hydride forming
      reactions  and  increase   solubility   of   interfering  reduced   metal
      precipitat

            4.2.6  Gas-Liquid Separator:   A glass apparatus for  collecting  and
      separating liquid  and gaseous  products (P.T.   Analytical  accessory  or
      equivalent) which allows the liquid fraction to drain to waste and gaseous
      products above  the liquid  to be  swept by a regulated  carrier  gas (argon)
      out of the cell for analysis.  To avoid undue carrier  gas dilution,  the
      gas volume above the  liquid  should not exceed 20 mL.   See Figure 1  for an
      acceptable separator  shape.

            4.2.7  Condenser:  Moisture picked up  by the carrier gas must  be
      removed before encountering  the  hot  absorbance cell.   The moist carrier
      gas with the  hydrides is dried by passing the gasses through a small (< 25

                                   7062-2                       Revision  0
                                                                 September 1994

-------
      ml) volume condenser coil (Ace Glass Model  6020-02  or equivalent) that is
      cooled to 5°C by a water chiller (Neslab RTE-110 or equivalent).  Cool tap-
      water in place of a chiller is acceptable.

            4.2.8  Flow Meter/Regulator:  A meter capable of  regulating up to 1
      L/min of argon carrier gas is recommended.

      4.3  Absorbance Cell:  A  17 cm or longer quartz tube T-cell  {windowless is
strongly suggested)  is recommended,  as  shown  in  Figure 1 (Varian Model  V6A-76
accessory or equivalent).   The cell  is  held in place by a  holder that positions
the  cell  about 1  cm over  a  conventional AA air-acetylene  burner head.   In
operation, the cell  is heated  to around 900°C.

      4.4  Atomic  absorption spectrophotometer:  Single or dual channel, single-
or  double-beam instrument  having  a  grating  monochrotnator,  photomultiplier
detector, adjustable slits,  a wavelength range of 190 to 800 nm» and provisions
for interfacing with  an appropriate recording device.

      4.5  Burner:  As recommended by the particular  instrument manufacturer for
an air-acetylene flame.  An  appropriate  mounting  bracket  attached to the burner
that suspends  the quartz absorbance cell  between 1 and 2 cm above the burner slot
is required.

      4.6  Antimony  and  arsenic hollow cathode  lamps  or antimony  and arsenic
electrodeless discharge lamps  and power supply.   Super-charged hollow-cathode
lamps or EDL lamps are recommended for maximum sensitivity.

      4.7    Strip-chart  recorder  (optional):         Connect  to  output  of
spectrophotometer.

5.0  REAGENTS

      5.1  Reagent water:   Water must be monitored  for  impurities.   Refer to
Chapter 1 for definition of Reagent water.

      5.2  Concentrated  nitric acid  (HN03):  Acid must be  analyzed to determine
levels of impurities.  If a method blank is 
-------
                                  QUARTZ CELL


                                  * ft  OUR HE ft
                                                                        TO
                                                                      CHlLLEft
                                                    CONDENSER—-»
                                                       MIXING
                                                        TCE*
                                                                •ftSSLIQUID
                                                                 SEPARATOR
   iMBlSCONHtCTCOl
   I OURINO  S«'tA I
  VALUE
(SAHPLIHO)
                          THERMOHfTER
                                                                 >_—* OR«IM
                         20 TORM COIL
                           (TEPLON)
                           «*!.*•
                          CtLANN}
Figure 1.  Continuous-flow sodium borohydride/hydride generator apparatus set-up
and an AAS sample introduction  system.
                                     7052-4
                                  Revision 0
                                  Septarber 1994


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      5.6  Urea (H2NCONH2):  A 5.00-g portion of reagent grade urea must be added
to  a 25-mL  aliquot of  each sample  for  removal  of excess  peroxide  through
degassing  (see Section 7,2),

      5.7  L-cysteine (C6H12N204S2):  A 1.00-g portion of reagent  grade  L-cystine
must  be  added to a  25-mL aliquot of  each sample for  masking  the effects  of
suppressing transition metals (see Section  7.2).

      5.8  20% Potassium iodide (1(1):  A 20% KI  solution (20 g reagent-grade  KI
dissolved  and brought to  volume  in  100 ml reagent water) must  be prepared for
reduction  of antimony and arsenic to their  +3 valence states.

      5.9  4% Sodium borohydride (NaBH4):   A 4%  sodium borohydride solution (20
g reagent-grade NaBH4 plus 2 g sodium hydroxide dissolved in 500 ml of  reagent
water) must  be  prepared for conversion  of the  antimony  and  arsenic  to  their
hydrides,

      5.10 Analyte solutions:

            5.10.1  Antimony and arsenic stock standard solution (1,000 mg/L):
      Either procure certified aqueous standards from a supplier and verify  by
      comparison  with  a  second  standard,  or  dissolve  1.197  g  of  antimony
      trioxide Sb203  and  1.320 g  of  arsenic trioxide  As203 in 100 ml of reagent
      water containing 4 g NaOH.  Acidify the solution with 20 ml concentrated
      HN03 and dilute to 1 liter.

            5.10,2   Intermediate antimony  and  arsenic  solution:   Pi pet  1  ml
      stock antimony and  arsenic solution  into a  100-mL  volumetric flask and
      bring  to  volume  with  reagent  water  containing  1.5  ml  concentrated
      HNOg/liter (1  ml  = 10 //g each  of  Sb  and As).

            5.10.3   Standard  antimony and arsenic solution:    Pi pet  10  ml
      intermediate antimony and  arsenic solution  into a  100-mL volumetric  flask
      and  bring to  volume with  reagent  water containing 1.5  mL concentrated
      HNO-j/liter (1  ml  - 1 #g each of Sb  and As).

6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1  All  samples must have been collected  using a  sampling  plan that
addresses the considerations discussed in Chapter Nine of this manual,

      6.2  All  sample containers must be prewashed with detergents, acids, and
reagent  water.  Plastic and glass containers are both suitable.

      6.3   Special   containers   (e.g.,  containers used  for volatile  organic
analysis) may have to be used if very volatile antimony and  arsenic compounds are
suspected to  be  present in the  samples.

      6.4  Aqueous samples must  be acidified to  a pH of <2 with nitric acid.

                                    7062-5                        Revision 0
                                                                  September 1994

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       6.5  Nonaqueous samples shall  be refrigerated, when possible, and analyzed
 as  soon  as  possible.

 7.0  PROCEDURE

       7.1   Place a 100-mL portion of an aqueous sample or extract or 1.000 g  of
 a dried  solid sample  in  a  250-mL  digestion  beaker.   Digest  aqueous  samples and
 extracts according to Method 3010.  Digest solid samples according to Method 3050
 {furnace M option) with the following modifications:  add 5 ml of concentrated
 hydrochloric  acid  just  prior  to the final  volume reduction  stage to aid  in
 antimony recovery; the final volume  reduction should be to less  than  5 ml but not
 to  dryness  to adequately  remove  excess hydrogen  peroxide  (see note).   After
 dilution to volume, further dilution with diluent  may be  necessary  if analytes
 are known to exceed 400 f/g/L or if interferents are expected to exceed 4000 mg/L
 in  the digestate.

            Note:  For solid digestions, the volume reduction stage  is critical
            to obtain  accurate data, especially for  arsenic.   Close monitoring
            of each sample  is  necessary when this  critical  stage  is reached.

       7,2   Prepare samples for hydride analysis by  adding 5.00 g urea, 1.00 g  L-
 cysteine, and 20 ml concentrated HC1 to a 25-mL aliquot of digested  sample in a
 50-mL volumetric flask.  Heat in a water bath until  the L-cysteine has dissolved
 and  effervescence  has  subsided   (At   least   30  minutes  is  suggested.     If
 effervescense is still seen, repeat step 7.1  with more volume reduction,}.  Bring
 flask to volume with reagent water before analyzing.   A 1:1  dilution correction
 must be made in the final concentration calculations.

      7.3   Prepare working  standards  from the standard  antimony  and  arsenic
 solution.   Transfer  0, 0.5, -1.0,  1.5,  2.0, and 2.5 mL  of standard  to 100-mL
 volumetric  flasks and  bring  to volume with  diluent.  These  concentrations  will
 be  0, 5, 10, 15, 20, and 25 fjg  Sb and As/liter.

      7.4   If EP extracts  (Method  1310}  are  being  analyzed for arsenic, the
method  of   standard  additions  must be  used.   Spike  appropriate  amounts  of
 intermediate or standard antimony and arsenic  solution to three 25  ml aliquots
of  each  unknown.   Spiking volumes should be kept  less  than 0.250 ml to  avoid
excessive spiking dilution  errors.

      7.5   Set  up instrumentation  and  hydride generation  apparatus and  fill
 reagent containers.  The sample and  blank flows should be  set around  4.2  mL/min,
the borohydride flow around 2.1 mL/min,  and the potassium iodide flow around 0.5
mL/min.  The argon carrier gas  flow is adjusted  to about 200 mL/min.  For the AA,
use the 217.6-nm wavelength  and 0.7-nm slit width (or manufacturer's  recommended
 slit-width} without background correction  if analyzing  for antimony.   Use the
193.7-nm wavelength and 0.7-nm slit width (or  manufacturer's recommended  slit-
width) with background correction for the analysis  of arsenic.   Begin all  flows
and allow 10 minutes for warm-up.
                                    7062-6                        Revision 0
                                                                  September 1994

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      7,6  Place sample feed line into a prepared sample solution and start pump
to  begin  hydride generation.   Wait  for a maximum  steady-state signal on  the
strip-chart  recorder or output  meter.   Switch to  blank  sample and watch  for
signal to decline to baseline before switching to the next sample and beginning
the next analysis.   Run standards first  (low  to  high), then unknowns.   Include
appropriate QA/QC solutions, as required.  Prepare calioration curves and convert
absorbances to concentration.    If a heating  coil is not being used, KI must be
added to the samples and heated  for thirty minutes  to ensure  reduction.

        CAUTION:  The  hydrides  of  antimony and   arsenic   are  very toxic.
                  Precautions must be taken to avoid inhaling the gas,

      7.7  If the method of standard additions was  employed,  plot the  measured
concentration  of the  spiked samples  and unspiked  sample versus  the spiked
concentrations.  The spiked concentration axis intercept will be the method of
standard additions  concentration.   If the plot  does  not  result in a  straight
line, a  nonlinear  interference is present.   This  problem  can  sometimes be
overcome by dilution or addition of other reagents  if there is some knowledge
about the waste.  If the method of standard additions was  not required,  then  the
concentration is determined from a standard calibration curve.

8.0  QUALITY CONTROL

      8.1  See section 8.0  of Method 7000.

9.0  METHOD PERFORMANCE

      9.1  The relative standard deviations obtained by a single laboratory  for
7 replicates  of a contaminated soil were 18% for antimony at 9.1 ug/L  in  solution
and 4.6% for  arsenic at 68 ug/L in solution.  The average percent recovery of  the
analysis of an 8 jjg/L spike on ten different samples  is 103.7% for arsenic and
95.6% for antimony.

10.0  REFERENCES

1.    Methods  for  Chemical  Analysis  of  Water  and  Wastes,  EPA-60Q/4-82r055,
      December 1982, Method 206.3.

2.    "Evaluation of Hydride  Atomic Absorption Methods  for Antimony, Arsenic,
      Selenium, and Tin",  an EMSL-LV internal  report  under Contract 68-03-3249,
      Job Order  70.16,  prepared for T.  A,  Hinners  by  D.  E.  Dobb,  and J,  D.
      Lindner of Lockheed Engineering  and Sciences Co.,  and L. V. Beach of the
      Varian  Corporation.
                                    7062-7                        Revision 0
                                                                  September 1994
                                          \

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                                    METHOD 7062
ANTIHONY AND  ARSENIC  (ATOMIC  ABSORPTION,  BORQHYDRIDE  REDUCTION)
 7.1 Use Method
3050 (furnace A A
option) to digest
  1.0 g sample.
                                                                   7.1 U*B
                                                                Method 3O10
                                                                to dig«*I 100
                                                                 ml »amplo.
         7.1 Add
        o nc»ntret»d
          HCI.
       7.1  Do final
         volume
       reduction end
       dilution, ec
        described.
            Vee
        7.1 Fyrthir
        dilute with
         diluent.
                                7.2 Add to
                                aliquot urea;
                               L-cysteine, HCI:
                               heat H2O bath;
                               bring to volume.
                                 7.3 Prepare
                               standards from
                               •tindard (tock
                               solutions ot Sb
                                  and As.
                                                                 7.4 Use the
                                                                  method of
                                                                   etandard
                                                                addition* on EP
                                                                extracts, only.
                              7.B - 7.6 Analyze
                                 the sample
                                mine hydride
                                 gene ration
                                 apparatug.
7.E -7.8 Analyze
  the aampl*
 using hydride
  generation
  appantua.
                                  7.6 • 7.7 Determine
                                   Sb and Ac cane,
                                    from ttandtrd
                                     calibration
                                       curve.
                                                             7.7 Determine
                                                               Sb and As
                                                             concentrations
                                                             by Method of
                                                           Standard Additions,
                                       Stop
                                        7062-8
                                                                             Revision  0
                                                                             Septarter 1994

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                                 METHOD 7080A
                 BARIUH (ATOMIC ABSORPTION,  DIRECT ASPIRATION)

1.0  SCOPE AND APPLICATION
      1.1   See Section 1.0 of Method 7000.
2,0  SUMMARY OF METHOD
      2.1   See Section 2.0 of Method 7000.
3.0  INTERFERENCES
      3.1   See Section 3.0 of Method 7000 if interferences are suspected.
      3.2   High hollow cathode current settings and a narrow spectral band pass
must  be used,  because  both   barium  and  calcium emit  strongly  at  barium's
analytical wavelength.
      3.3   Barium  undergoes   significant  ionization  in  the  nitrous  oxide/
acetylene flame, resulting in a significant decrease in sensitivity.  All
samples and standards must contain a ionization suppressant.  The type of
suppressant and concentration used must be documented.
4.0  APPARATUS AND MATERIALS
      4.1   For basic apparatus, see Section 4.0 of Method 7000.
      4.2   Instrument parameters (general):
            4.2.1  Barium hollow cathode lamp.
            4.2.2  Wavelength:  553.6 nm.
            4.2.3  Fuel:  Acetylene.
            4.2.4  Oxidant:  Nitrous oxide,
            4.2.5  Type of flame:  Fuel  rich.
            4.2.6  Background  correction:   Not required.
5.0  REAGENTS
      5.1   See Section 5.0 of Method 7000.
      5.2   Preparation of standards:
            5.2.1    Stock  solution:     Dissolve  1.7787  g  barium  chloride
      (BaCl2'2H20)  analytical   reagent grade  in  reagent water and  dilute to 1
      liter (1000 mg/L).   Alternatively,  procure a certified standard  front a
      supplier and verify by comparison  with a second standard.
            5.2.2    Prepare  dilutions  of the  stock solution to  be used  as
      calibration standards at the time of analysis.  The calibration standards

                                  7080A - 1                       Revision 1
                                                                  Septenter 1994

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      should  be  prepared  using  the  same  type  of  acid  and  at  the  sane
      concentration  as  will  result  in  the  sample  to  be  analyzed  after
      processing.  All   calibration  standards and samples  should  contain the
      ionization suppressant.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See Chapter Three, Section 3.1.3,  Sample Handling and  Preservation.

7,0   PROCEDURE

      7.1   Sample preparation: The procedures for  preparation of the sample are
given in Chapter Three, Section 3.2.

      7.2   See Method 7000, Section  7.2, Direct Aspiration.

8.0  QUALITY CONTROL

      8.1   See Section 8.0 of Method 7000.

9.0  METHOD PERFORMANCE

      9.1   The performance characteristics for an aqueous sample free of inter-
ferences are:

      Optimum concentration range:  1-20 mg/L with a wavelength of  553.6 nrn.
      Sensitivity:  0.4 mg/L.
      Detection limit:  0.1 mg/L.

      9.2   In a single laboratory, analysis of a mixed  industrial-domestic waste
effluent, digested with Method  3010, at concentrations of 0.4 and 2 mg Ba/L gave
standard deviations  of ±0.043 and  +0.13,  respectively.   Recoveries at  these
levels were 94% and 113%, respectively.

10.0  REFERENCES

1.    Methods  for  Chemical  Analysis  of Water  and Wastes,  EPA-600/4-82-055,
December 198E, Method 208.1.
                                  7080A  -  2                       Revision 1
                                                                  September 1994
                                                                             \

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                   METHOD 7080A
BARIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
            (    Start    ]
               5.2 Prepare
               standard *.
              7.1 For cample
              preparation see
            Chapter 3, Section
                  3.2.
             7.2 Analyze using
               Method 7000
               Section 7,2.
            (     Stop     J
                     7080A - 3
Revision  1
September 1994

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                                 METHOD 7131A
                CADMIUM  (ATOMIC ABSORPTION, FURNACE TECHNIQUE)

1.0  SCOPE AND APPLICATION
      1.1   See Section  1.0 of Method 7000.

2.0  SUMMARY OF METHOD
      2.1   See Section  2.0 of Method 7000.

3.0  INTERFERENCES
      3.1   See Section  3.0 of Method 7000 if interferences are suspected.
      3.2   In addition to the normal interferences experienced during graphite
furnace analysis,  cadmium analysis can suffer from severe nonspecific absorption
and light scattering caused by matrix components during atomization. Simultaneous
background correction 1s required to avoid erroneously high results.
      3.3   Excess  chloride   may  cause  premature  volatilization of  cadmium.
Ammonium  phosphate  used  as   a  matrix  modifier  minimizes this  loss.    Other
modifiers may be used as long as it is documented with the type of suppressant
and concentration.
      3.4   Many plastic pipet  tips  (yellow)  contain cadmium.   Use "cadmium-
free" tips.

4.0  APPARATUS AND MATERIALS
      4.1   For basic apparatus, see Section 4.0 of Method 7000.
      4.2   Instrument parameters (general):
            4.2.1    Drying time  and temp:   30 sec at 125°C.
            4.2.2    Ashing time  and temp:   30 sec at 500°C.
            4.2.3    Atomizing time and temp:  10 sec at 1900°C.
            4.2.4    Purge gas:  Argon.
            4.2.5    Wavelength:   228.8 nm,
            4.2.6    Background correction:  Required.
            4.2.7   Other operating parameters should be set as specified by the
      particular instrument manufacturer.
                                  7131A -  1                       Revision 1
                                                                  September 1994

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            NOTE: The above concentration values and instrument  conditions are
            for a Perkin-Elmer HGA-2100, based on the use  of  a  20-uL  injection,
            continuous-flow purge gas,  and nonpyrolytic graphite.  Smaller sizes
            of furnace  devices  or those employing faster rates  of atomization
            can be  operated using lower atomization  temperatures for  shorter
            tiie periods than the above-recommended settings.


5.0  REAGENTS

      5.1   See Section 5.0 of Method 7000.

      5.2   Preparation of standards:

            5.2.1     Stock  solution:    Dissolve  1.000  g  of  cadmium metal
      (analytical reagent grade) in 20  ml of 1:1 HN03 and dilute to 1  liter with
      reagent  water.    Alternatively,   procure  a  certified  standard  from  a
      supplier and verify by comparison with a second standard.

            5.2.2   Prepare dilutions of the stock cadmium solution  to  be used
      as calibration  standards  at the  time  of analysis.   To each  100 ml of
      standard and sample alike add 2.0 ml of the ammonium phosphate solution.
      The calibration standards should be prepared to contain 0.5% (v/v) HN03.

            5.2.3     Ammonium phosphate  solution (40%);    Dissolve 40  g  of
      ammonium phosphate,  (NH4)2HP04 (analytical reagent grade),  in reagent water
      and dilute to 100 ml,


6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1   See Chapter  Three, Section  3.1.3, Sample Handling and Preservation,


7.0  PROCEDURE

      7.1   Sample preparation:  The procedures  for preparation of the  sample are
provide-:  'n Chapter Three, Section 3.2.

      7;2   See Method 7000, Section 7.3, Furnace Procedure.   The  calculation is
provider   i Method 7000, Section 7.4.


8.0  QUi-,-.TY CONTROL

      8.1   Refer to Section 8.0 of Method 7000 .


9.0  METHOD PERFORMANCE

      9.1   Precision and  accuracy data are available in Method  213.2  of Methods
for Chemical Analysis of Water and Wastes.
                                  7131A  -  2                       Revision 1
                                                                  September 1994

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      9.2   The performance characteristics for an aqueous sample free of  inter-
ferences are:

      Optimum concentration range:  0.5-10 ug/L.
      Detection limit:  0.1 ug/L.

      9.3   The data shown  in Table  1  were obtained from records of state and
contractor laboratories.   The  data are intended to  show the precision of the
combined sample preparation and analysis method.


10.0  REFERENCES

1.    Methods  for  Chemical Analysis  of  Water  and  Wastes,  EPA-600/4-82-055,
December 1982, Method 213.2.

2.    Gaskill, A.,  Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
                                  7131A  - 3                       Revision 1
                                                                  September 1994

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                       TABLE  1.  METHOD  PERFORMANCE DATA
Sample                       Preparation              Laboratory
Matrix                         Method                 Replicates
Lagoon soil                      3050            0.10,  0.095  ug/g

NBS SRM 1646 Estuarine  sediment  3050                   0.35  ug/g"

Solvent extract of oily waste    3030             1.39,  1.09  ug/L



"Bias  of -3% from expected value.
                                   7131A -  4                      Revision 1
                                                                  September 1994
                                                                                   \

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                 METHOD 7131A
CADMIUM  (ATOMIC ABSORPTION,  FURNACE TECHNIQUE)
1
f
5.2 Prepare
standards.
^
f
7. 1 For sample
preparation see
Chapter 3, Saciion
3.2.
^
f
7.2 Analyze using
Method 7000
Section 7.3.
1
f
             I    Stop    J
                  7131A - 5
Revision 1
September 1994

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                                 METHOD 7470A

             MERCURY IN LIQUID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
1.0   SCOPE AND APPLICATION

      1.1   Method 7470 is a cold-vapor atomic absorption procedure approved for
determining the concentration  of mercury in mobility-procedure extracts, aqueous
wastes, and ground waters.  (Method 7470 can  also  be  used for analyzing certain
solid and  sludge-type wastes; however,  Method  7471  is  usually  the method of
choice for these waste types.) All  samples must be subjected to  an  appropriate
dissolution step prior to analysis.

2.0   SUMMARY OF METHOD

      2.1   Prior to analysis, the liquid samples  must  be prepared according to
the procedure discussed in this method.

      2.2   Method 7470, a cold-vapor atomic absorption  technique,  is based on
the absorption of radiation at 253.7-nm by mercury  vapor.  The mercury is reduced
to the elemental  state and aerated from solution in a  closed system.  The mercury
vapor passes through a cell positioned in the light path of an atomic absorption
spectrophotometer.  Absorbance (peak height) is measured as a function of mercury
concentration.

      2.3   The typical detection limit for this method  is 0.0002 mg/L.

3.0   INTERFERENCES

      3.1   Potassium permanganate is added to eliminate possible interference
from sulfide.   Concentrations  as high as 20 mg/L  of sulfide as sodium sulfide do
not interfere with the recovery of added inorganic mercury from reagent water.

      3.2   Copper has also been reported  to  interfere;  however, copper concen-
trations as high as  10 mg/L  had  no effect on recovery of mercury from spiked
samples.

      3.3   Seawaters, brines, and industrial  effluents  high in chlorides require
additional  permanganate (as much  as 25 ml) because, during the oxidation step,
chlorides are converted to free chlorine,  which also  absorbs  radiation of 253.7
nm.  Care must therefore be taken  to ensure that free chlorine is absent before
the mercury is reduced  and  swept  into the cell.  This may be accomplished by
using an excess of hydroxylamine sulfate reagent (2.5 ml).  In  addition, the dead
air space in the BOD bottle must be purged before adding stannous  sulfate.  Both
inorganic and  organic  mercury spikes have been quantitatively  recovered from
seawater by using this technique.

      3.4   Certain volatile organic materials that absorb at this  wavelength may
also cause  interference.  A preliminary run without reagents should determine if
this type of interference is present.
                                  7470A  -  1                       Revision 1
                                                                  September 1994

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4.0   APPARATUS AND MATERIALS

      4.1   Atomic  absorption  spectrophotometer  or  equivalent:    Any atomic
absorption  unit  with  an open  sample presentation area in which  to mount the
absorption cell is suitable.  Instrument settings  recommended  by the particular
manufacturer  should  be  followed.    Instruments designed  specifically  for the
measurement of mercury us~  -2 the cold-vapor technique are commercially available
and may be substituted  for  the  atomic  absorption  speetrophotometer.

      4.2   Mercury hollow  cathode lamp or electrode!ess discharge lamp.

      4.3   Recorder:  Any  multirange variable-speed recorder that  is compatible
with the UV detection system is suitable.

      4.4   Absorption  cell:  Standard spectrophotometer cells 10 cm long with
quartz end windows may be used.  Suitable cells may be constructed from Plexiglas
tubing,  1 in.  O.D.  x  4.5  in.   The ends  are  ground perpendicular  to the
longitudinal axis, and quartz windows (1  in.  diameter x  1/16 in. thickness) are
cemented in place.  The cell is strapped to  a burner  for support and aligned in
the light beam by use of two 2-in.  x 2-in. cards.  One-in.-diameter  holes  are cut
in the middle of  each card.  The cards are then placed over each end of the cell.
The cell is then  positioned  and  adjusted vertically and horizontally to give the
maximum transmittance.

      4.5   Air pump:  Any peristaltic pump capable of delivering 1  liter air/min
may be used.  A Masterflex  pump with  electronic  speed control  has been found to
be satisfactory.

      4.6   Flowmeter:  Capable of measuring an air flow of 1 liter/min.

      4.7   Aeration tubing: A straight glass frit with a coarse porosity. Tygon
tubing is used for passage  of  the mercury vapor from the  sample  bottle to the
absorption cell and return.

      4.8   Drying tube:  6-in.  x  3/4-in.-diameter tube  containing 20 g of mag-
nesium perchlorate or a small reading lamp with 60-W bulb which may be used to
prevent condensation of moisture inside the cell.  The lamp should be positioned
to shine on the absorption cell  so that the air temperature in  the cell is about
10°C  above ambient.

      4     The  cold-vapor  generator  is  assembled  as  shown  in  Figure  1  of
referenc   1  or according  to the  instrument manufacturers  instructions.  The
apparatus shown  in  Figure   1  is a closed system.   An  open system,  where the
mercury vapor  is  passed through  the absorption  cell  only  once,  may  be  used
instead of the closed system.  Because mercury vapor is toxic, precaution must
be taken to avoid its  inhalation.  Therefore,  a  bypass has been included in the
system either to vent the mercury vapor into an exhaust hood or to pass the vapor
through some absorbing medium, such as:

            1.  Equal  volumes of 0.1 M KMn04 and 10% H2S04; or

            2.  0.25% Iodine in a 3% KI solution.


                                  7470A  - 2                       Revision 1
                                                                  September 1994

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      A  specially  treated  charcoal  that  will  adsorb  mercury  vapor  is  also
      available  from Barnebey  and  Cheney,  East 8th  Avenue  and North Cassidy
      Street, Columbus, Ohio  43219,  Cat. #580-13 or #580-22.

      4.10   Hot  plate or  equivalent - Adjustable and capable of maintaining a
temperature  of 90-95°C.

      4.11   Graduated cylinder  or equivalent.

5.0   REAGENTS

      5.1    Reagent Water:    Reagent water  will be  interference free.   All
references to water in this method will  refer to reagent water unless otherwise
specified.

      5.2    Sulfuric  acid (HZS04),  concentrated:  Reagent  grade.

      5.3    Sulfuric  acid, 0.5 N:  Dilute 14.0 ml of concentrated sulfuric acid
to 1.0 liter.

      5.4    Nitric  add (HNQ3}» concentrated:   Reagent  grade  of  low mercury
content.  If a high  reagent blank is obtained,  it may be necessary to distill the
nitric acid.

      5.5    Stannous  sulfate:   Add  25 g  stannous  sulfate to 250  ml  of  0.5 N
H2S04.   This mixture is a suspension and should be stirred continuously during
use.  {Stannous chloride may  be used in place of stannous sulfate.)

      5.6    Sodium  chloride-hydroxylamine sulfate solution:   Dissolve 12 g of
sodium chloride and 12 g of hydroxylamine sulfate in reagent water and dilute to
100 mL.   (Hydroxylamine hydrochloride may  be used in place of hydroxylamine
sulfate.}

      5.7    Potassium permanganate,  mercury-free,  5% solution  (w/v):  Dissolve
5 g of potassium permanganate in 100 ml of reagent water.

      5.8    Potassium persulfate, 5% solution (w/v):   Dissolve 5 g  of potassium
persulfate in 100 ml  of reagent water.

      5.9    Stock mercury solution:  Dissolve 0.1354 g of mercuric chloride in
75 ml of reagent  water.  Add 10 ml of concentrated HN03 and adjust the volume to
100.0 ml (1  ml = 1  mg Hg).  Stock solutions may also be purchased.

      5.10   Mercury working standard:  Make  successive dilutions of the stock
mercury solution to obtain a  working standard containing  0.1 ug per  mL.   This
working standard  and the dilutions of the  stock  mercury solution  should be
prepared fresh daily.  Acidity of the working standard should be maintained at
0.15% nitric acid.  This acid should be  added to the  flask,  as needed,  before
addition of  the aliquot.
                                   7470A  -  3                       Revision 1
                                                                  September 1994

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 6.0    SAMPLE  COLLECTION,  PRESERVATION, AND HANDLING

       6,1   All  samples must have  been  collected using  a sampling plan  that
 addresses the  considerations discussed in Chapter Nine  of this manual.

       6.2   All sample containers must be prewashed  with detergents, acids, and
 reagent water.  Plastic and glass containers are both suitable.

       6.3   Aqueous  samples must  be acidified  to   a  pH  <2  with  HN03.    The
 suggested maximum  holding times for mercury is 28 days.

       6.4   Nonaqueous samples shall be refrigerated,  when possible, and analyzed
 as soon as possible.

 7.0    PROCEDURE

       7.1   Sample preparation:  Transfer  100 mL,  or  an  aliquot  diluted to
 100 mL, containing <1.0 g  of mercury, to a 300-mL BOO bottle or equivalent.   Add
 5 mL of H2S04 and  2.5 mL of  concentrated  HNQ3, mixing after each addition.   Add
 15 mL of potassium permanganate solution  to each  sample  bottle.  Sewage samples
 way require additional permanganate.  Ensure that equal  amounts of permanganate
 are  added  to  standards and  blanks.    Shake  and add  additional  portions of
 potassium permanganate solution, if necessary, until the  purple color persists
 for at least  15 rain.  Add 8 mL of potassium persulfate to  each bottle and  heat
 for 2  hr in  a water bath maintained  at 95°C.   Cool and add 6  mL of sodium
 chloride-hydroxylamlne sulfate to reduce  the excess permanganate.   After a delay
 of at least 30 sec, add 5  n»L of  stannous  sulfate, immediately  attach the bottle
 to the aeration apparatus, and continue as described in Paragraph 7.3.

      7.2   Standard preparation:  Transfer 0-, 0.5-,  1.0-,  2.0-,  5.0-, and 10.0-
 mL aliquots of the mercury working standard, containing  0-1.0  ug of  mercury, to
 a series of 300-mL BOD bottles.  Add enough reagent water to each bottle to  make
 a total volume of 100 raL.  Mix thoroughly and add 5 mL of concentrated H2S04 and
 2.5 raL of concentrated HN03 to each bottle.  Add 15 mL of KMn04 solution to  each
 bottle and allow to stand  at least 15 min.  Add 8 mL of potassium persulfate to
 each bottle and heat for 2 hr  in a water  bath maintained at 95°C,  Cool and add
 6 mL  of sodium chloride-hydroxylamine sulfate  solution to reduce  the excess
 permanganate.  When the solution has been decolorized, wait 30 sec,  add 5 mL of
 the stannous  sulfate solution,  immediately attach the  bottle to  the aeration
 apparatus,  and continue as described in Paragraph 7.3.

      7.3   Analysis:   At this point the  sample is allowed  to  stand  quietly
without manual  agitation.  The circulating pump,  which  has previously   been
 adjusted to  a  rate of  1 liter/min,  is allowed to run  continuously.     The
 absorbance will increase  and  reach  a maximum within 30 sec.   As  soon  as  the
 recorder pen levels off (approximately 1 min), open the bypass valve and continue
the aeration until  the absorbance returns  to its minimum value.  Close the bypass
valve,  remove the  stopper  and frit  from the  BOD   bottle,   and  continue   the
aeration.  Because of instrument  variation refer to the manufacturers  recommended
operating conditions when using this method.
                                   7470A  -  4                       Revision 1
                                                                  September 1994

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      7.4   Construct a calibration curve by plotting the absorbances of stan-
dards versus micrograms of mercury.   Determine  the peak height of the unknown
from the chart and read the mercury value  from the  standard curve.  Duplicates,
spiked samples, and check standards should be routinely analyzed.

      7.5   Calculate  metal   concentrations  (1)  by  the method  of  standard
additions,  or  (2) from a  calibration curve.   All dilution  or concentration
factors must be taken into account. Concentrations  reported for multiphased or
wet samples must be appropriately qualified (e.g., 5 ug/g dry weight).

8.0   QUALITY CONTROL

      8.1  Refer to section 8.0 of Method 7000.

9.0   METHOD PERFORMANCE

      9.1   Precision and accuracy data are available in Method 245.1 of Methods
for Chemical Analysis of Water and Wastes.

10.0  REFERENCES

1.    Methods  for Chemical  Analysis  of  Water  and Wastes,  EPA-600/4-82-055,
December 1982,  Method 245.1.
                                  7470A  - 5                       Revision 1
                                                                  Septenber 1994

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                             METHOD 7470A
HERCURY  IN LIQUID WASTE  (MANUAL  COLD-VAPOR TECHNIQUE)
              Sample Preparation
                   Standard Preparation
  7.1 Tr*nif*r aliquot
  to bottla, add HjSO^
  and HNO& and mix.
                                7,2 Tranafar aliquot
                                 of (ha Hfl working
                                    atandard to
                                      battla.
    7.1  Add KMnO*
      and ahaka.
                                  7.2 Add raagant
                                  water, mix, add
                                    eoncantratad
                               7.1 Add mora
                               parmanganai*
                                if nac*«aary.
          I No
       7.1  Add
      pota**ium
    pftraulfatt, hail
    for 2 Hr>.t cool.
                                   7.2 Add KMn04
                                     pota»aium
                                   paraulfati, haai
                                 for 2 hr». and  cool.
                                   7.2 Add aodium
                                      cltiorid«-
                                    hydroxylanrtino
                                   •ulfat«. wait 30
                                      **condc.
    7.1 Add aodium
       cMorid*-
    hydroxylMnina
    •utfato, wait 30
       •aeonds.
   7.1 Add atannoua
     •ulfata, attach
      to aeration
      apparatui.
 7.3 Analyza
    •ampla.
7.2 Add §1 an no in
 aulfata, atiach
   to aaration
   apparatus.
 7.4 Conatruct
   calibraition
eurva, datarmrna
paak bvight and
   HO valtia.
                                 7.4 Routinaly
                              analvx* dupticant,
                                apikad aamplaa.
                                 7.5 Caleulat*
                                     matal
                                concantration*.
                               |     Stop     J


                              7470A  - 6
                                            Revision  1
                                            Septerber 1994

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                                 METHOD 7471A

       MERCURY IN SOLID OR SEMISOLID WASTE (MANUAL COLD-VAPOR TECHNIQUE)


1.0   SCOPE AND APPLICATION

      I.I   Method  7471  is approved for  measuring  total  mercury (organic and
inorganic) in soils, sediments, bottom deposits,  and sludge-type  materials. All
samples must be subjected to an appropriate dissolution  step  prior to analysis.
If this dissolution procedure  is  not  sufficient  to dissolve a specific matrix
type or sample, then this method is not applicable  for that matrix.

2.0   SUMMARY OF METHOD

      2,1   Prior to analysis,  the solid or semi-solid samples must be prepared
according to the procedures discussed in  this method.

      2.2   Method 7471, a cold-vapor atomic absorption  method, is based on the
absorption of radiation at the 253.7-nm wavelength by mercury vapor.  The mercury
is reduced to the elemental state  and  aerated from solution in a  closed system.
The mercury vapor passes through a cell  positioned in the light path of an atomic
absorption spectrophotometer.  Absorbance  (peak height) is measured as a function
of mercury concentration.

      2.3   The  typical  instrument detection  limit (IDL)  for this  method is
0.0002 mg/L.

3.0   INTERFERENCES

      3.1   Potassium permanganate is added to eliminate possible interference
from sulfide.   Concentrations as high as 20 mg/Kg  of  sulfide,  as sodium sulfide,
do not interfere with  the recovery  of  added inorganic mercury in  reagent water.

      3.2   Copper has also been reported  to interfere; however,  copper concen-
trations as high as 10 mg/Kg had no effect on  recovery  of mercury from spiked
samples,

      3.3   Samples high in chlorides require additional permanganate (as much
as 25 ml) because, during  the  oxidation step,  chlorides are  converted to free
chlorine, which also absorbs radiation of  253 nm.  Care must therefore be taken
to ensure that free chlorine is absent before the mercury is reduced and swept
into the cell.   This  may be accomplished  by using  an excess of hydroxylamine
sulfate reagent (25 ml).   In addition, the dead air space in the BOD bottle must
be purged before adding stannous sulfate.

      3.4   Certain volatile organic materials that absorb at this  wavelength may
also cause interference.  A preliminary run without reagents should determine if
this type of interference is present.

4.0   APPARATUS AND MATERIALS

      4.1   Atomic  absorption  spectrophotometer  or equivalent:   Any  atomic
absorption unit  with  an open sample  presentation area  in which to  mount the

                                   7471A - 1                       Revision 1
                                                                  September 1994

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 absorption cell is suitable.  Instrument settings recommended by the particular
 manufacturer  should be  followed.   Instruments  designed  specifically for  the
 measurement of mercury using the cold-vapor technique are commercially available
 and lay  be substituted  for  the  atomic  absorption spectrophotometer.

      4.2   Mercury  hollow  cathode  lamp  or electrodeless discharge  lamp.

      4.3   Recorder:  Any multirange variable-speed recorder that is compatible
 with the UV detection system is suitable.

      4.4   Absorption  cell:  Standard spectrophotometer cells  10 cm long with
 quartz end windows may be used.  Suitable  cells may be constructed from Plexiglas
 tubing,  1  in.  O.D.  x   4.5  in.   The  ends  are  ground perpendicular  to   the
 longitudinal axis, and quartz windows (1  in.  diameter x 1/16  in.  thickness)  are
 cemented in place.  The cell is strapped  to a burner  for support and  aligned in
 the light beam by  use of two 2-in. x  2-in. cards.  One-in,-diameter holes are  cut
 in the middle of each card.  The cards are then placed over each end of the cell.
 The cell is then positioned  and  adjusted vertically and horizontally to give  the
 maximum transmittance,

      4.5   Air pump: Any peristaltic pump capable of delivering 1 L/min air may
 be used.  A Hasterflex  pump with electronic  speed control has been found to be
 satisfactory.

      4.6   Flowmeter:   Capable of measuring an  air flow of 1 L/min.

      4.7   Aeration tubing:  A  straight glass frit with a coarse porosity. Tygon
 tubing is used  for  passage  of the mercury  vapor from the sample bottle to the
 absorption cell and  return.

      4.8   Drying  tube:   6-in.  x  3/4-in.-diameter  tube  containing  20 g  of
magnesium perchlorate or a small reading lamp with 60-W bulb which may be used
to prevent  condensation  of moisture  inside the  cell.    The lamp  should  be
positioned to shine  on  the  absorption  cell  so that the air temperature in the
cell  is about 10°C above ambient.

      4.9   The cold-vapor  generator  is assembled  as shown  in Figure 1  of
reference 1  or  according to  the instrument manufacturers instructions.   The
apparatus shown  in  Figure  1  is a closed  system.   An open  system,  where  the
mercury  vapor  is  passed through  the  absorption  cell  only once, may be  used
instead of the closed system.  Because mercury vapor is toxic, precaution must be
taken to avoid  its  inhalation.   Therefore,  a bypass  has been included in  the
system either to   vent  the  mercury  vapor into  an  exhaust  hood  or to pass  the
vapor through some absorbing medium, such as:

            1.     equal   volumes of 0.1  H KMn04 and 10% H2S04,  or
            2.     0.25%  iodine  in a 3% KI solution.


      A  specially treated  charcoal  that  will  adsorb  mercury  vapor  is  also
      available from Barneby and Cheney,  East  8th  Avenue and  North Cassidy
      Street,  Columbus,  Ohio 43219,  Cat.  #580-13 or #580-22.
                                   7471A  -  2                       Revision 1
                                                                  September 1994

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      4.10   Hot  plate  or equivalent - Adjustable and capable of maintaining  a
temperature  of 90~95°C.

      4.11   Graduated  cylinder or equivalent.

5.0   REAGENTS

      5.1    Reagent  Mater:   Reagent water  will be  interference free.   All
references  to water in  this method  refer to reagent  water  unless  otherwise
specified.

      5.2    Aqua regia:  Prepare immediately before use by carefully adding three
volumes of concentrated  HC1  to one  volume  of concentrated HN03.

      5.3    Sulfuric acid, 0.5 N:   Dilute 14.0 ml of concentrated sulfuric acid
to 1 liter.

      5.4    Stannous sulfate:   Add 25 g  stannous sulfate to 250  ml  of 0.5 N
sulfuric acid.  This mixture is  a  suspension  and  should  be stirred  continuously
during use.  A 10% solution of stannous chloride can be substituted  for stannous
sulfate,

      5.5    Sodium chloride-hydroxylamine  sulfate solution:   Dissolve 12 g of
sodium chloride and 12  g  of hydroxylamine sulfate in  reagent water and dilute to
100  ml.   Hydroxylamine  hydrochloride may be  used  in  place  of hydroxylamine
sulfate.

      5.6    Potassium permanganate,  mercury-free,  5% solution (w/v):  Dissolve
5 g of potassium permanganate in 100 ml of reagent water.

      5.7    Mercury stock  solution:  Dissolve 0.1354 g of mercuric chloride in
75 ml of reagent water.   Add 10 ml of concentrated  nitric acid and adjust the
volume to 100.0 ml (1.0 ml = 1.0 mg Hg).

      5.8    Mercury working  standard:   Make  successive  dilutions  of  the stock
mercury solution to obtain  a working standard containing 0.1 ug/mL.   This working
standard and the dilution of the  stock mercury solutions should  be prepared fresh
daily.   Acidity  of the working  standard should  be maintained at  0.15% nitric
acid.  This  acid should be  added  to the flask,   as needed, before adding the
aliquot.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6,1   All  samples  must have  been  collected using a sampling  plan that
addresses the considerations discussed in Chapter Nine of this manual.

      6.2   All sample  containers  must be prewashed with detergents, acids, and
reagent water.  Plastic and glass containers are both suitable.

      6.3   Non-aqueous  samples   shall  be  refrigerated, when  possible,  and
analyzed as  soon as possible."
                                   7471A  -  3                       Revision 1
                                                                  September 1994

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 7.0    PROCEDURE

       7.1    Sample  preparation:   Weigh triplicate 0.2-g portions  of  untreated
 sample and  place  in the  bottom of a BOD bottle.   Add  5 ml of  reagent  water  and       \
 5 ml  of aqua regia.  Heat  2  min  in a water  bath  at 95°C.  Cool; then  add  50 mL
 reagent water and 15 ml  potassium permanganate solution to each sample  bottle.
 Mix thoroughly and  place in  the  water bath  for 30 min at 95°C.  Cool  and  add 6
 ml of  sodium chloride-hydroxylamine sulfate to reduce  the excess permanganate.

             CAUTION:  Do  this addition under  a hood,   as C12  could  be evolved.
             Add 55  ml of reagent water.  Treating each bottle  individually,  add
             5 ml  of stannous sulfate and  immediately  attach the bottle to  the
             aeration  apparatus.   Continue as  described under  step  7.4.

       7.2    An alternate digestion procedure employing an autoclave may  also be
 used.   In this method, 5 ml  of concentrated H2S04 and  2 ml of  concentrated HN03
 are added to the  0.2 g of sample.  Add 5 ml of  saturated KMn04 solution  and  cover
 the bottle  with a piece  of aluminum foil.   The samples are  autoclaved at  121°C
 and 15 Ib for 15 min.  Cool, dilute to a volume of  100 mL with reagent water,  and
 add 6 ml of sodium chloride-hydroxylamine  sulfate solution to  reduce the excess
 permanganate.  Purge the  dead air space and continue as described under  step 7.4.
 Refer to the caution statement in section 7.1 for the proper protocol  in reducing
 the excess  permanganate  solution  and  adding stannous  sulfate.

       7.3    Standard preparation:  Transfer 0.0-,  0.5-, 1.0-, 2.0-,  5.0-,  and  10-
 mL aliquots of the mercury working standard, containing 0-1.0  ug of  mercury,  to
 a series of 300-mL BOD bottles or equivalent.  Add enough reagent water to each
 bottle  to make a  total volume of  10 ml.  Add  5 ml of  aqua regia and heat  2  min
 in a water bath at 95°C.  Allow the sample to  cool; add 50 mL  reagent  water  and
 15 ml  of KMn04 solution  to  each  bottle   and  return   to  the water bath for  30
 min.   Cool  and add  6 ml of  sodium chloride-hydroxylamine  sulfate solution  to
 reduce  the  excess permanganate.    Add 50  ml of reagent water.   Treating each
 bottle  individually, add 5 raL of  stannous sulfate solution,  immediately attach
 the bottle to  the aeration apparatus, and continue as  described in
 Step 7.4.

      7.4   Analysis:  At  this  point, the  sample  is  allowed  to stand quietly
without  manual agitation.    The  circulating  pump,  which has  previously been
 adjusted to a rate of 1  L/min,  is  allowed to run continuously.   The absorbance,
 as exhibited either on the  spectrophotoraeter or the recorder,  will   increase  and
reach  maximum within 30  sec.    As  soon  as  the recorder   pen   levels  off
 (approximately 1  min), open the bypass valve and continue the aeration  until  the
absorbance  returns  to its  minimum value.    Close  the  bypass valve, remove  the
fritted tubing from the BOD bottle, and continue the aeration.

      7.5   Construct a calibration curve by plotting  the absorbances of  stan-
dards versus  micrograms  of mercury.   Determine the peak  height of the unknown
from the chart and read the mercury value from the standard curve.   Duplicates,
spiked samples, and check standards should be routinely analyzed.

      7.6   Calculate metal  concentrations:   (1) by  the  method  of  standard
additions,  (2) from a calibration curve,  or (3)  directly  from  the  instrument's
concentration read-out.  All dilution or concentration factors must  be taken into

                                   7471A - 4                      Revision  1
                                                                  September 1994

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account.   Concentrations  reported  for  muTtiphased  or wet  samples  must  be
appropriately qualified (e.g., 5 ug/g dry weight).

8.0   QUALITY CONTROL

      8.1  Refer to section 8.0 of Method 7000.

9.0   METHOD PERFORMANCE

      9.1   Precision and  accuracy data are available in Method 245.5 of Methods
for Chemical  Analysis of Water and Wastes.

      9.2   The data shown in Table  1 were  obtained from records of state and
contractor laboratories.   The data  are  intended to  show the  precision of the
combined sample preparation and  analysis  method.

10.0  REFERENCES

1.    Methods  for  Chemical Analysis of   Water  and  Wastes,  EPA-600/4-82-055,
December 1982, Method 245.5.

2.    Gaskill, A.,  Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2,  EPA Contract No, 68-01-7075, September 1186.
                                  7471A - 5                       Revision 1
                                                                  September 1994

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                      TABLE  1. METHOD  PERFORMANCE DATA
Sample                          Preparation            Laboratory
Matrix                           Method               Replicates
Emission control dust          Not known              12,  12  ug/g

Wastewater treatment sludge    Not known           0.4,  0.28  ug/g
                                 7471A  - 6                       Revision 1
                                                                 September 1994

-------
                                METHOD 7471A
MERCURY  IN  SOLID  OR  SEHISOLID  WASTE (MANUAL  COLD-VAPOR TECHNIQUE)
                            [     Start     I
                               7.5 Conetruct
                                caJib ration
                              curve; determine
                              paak height and
                                 Hg value.
                                7.E Routinely
                              analyze duplicatet.
                               •pikad aamplat.
                                7.6 Calculate
                                   metal
                               concentre tione.
f    Stop    J

  7471A  -  7
Sample Preparatfon
/ Typ
f Dig"
\ Met!
\
r
\^ Type
nod? jS
Type
7.1 Weigh triplicate
samples, and reagent
water »nd
aqua regia.
^l
f
7.1 Heat, cool,'
add reagent water
and KMnO . .
1
^

Standard Preparation

1
r
7.3 Tranifei aliquota
of Hg working
•tandardt to
bottle*.

1
,
7.3 Add reagent
water to volume,
and *Qua regia,
heat and coal.
r
7.2 Add
ICMn04, cover,
heat and cool,
dilute with
reagent water.
r i
7.1 Heat, cool,
add sodium
chloride-
hydroxylamine
eulfate.
1

7.1 Add! reagent
water, etannoue
(ulfata, attach
to aeration
apparatus.

t

r
7.2 Add eodium
chloride-
hydroxvlamine
culfata, purge
. dead air epec*.
i
7.4

r
Analyze
triple.
1




r
7.3 Add reagent
water and KMn04
aolutton. Neat
end cool.
,
r
7.3 Add todiurn '
chloride*
hydroxvlamine
culfata end
reegem water.
1
7.3
etannou
appc
r
Add
* eulfate,
o aeration
ratu*.
                                                                      Revision 1
                                                                      September 1994
                      \

-------

-------
                                 METHOD  7741A

                 SELENIUM (ATOMIC ABSORPTION,  GASEOUS HYDRIDE)
 1.0    SCOPE AND  APPLICATION

       1.1   Method  7741  is an  atomic  absorption  procedure that  is  approved  for
 determining the concentration of selenium in wastes, mobility-procedure extracts,
 soils,  and ground water, provided that  the sample matrix does not  contain high
 concentrations of chromium,  copper,  mercury, silver, cobalt, or molybdenum.   All
 samples must be  subjected to an appropriate dissolution  step prior  to analysis.
 Spiked  samples  and  relevant  standard  reference materials  are  employed  to
 determine applicability  of  the method to a  given waste.  If interferences  are
 present the analyst  should consider using Method  7740.

 2.0   SUMMARY OF METHOD

      2.1   Samples are prepared according to the nitric/sulfuric acid digestion
 procedure described in this method.   Next,  the  selenium  in  the digestate is
 reduced to Se(IV) with tin chloride.   The Se(IV) is then  converted to  a volatile
 hydride  with  hydrogen produced  from  a zinc/HCl  or  sodium   borohydrate/HCl
 reaction.

      2.2   The  volatile hydride is swept into an argon-hydrogen flame located
 in the  optical  path of an atomic  absorption  spectrophotometer; the resulting
 absorbance is proportional to  the selenium concentration.

      2.3   The  typical detection limit  for this method is 0.002 mg/L.

3.0   INTERFERENCES

      3.1   High concentrations of chromium, cobalt, copper, mercury, molybdenum,
nickel, and silver can cause analytical  interferences.

      3.2   Traces of nitric acid left following the sample work-up  can result
in analytical interferences.   Nitric  acid must be distilled off the sample by
heating the sample until fumes of S03 are observed.

      3.3   Elemental selenium and many of its compounds are volatile;  therefore,
certain samples may be subject to losses of selenium during sample preparation.

4.0   APPARATUS AND MATERIALS

      4.1   100-mL beaker.

      4.2   Electric  hot plate  or  equivalent  -  Adjustable  and  capable  of
maintaining a temperature of 90-95°C.

      4.3   A commercially available zinc slurry hydride generator or a generator
constructed from the following material  (see Figure 1);
                                   7741A -  1                       Revision 1
                                                                  September 1994

-------
            4.3.1    Medicine dropper:  Fitted  into  a  size "0" rubber  stopper
      capable  of delivering  1.5 ml.

            4.3.2    Reaction flask:   50-mL, pear-shaped, with two 14/20  necks
      (Scientific Glass, JM-5835).

            4.3.3   Gas inlet-outlet tube:  Constructed from a  micro cold-finger
      condenser  (JM-3325)  by cutting  the  portion below the 14/20 ground-glass
      joint,

            4.3.4   Magnetic  stirrer:  To homogenize the zinc slurry.

            4.3.5   Polyethylene drying tube:  10-cm,  filled with glass  wool to
      prevent  particulate matter from entering the burner.

            4.3.6   Flow meter:  Capable of measuring 1 liter/min.

      4.4   Atomic absorption spectrophotometer:  Single or dual channel,  single-
or double-beam instrument with a grating monochrometor, photomultiplier detector,
adjustable  slits,   a  wavelength  range  of  190-800  nm,   and provisions for
interfacing with a strip-chart recorder and  simultaneous background correction.

      4.5   Burner:  Recommended by the particular instrument manufacturer for
the argon-hydrogen flame.

      4.6   Selenium hollow cathode lamp or electrode!ess discharge lamp.

      4.7   Strip-chart recorder (optional).

5.0   REAGENTS

      5.1   Reagent water:  Water should be monitored for impurities.   Reagent
water will  be interference free.   All  references to water will refer to  reagent
water.

      5.2   Concentrated nitric  acid:   Acid  should  be analyzed  to  determine
levels of impurities.   If a method blank made with the acid is 
-------
      5.7   Stannous  chloride solution:   Dissolve  100  g SnCl2 in  100 mL of
concentrated HC1.

      5.8   Selenium  standard stock  solution:   1,000  mg/L solution  may be
purchased, or prepared as follows:  Dissolve 0.3453  g of  selenious acid (assay
94.6% of H2Se03)  in reagent water.  Add to a 200-mL  volumetric flask and bring
to volume (1 ml =  1 rag Se),

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All  samples  must have  been  collected using  a  sampling  plan that
addresses the considerations discussed in Chapter Nine of this manual.

      6.2   All sample containers must be prewashed  with detergents, acids, and
reagent water.  Plastic and glass containers are both suitable.

      6.3   Special  containers   (e.g.,  containers  used  for  volatile   organic
analysis) may  have to be used  if very volatile selenium compounds  are to be
analyzed.

      6.4   Aqueous samples must be acidified to a pH of <2 with nitric acid.

      6.5   Nonaqueous samples shall be refrigerated,  when possible, and analyzed
as soon as possible.

7.0   PROCEDURE

      7.1   Sample preparation:

            7.1.1   To a 50-mL aliquot of digested  sample (or,  in  the case of
      extracts, a 50-mL sample)   add  10  mL  of   concentrated  HN03  and 12 mL of
      18 N H2S04.   Evaporate the sample on a hot plate until white S03 fumes are
      observed (a  volume of  about 20  mL).  Do not  let it char.   If  it chars,
      stop the digestion,  cool,  and add additional HN03.  Maintain an excess of
      HN03 (evidence of brown  fumes) and do not let  the solution darken  because
      selenium may be reduced and  lost.   When  the sample remains  colorless or
      straw yellow during evolution of S03 fumes,  the digestion is  complete.

            Caution: Venting reaction vessels should be done with
            caution and only under a fume hood or well ventilated
            area.

            7.1.2   Cool the  sample,  add  about 25 mL reagent water,  and again
      evaporate to S03 fumes just to expel oxides of nitrogen.  Cool.  Add 40 mL
      concentrated HCl and bring to a volume of 100 mL with reagent water.

      7.2   Prepare working standards from the  standard  stock solutions.  The
following procedures provide standards in the optimum range.

            7.2.1    To  prepare  a working stock solution, pipet  1  mL standard
      stock solution (see Paragraph 5.8) into a 1-liter volumetric flask.  Bring
      to volume with  reagent  water  containing  1.5 mL concentrated HNOg/liter.
      The  concentration  of this solution is 1 mg Se/L (1 mL = 1  ug  Se).

                                   7741A  - 3                       Revision 1
                                                                  September  1994

-------
             7.2.2    Prepare  six working  standards by transferring 0, 0.5,  1.0,
       1.5,  2.0,  and  2,5 ml of the working  stock solution  (see Paragraph 7.2.1)
       into  100-mL volumetric  flasks.   Bring to  volume  with  diluent.   The
       concentrations of these working standards are 0,  5,  10,  15, 20, and 25 ug
       Se/L.

       7.3    Standard additions;

             7.3.1     Take  the 15-,  20-,  and 25-ug  standards and  transfer
       quantitatively 25 ml from each into separate 50-mL volumetric flasks.  Add
       10 ml of the prepared sample to  each.  Bring to volume with reagent water
       containing 1.5 ml HNQ^liter.

             7.3.2    Add  10 mL  of  prepared sample  to a 50-mL volumetric flask.
       Bring to volume with reagent water containing  1.5 mL HN03/liter.  This is
       the blank.

       7.4    Follow  the manufacturer's  instructions for  operating  an  argon-
hydrogen flame.   The argon-hydrogen flame  is  colorless;  therefore,  it  may be
useful to  aspirate  a low concentration  of  sodium to  ensure  that  ignition has
occurred.

       7.5   The 196.0-nm wavelength shall be used for the  analysis of selenium.

       7.6   Transfer a 25-mL portion of the digested sample or standard to the
reaction vessel.  Add 0.5 mL SnCl2  solution. Allow at least 10 min for the metal
to be reduced to its lowest oxidation  state.  Attach the reaction vessel to the
special gas  inlet-outlet  glassware.    Fill  the medicine dropper with  1.50 mL
sodium borohydrate  or  zinc slurry that  has been  kept  in  suspension  with the
magnetic stirrer. Firmly insert the stopper containing the  medicine dropper into
the side neck of the reaction  vessel.   Squeeze the  bulb to introduce  the zinc
slurry or sodium borohydrate into  the  sample or standard  solution.   The metal
hydride wiTl produce a peak almost immediately.  When the  recorder  pen returns
partway to the base  line, remove the reaction vessel.

8.0   QUALITY CONTROL

      8,1  Refer to  section 8.0 of Method 7000.

9.0   METHOD PERFORMANCE

      9.1   Precision and accuracy data are available in Method 270.3 of Methods
for Chemical Analysis of Water and Wastes.

10.0  REFERENCES

1.    Methods for  Chemical Analysis  of  Water and Wastes,  EPA-6QO/4-82-055,
December 1982, Method 270.3.
                                   7741A  -  4                       Revision 1
                                                                  September 1994

-------
                        METHOD  7741A
    SELENIUM  (ATOMIC ABSORPTION, GASEOUS HYDRIDE)
                       C  Start    J
                  Pr«pir*tion
S*Bpl« Preparation
  7.2.1 Pip.t
    • toek
 •olution into
 fla*k; bring
   te vein**
72.2 Pr«p«r«
  S* irorlcing
•tamdaxd* tram
alack i
7.3,1 Tc*saf*r
  3 *taadani
 portiona,*dd
•*Kpl*,bring to
                         7741A  - 5
                                Revision 1
                                           1994

-------

-------
                                  METHOD 7742

              SELENIUM fATOHIC ABSORPTION. BOROHYDRIDE REDUCTION)
 1.0   SCOPE  AND APPLICATION

       1.1   Method 7742 is an atomic absorption procedure for  determining  3 jjg/L
 to 750 fjq/L concentrations of selenium  in wastes, mobility procedure extracts,
 soils,  and  ground water.   Method 7742  is  approved for  sample matrices that
 contain  a  total  of  up to 1000  mg/L concentrations of  cobalt, copper,  iron,
 mercury,  and  nickel. A  solid  sample can contain  up  to 10%  by weight of the
 interferents  before  exceeding 1000  mg/L in  a  digested sample.   All  samples
 including aqueous matrices must be subjected to  an  appropriate dissolution step
 prior to analysis.  Spiked samples and relevant standard reference materials are
 employed to determine the applicability of the method to a given waste.

 2.0   SUMMARY OF METHOD

       2.1   Samples are prepared according to the nitric  acid digestion procedure
 described   in   Method   3010   for   aqueous   and   extract   samples   and  the
 nitric/peroxide/hydrochloric acid digestion procedure described  in Method 3050
 (furnace  AA option)   for sediments,  soils,   and  sludges.   Excess  peroxide is
 removed  by  evaporating  samples  to near-dryness at the end  of the digestion
 followed by dilution to volume and degassing the samples  upon addition  of urea.
 The  selenium  is  converted  to the 44 oxidation  state during  digestion  in HC1.
 After  a 1:10 dilution, selenium is then  converted to its volatile hydride using
 hydrogen  produced from  the  reaction  of the  acidified  sample with sodium
 borohydride in a continuous-flow hydride generator.

       2.2   The volatile  hydrides  are  swept into,  and  decompose in,   a heated
 quartz  absorption  cell  located  in the optical path  of an  atomic  absorption
 spectrophotometer.    The  resulting  absorption  of  the  lamp  radiation  is
 proportional to the  selenium concentration.

       2.3   The typical detection limit for this method is 3 //g/L.

3.0   INTERFERENCES

      3.1   Very  high (>1000 mg/L)  concentrations of cobalt,  copper,  iron,
mercury, and,  nickel  can  cause analytical interferences  through precipitation as
reduced metals and associated blockage of transfer lines and fittings.

      3.2   Traces of peroxides left following the sample work-up can result in
analytical  interferences.  Peroxides  must be  removed by evaporating each sample
to  near-dryness  followed  by  reacting  each sample  with  urea and   allowing
sufficient  time for degassing before analysis (see Sections 7.1 and 7.2).

      3.3   Even  after acid digestion,  flame gases and organic compounds  may
remain  in the  sample.   Flame  gases  and  organic  compounds  can  absorb at  the
analytical  wavelengths and background correction should be used.

                                    7742-1                        Revision 0
                                                                  September  1994

-------
4.0  APPARATUS AND MATERIALS

      4,1  Electric hot  plate:   Large enough to hold  at  least  several  100 mL
Pyrex digestion beakers.

      4.2   A  continuous-flow hydride  generator:    A commercially  available
continuous-flow  sodium  borohydride/HCl  hydride  generator  or  a  generator
constructed similarly to that shown in  Figure 1 (P. S. Analytical or equivalent).

            4.2.1  Peristaltic Pump: A four-channel, variable-speed peristaltic
      pump to permit regulation of liquid-stream flow rates (Ismatec Reglo-100
      or equivalent).   Pump  speed and tubing diameters should  be  adjusted to
      provide  the  following  flow rates:    sample/blank  flow  =  4.2  mL/min;
      borohydride  flow  =  2.1  mL/min.

            4.2.2  Sampling Valve (optional):    A sampling valve (found in the
      P. S, Analytical Hydride Generation System  or equivalent)  that  allows
      switching between samples and blanks (rinse  solution) without introduction
      of air into  the system  will provide more signal  stability.

            4.2.3  Transfer Tubing and Connectors: Transfer tubing (1 mm I.D.),
      mixing T%  and connectors are made of  fluorocarbon  (PFA or TFH)  and are
      of compatible  sizes to form  tight,   leak-proof connections  (Latchat,
      Technicon, etc. flow injection apparatus accessories or equivalent).

            4.2.4  Mixing Coil:  A 20-turn coil made by wrapping transfer tubing
      around a 1-cm  diameter  by 5-cm  long plastic or  glass rod (see Figure 1).

            4.2.5   Mixing  Coil  Heater,  if appropriate:   A  250-mL  Erlenmeyer
      flask containing  100 mL of water  heated to boiling on a dedicated  one-
      beaker hotplate (Corning PC-35 or  equivalent).   The  mixing  coil  in 4.2.4
      is immersed  in the  boiling water to speed kinetics of the hydride forming
      reactions  and   increase   solubility   of   interfering  reduced   metal
      precipitates.

            4.2.6  Gas-Liquid Separator:   A glass apparatus  for  collecting and
      separating  liquid  and  gaseous  products (P. S.  Analytical  accessory  or
      equivalent) which allows the liquid fraction to drain to waste and gaseous
      products above the  liquid  ~o be  swept by a  regulated carrier  gas  (argon)
      out  of the cell for anal   s.  To avoid undue carrier  gas dilution,  the
      gas  volume above the  liqi-  .  should not exceed 20 mL.   See Figure 1  for an
      acceptable separator  shape.

            4.2.7  Condenser:  Moisture picked up  by the carrier gas must  be
      removed  before encountering the  hot absorbance cell.   The moist  carrier
      gas with the hydrides is dried by passing the gasses through a small (< 25
      mL) volume condenser  coil (Ace Glass Model  6020-02 or equivalent)  that is
      cooled to 5°C by a water chiller  (Neslab  RTE-110 or equivalent).  Cool  tap-
      water in place of a chiller is acceptable.
                                    7742-2                         Revision  0
                                                                  September 1994

-------
            4.2.8  Flow Meter/Regulator:  A meter capable of regulating yp to  1
      L/min of argon carrier gas  is  recommended.

      4.3  Absorbance Cell: A  17-cm  or longer quartz tube T-cell  (windowless is
strongly suggested)  is  recommended,  as  shown in Figure 1 (Varian Model VGA-76
accessory or equivalent).  The cell is held in place by a holder that positions
the  cell  about  1  cm over  a  conventional  AA air-acetylene burner head.   In
operation, the cell  is heated  to  around  900°C.

      4.4   Atomic  absorption  spectrophotometer:   Single-  or  dual-   channel,
single- or double-beam instrument having a grating monochromator, photomultiplier
detector, adjustable slits, a wavelength range of 190 to 800 nm, and provisions
for  interfacing with  an appropriate  recording device.

      4.5  Burner:  As recommended by the particular instrument manufacturer for
an air-acetylene flame.   An appropriate mounting bracket attached to the burner
that suspends the quartz absorbance cell between 1 and 2 cm above the burner slot
is required.

      4.6  Selenium hollow  cathode lamp or selenium electrodeless discharge lamp
and  power  supply.   Super-charged   hollow-cathode, lamps  or  EDL  lamps  are
recommended for maximum sensitivity.
      4.7     Strip-chart
spectrophotometer.

5.0  REAGENTS
recorder  (optional):
Connect  to  output  of
      5.1  Reagent water  ;   Water must be monitored for impurities.   Refer to
Chapter 1 for definition of Reagent water.

      5.2  Concentrated nitric acid (HN03):   Acid must be analyzed to determine
levels of impurities.  If a method blank  is 
-------
                                QUARTZ  CELL


                                * ft  DURHER
                                                                      TO
                                                                   CHILLER
  ,  *f
  •DISCONNECTS
  OURJHO 5*Xfn
  _  Brim VI IS
tv
"j
                                                               __—» Oft* IN
                       20 TURN COIL
                         (TEFLON)
                         NOTM.HTC—»
                         WALUC
Figure 1.  Continuous-flow sodium borohydride/hydride generator apparatus setup
and an AAS sample  introduction system
                                     7742-4
                                                      Revision 0
                                                      September 1994

-------
      5.7  4% Sodium Borohydride (NaBH4);  A 4 % sodium borohydride solution (20
g reagent-grade NaBH4 plus 2 g sodium hydroxide dissolved in 500 ml of reagent
water) must be prepared for conversion of the selenium to its hydride.

      5.8  Selenium solutions:

            5.8.1   Selenium  standard stock  solution  (1,000  mg/L):   Either
      procure  certified  aqueous  standards  from  a  supplier   and  verify  by
      comparison with a second standard,  or dissolve  0.3453 g of selenious acid
      (assay 96.6% of H2Se03)  in 200  ml  of reagent water (1 ml =  1 rag Se).

            5.8.2   Selenium  working stock solution:   Pipet  1 ml  selenium
      standard stock solution  into all volumetric  flask and  bring to volume
      with  reagent water containing  1.5  ml concentrated  HNOg/liter.    The
      concentration of this solution is  1 mg Se/L (1 ml = 1 yq  Se).

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All  samples must  have been  collected  using a sampling  plan  that
addresses the considerations discussed in Chapter Nine of this  manual,

      6.2  All sample containers must be prewashed with detergents,  acids,  and
reagent water.  Plastic and glass containers are both suitable.

      6.3   Special  containers (e.g.,  containers  used  for  volatile  organic
analysis) may have to be used  if very volatile selenium compounds are suspected
to be present in the samples.

      6.4  Aqueous samples must be acidified to a pH of <2 with  nitric acid.

      6.5  Nonaqueous samples shall be refrigerated, when possible, and analyzed
as soon as possible,

7.0  PROCEDURE

      7.1  Place a 100-mL  portion  of  an aqueous sample or extract or 1.000 g of
a dried solid sample in a 250-mL digestion beaker.   Digest aqueous samples  and
extracts according to Method 3010.  Digest solid samples according to Method 3050
(furnace AA option) with the following modifications:  add 5 mL of concentrated
hydrochloric acid  just  prior  to  the final  volume  reduction  stage to  aid  in
conversion of selenium to  its plus four state;  the final volume reduction should
be to less than 5  ml  but  not  to dryness to adequately  remove excess hydrogen
peroxide (see note).  After dilution to volume, further dilution with diluent may
be necessary if the analyte is known to exceed 750 //g/L or if interferents  are
expected to exceed  a total of 1000 mg/L in the digestate.

            Note:   For solid digestions,  the volume reduction stage is critical
            to obtain  accurate data.    Close monitoring  of each  sample  is
            necessary when this critical  stage in the digestion  is reached.
                                    7742-5                        Revision 0
                                                                  September 1994

-------
       7.2  Prepare samples for hydride analysis  by adding 1.00 g urea, and 20 ml
concentrated HC1 to a 5.00 mi  aliquot  of digested sample in  a 50-mL  volumetric
flask.  Heat in a water bath to dissolve salts and reduce selenium (at  least 30
minutes  is  suggested).    Bring  flask to  volume  with  reagent  water  before
analyzing.    A  ten-fold  dilution  correction  must  be   made   in  the   final
concentration calculations.

       7.3  Prepare working standards from the standard  stock  selenium solution.
Transfer 0,  0.5,  1.0, 1.5,  2.0,  and 2.5 ml  of standard  to 100-mL  volumetric
flasks and bring to volume with diluent.  These concentrations will be 0,  5,  10,
15, 20, and 25 pg Se/L.

       7.4   If  EP extracts (Hethod  1310} are  being  analyzed for selenium,  the
method of standard additions  must  be used.  Spike appropriate amounts  of working
standard selenium  solution  to three 25 ml  aliquots  of each unknown.  Spiking
volumes should  be  kept  less  than  0.250 mL to avoid  excessive spiking  dilution
errors.

       7.5   Set up  instrumentation  and hydride  generation  apparatus and fill
reagent containers.  The sample and  blank flows should be set  around 4.2 mL/min,
and the  borohydride flow around  2.1 mL/min.   The  argon  carrier  gas  flow is
adjusted to about 200 mL/min.  For the AA, use the 196.0-nm wavelength  and 2.0-nra
slit width  (or manufacturer's recommended slit-width) with background correction.
Begin all flows and allow the instrument to  warm-up according to the  instrument
manufacturer's instructions.

      7.6  Place sample  feed  line  into a prepared sample solution  and  start pump
to begin hydride  generation.   Wait for a maximum steady-state  signal on  the
strip-chart recorder.   Switch to blank  sample and watch for  signal  to  decline to
baseline before switching to  the  next sample and beginning the next analysis.
Run standards  first  (low to  high),  then unknowns.   Include appropriate QA/QC
solutions,  as required.  Prepare calibration curves and convert absorbances to
concentration.   See following analytical flowchart.

      CAUTION:  The hydride of selenium 1s very toxic.   Precautions  must  be taken
      to avoid inhaling the gas.

      7.7  If the method of standard additions was employed, plot the measured
concentration  of  the  spiked samples  and  unspiked  sample   versus the spiked
concentrations.  The spiked concentration axis  intercept will be the method of
standard additions concentration.   If the plot  does not result  in a  straight
line,   a  nonlinear  interference is  present.    This  problem can  sometimes  be
overcome by dilution or  addition  of other reagents  if there is some knowledge
about the waste.   If the method of standard additions  was not  required,  then  the
concentration is determined from a standard  calibration curve.
8.0  QUALITY CONTROL

      8,1  Refer to Section 8.0 of Hethod 700/0.
                                    7742-6                        Revision 0
                                                                  September 1994

-------
9.0  METHOD PERFORMANCE

      9,1  The relative standard deviation obtained by a single laboratory for
7 replicates of a contaminated soil was 18% for selenium at 8.2 ug/L  in solution.
The average percent recovery of  the analysis of an 2fjg/l  spike on ten different
samples is 100.5% for selenium.

10.0  REFERENCES

1.    Methods  for  Chemical  Analysis  of  Water  and Wastes,  EPA-600/4-82-055,
      December 1982, Method 206.3.

2.    "Evaluation of Hydride Atomic Absorption  Methods  for Antimony,  Arsenic,
      Selenium, and Tin",  an EMSL-LV internal report under Contract 68-03-3249,
      Job Order  70.16,  prepared for  T.  A. Hinners by D.  E. Dobb, and  J.  D.
      Lindner of Lockheed Engineering  and Sciences Co.,  and L. V.  Beach of the
      Varlan Corporation.
                                    7742-7                        Revision 0
                                                                  September 1994

-------
                                 METHOD  7742
SELENIUM  (ATOMIC  ABSORPTION,  BOROHYDRIDE  REDUCTION)
 7.1 Use Method
3060 (furnace AA
option) to digest
  1.0 B temple.
       7,1 • 7.4
      Digest with
       H203 as
     described in
     Method 3050.
        7.8 Add
      concentrated
         HCI.
      7.8 Do final
        volume
      reduction and
      dilution, as
       d»«cribed.
       7.1 Furthor
       dilute with
        diluent.
                                7.2 Add urea
                              and cone. HCI to
                               aliquot; heit in
                                 H20 bath;
                              bring to volume.
                                      I
                                7.3 Prepare
                                  working
                               standard! from
                               stand*™* «tock
                                Se aalution,
                                    7.4 Spike 3
                                   aliquot* with
                                     working
                                    atandard Se
                                     aolution.
                             7.S - 7,8 Analyze
                                the temple
                               using hydride
                               - generation
                                apparatus.
                                  7.7 Determine
                                  Se cone, from
                                    atandard
                                    calibration
                                     curve.
                                                                  7.1 Use
                                                               Method 3010
                                                               to digest 100
                                                                ml • am pie
                                                             7.4 U*m tha
                                                              m>thod of
                                                              itsnderd
                                                             addition* on
                                                            extracta, only.
                                                           7.S -7.6 Anelyze
                                                              the sample
                                                             using hydride
                                                              Qerte ration
                                                              apparatus.
7.7 Determine
     Se
concentrations
  from linear
    plot.
                                      Stop
                                       7742-8
                                                                             Revision  0
                                                                             Septenter  1994

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                                 METHOD 8000A

                              GAS CHROMATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   Gas  chromatography  is  a quantitative  technique  useful  for  the
analysis  of organic  compounds capable  of  being  volatilized without  being
decomposed or chemically  rearranged.   Gas chromatography (GC), also  known as
vapor phase chromatography (VPC),  has two subcategories distinguished by: gas-
solid chromatography (GSC), and gas-liquid  chromatography  (GLC)  or gas-liquid
partition chromatography  (GLPC).   This  last group  is  the most commonly used,
distinguished by type of column adsorbent or packing.

      1.2   The chromatographic methods are recommended  for use only by, or under
the close supervision of,  experienced residue analysts.


2.0   SUMMARY OF METHOD

      2.1   Each organic analytical method that follows provides a recommended
technique  for  extraction, cleanup,  and occasionally,  derivatization  of  the
samples to be analyzed.  Before the prepared sample is  introduced into the GC,
a procedure for standardization must be followed to determine the recovery and
the  limits of  detection   for  the  analytes of  interest.    Following  sample
introduction into the GC,  analysis proceeds with a comparison of sample values
with standard values.   Quantitative analysis  is achieved through integration of
peak area or measurement of peak height.


3.0   INTERFERENCES

      3.1   Contamination  by carryover can occur whenever high-concentration and
low-concentration samples  are sequentially analyzed.  To reduce carryover,  the
sample syringe or purging  device must be rinsed out between samples with water
or solvent. Whenever an unusually concentrated  sample is encountered, it should
be followed by  an  analysis of  a solvent blank or of water  to  check for cross
contamination.  For volatile samples containing large amounts of water-soluble
materials,  suspended   solids,  high  boiling compounds or  high  organohalide
concentrations, it may be necessary to wash  out  the syringe or purging device
with a detergent solution, rinse it with distilled water,  and then dry it in a
105°C oven between  analyses.


4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph - Analytical system complete with gas chromatograph
suitable  for  on-column  injections and  all required  accessories,  including
detectors, column supplies, recorder, gases, and  syringes.   A  data system for
measuring peak height and/or peak areas is recommended.

      4.2   Gas chromatographic  columns - See the  specific determinative method.
Other packed or  capillary  (open-tubular) columns may be  used  if the requirements

                                   8000A  -  1                         Revision 1
                                                                     July 1992

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of Section 8.6 are met.


5.0   REAGENTS

      5.1   See the specific determinative method for the reagents needed.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to this  chapter,  Organic Analytes,
Section 4.1.


7.0   PROCEDURE

      7.1   Extraction - Adhere to those procedures specified in the referring
determinative method.

      7.2   Cleanup and separation - Adhere to those procedures specified in the
referring determinative method.

      7.3   The recommended gas chromatographic columns and operating conditions
for the instrument are specified in the referring determinative method.

      7.4   Calibration

            7.4.1 Establish gas chromatographic operating parameters equivalent
      to those indicated in Section 7.0 of the determinative method of interest.
      Prepare   calibration  standards  using  the   procedures   indicated  in
      Section 5.0  of the  determinative method  of  interest.    Calibrate the
      chromatographic  system  using  either  the  external  standard  technique
      (Section 7.4.2) or the internal standard technique (Section 7.4.3).

            7.4.2 External  standard calibration procedure

                  7.4.2.1     For each analyte of  interest, prepare calibration
            standards at a  minimum of five concentrations by adding volumes of
            one or more  stock  standards  to  a volumetric flask and diluting to
            volume with an  appropriate solvent.   One of the external standards
            should be at a  concentration near, but above, the method detection
            limit.  The other concentrations should correspond to the expected
            range of concentrations found in real samples or should define the
            working range  of the detector.

                  7.4.2.2     Inject  each   calibration  standard  using  the
            technique that will  be used to introduce the actual samples  into the
            gas chromatograph  (e.g.  2-5  /xL  injections, purge-and-trap, etc.).
            Tabulate peak  height  or  area responses against  the  mass injected.
            The results  can be used  to  prepare a  calibration  curve  for each
            analyte.  Alternatively,  for samples  that are introduced into the
            gas chromatograph using a syringe, the ratio of the  response to the
            amount  injected,  defined as the calibration factor  (CF),  can be
            calculated for each analyte at each  standard concentration.  If the

                                   8000A - 2                        Revision  1
                                                                     July 1992

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percent relative standard deviation (%RSD) of the calibration factor
is  less  than 20%  over  the working  range,  linearity  through  the
origin can be  assumed,  and the average  calibration  factor can be
used in place of a calibration curve.

      taxation factor -

      *     For multi response  pesticides/PCBs, use the total area of
            all peaks used for quantitation.

      7.4,2.3     The  working  calibration   curve  or  calibration
factor must be verified  on  each  working day  by the injection of one
or more  calibration  standards.   The frequency of  verification is
dependent on the detector.  Detectors, such  as the electron capture
detector,  that  operate   in  the   sub-nanogram   range  are  more
susceptible to changes in detector response  caused by GC column and
sample   effects.     Therefore,   more  frequent   verification   of
calibration  is  necessary.   The flame ionization detector  is much
less sensitive  and requires  less frequent  verification.   If  the
response for any analyte varies  from  the  predicted response by more
than ± 15%,  a  new calibration  curve  must  be  prepared for that
analyte.   For  methods 8010,   8020, and 8030, see Table  3  in each
method for calibration and quality control acceptance criteria.

                           Rt  -  R2
      Percent Difference = — -  x 100
where:

      R,    =     Calibration Factor from first analysis.

      R2    =     Calibration Factor from succeeding analyses.

7.4.3 Internal standard calibration procedure

      7.4.3.1     To use this approach,  the analyst must select one
or more internal standards that are similar in analytical behavior
to the compounds of interest.  The analyst must further demonstrate
that the measurement  of the internal  standard is  not  affected by
method  or  matrix  interferences.    Due to  these  limitations,  no
internal standard applicable to all samples can be suggested.

      7.4.3.2     Prepare calibration standards at a minimum of five
concentrations for each  analyte of interest by adding volumes of one
or more stock standards  to a volumetric  flask.  To each calibration
standard,  add a  known  constant amount of  one  or more  internal
standards and dilute to  volume with  an appropriate solvent.  One of
the  standards  should  be  at  a concentration  near,  but  above,  the
method detection limit.   The other concentrations should correspond
to the  expected  range of concentrations found in  real  samples or
should define the working range of the detector.
                       8000A  -  3                         Revision 1
                                                         July 1992

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            7.4.3.3     Inject each calibration standard  using  the same
      introduction technique that will be applied  to  the  actual  samples
      (e.g.  2 to 5 pL injection, purge-and-trap,  etc.).  Tabulate the peak
      height or area responses  against the concentration of each compound
      and internal  standard.   Calculate  response  factors  (RF)  for each
      compound  as follows:

            RF     -     (AsCis)/{AisCs)

      where :

            As     =     Response for the  analyte to be measured,

            A1s    -     Response for the  internal  standard.

            Cis    =     Concentration of  the internal  standard,  /*g/L.

            C     «     Concentration of the  analyte to be  measured,
            If the  RF  value over the working  range is constant  {< 20%
      RSD), the RF can  be assumed to be invariant, and the average RF can
      be used for  calculations.  Alternatively,  the results can be used to
      plot a calibration curve of response ratios, Ag/Ajg versus RF.
            7.4.3.4     The  working  calibration  curve  or  RF  must  be
      verified on  each working day  by the measurement  of one  or more
      calibration standards.  The frequency of verification is dependent
      on the detector.   Detectors,  such as the electron capture detector,
      that  operate  in  the  sub-nanogram  range  are  more  susceptible  to
      changes in  detector response caused by GC column and sample effects.
      Therefore,  more frequent verification of calibration is necessary.
      The flame  ionization detector  is much less  sensitive and requires
      less frequent verification.   If the response for any analyte varies
      from the predicted response  by more  than  ±  15%,  a new calibration
      curve must be prepared for that compound.   For methods 8010, 8020,
      and 8030,  see  Table  3 in each method for calibration and quality
      control acceptance criteria.

7.5   Retention time windows

      7.5.1 Before establishing windows, make sure the GC system  is within
optimum  operating conditions.   Make  three  injections  of  all  single
component  standard  mixtures  and  multiresponse  products   (i.e.  PCBs)
throughout the course  of a  72  hour period.   Serial  injections over less
than a 72 hour period result in retention  time  windows that  are too tight.

      7.5.2 Calculate the standard  deviation of  the three retention times
(use any function of  retention time; including  absolute retention time, or
relative  retention  time)   for  each  single  component   standard.    For
multiresponse  products, choose  one  major  peak from  the  envelope  and
calculate the  standard deviation  of the three  retention  times  for that
peak.    The  peak chosen  should  be  fairly  immune  to  losses  due  to
degradation and weathering in samples.

                             8000A  -  4                         Revision  1
                                                               July 1992

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            7.5.2.1     Plus or minus three times the standard deviation
      of the  retention times for each standard will  be used to define the
      retention time window; however, the experience of the analyst should
      weigh  heavily  in  the  interpretation  of  chromatograms.    For
      multiresponse analytes  (i.e.  PCBs),  the  analyst  should  use  the
      retention  time  window,   but  should  primarily  rely  on  pattern
      recognition.

            7.5.2.2     In those cases where the  standard deviation for a
      particular  standard  is  zero,  the  laboratory must  substitute  the
      standard deviation of a close eluting,  similar compound to develop
      a valid retention  time window.

      7.5.3 The laboratory must  calculate retention time windows for each
standard on each GC column and whenever a new  GC column is installed.  The
data must be retained  by the laboratory.

7,6   Gas chromatographic analysis

      7.6.1 Introduction of organic compounds into the gas chromatograph
varies depending on the volatility of the compound.  Volatile organics are
primarily introduced by  purge-and-trap  (Method  5030).  However, there are
limited  applications  (in  Method   5030)  where  direct   injection   is
acceptable.   Use of Method 3810 or 3820  as  a  screening  technique  for
volatile organic  analysis  may  be valuable with  some sample  matrices to
prevent overloading and  contamination  of the  GC systems.   Semi volatile
organics are introduced  by direct injection.

      7.6.2 The appropriate detector(s) is given  in the specific method.

      7.6.3 Samples are  analyzed in a  set referred  to  as  an  analysis
sequence.   The  sequence  begins with instrument  calibration  followed by
sample  extracts   interspersed  with  multi-concentration   calibration
standards.   The sequence  ends when the set of  samples has been injected or
when qualitative and/or  quantitative QC criteria  are exceeded.

      7.6.4 Direct Injection -  Inject 2-5 /uL of the sample extract using
the solvent flush technique, if the extract is manually injected.  Smaller
volumes (1.0 /uL) can be injected, and the solvent flush technique is  not
required, if automatic devices  are employed.   Record the volume injected
to the nearest 0.05 pL and the resulting peak size in area units or peak
height.

      7.6.5 If the responses exceed the linear range of the system, dilute
the extract and reanalyze.   It  is recommended that extracts be diluted so
that all peaks  are on scale.   Overlapping peaks are not  always evident
when  peaks are  off  scale.    Computer  reproduction  of  chromatograms,
manipulated to ensure all peaks  are  on scale  over  a 100-fold range,  are
acceptable  if linearity  is demonstrated.   Peak  height measurements  are
recommended over peak area integration when overlapping peaks cause errors
in area integration.

      7.6.6 If   peak  detection  is  prevented   by  the  presence   of
interferences, further cleanup  is required.

                            8000A  -  5                         Revision 1
                                                               July 1992

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            7.6.7 Examples of chromatograms for the  compounds  of Interest are
      frequently available in the referring analytical  method.

            7.6.8 Calibrate  the  system  immediately  prior  to  conducting  any
      analyses (see Section  7.4).   A mid-concentration standard must  also be
      injected at  intervals specified  in  the method  and at  the  end of the
      analysis  sequence.    The  calibration  factor  for  each  analyte  to  be
      quantitated,  must not  exceed a 15% difference when compared to the initial
      standard of  the analysis  sequence.   When  this  criterion is  exceeded,
      inspect  the  GC  system  to determine the  cause and  perform  whatever
      maintenance  is  necessary  (see Section  7.7)  before  recalibrating  and
      proceeding with  sample analysis.  All  samples that were injected after the
      standard exceeding  the criterion  must be reinjected to  avoid  errors in
      quantitation, if the  initial  analysis  indicated  the presence of  the
      specific target  analytes  that  exceeded the criterion.

            7.6.9 Establish daily retention time windows for each analyte.  Use
      the retention time for each analyte from Section 7.6.8 as the midpoint of
      the window for  that  day.   The daily retention  time  window equals the
      midpoint ± three times the standard deviation determined  in Section 7.5.

                  7.6.9.1     Tentative identification of an  analyte occurs when
            a peak  from a sample extract falls within the  daily retention time
            window. Normally, confirmation  is required: on  a second GC column,
            by  GC/MS  if   concentration   permits,   or  by   other   recognized
            confirmation techniques.  Confirmation may not be necessary if the
            composition  of  the  sample  matrix  is well established  by  prior
            analyses.

                  7.6.9.2     Validation of GC system qualitative performance:
            Use  the  mid-concentration  standards  interspersed  throughout  the
            analysis sequence (Section  7.6.8) to  evaluate this criterion.  If
            any of  the  standards  fall outside their daily retention time window,
            the system is out of control.   Determine the  cause of  the problem
            and correct it  (see  Section 7.7).  All  samples  that  were injected
            after the  standard  exceeding the  criteria  must be  reinjected to
            avoid false negatives and possibly false positives.

      7.7   Suggested  chromatography system maintenance - Corrective measures may
require any one or  more of the  following remedial  actions.

            7.7.1 Packed columns -  For  instruments with injection  port traps,
      replace the demister trap,  clean,  and  deactivate the glass injection port
      insert or  replace  with a  cleaned  and deactivated  insert.    Inspect the
      injection end of the column and remove any foreign material  (broken glass
      from the rim of the column or  pieces  of  septa).   Replace the glass wool
      with fresh deactivated glass wool.  Also, it may  be necessary  to remove
      the first few millimeters  of the packing material if any discoloration is
      noted, also  swab  out  the  inside  walls  of  the  column  if any residue is
      noted.  If these procedures fail to eliminate the degradation problem, it
      may be  necessary to  deactivate  the  metal  injector body  (described in
      Section 7.7.3) and/or repack/replace the column.
                                  800QA  -  6                         Revision 1
                                                                     July 1992

-------
      7.7.2 Capillary columns - Clean and deactivate the glass injection
port insert or replace with a cleaned and deactivated insert.  Break off
the first few inches, up to  one  foot,  of the  injection  port side of the
column.   Remove  the  column  and  solvent  backflush according  to  the
manufacturer's instructions.   If these  procedures  fail  to eliminate the
degradation problem,  it may be  necessary to deactivate the metal injector
body and/or replace the column.

      7.7.3 Metal   injector body  -  Turn  off  the  oven  and  remove  the
analytical column when the oven  has cooled.   Remove the glass injection
port insert (instruments with  off-column  injection  or Grob).  Lower the
injection port temperature  to  room temperature.   Inspect the injection
port and remove any noticeable foreign material.

            7.7.3.1     Place a beaker  beneath  the  injector port inside
      the GC oven.  Using a wash  bottle,  serially rinse the entire inside
      of the  injector  port with  acetone and  then  toluene;  catching the
      rinsate in the  beaker.

            7.7.3.2     Prepare a solution of deactivating agent (Sylon-CT
      or equivalent)  following manufacturer's directions.  After all metal
      surfaces inside the injector body have been thoroughly coated with
      the deactivation  solution,  serially rinse the injector body with
      toluene, methanol, acetone, and hexane.  Reassemble the  injector and
      replace the GC  column.

7.8   Calculations

      7.8.1 External  standard  calibration -  The concentration  of each
analyte  in  the sample may  be  determined by  calculating the  amount  of
standard purged or  injected, from the peak response,  using  the calibration
curve  or the  calibration  factor determined  in  Section  7.4.2.    The
concentration of a specific analyte is calculated as follows:

      Aqueous samples

      Concentration (Mg/L) = [(Ax)(A)(Vt)(D)]/[(As)(V,.)(Vs)]

where:

      Ax    =     Response for the analyte in  the sample,  units may be in
                  area counts or  peak height.

      A     =     Amount of standard injected or purged, ng.

      As    =     Response for the external standard, units  same as for
                  • !„ •

      V,.    =     Volume of  extract  injected,  /xL.   For purge-and-trap
                  analysis, V,.  is not  applicable and therefore =  1.

      D     =     Dilution factor,  if dilution  was  made on  the sample
                  prior to  analysis.    If no  dilution was made, D  =  1,
                  dimensionless.

                             8000A - 7                         Revision 1
                                                               July 1992

-------
      Vt    -     Volume  of  total   extract,   /xL.    For  purge-and-trap
                  analysis, Vt is not applicable and therefore = 1.

      Vs    •     Volume of sample extracted or purged, mL.


Nonaaueous samples

      Concentration (Mg/kg) »  [(Ax)(A)(Vt)(D)]/[(As)(V.)(W)]

where:

      W     -     Weight of sample extracted or purged, g.  The wet weight
                  or dry weight may be used, depending upon the specific
                  applications of the data.

      Ax,  A8,  A, V , D,  and  V,  have the same  definition  as for aqueous
samples when a solid sample is purged (e.g., low concentration soil) for
volatile  organic analysis  or  for  semi volatile  organic  and pesticide
extracts.   When the nonaqueous  sample  is  extracted for  purge  and trap
analysis, Vf - volume of methanol extract added to reagent water for purge
and trap analysis.

      7.8.2 Internal standard calibration - For each analyte of interest,
the concentration of that analyte in the  sample is calculated  as follows:

      Aqueous samples

      Concentration (Mg/L) =  [(Ax)(Ci8)(D)]/[(Ais)(RF)(Vs)]
where:
      Ax    -     Response of the analyte being measured,  units may be  in
                  area counts or peak height.

      Ci8    -     Amount of internal standard  added to extract  or  volume
                  purged, ng.

      D     -     Dilution factor,  if  a  dilution was  made on the  sample
                  prior  to  analysis.   If  no dilution was made,  D =  1,
                  dimensionless.

      A.8    -     Response of the internal standard, units same as  Ax.

      RF    «     Response factor for  analyte, as determined  in Section
                  7.4.3.3.

      V8    -     Volume of water extracted  or purged, ml.

      Nonaaueous samples

      Concentration (Mg/kg) = [(A8)(Cl8)(D)]/[(Ais)(RF)(Ws)]
                             8000A - 8                        Revision  1
                                                               July  1992

-------
      where:

            Ws    =     Weight of sample extracted, g.  Either a dry weight or
                        wet weight  may be  used,  depending upon  the specific
                        application of the data.

            As,  Cis,  D, ASs,  and RF  have the  same definition as  for aqueous
      samples.


8.0   QUALITY CONTROL

      8.1   Each laboratory that uses  these methods is required  to  operate a
formal quality control program.  The minimum requirements of this program consist
of an initial  demonstration of laboratory capability and an ongoing analysis of
spiked samples  to  evaluate and document quality data.  The  laboratory should
maintain records to document the quality of the data  generated.   Ongoing data
quality checks are compared with established performance criteria to determine
if the results of analyses meet the performance characteristics of the method.
When results of sample  spikes  indicate atypical  method performance,  a quality
control check standard should  be analyzed to confirm that the measurements were
performed in an in-control mode of operation.

      8.2   Before  processing  any  samples, the  analyst   should  demonstrate,
through the analysis of a  reagent blank, that interferences from the analytical
system, glassware,  and reagents are under control.   Each time a set of samples
is extracted or there  is  a change in  reagents,  an  organic-free  reagent  water
blank  should   be   processed   as  a   safeguard  against   chronic  laboratory
contamination.  The blank  samples should be carried through  all  stages of the
sample preparation and measurement steps.

      8.3   For each analytical batch (up to  20 samples), a  reagent blank, matrix
spike, and duplicate or matrix spike duplicate should be analyzed (the frequency
of the spikes may be different  for different monitoring programs).   The blank and
spiked samples should be carried through all  stages of the sample preparation and
measurement steps.

      8.4   The experience of  the  analyst  performing gas chromatography  is
invaluable to the  success  of the methods.  Each day that analysis is performed,
the  daily  calibration  sample  should  be  evaluated  to  determine  if  the
chromatographic system is  operating properly.   Questions  that should be asked
are: Do  the peaks  look normal?;  Is the response  obtained comparable to the
response  from  previous calibrations?    Careful  examination  of   the  standard
chromatogram can indicate whether  the  column  is still good, the  injector  is
leaking,  the injector septum  needs replacing, etc.   If any changes are made to
the system (e.g. column changed), recalibration of the  system should take place.

      8,5   Required instrument QC

            8.5.1  Step 7.4 requires that the %RSD vary by  < 20% when comparing
      calibration  factors  to  determine if  a five  point calibration  curve  is
      linear.
                                  8000A  - 9                         Revision 1
                                                                     July 1992

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            8.5.2 Section 7.4 sets a limit of ±  15% difference  when comparing
      daily response  of a  given analyte  versus  the  initial  response.    For
      Methods  8010, 8020, and 8030,  follow the  guidance on limits specified 1n
      Section  7.4.3.4.   If the limit is exceeded,  a  new  standard curve should be
      prepared unless  instrument maintenance  corrects the  problem for  that
      particular analyte.

            8.5.3 Step 7.5 requires the establishment of retention time windows.

            8.5.4 Section 7.6.8 sets  a  limit of + 15% difference when comparing
      the response from the continuing calibration  standard of a given analyte
      versus any succeeding standards analyzed  during an analysis sequence.

            8.5.5 Step  7.6.9.2  requires  that all  succeeding standards in an
      analysis sequence  should  fall within  the daily retention time window
      established by the first standard of the  sequence.

      8.6   To  establish the  ability  to generate acceptable  accuracy  and
precision, the analyst should perform the following operations.

            8.6.1 A quality control  (QC)  check sample  concentrate  is required
      containing each analyte of interest.  The QC check sample concentrate may
      be  prepared  from  pure standard  materials,  or  purchased as  certified
      solutions.   If prepared by the laboratory, the QC  check sample concentrate
      should be made  using  stock standards prepared independently  from  those
      used for calibration.

                  8.6.1.1     The  concentration   of  the  QC   check   sample
            concentrate  is   highly   dependent   upon   the  analytes   being
            investigated.  Therefore, refer to Method 3500, Section 8.0 for the
            required concentration of the QC  check  sample concentrate.

            8.6.2 Preparation of QC check samples

                  8.6.2.1     Volatile organic analytes (Methods  8010, 8020, and
            8030} - The QC check sample is prepared by  adding 200 ^l of the QC
            check sample concentrate (Step 8.6.1) to 100 ml of water.

                  8.6.2.2     Semivolatile organic analytes (Methods 8040, 8060,
            8070, 8080, 8090,  8100,  8110,  and  8120) - The  QC check sample is
            prepared by adding 1.0 mL of the  QC check sample concentrate  (Step
            8.6.1) to each of four 1-L aliquots of  water.

            8.6.3 Four aliquots of the well-mixed QC check sample are analyzed
      by the same procedures used to analyze actual  samples (Section 7.0 of each
      of the methods).   For volatile  organics, the preparation/analysis process
      is purge-and-trap/gas chromatography.  For semivolatile organics,  the QC
      check samples should undergo solvent extraction (see  Method 3500) prior to
      chromatographic analysis.

            8.6.4 Calculate the average recovery (x) in M9/U and the standard
      deviation of the recovery (s)  in M9/L, for each analyte of interest using
      the four results.
                                  8000A - 10                        Revision 1
                                                                     July 1992

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            8.6.5 For  each  analyte  compare  s  and x  with the  corresponding
      acceptance criteria for precision and accuracy,  respectively, given the QC
      Acceptance Criteria Table  at the end of each of the determinative methods.
      If s and x for all  analytes of  interest meet the acceptance criteria,  the
      system performance is acceptable and analysis  of actual samples canj)egin.
      If any individual s exceeds the precision  limit or any individual x falls
      outside  the   range  for  accuracy,  then the   system   performance   is
      unacceptable for that analyte.

            NOTE: The  large number  of  analytes in each  of the  QC  Acceptance
                  Criteria Tables present a substantial probability that one or
                  more will fail at  least one of the  acceptance  criteria when
                  all analytes of a given method are  determined.

            8.6.6 When one or more  of the analytes  tested fail  at least one of
      the acceptance criteria,  the  analyst  should proceed according  to Step
      8.6.6.1 or 8.6.6.2.

                  8.6.6.1     Locate  and correct the  source of  the problem  and
            repeat  the  test  for  all   analytes of  interest  beginning with
            Step 8.6.2.

                  8.6.6.2     Beginning with Step 8.6.2, repeat  the  test only
            for those analytes that failed to meet criteria.  Repeated failure,
            however, will confirm a general problem  with the measurement system.
            If this  occurs, locate and  correct  the source of  the  problem  and
            repeat  the  test  for   all  compounds of   interest  beginning with
            Step 8.6.2.

      8.7   The laboratory should,  on an  ongoing basis, analyze a reagent blank
and a matrix spiked duplicate  for  each  analytical batch (up to  a  maximum of 20
samples/batch) to assess accuracy.  For soil and waste samples  where detectable
amounts of organics are present, replicate samples  may be appropriate in place
of spiked duplicates.  For laboratories analyzing one to ten samples per month,
at least one spiked sample per month  is required.

            8.7.1 The. concentration  of  the  spike in  the sample  should  be
      determined as follows:

                  8.7.1.1     If, as  in compliance monitoring, the concentration
            of a  specific analyte  in  the sample  is  being checked  against  a
            regulatory concentration  limit,  the  spike should be at that limit,
            or 1 to 5 times higher than the background concentration determined
            in Step 8.7.2, whichever  concentration  would  be larger.

                  8.7.1.2     If the concentration  of a  specific analyte in  a
            water sample is not  being checked against a limit  specific to that
            analyte, the  spike  should  be at  the same concentration  as  the QC
            reference  sample  (Step  8.6.2)  or  1 to  5 times  higher  than  the
            background  concentration  determined   in  Step 8.7.2,   whichever
            concentration would  be  larger.  For other matrices,  the recommended
            spiking concentration  is  20 times the EQL.


                                  8000A - 11                         Revision  1
                                                                     July 1992

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            8.7.1.3     For semivolatile organics,  it may not be possible.
      to determine the background concentration  levels  prior to spiking
      (e.g. maximum holding  times will be exceeded).  If  this  is the case,
      the spike concentration should be (1)  the regulatory concentration
      limit, if any; or,  if none (2) the larger of either 5 times higher
      than  the  expected background  concentration or  the QC  reference
      sample  concentration  (Step   8.6.2).     For  other  matrices,  the
      recommended spiking concentration is 20 times the EQL.

      8.7.2 Analyze  one unspiked   and   one  spiked  sample  aliquot  to
determine percent recovery  of each of the spiked compounds.

            8.7.2.1     Volatile  organics  -   Analyze   one  5-mL  sample
      aliquot  to determine  the background  concentration  (B)   of  each
      analyte.    If  necessary,  prepare  a  new  QC  reference  sample
      concentrate   (Step 8.6.1)    appropriate    for    the   background
      concentration in the  sample.   Spike a second  5-mL  sample aliquot
      with 10 juL of the QC  reference sample concentrate  and analyze it to
      determine  the  concentration  after spiking  (A)  of  each  analyte.
      Calculate each percent recovery (p) as 100(A - B)%/T,  where  T is the
      known true value of the spike.

            8.7.2.2     Semivolatile organics - Analyze one  sample aliquot
      (extract of  1-L  sample)  to determine  the background concentration
      (B)  of  each analyte.   If necessary,  prepare  a  new QC  reference
      sample  concentrate (Step  8.6.1)   appropriate  for the  background
      concentration in the  sample.  Spike a second 1-L sample aliquot with
      1.0 mL  of  the QC  reference sample concentrate and  analyze  it to
      determine  the  concentration  after spiking  (A)  of  each  analyte.
      Calculate each percent recovery (p) as 100(A - B)%/T,  where  T is the
      known true value of the spike.

      8.7.3 Compare the percent recovery (p) for each analyte in a water
sample with  the corresponding  criteria  presented in the  QC Acceptance
Criteria Table  found  at the end of each of the determinative  methods.
These acceptance  criteria  were calculated  to  include  an  allowance  for
error in  measurement of both  the  background  and  spike concentrations,
assuming a spike to background ratio of 5:1.   This error  will be accounted
for to the extent that the  analyst's  spike to background ratio approaches
5:1.   If  spiking  was performed at  a concentration  lower than  the QC
reference sample concentration  (Step 8.6.2),  the analyst  should use either
the  QC  acceptance  criteria presented  in  the  Tables,  or  optional  QC
acceptance criteria calculated for the specific  spike concentration.   To
calculate  optional  acceptance  criteria for  the  recovery  of  an   analyte:
(1)  Calculate accuracy  (x')  using  the  equation found  in  the Method
Accuracy and  Precision as  a Function of Concentration  Table  (appears at
the   end   of  each   determinative   method),   substituting   the  spike
concentration (T)  for  C; (2) calculate  overall_precision (S')  using the
equation in the same Table,  substituting x' for x; (3) calculate the range
for recovery at the spike concentration as (lOOx'/T) ± 2.44(100S'/T)%.

      8.7.4 If any  individual  p falls outside the designated  range  for
recovery,  that  analyte  has failed  the  acceptance  criteria.    A check
standard  containing each  analyte   that  failed  the  criteria should be

                            8000A -  12                        Revision  1
                                                               July  1992

-------
      analyzed as described in Step 8.8.

      8.8   If any analyte in a water sample fails the acceptance criteria for
recovery in Step 8.7, a QC reference standard containing each analyte that failed
should be prepared and analyzed.

      NOTE; The frequency for the required analysis of a QC reference standard
            will  depend upon the number of analytes being simultaneously tested,
            the complexity of the sample  matrix,  and the  performance  of the
            laboratory.  If the entire list of analytes given in a method should
            be measured  in  the sample  in  Step  8.7,  the probability  that the
            analysis of a QC check standard will be required is high.   In this
            case, the QC  check  standard  should  be routinely analyzed  with the
            spiked sample.

            8.8.1 Preparation of the QC  check sample  - For volatile organics,
      add 10 ;uL of the  QC check  sample  concentrate (Step 8.6.1  or 8.7.2) to 5
      ml of water.  For  semivolatile organics, add 1.0  ml of the QC check sample
      concentrate (Step 8.6.1  or  8.7.2)  to 1 L of water.  The  QC  check sample
      needs only to  contain  the analytes that failed  criteria  in  the test in
      Step  8.7.    Prepare the  QC  check  sample  for  analysis  following  the
      guidelines given in Method 3500 (e.g. purge-and-trap, extraction, etc.).

            8.8.2 Analyze the  QC  check  sample to  determine the concentration
      measured (A) of  each  analyte.   Calculate  each  percent recovery  (ps) as
      100(A/T)%,  where T is the true value of the standard  concentration.

            8.8.3 Compare the percent recovery  (ps) for each  analyte  with the
      corresponding QC  acceptance criteria found in the appropriate  Table in
      each of the methods. Only analytes that failed the test in Step 8.7 need
      to be compared with these criteria.  If the recovery  of any such analyte
      falls outside the designated range,  the laboratory performance  for that
      analyte  is  judged  to   be  out  of  control,  and  the  problem should  be
      immediately identified  and corrected.  The  result for  that analyte in the
      unspiked  sample   is  suspect  and   may  not  be  reported  for  regulatory
      compliance purposes.

      8.9   As part of the QC program for the laboratory,  method  accuracy for
each matrix studied  should be  assessed and records should be maintained.  After
the analysis of five spiked samples  (of  the  same  matrix type)  as  in Step 8.7,
calculate the  average  percent recovery  (p) and  the standard deviation  of the
percent recovery (s ).   Express the  accuracy assessment as  a percent  recovery
interval from  p - 2s  to  p +  2sp.   If  p = 90% and sp  = 10%,  for  example, the
accuracy interval  is expressed as 70-110%.  Update the accuracy assessment for
each analyte  on  a regular  basis (e.g.  after  each five to ten  new  accuracy
measurements).

      8.10  Calculate surrogate control  limits as follows:

            8.10.1      For each sample analyzed, calculate  the percent recovery
      of each surrogate in the sample.

            8.10.2      Calculate the average percent recovery (p) and standard
      deviation of the  percent recovery  (s)  for  each of  the  surrogates when

                                  8000A - 13                        Revision 1
                                                                     July 1992

-------
      surrogate data from 25 to 30 samples for each matrix is available.

            8.10.3      For  a given  matrix,  calculate  the  upper and  lower
      control limit for method performance  for  each  surrogate standard.   This
      should be done as follows:

            Upper Control  Limit (UCL) = p + 3s
            Lower Control  Limit (LCL) = p - 3s

            8.10.4      For  aqueous  and   soil  matrices,   these  laboratory
      established surrogate control  limits  should,  if  applicable,  be  compared
      with  the  control  limits in  Tables A and B of  Methods 8240 and  8270,
      respectively.   The  limits  given  in these methods  are multi-laboratory
      performance based limits for  soil  and  aqueous samples, and therefore, the
      single-laboratory limits established  in Step 8.10.3  should  fall  within
      those given in Tables A and B for these  matrices.

            8.10.5      If  recovery  is  not within  limits,  the following  is
      required.

            •     Check  to  be  sure  there are no  errors   in  calculations,
                  surrogate  solutions  and  internal  standards.    Also,  check
                  instrument performance.

            •     Recalculate the data  and/or reanalyze the  extract  if any of
                  the above checks reveal a problem.

            «     Reextract and reanalyze the  sample  if none  of the above are a
                  problem or flag the data as  "estimated concentration."

            8.10.6      At a minimum, each  laboratory  should update  surrogate
      recovery limits on a matrlx-by-matrix basis,  annually.

      8.11  It  is  recommended that  the  laboratory  adopt  additional  quality
assurance practices for use with this method.   The  specific practices  that are
most productive depend upon the needs of the  laboratory and the nature of the
samples.   Field duplicates  may  be  analyzed  to assess the precision of the
environmental measurements. When doubt exists  over  the  identification of a peak
on the chromatogram, confirmatory techniques such as gas chromatography with a
dissimilar  column,  specific  element  detector, or mass spectrometer should be
used.   Whenever possible,  the  laboratory  should  analyze  standard  reference
materials and participate in relevant performance evaluation studies.


9.0   METHOD PERFORMANCE

      9.1   The  method  detection   limit  (MDL)  is  defined  as  the  minimum
concentration  of a  substance that  can  be  measured  and  reported  with  99%
confidence that the value is above zero.  The  MDL concentrations listed in the
referring analytical methods were  obtained  using water.   Similar results were
achieved using representative  wastewaters.  The MDL  actually achieved in a given
analysis will vary depending on instrument sensitivity and matrix effects.
                                  8000A - 14                        Revision 1
                                                                     July 1992

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      9.2   Refer to the determinative method  for  specific method performance
information.


10.0  REFERENCES

1.    U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
      Analysis of Pollutants Under the Clean Water Act; Final  Rule and Interim
      Final Rule and Proposed Rule," October 26, 1984.

2.    U.S.  EPA Contract  Laboratory Program,  Statement of  Work  for  Organic
      Analysis, July 1985, Revision.
                                  8000A - 15                        Revision 1
                                                                     July 1992

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                                  METHOD  8000A
                              GAS CHROMATOGRAPHY
     Start
 7.1  Refer  to
 determinative
 procedure  for
  ex t raction
   procedure
recommendation,
                                  Internal Standard
                                                            External  Standard
                       74.3.1  Select
                     internal standards
                       having behavior
                         similar  to
                        compounds  of
                          interes t ,
                                                  7.4.2.1 Prepare
                                                   calibration
                                                standards for each
                                                   compound of
                                                    interest.
7 .2 Refer to
determinative
pr ocedure f or
cleanup and
prepara tion
procedure
recommendations .


743.2 Prepare
ca 1 ibra tion
s tandards .


                                                                         74.2.2 Inject
                                                                           calibration
                                                                       standards, prepare
                                                                        calibration curve
                                                                         or calculate
                                                                       calibration factor.
7.4.1  Establish
chr oma tographic
  conditions .
7433  Inject
  ca 1 ibra tion
  s tandard j ,
 calculate RF
                       7.4.34  Verify
                     wor king calibration
                      curve or  RF  each
                            day.
                                                                         74.23 Verify
                                                                       working calibration
                                                                         curve each day.
                          7.5 Calculate
                         retention time
                            windows.
                                     8000A  -  16
                                                           Revision 1
                                                            July 1992

-------
                                       METHOD 8000A
                                         continued
                                          Semivolatile*
     7.6,1 If
    necessary,
  • creeii cample*
  by Method 3810
     or 3820.
  7.6,1 Introduce
 coicpsunds  into  GC
 by purge-and-trap
or direct injection
  (Method 5030),
7,6,1 Introduce
compounds  into
 GC by direct
  injection.
 7,6,4  Inject
 sample*  using
 sol vent  flush
  technique,
record  volume.
                                                     7,6.5 Dilute
                                                      extract and
                                                      reanalyze.
                                                       7.6.6 Do
                                                        fur ther
                                                       cleanup.
                                                                                        7
                       7.6.8 Calibrate
                           system
                         immediately
                          prior to
                          analyses,
                       7.6,9 Establish
                       daily retention
                        tine uindovs
                          for each
                          analyte.
                         7,7 Perform
                       chroma tograpHy
                           system
                       maintenance, if
                           needed.
                        7.8 Calculate
                      concentration  of
                     each analyte, tiling
                     appropriate  formula
                     for matrix and  type
                        of standard.
                                                                                Stop
                                        8000A  -  17
                                 Revision  1
                                  July  1992

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                                 METHOD 801OB

             HALOGENATED  VOLATILE ORGANICS BY GAS CHROHATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   Method 8010  is  used  to  determine  the  concentration  of  various
volatile  halogenated   organic  compounds.    The  following  compounds  can  be
determined by this method:
Approoriate Technique
Compound Name
Ally! chloride
Benzyl chloride
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl ) ether
Bromoacetone
Bromo benzene
Bromodi chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane
Chl oromethane
Chloromethyl methyl ether
Chloroprene
4-Chlorotoluene
Di bromochl oromethane
l,2-Dibromo-3-chloropropane
Dibromomethane
1 , 2-Dichl orobenzene
1,3-Dichlorobenzene
1 ,4-Dichl orobenzene
l,4-Dichloro-2-butene
Dichl orodifl uoromethane
1 , 1-Dichloroethane
l,2-D1chloroethane
1,1-Dichloroethene
trans-l,2-Dichloroethene
Dichl oromethane
1 , 2-Dichl oropropane
l,3-Dichloro-2-propanol
cis-1 ,3-Dichloropropene
trans-l,3-Dichloropropene
Epichlorhydrin
CAS No.3
107-05-1
100-44-7
111-91-1
39638-32-9
598-31-2
108-86-1
75-27-4
75-25-2
74-83-9
56-23-5
108-90-7
75-00-3
107-07-03
110-75-8
67-66-3
544-10-5
74-87-3
107-30-2
126-99-8
106-43-4
124-48-1
96-12-8
74-95-3
95-50-1
541-73-1
106-46-7
764-41-0
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
75-09-2
78-87-5
96-23-1
10061-01-5
10061-02-6
106-89-8
Purge-and-Trap
b
PP
PP
b
PP
b
b
b
b
b
b
b
pp
b
b
pc
b
PP
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
PP
b
b
PP
Direct
Injection.
b
b
pc
b
b
b
b
b
b
b
b
b
b
b
b
pc
b
pc
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
                                  8010B - 1
    Revision 2
September 1994

-------
Compound Name
CAS No,a
  Appropriate Technique
                   Direct
Pyrge-and-Trap     Injection
Ethyl ene di bromide
Methyl iodide
1,1,2,2-Tetrachloroethane
1,1,1 , 2-Tetrachl oroethane
Tetrachloroethene
1 , 1 , 1-Tri chl oroethane
1 , 1 ,2-Tri chl oroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane
Vinyl Chloride
106-93-4
74-88-4
79-34-5
630-20-6
127-18-4
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
75-01-4
b
PP
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
a  Chemical Abstract Services Registry Number
b  Adequate response using this technique
pp Poor purging efficiency, resulting in high
pc Poor chromatographic performance.
         EQLs
      1.2    Table  1 indicates compounds that may be analyzed  by this method and
lists the method detection limit for each compound in organic-free reagent water.
Table 2 lists the estimated quantitation limit for other matrices.


2.0   SUMMARY OF METHOD

      2.1    Method  8010  provides  gas  chromatographic  conditions  for  the
detection of halogenated volatile organic compounds.  Samples can be introduced
into the GC using direct injection or purge-and-trap (Method 5030),  Ground water
samples must be analyzed using Method 5030.  A temperature program is  used in the
gas chromatograph to separate the organic compounds.  Detection is achieved by
a electrolytic conductivity detector (HECD).

      2.2    The method provides an optional  gas  chromatographic column that may
be helpful in resolving the analytes from co-eluting non-target compounds and for
analyte confirmation.


3.0   INTERFERENCE;*

      3.1    Refer  to Methods 5030  and 8000.

      3.2    Samples  can  be  contaminated  by diffusion  of  volatile  organics
(particularly chlorofluorocarbons  and  methylene chloride) through  the  sample
container septum  during  shipment  and  storage.   A  trip blank prepared  from
organic-free reagent water and carried  through sampling and subsequent storage
and handling can serve as a check on such contamination.
                                   8010B  -  2
                               Revision 2
                           September 1994

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4.0    APPARATUS AND MATERIALS

       4.1    Gas chromatograph

             4.1.1  Gas  chromatograph  -  analytical   system  complete  with gas
       chromatograph suitable for on-column  injections or purge-and-trap sample
       introduction  and  all required accessories,  including detector, analytical
       columns,  recorder,  gases,  and syringes,  A data system for measuring peak
       heights and/or peak areas  is  recommended,

             4,1.2  Columns

                   4.1.2.1    Column 1  -  8  ft  x  0.1  in.  ID  stainless steel  or
             glass  column packed with 1%  SP-1000  on  Carbopack-B  60/80 mesh or
             equivalent.

                   4.1.2.2    Column 2  -  6  ft  x  0.1  in.  ID  stainless steel  or
             glass  column packed with chemically  bonded  n-octane  on Porasil-C
             100/120 mesh (Durapak)  or equivalent.

             4.1.3  Detector - Electrolytic conductivity  (HECD).

       4.2    Sample   introduction apparatus,  refer  to   Method  5030  for  the
appropriate  equipment for sample  introduction purposes.

       4.3    Syringes,  5 ml  Luerlok  glass  hypodermic and a 5 ml, gas-tight with
shutoff valve.

       4.4    Volumetric  flask, Class  A,  Appropriate  sizes  with  ground  glass
stoppers.

       4.5    Microsyringe, 10 and 25 /aL with  a 0.006 in. ID needle (Hamilton 702N
or equivalent)  and  a 100  pi.

       4.6    Analytical  balance - 0.0001 g.


5.0    REAGENTS

       5.1    Reagent grade  chemicals  shall  be  used in  all  tests.    Unless
otherwise  indicated,  it  is  intended  that  all  reagents  shall conform to the
specifications of the Committee on Analytical Reagents of the American Chemical
Society, where  such specifications  are  available.  Other grades  may  be  used,
provided it is first ascertained  that the reagent  is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.

       5.2    Organic-free  reagent water.   All references to water in this method
refer to organic-free reagent water, as  defined in Chapter One.

       5.3    Methanol, CH3OH.  Pesticide  quality or equivalent.  Store away from
other solvents.
                                   8010B  -  3                         Revision 2
                                                                September 1994

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      5.4   Stock standards - Stock solutions may be prepared  from pure standard
materials or  purchased as  certified  solutions.   Prepare stock  standards  in
methanol  using assayed  liquids or gases,  as appropriate.  Because of the toxicity
of some of  the organohalides,  primary dilutions of these  materials  should  be
prepared  in a hood,

            5.4.1 Place about 9.8 ml of methanol in a 10 ml tared ground glass
      stoppered volumetric  flask.  Allow the  flask to stand, unstoppered,  for
      about 10 minutes until all  alcohol-wetted  surfaces have dried.  Weigh the
      flask to the nearest 0.0001 g.

            5.4.2 Add  the  assayed reference material, as described below.

                  5.4.2.1     Liquids.   Using  a  100 pL syringe, immediately add
            two or more drops of assayed reference material to the flask; then
            reweigh.   The  liquid must fall  directly  into  the  alcohol  without
            contacting the neck of the flask.

                  5.4.2.2     Gases.   To prepare  standards for any  compounds
            that   boil   below   30°C   (e.g.   bromomethane,    chloroethane,
            chloromethane,   dichlorodifluoromethane,   trichlorofluoromethane,
            vinyl chloride),  fill  a  5  ml  valved  gas-tight  syringe with  the
            reference  standard to the 5.0 mL  mark.  Lower the needle  to 5  mm
            above  the methanol  meniscus.     Slowly  introduce  the  reference
            standard above  the surface  of  the liquid.  The  heavy gas  rapidly
            dissolves  in the methanol.  This may also  be accomplished by using
            a  lecture  bottle equipped with a Hamilton Lecture Bottle  Septum
            (186600).  Attach Teflon  tubing  to the side-arm relief  valve  and
            direct a gentle stream of gas into the methanol meniscus,

            5.4.3 Reweigh, dilute to  volume, stopper,  and then mix by inverting
      the flask several times.   Calculate the concentration  in milligrams  per
      liter (mg/L) from the net gain in weight.  When compound purity is assayed
      to  be  96% or  greater, the  weight  may  be   used  without correction  to
      calculate the  concentration of the stock standard.  Commercially prepared
      stock standards may  be used at any concentration if they are certified  by
      the manufacturer or by an independent  source.

            5,4.4 Transfer  the  stock standard  solution  into a bottle  with  a
      Teflon lined screw-cap.  Store,  with minimal  headspace, at -10°C to -20°C
      and protect from light.

            5,4.5 Prepare fresh  stock standards for gases  weekly  or  sooner  if
      comparison with check standards indicates  a  problem.  Reactive  compounds
      such  as  2-chloroethyl  vinyl ether may need  to  be prepared more frequently.
      All  other  standards  must be replaced  after six months.   Both  gas  and
      liquid standards must be monitored closely by comparison to the  initial
      calibration curve and  by  comparison  to QC check  standards.    It  may  be
      necessary to replace the standards  more frequently if either check exceeds
      a 20% drift.

            5.4.6 Optionally calibration using a certified gaseous mixture can
      be  accomplished  daily  utilizing commercially available gaseous  analyte


                                  8010B - 4                         Revision 2
                                                               September 1994

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       mixture of  bromomethane,  chloromethane, chloroethane,  vinyl  chloride,
       dichlorodifluoromethane  and  trichlorofluoromethane  in  nitrogen.  These
       mixtures of documented  quality are  stable for  as  long  as  six  months
       without refrigeration.  (VOA-CYL III,  RESTEK Corporation,  Cat.  #20194  or
       equivalent).

       5.5    Secondary  dilution  standards.  Using  stock  standard  solutions,
prepare  secondary  dilution standards  in  methanol, as  needed,  containing the
compounds of  interest, either singly or mixed together.   The secondary dilution
standards should be prepared at concentrations such that the aqueous  calibration
standards prepared in Sec. 5.6 will  bracket  the working  range  of  the analytical
system.  Secondary  dilution standards should  be stored with minimal headspace for
volatiles  and  should  be  checked  frequently  for  signs  of degradation   or
evaporation, especially just prior to preparing calibration standards from them.

       5.6    Calibration  standards.      Prepare   calibration   standards   in
organic-free  reagent water from the secondary dilution of  the stock standards,
at a minimum  of five concentrations.  One of the concentrations  should  be at a
concentration  near,  but  above,  the  method detection  limit.    The  remaining
concentrations should  correspond  to the  expected  range  of the  concentrations
found  in real samples  or should define  the working range of the SC.   Each
standard should contain each analyte for detection by  this  method (e.g.  some or
all of the  compounds  listed in Table 1 may  be included).  In  order to prepare
accurate aqueous standard solutions, the following  precautions  must be  observed.

             5.6.1  Do  not inject more  than  20 jiL  of  alcoholic standards into
       100 ml  of water.

             5.6.2  Use  a 25  #L  Hamilton   702N   microsyringe   or  equivalent
       (variations  in   needle  geometry will  adversely  affect  the  ability  to
       deliver reproducible volumes of methanolic standards  into  water).

             5.6,3  Rapidly  inject  the  alcoholic  standard  into   the   filled
       volumetric flask.  Remove the  needle as fast  as  possible after injection,

             5.6.4  Mix aqueous standards by inverting the flask three  times only,

             5.6.5  Fill  the  sample syringe from the standard solution  contained
       in the  expanded  area  of  the flask  (do not  use  any solution contained  in
       the neck of the flask).

             5.6.6  Never use pipets to dilute or   transfer  samples  or aqueous
       standards.

             5.6.7  Aqueous standards are not  stable  and should be discarded after
       one hour, unless  properly  sealed and  stored.  The aqueous standards can
       be stored up to 24  hours, if held in sealed  vials with zero headspace,

       5.7    Internal  standards (if internal  standard  calibration  is used) - To
use this approach,  the analyst must  select one or more internal standards that
are similar in analytical behavior to the compounds  of  interest.  The analyst
must further  demonstrate  that the measurement  of  the  internal  standard  is not
affected by method or matrix interferences.   Because  of these limitations,  no


                                  8010B - 5                         Revision 2
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 Internal  standard can  be  suggested that  is  applicable to all  samples.   The
 compounds  recommended for use  as  surrogate spikes (Sec.  5.8)  have been used
 successfully as internal standards, because of their generally unique retention
 tiroes.

             5.7.1 Prepare  calibration   standards  at  a  minimum  of  five
       concentrations  for each  analyte  of interest  as described  in  Sec.  5.6.

             5.7,2 Prepare a spiking solution  containing  each of the internal
       standards  using the procedures  described  in Sees.  5.4  and  5.5.   It  is
       recommended that  the  secondary  dilution   standard  be  prepared  at  a
       concentration  of  15 ng/pL  of  each internal standard compound.   The
       addition  of 10 pi  of  this standard to  5.0  ml of sample or calibration
       standard would  be equivalent  to  30
             5.7.3  Analyze  each  calibration  standard  according to  Sec.  7.0,
       adding  10 pi  of  internal  standard  spiking  solution  directly  to  the
       syringe.

       5.8    Surrogate  standards  -   The  analyst  should  monitor  both  the
performance  of  the analytical system  and  the effectiveness of the  method in
dealing  with  each  sample  matrix  by  spiking   each  sample,   standard,  and
organic-free reagent water  blank with surrogate halocarbons.  A  combination of
bromoehloromethane, bromochlorobenzene and  bromof 1 uorobenzene is recommended to
encompass the  range of temperature  program  used in this method.   From stock
standard solutions prepared as in Sec.  5.4,  add a  volume to give  750 ^g of each
surrogate to 45  ml  of organic-free  reagent water contained in a 50 ml volumetric
flask, mix,  and dilute to volume  for  a  concentration of 15 ng/^L.  Add 10 pL of
this surrogate spiking solution directly  into the 5 ml syringe with every sample
and reference standard analyzed.  If the internal  standard calibration procedure
is used, the surrogate compounds  may  be added  directly to the internal standard
spiking solution (Sec. 5.7.2).


6.0    SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

       6.1    See  the introductory material  to  this  Chapter, Organic  Analytes,
Sec. 4.1.
7.0   PROCEDURE

      7.1   Volatile  compounds  are introduced  into the gas chromatograph using
either direct  injection or purge-and-trap (Method 5030).  Method 5030 may be used
directly on ground  water samples or low-concentration  contaminated  soils and
sediments.  For medium-concentration  soils  or sediments, methanolic extraction,
as described in Method 5030,  may be necessary prior to purge-and-trap analysis.

      7.2   Gas chromatographic conditions  (Recommended)

            7,2.1  Column 1:

            Helium  flow  rate =  40 mL/min


                                  8010B  -  6                        Revision 2
                                                                September 1994

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            Temperature program:
                   Initial  temperature  =  45°C, hold for 3 minutes
                   Program  =               45°C to 220°C at 8°C/fflin
                   Final temperature  =     220°C, hold for 15 minutes.

            7.2,2  Column 2:

            Helium flow rate = 40 mL/min
            Temperature program:
                   Initial  temperature  =  50°C, hold for 3 minutes
                   Program  -               50°C to 170°C at 6°C/min
                   Final temperature  =     170°C, hold for 4 minutes.

      7.3   Calibration. The procedure for internal or external calibration may
be used.  Refer to Method 8000 for a description of each of these procedures. Use
Table 1 and Table 2 for guidance on selecting the lowest point on the calibration
curve.

            7.3.1. Cal ibration must take place using the same sample introduction
      method that will be  used to analyze actual samples  (see Sec. 7.4.1).

      7.4   Gas chromatographic analysis

            7.4.1  Introduce volatile compounds into the gas chromatograph using
      either Method 5030 (purge-and-trap) or  the  direct injection method (see
      Sec.  7.4.1.1).   If the internal  standard calibration  technique is used,
      add 10 /uL of internal standard to the sample prior  to purging.

                   7.4.1.3     In very limited applications (e.g. aqueous process
            wastes) direct injection of the sample onto  the GC  column  with  a
            10 ML  syringe may be appropriate.   The  detection limit is very high
            (approximately 10,000 ng/L) therefore,  it is only  permitted where
            concentrations  in excess of 10,000 /ug/L are expected or for water-
            soluble compounds that do not  purge.  The system must be calibrated
            by direct  injection (bypassing the purge-and-trap device).

            7.4.2  Method 8000 provides instructions  on the analysis sequence,
      appropriate  dilutions,  establishing daily  retention  time windows,  and
      identification criteria.   Include a mid-concentration standard after each
      group of 10 samples  in  the analysis sequence.

            7.4.3  Table 1  summarizes the  estimated retention times  on the two
      columns for a number of organic  compounds  analyzable  using this method;
      An  example of the separation achieved by Column 1 is shown in Figure 1.

            7.4.4  Record the sample volume purged or  injected and the resulting
      peak  sizes (in area  units  or peak heights).

            7.4.5  Refer  to  Method  8000   for  guidance  on   calculation  of
      concentration.

            7.4.6  If analytical  interferences are suspected, or for the purpose
      of  confirmation, analysis  using the second GC column is recommended.


                                  8010B - 7                         Revision  2
                                                                September 1994

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             7.4.7 If the  response  for a peak  is  off-scale,  i.e., beyond  the
       calibration range of the standards, prepare a dilution of the sample with
       organic-free reagent water.  The dilution must be performed  on  a  second
       aliquot  of the sample  which has  been  properly  sealed  and  stored  prior to
       use.
8.0    QUALITY  CONTROL

       8.1    Refer to Chapter One  for specific quality control procedures and
Method 8000  for gas  chromatographic  procedures.  Quality control to ensure the
proper operation  of  the  purge-and-trap device  is covered in Method 5030.

       8.2    Quality control required  to  validate the GC  system operation is
found  in Method 8000.

             8.2.1 The quality control check sample  concentrate (Method 8000)
       should contain each  analyte  of interest  at a concentration of 10 mg/L in
       methane!.

             8.2.2 Table 3  indicates  the calibration and QC  acceptance criteria,
       for  water  samples, for this method.   Table  4  gives  method accuracy and
       precision  as  functions  of  concentration,  for  water  samples,  for  the
       analytes  of interest.   The  contents  of both  Tables should be  used to
       evaluate a  laboratory's  ability to  perform and generate acceptable data
       by this method.

       8.3    Calculate surrogate  standard  recovery  on all  samples,  blanks,  and
spikes.  Determine if recovery is  within limits  (limits established by performing
QC procedure outlined in Method 8000).

             8.3.1 If recovery  is not within  limits,  the following is required:

                   •    Check  to  be  sure  that  there   are   no   errors   in
             calculations,  surrogate  solutions and internal standards.   Also,
             check instrument performance.

                   •     Recalculate  the data  and/or re-analyze  the  sample if
             any of the  above checks  reveal a problem.

                   •    Re-extract  and re-analyze  the sample  if none  of  the
             above are a  problem  or flag the  data as  "estimated concentration".


9.0   METHOD PERFORMANCE

      9.1    This method was tested  by 20 laboratories  using  organic-free reagent
water, drinking water, surface water, and three industrial wastewaters spiked at
six concentrations over the range 8.0-500 isg/l.  Single  operator precision,
overall precision, and method accuracy were found to  be directly related to the
concentration of the analyte,  and essentially independent of the sample matrix.
Linear equations to describe these relationships are presented in Table 4.
                                   8010B  -  8                        Revision 2
                                                                September 1994

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      9.2    The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique, and by the calibration procedure used.

      9.3    The method detection limits reported in Table I were generated under
optimum analytical conditions by an Agency contractor  (Ref. 6) as guidance, and
may not be readily achievable by all laboratories at all times,


10.0  REFERENCES

1.    Bellar, T.A.; Lichtenberg, J.J.  J.  Amer. Water Works Assoc, 1974. 66(12).
      pp. 739-744.

2.    Bellar,  T.A.;  Lichtenberg,  J.J.,  Semi-Automated Headspace  Analysis  of
      Drinking  Waters  and  Industrial  Waters for Purgeable  Volatile Organic
      Compounds, Measurement of Organic Pollutants in Water and Wastewater; Van
      Hall,  Ed.; ASTM STP 686, pp  108-129, 1979.

3.    "Development and Application  of Test Procedures for Specific Organic Toxic
      Substances  in  Wastewaters: Category 11 -  Purgeables  and Category  12  -
      Acrolein,  Aerylonitrile,  and Dichlorodifluoromethane";  report  for  EPA
      Contract 68-03-2635.

4.    U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
      Analysis of Pollutants Under the Clean Water Act: Final  Rule and Interim
      Final  Rule and Proposed Rule", October 26,  1984.

5.    "EPA Method  Validation Study 23,  Method  601 (Purgeable .Halocarbons}";
      report for EPA Contract 68-03-2856.

6.    Gebhart, J.E., S.V. Lucas, S.J.  Naber,  A.M.  Berry, T.H.  Danison and H.M.
      Burkholder, "Validation of SW-846  Methods 8010,  8015,  and  8020"; Report
      for  EPA Contract  68-03-1760,  Work Assignment  2-15;   US   EPA,  EMSL-
      Cincinnati, 1987.
                                  8010B  - 9                         Revision 2
                                                                September 1994

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                       TABLE 1.
CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
           FOR HALOGENATED VOLATILE ORGANICS
Compound
Ally! chloride*^
Benzyl chloride*'0
Bi s ( 2 -chl oroethoxy ) methane*
Bis(2-chloroisopropyl ) ether*
Bromo benzene
Bromodi chl oromethane
Bromoform*
Bromomethane*
Carbon tetrachloride*
Chl oroacetal dehyde*
Chlorobenzene*
Chl oroethane
Chloroform*
1-Chlorohexane
2-Chloroethylt vinyl ether*
Chl oromethane*
Chloromethyl methyl ether*
4-Chlorotoluene
Di bromochl oromethane
l,2-Dibromo-3-chloropropane*
Dibromome thane*
I , 2-Dichlorobenzene*
1 , 3 -Di chl orobenzene*
1,4-Dichlorobenzene*
l,4-Dichloro-2-butene*
Di chl orodi f 1 uoromethane*'d
1 , 1 -Dichl oroethane*
1 , 2-Dichl oroethane*
1 , 1 -Dichl oroethene*
trans- 1,2-Di chl oroethene*
DI chl oromethane*
1 , 2-Di chl oropropane*
trans-1 ,3-Dichl oropropene*
Ethyl ene di bromide
1,1,2 , 2-Tetrachl oroethane*
1,1,1 , 2-Tetrachloroethane*
Tetrachl oroethene
1,1,1-Trichloroethane^
1, 1,2-Trichloroethane*
CAS
Registry
Number
107-05-1
100-44-7
111-91-1
39638-32-9
108-86-1
75-27-4
75-25-2
74-83-9
56-23-5
107-20-0
108-90-7
75-00-3
67-66-3
544-10-5
110-75-8
74-87-3
107-30-2
106-43-4
124-48-1
96-12-8
74-95-3
95-50-1
541-73-1
106-46-7
764-41-0
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
75-09-2
78-87-5
10061-02-5
106-93-4
79-34-5
630-20-6
127-18-4
71-55-6
79-00-5
Retention Time
(minutes)
Column 1 Column 2
10.17
30.29
38.60
34.79
29.05
15.44
21.12
2.90
14.58
(b)
25.49
5.18
12.62
26.26
19.23
1.40
8.88
34.46
18.22
28.09
13.83
37.96
36.88
38.64
23.45
3.68
11.21
13.14
10.04
11.97
7.56
16.69
16.97*
19.59
23.12
21.10
23.05
14.48
18.27
(b)
(b)
(b)
(b)
(b)
14.62
19.17
7.05
11.07
(b)
18.83
8.68
12.08
(b)
(b)
5.28
(b)
(b)
16.62
(b)
14.92
23.52
22.43
22.33
(b)
(b)
12.57
15.35
7.72
9.38
10.12
16.62
16.60
(b)
(b)
21.70
14.97
13.10
18.07
Method
Detection
Limit3
(MA)
(b)
(b)
(b)
(b)
(b)
0.002
0.020
0.030
0.003
(b)
0.001
0.008
0.002
(b)
0.130
0.010
(b)
(b)
(b)
0.030
(b)
(b)
(b)
(b)
(b)
(b)
0.002
0.002
0.003
0.002
(b)
(b)
0.340
(b)
0.010
(b)
0.001
0.003
0.007
                      8010B - 10
    Revision 2
September 1994

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                                   TABLE 1.
                                   Continued
   Compound
CAS
Registry
Number
  Retention Time
     (minutes)
Column 1   Column
          Method
          Detection
          Limit8
          (M9/U
Trichloroethene
Trichlorofluoromethane*
1,2,3-Trichloropropane*
Vinyl Chloride*
 79-01-6
 75-69-4
 96-18-4
 75-01-4
 17.40
  9.26
 22.95
  3.25
13,12
 (b)
 (b)
 5.28
0,001
 (b)
 (b)
0.006
a = Using purge-and-trap method (Method 5030). See Sec. 9.3.
b = Not determined
* = Appendix VIII compounds
c = Demonstrated very erratic results when tested by purge-and-trap
d = See  Sec.  4.10.2  of Method  5030 for  guidance on  selection  of  trapping
    material
e = Estimated retention time
                                   TABLE 2.
             DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQL)
                             FOR VARIOUS  MATRICES3
               Matrix
                  Factor
               Ground water                             10
               Low-concentration soil                    10
               Water miscible liquid waste             500
               High-concentration soil  and sludge     1250
               Non-water miscible waste               1250
               EQL = [Method detection limit (see Table 1)] X [Factor found in
               this table].  For non-aqueous samples,  the  factor  is  on a wet-
               weight basis.  Sample EQLs are highly matrix-dependent.  The EQLs
               listed herein are provided  for  guidance and may not  always be
               achievable.
                                  8010B -  11
                                   Revision  2
                               September 1994


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                             TABLE  3.
              CALIBRATION AND QC ACCEPTANCE CRITERIA8


Analyte
Bromodichl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chi oroethane
2-Chloroethyl vinyl ether
Chloroform
Chi oromethane
Di bromochl oromethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans -1,2-Dichloroethene
Dichl oromethane
1,2-Dichloropropane
cis-1 ,3-Dichloropropene
trans-l,3-Dichloropropene
1 , 1 ,2 ,2-Tetrachl oroethane
Tetrachl oroethene
1 , 1 , 1 -Trichl oroethane
1,1,2 -Trichl oroethane
Trichloroethene
Trichlorofluoromethane
Vinyl chloride
Range Limit Range
for Q for S for x
(M9/LJ (M9A) (Mi/L)
15.2-24,8 4,3 10.7-32.0
14.7-25.3 4.7 5.0-29.3
11.7-28.3 7,6 3.4-24.5
13.7-26.3 5.6 11.8-25.3
14.4-25.6 5.0 10.2-27.4
15.4-24.6 4.4 11.3-25,2
12.0-28.0 8.3 4.5-35.5
15.0-25.0 4.5 12.4-24.0
11.9-28.1 7.4 D-34.9
13.1-26.9 6.3 7.9-35.1
14.0-26.0 5.5 1,7-38.9
9.9-30.1 9.1 6.2-32.6
13.9-26.1 5.5 11.5-25.5
16.8-23.2 3.2 11.2-24.6
14.3-25.7 5.2 13.0-26.5
12.6-27.4 6.6 10.2-27.3
12.8-27.2 6.4 11.4-27.1
15.5-24.5 4.0 7.0-27.6
14.8-25.2 5.2 10.1-29.9
12.8-27.2 7.3 6.2-33.8
12.8-27.2 7.3 6.2-33.8
9.8-30.2 9.2 6.6-31.8
14.0-26.0 5.4 8.1-29.6
14.2-25.8 4.9 10.8-24.8
15.7-24.3 3.9 9.6-25.4
15.4-24.6 4.2 9.2-26.6.
13.3-26.7 6.0 7.4-28.1
13.7-26.3 5,7 8.2-29.9
Range
P, P
(*)"
42-172
13-159
D-144
43-143
38-150
46-137
14-186
49-133
D-193
24-191
D-208
7-187
42-143
47-132
51-147
28-167
38-155
25-162
44-156
22-178
22-178
8-184
26-162
41-138
39-136
35-146
21-156
28-163
Q = Concentration measured in QC check sample, in M9/L.
S = Standard deviation of four recovery measurements, in jag/L.
x = Average recovery
P, Ps = Percent recovery
D = Detected; result
for four recovery measurements, in
measured.
must be greater than zero.
M9A.


Criteria from 40  CFR Part 136 for Method 601  and were calculated assuming
a QC check sample concentration  of 20 M9A.
                           8010B - 12
    Revision 2
September 1994

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                                TABLE 4.
       METHOD ACCURACY AND  PRECISION  AS  FUNCTIONS OF CONCENTRATION3
Analyte
Bromodichl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethyl vinyl etherb
Chloroform
Chi oromethane
Di broraochl orotnethane
1 , 2-Di chl orobenzene
1,3-Dichlorobenzene
1, 4 -DI chl orobenzene
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichl oroethene
trans- 1, 2-DI chl oroethene
Dichl oromethane
1 , 2-Di chl oropropantb
cis-l,3-Dichloropropeneb
trans-l,3-Dichloropropeneb
1,1,2,2-Tetrachloroethane
Tetrachl oroethene
1,1,1 -Tri chl oroethane
1,1, 2 -Tri chloroethane
Tri chl oroethene
Tri chl orof 1 uoromethane
Vinyl chloride
Accuracy, as
recovery, x'
(P9/L)
1.12C-1.02
0.96C-2.05
0.76C-1.27
0.98C-1.04
l.OOC-1,23
0.99C-1.53
l.OOC
0.93C-0.39
0.77C+0.18
0.94C+2.72
0.93C+1.70
0.95C+0.43
0.93C-0.09
0.95C-1.08
1.04C-1.06
0.98C-0.87
0.97C-0.16
0.91C-0.93
l.OOC
l.OOC
l.OOC
0.95C+0.19
Q.94C+0.06
0.90C-0.16
0.86C+0.30
0.87C+0.48
0.89C-0.07
0.97C-0.36
Single analyst
precision, s '
(MA)
0.11X+0.04
0.12X+0.58
0.28X+0.27
0.15X+0.38
0.15X-0.02
0.14X-0.13
0.20X
0.13X+0.15
0.28X-0.31
0.11X+1.10
0.20X+0.97
0.14X+2.33
0.15X+0.29
0.08X+0.17
0.11X+0.70
0.21X-0.23
0.11X+1.46
0.11X+0.33
0.13X
0.18X
0.18X
0.14X+2.41
0.14X+0.38
0.15X+0.04
0.13X-0.14
0.13X-0.03
0.15X+0.67
0.13X+0.65
Overall
precision,
S' (M9/L)
0.20X+1.00
0.21X+2.41
0.36X+0.94
0.20X+0.39
0.18X+1.21
0.17X+0.63
0.35X
0.19X-0.02
0.52X+1.31
0.24X+1.68
0.13X+6.13
0.26X+2.34
'0.20X+0.41
0.14X+0.94
0.15X+0.94
0.29X-0.04
0.17X+1.46
0.21X+1.43
0.23X
0.32X
0.32X
0.23X+2.79
0.18X+2.21
0.20X+0.37
0.19X-I-0.67
0.23X+0.30
0.26X+0.91
0.27X+0.4.0
Expected recovery for one or more measurements of a sample containing
a concentration of C, in pg/L.

Expected  single analyst  standard deviation  of measurements  at  an
average concentration of x,  in
x' =
s'=
S' =  Expected  interlaboratory  standard  deviation  of  measurements  at  an
      average concentration found of x» in tig/L.

C  =  True value for the concentration, in M9/L.

X  =  Average  recovery  found  for  measurements  of  samples  containing  a
      concentration of C, in ^g/L.

a From 40 CFR Part 136 for Method 601.

b Estimates based  upon the performance  in  a  single laboratory.
                               8010B - 13
                                                           Revision 2
                                                       September 1994

-------
                       FIGURE 1.
GAS  CHROHATOGRAM  OF HALOGENATED VOLATILE ORGANICS
                                 Coltmn;
                                 Program:
                                 Detector:
IX SP-1000 on C«rbopack-B
45*C-3 Ninutes, 8'C/Hinutt to 220*C
«»U TOO-* lleetrolytie Conductivity
                          M
                      8010B -  14
                     Revision 2
                September  1994

-------
                                      METHOD 801OB
             HALOGENATED  VOLATILE  ORGANICS  BY GAS  CHRQMATOGRAPHY
        Start
7,1 Introduce compounds
into gat chrornatograph
  by direct injection or
    purge-and-trap
    (Method 5030)
     7.2 Set gas
    chrornatograph
      condition.
     7.3 Calibrate
 (refer to Method 8000}
    7.4.1 Introduce
  volatile compounds
into gas chrcmatograph
  by puige-and-trnp or
    direct injection.
  7.4.2 Follow Method
   8000 for analysis
    sequence,  etc.
7.4.4 Record volume
 purged or injected
  and peak sizes.
   7,4.5 Calculats
    concentration
(r»f«r to MathoeJ 8000)
      7.4.6 Art
      analytical
    interferences
     •uspected?
                                            7.4.7 t«
                                          response for
                                             a peak
                                           off-ecele?
                                                                   7.4.6 Analyze using
                                                                    •econd GC column.
                               7.4.7 Dilute second
                                aliquot of sample.
                                       8010B  -  15
                                              Revision 2
                                         September  1994

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                                 METHOD 8011

              1.2-DIBROMOETHANE AND 1.2-DIBROMO-3-CHLOROPROPANE
                   BY MICROEXTRACTION AND GAS CHROMATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   This method  is applicable to  the  determination of  the  following
compounds in drinking water and ground water:
      Compound Name                                   CAS No.8


      1,2-Dibromoethane (EDB)                         106-93-4
      l,2-Dibromo-3-chloropropane (DBCP)               96-12-8


      8  Chemical  Abstract  Services  Registry  Number.

      1.2   For compounds and matrices other than those listed in Section 1.1,
the laboratory  must demonstrate  the  usefulness of  the method  by  collecting
precision  and  accuracy  data  on  actual  samples  and  provide  qualitative
confirmation of results by gas chromatography/mass spectrometry (GC/MS).

      1.3   The experimentally determined  method detection limits (MDL) for EDB
and DBCP were  calculated to be  0.01  pg/L.   The  method has been shown  to  be
useful for  these analytes over a concentration range of approximately 0.03 to 200
jig/L.  Actual detection limits are highly  dependent upon the characteristics of
the gas chromatographic system, sample matrix,  and calibration.

      1.4   This method  is  restricted to use  by  or under  the  Supervision  of
analysts experienced in the use of gas chromatography and in the interpretation
of gas  chromatograms.  Each analyst must  demonstrate the ability to generate
acceptable results with this method using the procedure described in Section 8.2,

      1.5   1,2-Dibromoethane   and    l,2-Dibromo-3-chloropropane  have   been
tentatively classified  as  known  or  suspected human  or  mammalian carcinogens.
Pure standard materials and stock standard solutions of these compounds should
be handled  in a  hood.  A NIOSH/MESA approved  toxic  gas respirator  should be worn
when the analyst handles high concentrations of these toxic compounds.


2.0   SUMMARY OF METHOD

      2.1   Thirty five ml  of sample are extracted with 2 ml of hexane.  Two  pl
of the  extract are  then injected  into a gas  chromatograph equipped  with a
linearized electron  capture detector for separation and analysis. Aqueous matrix
spikes are  extracted and analyzed  in an identical  manner  as the samples in order
to compensate for possible extraction  losses.

      2.2   The extraction  and analysis time is  30  to  50  minutes per sample

                                  8011 -  1                          Revision 0
                                                                     July 1992

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depending upon the analytical conditions chosen.  See Table 1 and Figure 1.

      2.3   Confirmatory evidence is obtained using a different column (Table 1).


3.0   INTERFERENCES

      3.1   Impurities  contained  in the  extracting solvent  (hexane)  usually
account for the majority of the analytical problems.  Reagent blanks should be
analyzed for each new bottle  of hexane before use.   Indirect daily checks on the
hexane are obtained by monitoring the reagent blanks.  Whenever an interference
is noted in the method or instrument blank, the  laboratory should reanalyze the
hexane.   Low  level  interferences  generally can be  removed  by  distillation or
column chromatography, however,  it  is generally  more economical to obtain a new
source of hexane solvent.  Interference-free hexane is defined as containing less
than 0.01 ng/L of the analytes.  Protect interference-free hexane by storing it
in an area known to be free of organochlorine solvents.

      3.2   Several  instances of  accidental  sample  contamination have  been
attributed to diffusion  of volatile organics through  the  septum seal  into the
sample bottle during shipment and storage.  Trip blanks must be used to monitor
for this problem.

      3.3   This liquid/liquid extraction technique extracts a wide boiling range
of non-polar  organic  compounds  and, in addition,  extracts  some  polar organic
compounds.

      3.4   EDB at low concentrations may be masked  by very high concentrations
of dibromochloromethane (DBCM), a common chlorinated drinking water contaminant,
when using the confirmation column.


4.0   APPARATUS AND MATERIALS

      4.1   Microsyringe - 10, 25,  and  100 pi with a 2 in.  x 0.006 in. needle
(Hamilton 702N or equivalent).

      4.2   Gas Chromatograph

            4.2.1 The GC must be capable of temperature programming and should
      be  equipped with  a linearized electron capture detector and a capillary
      column  splitless  injector.

            4.2.2 Columns

                  4.2.2.1     Column  A  -  0.32  mm  ID x  30  m fused  silica
            capillary with dimethyl silicone mixed  phase (Durawax-DX 3, 0.25 p,m
            film, or equivalent).

                  4.2.2.2     Column B (confirmation column)  - 0.32 mm  ID x 30 m
            fused silica capillary  with methyl  polysiloxane phase  (DB-1, 0.25 /urn
            film, or equivalent).

      4.3   Volumetric  flasks, Class A  - 10 mL.

                                    8011 - 2                         Revision 0
                                                                     July 1992

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      4.4   Glass bottles - 15 ml, with Teflon lined screw caps or crimp tops.

      4.5   Analytical balance - 0.0001 g.

      4.6   Graduated cylinder - 50 ml.

      4.7   Transfer pi pet.


5.0   REAGENTS

      5.1   Reagent grade chemicals shall be used in all  tests. Unless otherwise
indicated, it is intended that all  reagents shall conform to the specifications
of the Committee on Analytical Reagents of the American  Chemical Society, where
such specifications are available. Other grades may be used, provided it  is first
ascertained that the reagent  is  of sufficiently  high  purity to permit its use
without lessening the accuracy of the determination.

      5.2   Organic-free reagent water - All references  to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Hexane, C6H14 - UV grade (Burdick and Jackson #216 or equivalent).

      5.4   Methyl alcohol, CH3OH - Demonstrated  to be free of analytes.

      5,5   Sodium chloride,  NaCl - Pulverize  a batch  of NaCl and place it in a
muffle  furnace  at room  temperature.    Increase  the temperature to  400°C for
30 minutes.  Store in a capped bottle.

      5.6   1,2-Dibromoethane  (99%),   C2H4Br2,  (Aldrich  Chemical   Company,  or
equivalent).

      5.7   l,2-Dibromo-3-chloropropane  (99.4%),  C3H5Br2Cl,  (AMVAC  Chemical
Corporation, Los Angeles, California, or equivalent).

      5.8   Stock  standards  - These  solutions may be  purchased  as certified
solutions or prepared from pure standards using the following procedures:

            5.8.1 Place  about  9,8 ml  of methanol   into  a 10 ml ground  glass
      stoppered volumetric flask.   Allow the  flask to stand, unstoppered, for
      about 10 minutes and weigh to the nearest 0.0001 g.

            5.8.2 Use a  25 #L syringe  and  immediately add two or more  drops
      (» 10 /*L)  of standard  to  the flask.    Be  sure  that  the  standard  falls
      directly into the alcohol without contacting the neck of the flask.

            5.8.3 Reweigh, dilute to volume, stopper,  and  then mix  by inverting
      the flask several  times.   Calculate the concentration in milligrams per
      liter (mg/L) from the net gain in weight. When compound purity is assayed
      to  be  96%  or  greater,  the weight may be  used  without correction  to
      calculate the concentration of the stock standard.

            5.8.4 Store stock standards  in 15 ml bottles equipped  with Teflon
      lined screw-caps or crimp tops.  Stock standards are stable for at least

                                   8011 - 3                         Revision 0
                                                                     July 1992

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      four weeks when stored at 4°C  and away from light.

      5.9   Intermediate  standard  -   Use   stock  standards   to  prepare  an
intermediate standard that contains both analytes in methanol.  The intermediate
standard should be  prepared  at a concentration that can  be easily diluted to
prepare aqueous calibration standards that will bracket the working concentration
range.   Store  the  intermediate  standard  with minimal  headspace  and  check
frequently for signs  of deterioration or evaporation,  especially  just before
preparing calibration standards.  The storage time described for stock standards
also applies to the intermediate standard.

      5.10  Quality control  (QC) reference sample -  Prepare a QC reference sample
concentrate at 0.25 mg/L of both analytes from standards from a different source
than the standards used for the stock standard.

      5.11  Check  standard  -  Add  an appropriate  volume  of the intermediate
standard to an aliquot of organic-free reagent water in a volumetric flask.  Do
not add more than 20 jiL of  an  alcoholic intermediate standard  to the water or
poor precision will  result.   Use a 25 #L microsyringe and  rapidly inject the
alcoholic  intermediate  standard  into the expanded area of the  almost filled
volumetric flask.  Remove the needle as quickly as possible after injection.  Mix
by inverting the flask several times.  Discard  the contents contained in  the neck
of the flask.  Aqueous calibration standards  should be prepared every 8 hours.


6.0   SAMPLE COLLECTION, PRESERVATION, AND STORAGE

      6.1   See the  introductory material  to  this  chapter, Organic Analytes,
Section 4.1.
7.0   PROCEDURE

      7.1   Recommended Chromatographic Conditions

      Two gas  chromatography columns are  recommended.   Column A  is a highly
efficient column that provides separations for EDB and DBCP without interferences
from trihalomethanes.   Column A should be used as the primary analytical column
unless routinely occurring analytes  are  not  adequately resolved.   Column B is
recommended for use as a confirmatory  column  when GC/MS  confirmation is not
available.  Retention times for EDB and DBCP on these columns are presented in
Table 1.

      Column A:

      Injector  temperature:                     200°C.
      Detector  temperature:                     290°C.
      Carrier gas  (Helium) Linear velocity:     25 cm/sec.
      Temperature  program:
            Initial temperature:                40°C, hold for 4 min.
            Program:                            40°C to 190°C  at 8°C/min.
            Final  temperature:                  190°C,   hold  for  25  min.,  or
                                                until   all  expected   analytes
                                                have eluted.

                                   8011  -  4                          Revision 0
                                                                      July 1992

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See Figure 1 for a sample chromatogram and Table 1 for retention data.

Column B:

Injector temperature:                     200°C.
Detector temperature:                     290°C.
Carrier gas (Helium) Linear velocity:     25 cm/sec.
Temperature program:
      Initial  temperature:                40°C,  hold for 4 min.
      Program:                            40°C to 270°C  at 10°C/min.
      Final temperature:                  270°C,  hold  for  10 min.,  or
                                          until  all  expected  analytes
                                          have eluted.

See Table 1 for retention data.

7.2   Calibration

      7.2.1 Prepare  at  least  five  calibration  standards.    One  should
contain EDB and DBCP at  a concentration near, but greater than, the method
detection  limit  (Table  1) for each  compound.   The others  should  be at
concentrations  that bracket  the  range  expected in  the samples.   For
example,  if the MDL is  0.01  /ig/L,  and a  sample  expected  to  contain
approximately 0.10 /xg/L is to be analyzed, aqueous calibration standards
should be prepared at concentrations of 0.03 /ig/L,  0.05 /xg/L, 0.10 /xg/L,
0.15 /ig/U and 0.20  /xg/L.

      7.2.2 Analyze each calibration standard and tabulate peak height or
area  response versus  the concentration in  the standard.   Prepare  a
calibration curve  for  each  compound.    Alternatively,  if  the  ratio of
response  to  concentration (calibration  factor)  is  a constant  over the
working  range (<  10%  relative  standard deviation),  linearity can be
assumed and the average ratio or calibration factor can be  used in place
of a calibration curve.

7.3   Sample preparation

      7.3.1 Remove  samples and standards from storage and allow them to
reach room temperature.

      7.3.2 For  samples and  field  blanks contained  in  40 mL  bottles,
remove the container cap.   Discard  a 5  mL  volume using a 5 mL transfer
pipet.  Replace the  container cap and weigh the container with  contents to
the nearest 0.1  g  and  record  this  weight  for  subsequent sample volume
determination.

      7.3.3 For  calibration   standards,  check  standards,  QC reference
samples,  and  blanks, measure  a  35  mL  volume  using  a  50  mL graduated
cylinder and transfer it to a 40 mL sample container.

7.4   Extraction

      7.4.1 Remove the container cap and add 7 g of NaCl  to all  samples.


                             8011 -  5                         Revision 0
                                                               July  1992

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      7.4.2 Recap the sample container and dissolve the NaCl by shaking by
hand for about 20 seconds.

      7.4.3 Remove the  cap and using  a transfer  pi pet,  add 2.0  ml  of
hexane.  Recap and shake vigorously by hand for 1 minute.  Allow the water
and  hexane  phases  to separate.    If  stored  at  this  stage,  keep  the
container upside down.

      7.4.4 Remove the  cap and carefully  transfer a  sufficient amount
(0.5-1.0 ml)  of  the hexane layer  into  a vial using  a disposable glass
pipet.

      7.4.5 Transfer  the  remaining hexane  phase,  being careful  not  to
include any of the water phase, into a second vial.  Reserve this second
vial at 4°C  for reanalysis if  necessary.

7.5   Analysis

      7.5.1 Transfer  the  first  sample  vial  to an  autosampler  set up  to
inject  2.0  jj.1   portions  into  the  gas  chromatograph  for  analysis.
Alternately,  2 /nL  portions  of samples,  blanks  and  standards   may  be
manually injected,  using  the  solvent flush technique,  although  an auto
sampler is strongly recommended.

7.6   Determination of sample volume

      7.6.1 For samples and field blanks, remove the cap from the sample
container. Discard  the  remaining  sample/hexane mixture.   Shake  off the
remaining few drops  using  short, brisk wrist movements. Reweigh the empty
container with  original  cap and calculate  the net weight of  sample  by
difference to  the nearest 0.1 g.   This  net weight  is equivalent to the
volume of water extracted.

7.7   Calculations

      7.7.1 Identify EDB and DBCP  in the  sample chromatogram by comparing
the retention time of the  suspect peak to retention times generated by the
calibration standards and the check standard.

      7.7.2 Use the  calibration curve or calibration factor to directly
calculate the uncorrected  concentration  (C?) of each analyte in the sample
(e.g. calibration factor x response).

      7.7.3 Calculate the  sample volume  (Vs)  as equal  to  the net sample
weight:

      Vs (ml)  = gross weight (grams) -  bottle tare (grams)

      7.7.4 Calculate the corrected sample concentration as:

      Concentration  (pg/L) =Ct x 35
                                vs

      7.7.5 Report the results for  the unknown samples in p$/L.  Round the

                             8011  - 6                         Revision 0
                                                               July 1992

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      results to the nearest 0.01 pg/L or two significant figures.


8.0   QUALITY CONTROL

      8.1   Each laboratory that uses this method is required to operate a formal
quality control program,

            8.1.1 The laboratory  must make  an initial  determination of  the
      method detection limits and demonstrate the ability to generate acceptable
      accuracy and precision with this method.  This  is established as described
      in Section 8.2.

            8.1.2 In recognition of laboratory advances that  are occurring in
      chromatography, the laboratory is permitted certain options  to improve the
      separations  or lower  the  cost of  measurements.    Each   time  such  a
      modification is made to the method, the analyst is required to repeat the
      procedure in Section 7.1  and 8.2.

            8.1.3 The laboratory  must analyze a reagent and calibration blank to
      demonstrate  that  interferences  from the  analytical  system  are  under
      control every twenty samples or  per  analytical batch, whichever is more
      frequent.

            8.1.4 The laboratory  must,  on an ongoing basis,  demonstrate through
      the  analyses  of  QC  reference   samples  and  check  standards  that  the
      operation of the measurement system is in control.  The  frequency of the
      check  standard  analyses  is  equivalent to  5% of all  samples or  every
      analytical batch,  whichever is more frequent.   On  a weekly  basis,  the QC
      reference sample must be  run.

      8.2   To establish the ability to achieve low detection  limits and generate
acceptable  accuracy  and  precision,  the analyst  must  perform   the  following
operations:

            8.2.1 Prepare seven samples each at a  concentration  of 0.03

            8.2.2 Analyze  the  samples according  to the method   beginning  in
      Section 7.0.

            8.2.3 Calculate the  average concentration  (X)  in   [ig/L  and  the
      standard deviation  of the  concentrations (s)  in ng/L,  for each analyte
      using the seven results.   Then calculate the MDL  at 99% confidence level
      for seven replicates as  3.143s.

            8.2.4 For each analyte in an   aqueous  matrix   sample,  X must  be
      between 60%  and 140% of  the  true value.  Additionally, the MDL  may not
      exceed the  0.03 ng/L spiked concentration.    If  both analytes  meet the
      acceptance criteria, the  system  performance  is acceptable and analysis of
      actual samples can  begin.  If either  analyte  fails to meet a  criterion,
      repeat the test.   It is  recommended  that the laboratory repeat  the MDL
      determination on a regular basis.

      8.3   The laboratory must demonstrate on a  frequency  equivalent to 5% of

                                   8011 - 7                         Revision 0
                                                                     July 1992

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the sample load or once per analytical batch,  whichever is more frequent, that
the measurement  system is in  control  by analyzing  a  check standard  of both
analytes at 0.25 ng/L.

            8.3.1 Prepare  a  check  standard  (0.25  |ig/L)  by  diluting  the
      intermediate standard with water to 0.25 ng/L.

            8.3.2 Analyze the sample according to Section  7.0 and calculate the
      recovery for each analyte.  The recovery must be between 60% and 140% of
      the expected value  for aqueous  matrices.   For non-aqueous matrices, the
      U.S. EPA will set criteria after more interlaboratory data are gathered.

            8.3.3 If  the  recovery  for  either  analyte  falls  outside  the
      designated range, the  analyte fails the acceptance  criteria.   A second
      calibration verification  standard containing each analyte  that failed must
      be analyzed.  Repeated failure, however, will  confirm a general problem
      with the  measurement system.   If this  occurs,  locate  and correct the
      source of the problem and repeat the test.

      8.4   On a weekly basis,  the  laboratory must% demonstrate the  ability to
analyze a QC reference sample.

            8.4.1 Prepare a QC  reference sample at  0.10 jig/L by diluting the QC
      reference sample concentrate  (Section 5.9).

            8.4.2 For each analyte  in an  aqueous matrix,  the recovery must be
      between 60% and  140% of the expected value.  When either analyte fails the
      test, the analyst must repeat the  test only for that  analyte which failed
      to meet the criteria.  Repeated failure, however, will confirm a general
      problem with the measurement  system  or  faulty samples and/or standards.
      If this occurs,  locate and correct  the  source of the problem and repeat
      the test.  For non-aqueous matrices,  the U.S.  EPA will set criteria after
      more interlaboratory data are gathered.

      8.5   Instrument  performance  - Check  the  performance  of the  entire
analytical system daily using data  gathered from analyses  of blanks, standards,
and replicate samples.

            8.5.1 Peak tailing  significantly in excess  of that  shown  in the
      chromatogram (Figure 1) must be corrected.  Tailing  problems  are generally
      traceable to active sites on  the GC column or to the detector operation.

            8.5.2 Check the precision between replicate  analyses.  A properly
      operating  system  should  perform  with an   average relative  standard
      deviation of less  than 10%.   Poor precision is generally  traceable to
      pneumatic leaks, especially at the injection port.


9.0   METHOD PERFORMANCE

      9.1   Method detection limits are presented in Table 1.  Single laboratory
accuracy and precision at several concentrations in tap water  are presented in
Table 2.
                                   8011 - 8                         Revision 0
                                                                     July 1992

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      9.2   In a preservation study extending over a 4 week period, the average
percent recoveries and relative standard deviations presented  in Table 3 were
observed for organic-free reagent water (acidified),  tap water and ground water.
The  results  for acidified  and non-acidified  samples  were not  significantly
different.
10.0  REFERENCES

1.    Optimization of Liouid-Liquid Extraction Methods for Analysis of Orqanics
      in Water. EPA-600/S4-83-052, 1984.

2.    Henderson, J.E.; Peyton, G.R.;  Glaze, W.H.  Identification and Analysis of
      Organic Pollutants in Water; Keith, L.H.,  Ed; Ann Arbor Sci.: Ann Arbor,
      MI; 1976.

3.    Richard J.J.; Junk, G.A. Journal AWWA 1977, 69, 62.

4.    Budde, W.L.; Eichelberger, J.W. Organic Analyses Using Gas Chromatographv-
      Mass Spectrometry; Ann Arbor Science: Ann  Arbor,  MI;  1978.

5.    Glaser, J.A.; et al.  Environmental  Science  and Technology 1981, 15, 1426.

6.    Methods for  the  Determination of  Organic Compounds in  Finished Drinking
      Water and Raw Source Water; U.S. Environmental Protection Agency. Office
      of  Research  and  Development.   Environmental  Monitoring  and  Support
      Laboratory.  ORD Publication Offices  of Center for  Environmental Research
      Information:  Cincinnati,  OH 1986.
                                   8011 - 9                         Revision 0
                                                                     July 1992

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                                   TABLE 1.
               CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION
                 LIMITS  (MDL)  FOR  1,2-DIBROMOETHANE  (EDB) AND
                      l,2-DIBROMO-3-CHLOROPROPANE (DBCP)
Analyte
Retention Time, Minutes

Column A    Column B      MDL (M9/L)
EDB

DBCP
 9.5

17.3
 8.9

15.0
0.01

0.01
Column A:  Durawax-DX 3

Column B:  DB-1
                                   TABLE 2.
                   SINGLE LABORATORY ACCURACY AND PRECISION
                         FOR EDB  AND  DBCP  IN  TAP  WATER



Analyte
EDB


DBCP



Number
of
Samples
7
7
7
7
7
7

Spike
Concentration
(MA)
0.03
0.24
50.0
0.03
0.24
50.0

Average
Recovery
(*)
114
98
95
90
102
94
Relative
Standard
Deviation
(%)
9.5
11.8
4.7
11.4
8.3
4.8
                                   8011  -  10
                                Revision 0
                                 July 1992

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                             TABLE 3.
                ACCURACY AND PRECISION AT 2.0 pg/L
                    OVER A 4-WEEK STUDY PERIOD


Analyte
EDB




DBCP






Matrix1
RW-A
GW
GW-A
TW
TW-A
RW-A
GW
GW-A
TW
TW-A

Number
of Samples
16
15
16
16
16
16
16
16
16
16
Average
Accuracy
(% Recovery)
104
101
96
93
93
105
105
101
95
94
Relative
Std. Dev.
(%)
4.7
2.5
4.7
6.3
6.1
8.2
6.2
8.4
10.1
6.9
RW-A  =     Organic-free reagent water at pH 2
GW    =     Ground water, ambient pH
GW-A  =     Ground water at pH 2
TW    =     Tap water, ambient pH
TW-A  =     Tap water at pH 2
                             8011  -  11                         Revision 0
                                                               July 1992

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                   FIGURE 1.
SAMPLE CHROMATOGRAM FOR EXTRACT OF WATER SPIKED
        AT 0,114 M9/L  WITH  EDB AND DBCP
                              COLUMN:  Fused silica capillary
                              LIQUID PHASE:  Durawax-OX3
                              FILM THICKNESS:  0.25 \m
                              COLUMN DIMENSIONS:   30 M x 0.317
                                 II
         10   11   14  It   It
                 TIME (MIN)
20   aa   24
10
                    8011  -  12
                     Revision 0
                      July 1992

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                       METHOD 8011
1,2-DIBROMOETHANE AND  l,2-DIBROMO-3-CHLOROPROPANE
     BY MICROEXTRACTION AND GAS CHROMAT06RAPHY
         Start
      7 .2 Calibrate
       inat russen t'
        prepare
       ca1ibralion
        curve .
       ? 2 Check
      instrument
      performance.
      7.3 Prepare
       samples.
  7,4.1 Add
  NaCl to
  7.4.3 ftdd
 hexariB and
   ex tract
   sample.
                           7,4.4 Put
                            part of
                          extract in
                             vial
 7.4.5 Save
remainder  of
 extract for
  possible
 rcanaJLysis .
 7 , 5 ftnmlyze
   by GC-
7.& Determine
  aampie
                   7 .7 Calculate
                  concentrations.
   Stop
                         8011  - 13
                                        Revision 0
                                         July 1992

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                                 METHOD 8015A

            NONHALOGENATED VOLATILE ORGANICS BY GAS CHROMAT06RAPHY
1.0   SCOPE AND APPLICATION

      1.1   Method  8015  is  used to  determine the  concentration  of  various
nonhalogenated  volatile  organic compounds.   The  following compounds  can  be
determined by this method:
                                                     Appropriate Technique
                                                                      Direct
Compound Name                        CAS No.8       Purge-and-Trap     Injection
Diethyl ether
Ethanol
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
60-29-7
64-17-5
78-93-3
108-10-1
b
1
pp
PP
b
b
b
b
     a  Chemical Abstract Services Registry Number.
     b  Adequate response using this technique
     i  Inappropriate technique for this analyte
     pp Poor purging efficiency, resulting in high EQLs


2.0   SUMMARY OF METHOD

      2.1   Method 8015 provides gas chromatographic conditions for the detection
of certain nonhalogenated volatile organic compounds.  Samples may be introduced
into the GC using direct injection or purge-and-trap (Method 5030).  Ground water
samples must be analyzed by Method 5030.  A temperature program is used in the
gas chromatograph to separate the organic compounds.  Detection is achieved by
a flame ionization detector (FID).

      2.2   The method provides an optional gas chromatographic column that may
be helpful  in resolving the analytes from co-eluting non-target compounds and for
analyte confirmation,


3.0   INTERFERENCES

      3.1   Refer to Method 5030 and 8000.

      3.2   Samples  can  be  contaminated by  diffusion  of volatile  organics
(particularly chlorofluorocarbons  and  methylene chloride) through  the  sample
container  septum  during shipment  and storage.   A  trip blank  prepared  from
organic-free reagent water and carried through sampling and subsequent storage
and handling can serve as a check on such contamination.


                                   8015A  - 1                         Revision 1
                                                                     July 1992

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4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph

            4.1.1 Gas  Chromatograph  -  Analytical  system  complete  with  gas
      chromatograph suitable for on-column injections or purge-and-trap sample
      introduction and  all  required accessories,  including  detectors,  column
      supplies, recorder,  gases,  and syringes.  A data system for measuring peak
      heights and/or peak areas is recommended.

            4.1.2 Columns

                  4.1.2.1     Column 1 - 8 ft x 0.1 in. ID  stainless steel or
            glass column  packed  with  1% SP-1000 on  Carbopack-B  60/80  mesh or
            equivalent.

                  4.1.2.2     Column 2 - 6 ft  x  0.1  in.  ID stainless steel or
            glass  column  packed  with   n-octane  on   Porasil-C  100/120  mesh
            (Durapak) or equivalent.

            4.1.3 Detector - Flame ionization  (FID).

      4.2   Sample  introduction  apparatus  -  Refer  to  Method  5030 for  the
appropriate equipment for sample introduction purposes.

      4.3   Syringes - A 5 ml Luerlok glass hypodermic  and a 5 ml_, gas-tight with
shutoff valve.

      4.4   Volumetric  flasks,  Class  A  - Appropriate  sizes  with  ground glass
stoppers.

      4.5   Microsyringes -  10 and  25 /iiL with  a  0.006 in. ID needle (Hamilton
702N or equivalent) and a 100 pi.

      4.6   Analytical balance - 0.0001 g.


5.0   REAGENTS

      5.1   Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all  reagents shall conform  to the specifications
of the Committee on Analytical  Reagents  of the  American Chemical Society, where
such specifications are available. Other grades  may  be  used, provided it is first
ascertained that the  reagent  is  of sufficiently  high purity to permit its use
without lessening the accuracy of the determination.

      5.2   Organic-free reagent water - All  references to water in this method
refer to organic-free reagent water, as defined  in Chapter One.

      5.3   Methanol, CH3OH.   Pesticide  quality or  equivalent.  Store away from
other solvents.

      5.4   Stock standards - Stock solutions may be prepared from pure standard
materials  or  purchased as  certified  solutions.   Prepare  stock  standards in

                                   8015A -  2                         Revision 1
                                                                     July  1992

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methanol using assayed liquids.

            5.4.1 Place about 9.8 ml of methanol  in a 10 ml tared, ground-glass
      stoppered volumetric flask.   Allow  the  flask  to  stand,  unstoppered, for
      about 10 minutes or until all alcohol wetted surfaces have dried.  Weigh
      the flask to the nearest 0.0001 g.

            5.4.2 Using a 100 /iL syringe, immediately add two or more drops of
      assayed reference material to  the flask; then  reweigh.   The liquid must
      fall directly into the alcohol without contacting the neck of the flask.

            5.4.3 Reweigh, dilute to volume, stopper, and then mix by inverting
      the flask several times.   Calculate the concentration  in milligrams per
      liter (mg/L) from the net gain in weight. When compound purity is assayed
      to  be  96%  or  greater,  the  weight  may be used  without  correction  to
      calculate the concentration of the stock standard.  Commercially prepared
      stock standards may be  used at any concentration if they are certified by
      the manufacturer or by an independent source.

            5.4.4 Transfer the  stock standard solution  into  a  bottle  with  a
      Teflon lined screw-cap.  Store, with minimal headspace,  at -10°C to  -20°C
      and protect from light.

            5.4.5 Standards  must be  replaced after  6 months,  or sooner  if
      comparison with check standards indicates a problem.

      5.5   Secondary dilution standards  - Using  stock standard solutions, pre-
pare  in  methanol  secondary  dilution standards,  as  needed,  that  contain the
compounds of interest, either singly or mixed  together.  The secondary dilution
standards should be prepared at concentrations  such that the aqueous calibration
standards  prepared   in  Section  5.5 will  bracket  the  working  range  of the
analytical system.  Secondary dilution standards  should be stored with minimal
headspace for volatiles and should be checked frequently for  signs  of degradation
or evaporation, especially just  prior  to  preparing  calibration standards from
them.

      5.6   Calibration standards - Calibration standards at a minimum of five
concentrations are prepared  in water from the secondary  dilution of the stock
standards.   One  of  the concentrations  should  be at  a  concentration near, but
above,  the  method   detection  limit.    The  remaining  concentrations  should
correspond to  the expected range  of concentrations  found  in  real  samples or
should define the working range  of the GC.  Each standard  should contain each
analyte for detection by this method (e.g. some or all  of the compounds listed
in Section 1.1 may be included).   In order to  prepare accurate aqueous standard
solutions, the following precautions must be observed:

            5.6.1 Do  not  inject  more than  20 juL of alcoholic  standards into
      100 ml of water.

            5.6.2 Use  a  25  juL  Hamilton  702N  microsyringe  or  equivalent
      (variations  in needle  geometry  will adversely  affect  the  ability  to
      deliver reproducible volumes of methanolic  standards  into water).

            5.6.3 Rapidly  inject  the  alcoholic  standard  into  the  filled

                                   8015A  - 3                        Revision 1
                                                                     July 1992

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      volumetric flask.   Remove  the  needle as fast as possible after injection.

            5.6.4 Mix aqueous standards by inverting the flask three times only.

            5.6.5 Fill the sample syringe from the standard solution contained
      in the expanded area of the flask  (do not  use  any solution contained in
      the neck of the flask).

            5.6.6 Never use  pipets  to dilute  or transfer samples  or aqueous
      standards.

            5.6.7 Aqueous standards  are not stable and should be discarded after
      1 hour, unless properly sealed and stored.   The aqueous standards can be
      stored up to 24 hours,  if held in sealed vials with zero headspace.

      5.7   Internal standards (if internal  standard calibration is used) - To
use this approach, the analyst must select one or more internal  standards that
are similar in  analytical behavior  to the compounds  of interest.  The analyst
must further demonstrate that the measurement  of the internal  standard is not
affected by method  or matrix  interferences.   Because of these limitations, no
internal standard can be suggested that is applicable to all  samples.

            5.7.1 Prepare  calibration   standards   at   a  minimum   of   five
      concentrations for each parameter of interest as described  in Section 5.6.

            5.7.2 Prepare a  spiking  solution  containing each of the internal
      standards using the procedures described in Sections 5.4 and 5.5.  It is
      recommended  that   the   secondary  dilution  standard be   prepared  at  a
      concentration  of  15  ng/^L of  each  internal   standard  compound.    The
      addition  of  10  /^L of  this  standard to  5.0 ml  of  sample  or calibration
      standard would be equivalent to 30 /K|/L.

            5.7.3 Analyze each calibration  standard  according  to Section 7.0,
      adding  10 /il_ of  internal  standard  spiking   solution  directly to  the
      syringe.

      5.8   Surrogate standards  - The analyst should monitor both  the performance
of the analytical  system and the effectiveness of  the method in dealing  with each
sample matrix by spiking each sample,  standard, and water  blank with one or two
surrogate compounds recommended to  encompass  the range of temperature program
used in this method.  From stock standard solutions prepared as  in Section 5.4,
add a volume to give 750 /^g of each surrogate to 45 ml of water contained in a
50  ml  volumetric  flask,  mix,  and  dilute  to  volume  for a  concentration  of
15 ng/jiL.  Add  10 pi  of this  surrogate spiking solution directly into the 5 ml
syringe with  every sample and  reference standard analyzed.    If the internal
standard calibration  procedure  is used,  the surrogate  compounds may be added
directly to the internal standard spiking solution (Section 5.7.2).


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the introductory  material  to  this  Chapter,  Organic Analytes,
Section 4.1.
                                   8015A -  4                        Revision 1
                                                                     July 1992

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7.0   PROCEDURE

      7.1   Volatile compounds are introduced  into the gas chromatograph either
by direct injection or purge-and-trap  (Method 5030).  Method  5030 may be used
directly on ground  water samples or low-concentration  contaminated  soils and
sediments.   For high-concentration soils or sediments, methanolic extraction, as
described in Method  5030,  may be necessary prior to  purge-and-trap  analysis.
Method 5030 also provides guidance on the  analysis of aqueous miscible and non-
aqueous miscible liquid wastes (see Section 7.4.1.1).

      7.2   Chromatographic conditions (Recommended)

            7.2.1 Column 1

            Carrier gas (Helium) flow rate:     40 mL/min
            Temperature program:
                  Initial temperature:           45°C»  hold for 3 minutes
                  Program:                      45°C to  220°C  at 8°C/nrin
                  Final temperature:            220°C, hold for 15 minutes.

            7.2.2 Column 2

            Carrier gas (Helium) flow rate:     40 mL/min
            Temperature program:
                  Initial temperature:           50°C,  hold for 3 minutes
                  Program:                      50°C to  170°C  at 6°C/min
                  Final temperature:            170°C, hold for 4  minutes.

      7.3   Cal ibration - Refer to Method 8000 for proper  cal ibration techniques.

            7.3.1 Calibration must take place using the same sample introduction
      method that will be used to analyze actual samples (see Section 7.4.1).

            7.3.2 The  procedure  for internal or external calibration  may  be
      used.  Refer to  Method 8000 for a description of each  of these procedures.

      7,4   Gas chromatographic analysis

            7.4.1 Introduce volatile compounds into  the  gas chromatograph using
      either Method 5030  (purge-and-trap method)  or the direct  injection method.
      If the  internal standard  calibration  technique  is  used,  add  10 pi  of
      internal  standard to the sample prior to purging.

                  7.4.1.1     Direct injection  -  In very limited  applications
            (e.g. aqueous process wastes), direct injection of the sample into
            the GC  system with  a 10 p,l syringe  may be  appropriate.   One such
            application is for verification of the alcohol content  of an aqueous
            sample prior to determining if the sample is  ignitable  (Methods 1010
            or 1020).  In this  case, it  is suggested  that direct  injection be
            used. The detection limit is very high (approximately 10,000 M9/L);
            therefore, it  is  only permitted when concentrations  in  excess  of
            10,000 ng/l are expected or for water-soluble compounds that do not
            purge.  The system must be calibrated by  direct  injection (bypassing
            the purge-and-trap device).

                                   8015A -  5                         Revision 1
                                                                     July 1992

-------
                  Non-aqueous miscible wastes may  also be analyzed  by  direct
            injection if the  concentration of target  analytes in the  sample
            falls within the calibration range.   If dilution of the  sample is
            necessary,  follow the  guidance for  High Concentration samples in
            Method 5030, Section 7.3.3.2.

            7.4.2 Method 8000 provides instructions on  the  analysis  sequence,
      appropriate dilutions,  establishing  daily retention  time windows,  and
      identification criteria.   Include a mid-concentration standard after each
      group of 10 samples in the analysis  sequence.»

            7.4.3 Record the sample volume  purged or injected and the  resulting
      peak sizes (in area units or peak heights).

            7.4.4 Calculation of concentration is  covered in Method 8000.

            7.4.5 If analytical  interferences  are suspected, or for the purpose
      of confirmation,  analysis using the  second GC column is recommended.

            7.4.6 If the response for a peak is off-scale,  prepare a dilution of
      the sample with water.  The dilution  must be performed on a second aliquot
      of the sample which has been properly sealed and stored prior to use.


8.0   QUALITY CONTROL

      8.1   Refer to Chapter  One  for specific quality  control  procedures and
Method 8000 for gas chromatographic procedures.  Quality control  to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.

      8.2   Quality control  required to validate the GC system operation is found
in Method 8000, Section 8.6.

      8.3   Calculate surrogate standard recovery  on  all  samples,  blanks, and
spikes.  Determine if recovery is within limits (limits  established by performing
QC procedure outlined in Method 8000, Section 8.10).

            8.3.1 If recovery is not within limits, the following is  required:

            •     Check to  be  sure that  there are no  errors in calculations,
                  surrogate  solutions,  and internal  standards.    Also,  check
                  instrument performance.

            «     Recalculate the data and/or reanalyze  the  extract  if any of
                  the above checks reveal  a problem.

            »     Re-extract and re-analyze the sample if none of the above are
                  a problem or flag the data as  "estimated concentration".


9.0   METHOD PERFORMANCE

      9.1   The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique, and calibration procedures used.

                                   8015A -  6                        Revision  1
                                                                     July  1992

-------
      9.2   Specific method  performance  information  will  be  provided as  1t
becomes available.


10.0  REFERENCES

1.    Bellar, T.A.,  and J.J.  Lichtenberg, Determining  Volatile Organics  at
      Microgram-per-Liter Levels by  Gas Chromatography,  J. Amer. Water Works
      Assoc., 66(12).  pp. 739-744 (1974).

2.    Bellar, T.A., and J.J.  Lichtenberg, Semi-Automated  Headspace Analysis of
      Drinking Waters  and Industrial  Waters for  Purgeable Volatile  Organic
      Compounds,  in Van Hall, ed., Measurement of  Organic  Pollutants in Water
      and Wastewater,  ASTM STP 686,  pp. 108-129,  1979.

3.    Development and  Application of  Test Procedures for Specific Organic Toxic
      Substances in Wastewaters:  Category 11 -  Purgeables and  Category  12 -
      Acrolein,   Acrylonitrile,   and  Dichlorodifluoromethane,   Report for  EPA
      Contract 68-03-2635 (in preparation).
                                  8015A  -  7
Revision 1
 July 1992

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                           METHOD  8015A
NONHALOGENATED VOLATILE ORGANICS BY  GAS  CHROMATOGRAPHY
           Start
          7,2 Set
       ehromatographic
         condition!
        7 .3 Calibrate
          (refer to
        Method 8000)
       741 Introduce
       •ample into GC
         by direct
        injection or
       purge-and-trap,
        7.4.2 Follow
        Method 8000
        for analyvi*
         sequence,
           etc.
 744 Record
 vo1um» purged
     or
 injected.and
  peak siiea,
7,4,5 Calculate
concent cation*
   (refer to
 Method 80001.
   7 4 £ An
  analytical
 interferences
  •u»peeted?
 7,4.7 Is peak
 response off
    scale?
74,6 Anal?*i
•ample using
  second CC
   column.
7.4.7 Dilute
   second
 aliquot of
   tampl*
                             8015A  - 8
                                           Revision  1
                                            July  1992

-------

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                                 METHOD 8020A

               AROMATIC VOLATILE QRGANICS BY GAS CHROHATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   Method  8020  is  used  to  determine the  concentration  of  various
aromatic volatile organic compounds.  The following compounds can be determined
by this method:
                                                   Ajapropri ate Techn i que
                                                                    Direct
Compound Name                        CAS No.*       Purge-and-Trap  Injection
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Di Chlorobenzene
Ethyl benzene
Toluene
Xylenes
71-43-2
108-90-7
95-50-1
541-73-1
106-46-7
100-41-4
108-88-3

b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
a  Chemical Abstract Services Registry Number.
b  adequate response by this technique.

      1.2   Table 1 lists the method  detection limit for each target analyte in
organic-free reagent water.  Table 2 lists the estimated quantitation limit (EQL)
for other matrices.
2,0   SUMMARY OF METHOD

      2.1   Method 8020 provides chromatographic conditions for the detection of
aromatic volatile compounds.  Samples can be introduced into the GC using direct
injection  or purge-and-trap  (Method  5030),    Ground water  samples  must  be
determined  using  Method  5030.    A  temperature  program  is  used  in  the  gas
chromatograph to  separate  the  organic  compounds.   Detection is  achieved  by a
photo-ionization detector (PID).

      2.2   If interferences are encountered, the method provides an optional gas
chromatographic column  that may be  helpful  in  resolving  the  analytes  from the
interferences and for analyte confirmation.


3.0   INTERFERENCES

      3.1   Refer to Method 5030  and 8000.


                                  8020A  -  1                         Revision 1
                                                                September 1994

-------
      3.2   Samples  can  be  contaminated  by diffusion  of  volatile organics
 (particularly  chlorofluorocarbons  and methylene chloride)  through the sample
 container septum during shipment and storage.  A field sample blank prepared from
 organic-free reagent water and carried through sampling and  subsequent storage
 and handling can serve  as a check on such contamination.


 4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph

            4.1.1  Gas  Chromatograph  -  Analytical  system  complete  with  gas
      chromatograph suitable for on-column  injections or purge-and-trap sample
      introduction and  all  required accessories,  including  detectors,  column
      supplies, recorder, gases, and syringes.  A data  system  for measuring peak
      heights and/or peak areas is recommended.

            4.1.2  Columns

                   4.1.2.1    Column 1:  6 f t x 0.082 in  ID #304 stainless steel
            or glass  column  packed with  $%  SP-1200  and  1.75%  Bentone-34  on
            100/120 mesh Supelcoport,  or equivalent.

                   4.1.2.2    Column  2:   8  ft x  0.1 in ID stainless steel  or
            glass  column packed with  5%  1,2,3-Tris{2-cyanoethoxy)propane  on
            60/80 mesh Chromosorb  W-AW,  or equivalent,

            4.1.3  Detector - Photoionization (PID) (h-Nu  Systems, Inc.  Model
      PI-51-02 or equivalent).

      4.2   Sample  introduction  apparatus  - Refer to  Method  5030 for  the
appropriate equipment for sample introduction purposes.

      4.3   Syringes - A 5 ml Luerlok glass hypodermic and a 5  ml, gas-tight with
shutoff valve.

      4.4   Volumetric  flask, Class  A - Appropriate  sizes  with  ground  glass
si-uppers.

      4.5   Microsyringe - 10 and 25 ^L with a 0.006  in ID needle (Hamilton 702N
or equivalent)  and a 100 pi.

      4.6   Analytical  balance - 0.0001  g.


5.0   REAGENTS

      5.1   Organic-free reagent water.  All  references to water in this method
refer to organic-free reagent water,  as  defined  in Chapter One.

      5.2   Methanol  (CH3OH) - pesticide  quality or equivalent.  Store away from
other solvents.
                                  8020A  - 2                         Revision 1
                                                                September 1994

-------
      5.3   Stock standards -  Stock solutions may be prepared from pure standard
materials  or  purchased  as  certified solutions.   Prepare  stock standards  in
methanol  using  assayed  liquids.    Because  of  the toxicity  of  benzene and
1,4-dichlorobenzene, primary dilutions of these materials  should  be  prepared  in
a hood.

            5.3.1  Place about 9.8 ml of methanol  in a  10  ml tared ground glass
      stoppered  volumetric flask.   Allow the  flask to stand,  unstoppered, for
      about 10 min or until all alcohol wetted surfaces have dried.  Weigh the
      flask to the nearest 0.0001 g.

            5.3.2  Using a 100 /iL syringe, immediately  add two or more drops of
      assayed reference material  to  the  flask;  then reweigh.   The liquid must
      fall directly into the alcohol without contacting the neck of the flask.

            5.3.3  Reweigh, dilute to volume, stopper, and  then mix by inverting
      the flask  several  times.   Calculate the  concentration in milligrams per
      liter (mg/L) from the net gain  in weight.   When compound purity is assayed
      to  be  96%  or  greater,   the weight  may  be  used without  correction  to
      calculate the concentration of the  stock standard.  Commercially prepared
      stock standards may be used at any  concentration  if they are certified by
      the manufacturer or by an independent source.

            5.3.4  Transfer the  stock  standard solution  into  a  Teflon-sealed
      screw-cap bottle.  Store,  with minimal headspace, at  4°C and protect from
      light.

            5.3.5  All  standards must be replaced after 6  months, or sooner if
      comparison with check standards indicates a problem,

      5.4   Secondary  dilution  standards:   Using  stock   standard  solutions,
prepare in methanol secondary dilution standards,  as needed,  that contain the
compounds of interest,  either  singly or mixed together.  The secondary dilution
standards should be prepared at concentrations  such that the aqueous calibration
standards  prepared  in  Section  5.5  will  bracket the working  range  of  the
analytical system.  Secondary  dilution standards should be stored with minimal
headspace for volatiles and should be checked frequently for signs  of degradation
or evaporation,  especially just  prior to preparing calibration  standards from
them.

      5.5   Calibration standards:  Calibration standards  at a minimum of five
concentrations are prepared in  organic-free reagent water  from  the secondary
dilution of the  stock standards.   One  of the  concentrations  should be  at  a
concentration  near,  but above,  the method detection  limit.    The  remaining
concentrations should correspond to the  expected range of  concentrations found
in real samples  or should  define the working  range  of the  GC.   Each  standard
should contain each analyte for detection by this method (e.g.,  some or all  of
the compounds  listed in the target analyte list may be included).  In order to
prepare accurate aqueous standard solutions, the following precautions must be
observed.
                                  8020A  - 3                         Revision 1
                                                                September 1994

-------
            5.5.1  Do not  inject  more than 20 pi  of alcoholic standards  into
      100 ml of organic-free reagent water.

            5.5.2  Use  a  25  /iL  Hamilton  702N   microsyringe  or  equivalent
      (variations  in needle  geometry  will  adversely  affect the  ability to
      deliver reproducible volumes of methanolic standards into water).

            5.5.3  Rapidly  inject  the  alcoholic   standard   into   the  filled
      volumetric flask.  Remove the needle as fast  as possible after injection.

            5.5.4  Mix aqueous  standards by inverting the flask three  times only.

            5,5.5  Fill  the sample syringe from the standard solution contained
      in the expanded area of  the flask (do  not  use any solution contained in
      the neck of the flask).

            5.5.6  Never use pipets  to dilute or  transfer  samples  or aqueous
      standards.

            5.5.7  Aqueous standards are not stable  and should be discarded after
      1 hr, unless  properly  sealed and stored.  The aqueous  standards can be
      stored up to 24 hr, if held in sealed vials with zero headspace.

      5.6   Internal standards (if internal standard calibration is used):  To
use this approach, the analyst must select one or more internal  standards that
are similar in analytical behavior to  the compounds of  interest.   The analyst
must further demonstrate that  the measurement  of the internal standard is not
affected by method  or matrix  interferences.   Because of these limitations, no
internal  standard  can  be  suggested  that   is  applicable   to  all  samples.
Alpha, alpha,alpha-trifluorotoluene has  been  used  successfully as  an  internal
standard.

            5.6.1  Prepare  calibration   standards   at   a  minimum  of  five
      concentrations for each parameter of interest  as described in Section 5.5.

            5.6.2  Prepare a spiking  solution  containing  each of  the  internal
      standards using the procedures described in Sections 5.3 and 5.4.  It is
      recommended  that   the  secondary  dilution  standard  be prepared  at  a
      concentration of 15 mg/L  of each internal standard  compound.  The addition
      of 10 pi.  of this  standard  to  5.0 ml of sample or  calibration  standard
      would be equivalent to 30
            5.6.3  Analyze each calibration standard according to Section 7.0,
      adding  10  fjtl  of  internal  standard  spiking  solution  directly to  the
      syringe.

      5.7   Surrogate standards:  The analyst should monitor both the performance
of the analytical system and the effectiveness of the method in  dealing with each
sample matrix by spiking each sample, -standard, and organic-free reagent water
blank with surrogate compounds (bromochlorobenzene,  bromofluorobenzene, 1,1,1-
trifluorotoluene,  fluorobenzene,  and difluorobenzene  are  recommended)  which
encompass the range of the temperature program  used  in this method.  From stock


                                  8020A  -  4                        Revision 1
                                                                September 1994

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standard solutions prepared  as  in  Section  5.3,  add a volume to give 750 /Kg of
each surrogate  to 45  mL  of organic-free  reagent  water contained  in  a 50 ml
volumetric flask, mix,  and  dilute  to volume for a concentration  of 15 ng/#L.
Add 10 til of this surrogate  spiking solution directly into the 5 mL  syringe with
every  sample and reference  standard  analyzed.    If  the  internal   standard
calibration procedure is used, the  surrogate compounds  may  be added directly to
the internal standard  spiking solution  (Section 5.6.2),


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory material  to this chapter,  Organic Analytes,
Section 4.1.
7.0   PROCEDURE

      7.1   Volatile compounds are introduced  into the gas chroraatograph either
by direct injection or purge-and-trap  (Method  5030).   Method  5030 may be used
directly on ground  water samples or low-concentration  contaminated  soils and
sediments.   For medium-concentration soils or sediments, methanolic extraction,
as described in Method 5030,  may  be  necessary prior to purge-and-trap analysis.
Method 5030 also provides guidance on the analysis of aqueous miscible and non-
aqueous miscible liquid wastes (see Section 7.4.1,1 below).

      7.2   Gas chromatography conditions  (Recommended):

            7,2.1  Column 1:

            Carrier gas (He)  flow rate:  36 mL/min
            For lower boiling compounds:
                   Initial temperature:  50°C, hold for 2 min;
                   Temperature program:  50°C  to  90°C  at 6DC/min,  hold until
                                         all  compounds  have eluted.
            For higher boiling range of compounds:
                   Initial temperature:  50°C, hold for 2 min;
                   Temperature program:  50°C  to  110°C  at  3°C/min,  hold until
                                         all  compounds  have eluted.

            Column 1  provides  outstanding  separations  for  a  wide variety  of
      aromatic hydrocarbons.   Column 1  should be used as the primary analytical
      column because of its unique ability  to  resolve para-, meta-, and ortho-
      aromatic isomers.

            7.2.2  Column 2t

            Carrier gas (HeJ  flow rate:  30 mL/min
            Initial  temperature:          40°C, hold for 2 min;
            Temperature program:          40°C  to  100°C  at  2°C/min,  hold until
                                         all compounds  have eluted.
                                  8020A  - 5                         Revision 1
                                                                September 1994

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            Column 2, an  extremely  high  polarity column*  has been  used  for a
      number of years to resolve aromatic hydrocarbons from alkanes in complex
      samples.  However, because resolution between some of the aromatics is not
      as efficient as with Column 1, Column 2 should be used as  a confirmatory
      column.

      7.3    Calibration:  Refer to Method 8000 for proper calibration techniques.
Use Table  1  and  especially Table 2 for guidance on  selecting the lowest point on
the calibration curve.

            7.3.1   Calibration must take place using the same sample introduction
      method that  will be  used  to analyze actual samples (see Section  7,4.1).

            7.3.2   The procedure for  internal  or external calibration may  be
      used.  Refer to Method 8000 for a description of each of these procedures.

      7.4    Gas  chromatographic  analysis:

            7.4.1   Introduce volatile compounds into  the gas chromatograph  using
      either Method 5030 (purge-and-trap method) or the direct injection method.
      If the  internal  standard  calibration  technique  is  used,   add  10 juL  of
      internal standard  to the  sample prior to purging.

                   7.4.1.1    Direct injection:    In very  limited  applications
            (e.g.,  aqueous process wastes), direct injection of the sample into
            the  GC  system with  a  10  pi  syringe  may  be  appropriate.    The
            detection  limit is very high (approximately 10,000 fig/I); therefore,
            it is  only permitted when concentrations in excess of  10,000  jug/L
            are  expected or for water soluble compounds that do not purge.   The
            system must be calibrated by direct injection (bypassing the purge-
            and-trap  device).

                   Non-aqueous miscible wastes may also be analyzed by direct
            injection  if the concentration of  target  analytes  in the sample
            falls  within the  calibration  range.   If dilution of  the sample  is
            necessary,  follow the guidance  for High Concentration samples  in
            Method 5030, Section  7.3.3.2.

            7.4.2   Method  SOOO provides instructions on the  analysis sequence,
      appropriate  dilutions,  establishing  daily  retention  time  windows,  and
      identification  criteria.  Include a mid-concentration standard after each
      group  of 10  samples  in  the  analysis  sequence.

            7.4.3   Table 1  summarizes the estimated retention times and detection
      limits for a number of organic  compounds analyzable using this method.  An
      example  of the  separation  achieved  by  Column 1 is  shown  in Figure  1.
      Figure 2 shows  an  example of the  separation  achieved using  Column 2.

            7.4.4   Record the sample volume purged  or injected and  the resulting
      peak sizes (in  area  units or peak heights).

            7.4.5   Calculation of concentration  is covered in Method 8000.
                                  8020A - 6                         Revision  1
                                                                September 1994

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            7,4.6  If analytical  interferences are suspected, or for the purpose
      of confirmation, analysis using the second GC column  is recommended.

            7.4.7  If the  response  for  a peak is off scale,  i.e., beyond the
      calibration range of the standards, prepare a  dilution of  the sample with
      organic-free reagent water.   The  dilution  must be performed on a second
      aliquot of the sample which has been properly sealed  and  stored prior to
      use.
8.0   QUALITY CONTROL

      8.1   Refer to  Chapter One for specific quality  control  procedures and
Method 8000 for gas chromatographic procedures.  Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.

      8.2   Quality control  required to validate the GC system operation is found
in Method 8000.

            8.2.1  The quality control check  sample  concentrate (Method 8000)
      should contain each parameter of interest  at  a concentration of 10 mg/L
      in methane!.

            8.2.2  Table 3 indicates the  calibration  and QC acceptance criteria
      for this method.   Table 4 gives method accuracy  and precision as functions
      of concentration  for   the  analytes of  interest.   The contents  of both
      tables should be  used  to evaluate  a  laboratory's  ability  to perform and
      generate acceptable data by this method.

      8,3   Calculate surrogate  standard recovery on all  samples,  blanks, and
spikes.  Determine if recovery is  within limits (limits established by performing
QC procedure outlined in Method 8000).

            8.3.1  If recovery is not  within limits,  the following is required.

                   •    Check  to  be  sure   that  there   are   no  errors  in
                        calculations,    surrogate   solutions   and   internal
                        standards.  Also, check instrument performance.

                   •    Recalculate the data and/or reanalyze the extract if any
                        of the above  checks reveal  a  problem.

                   •    Reextract and  reanalyze the sample  if none of the above
                        are   a   problem   or   flag   the  data   as   "estimated
                        concentration",
                                   8020A  -  7                         Revision 1
                                                                September 1994
                           \

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9.0   METHOD PERFORMANCE

      9.1   This method was tested by 20 laboratories using organic-free reagent
water, drinking water,  surface water, and three industrial wastewaters spiked  at
six concentrations over the range 2.1  -  500 M9/L-   Single operator  precision,
overall precision, and method accuracy were found to be directly related to the
concentration of the  parameter and essentially independent of the sample matrix.
Linear equations to describe  these relationships are presented in Table 4.

      9.2   The accuracy and precision obtained will be determined  by  the sample
matrix, sample introduction technique, and by the calibration procedure used.

      9.3   The method  detection limits reported in Table  1 were generated under
optimum analytical conditions by an Agency contractor {Ref. 7) as guidance, and
may not be readily achievable by all  laboratories at all  times.


10.0  REFERENCES

1.    Bellar, T.A., and J.J.  Lichtenberg, J. Amer.  Water Works Assoc., 66(12),
      pp. 739-744, 1974.

2.    Bellar, T.A., and J.J. Lichtenberg,  "Semi-Automated Headspace Analysis of
      Drinking  Waters  and  Industrial  Waters  for  Purgeable  Volatile Organic
      Compounds", in  Van Hall  (ed.), Measurement of Organic Pollutants in Water
      and wastewater, ASTM STP 686,  pp. 108-129,  1979.

3.    Dowty,  B.J.,  S.R. Antoine, and J.L.  Laseter, "Quantitative and Qualitative
      Analysis of Purgeable Organics  by High Resolution Gas Chromatography and
      Flame  lonization  Detection",  in Van  Hall,  ed., Measurement  of Organic
      Pollutants in Water and Wastewater.  ASTM STP 686,  pp.  24-35,  1979.

4.    Development and Application of Test Procedures  for Specific Organic Toxic
      Substances in Wastewaters.  Category 11 - Purgeables  and Category  12 -
      Acrolein,  Acrylonitrile,  and  Dichlorodifluoromethane.   Report  for  EPA
      Contract 68-03-2635.

5.    "EPA Method Validation Study 24,  Method 602 (Purgeable Aromatics)", report
      for EPA Contract  68-03-2856.

6.    U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test  Procedures for the
      Analysis of Pollutants Under the Clean Water Act;  Final Rule and Interim
      Final Rule and  Proposed Rule",  October 26,  1984.

7.    Gebhart,  J.E.,  S.V.  Lucas, S.J.  Naber, A.M.  Berry,  T.H. Danison and H.M.
      Burkholder, "Validation of SW-846  Methods 8010, 8015,  and  8020"; Report
      for  EPA  Contract  68-03-1760,   Work  Assignment  2-15;   US EPA,  EMSL-
      Cincinnati, 1987."
                                  8020A  - 8                         Revision 1
                                                                September 1994

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                                  TABLE 1.
            CHRQMATOGRAPHIC CONDITIONS  AND METHOD DETECTION LIMITS
                        FOR AROMATIC VOLATILE ORGAN ICS



Compound
Benzene
Chlorobenzeneb
1,4-Dichlorobenzene
1,3-Dichlorobenzene
1,2-Dichlorobenzene
Ethyl Benzene
Toluene
Xyl enes
Retention
(mln)

Col. 1
3.33
9.17
16.8
18.2
25.9
8.25
5.75

time


Col. 2
2.75
8.02
1'6.2
15.0
19.4
6.25
4.25

Method
detection
limit8
Ug/U
0.2
0.2
0.3
0,4
0.4
0.2
0.2

a Using purge-and-trap method (Method 5030). See Sec. 9.3.
b Chlorobenzene and m-xylene may co-elute on some columns.
                                  TABLE 2.
             DETERMINATION OF  ESTIMATED QUANTITATION  LIMITS  (EQLs)
                             FOR VARIOUS  MATRICES8
      Matrix                                          Factor
      Ground water                                      10
      Low-concentration soil                             10
      Water miscible liquid waste                      500
      High-concentration soil  and sludge              1250
      Non-water miscible waste                        1250
      EQL =  [Method  detection limit  (see  Table 1)]  X  [Factor  found  in this
      table].  For non-aqueous  samples,  the factor is on  a  wet-weight basis.
      Sample EQLs are highly matrix-dependent.   The EQLs  determined herein are
      provided for guidance and may not always  be achievable.
                                  8020A  - 9                         Revision 1
                                                                September 1994

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                                   TABLE 3.
                            QC ACCEPTANCE CRITERIA*

Parameter
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1 , 3 -Di chl orobenzene
1, 4 -Di chlorobenzene
Ethyl benzene
Toluene
Range
for Q
(MflA)
15.4-24.6
16.1-23.9
13.6-26.4
14.5-25.5
13.9-26.1
12.6-27.4
15.5-24.5
Limit
for s
(M9/L)
4.1
3.5
5.8
5.0
5.5
6.7
4.0
Range
for x
(M9/U
10.0-27.9
12.7-25.4
10.6-27.6
12.8-25.5
11.6-25.5
10.0-28.2
11.2-27.7
Range
P, Ps
(*)
39-150
55-135
37-154
50-141
42-143
32-160
46-148
Q     =     Concentration measured in QC check sample,  in jug/L.

s     =     Standard deviation of four recovery measurements,  in M9/L.

x     =     Average recovery for four recovery measurements,  in ng/L.

P, PK  =     Percent recovery measured.

a     Criteria from 40 CFR Part  136  for Method  602,  using packed columns,  and
      were calculated assuming a check sample concentration of 20 (J,g/l.   These
      criteria are based directly upon the method performance data in Table 4.
      Where necessary, the  limits  for recovery have been  broadened  to.assure
      applicability of the limits to  concentrations below those used to develop
      Table 1. When capillary columns are used,  see Method 8021 for performance
      data.
                                  8020A - 10
    Revision 1
September 1994

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                                   TABLE  4.
          METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION


Parameter
Benzene
Chlorobenzene
1,2-Dichloro benzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Ethyl benzene
Toluene
Accuracy, as
recovery, x'
U9/L)
0.92C+0.57
0.95C+0.02
0.93C+0.52
0.96C-0.04
Q.93C-Q.09
0.94C+0.31
0.94C+0.65
Single analyst
precision, sr'
(M9/L)
0.09X+0.59
0.09X+0.23
0.17x-0.04
0.15x-0.10
Q.lSx+0.28
0,17x+0.46
0.09X+0.48
Overall
precision,
s' Ug/L)
0.21X+0.56
0,17x+0.10
0.22x+0.53
0.19x+0.09
0.20X+0.41
0.26x+0.23
O.lSx+0.71
X'
Expected  recovery  for  one  or  more  measurements  of  a  sample
containing concentration C, in
            Expected  single  analyst  standard deviation of  measurements  at an
            average concentration of x, in
S'


C

X
Expected interlaboratory  standard  deviation  of measurements' at an
average concentration found of x, in

True value for the concentration, in

Average recovery  found for  measurements  of samples  containing a
concentration of C, in
                                  8020A - 11
                                                        Revision 1
                                                    September 1994

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                  Figure  1
Chromatogram of Aromatic Volatile Organics
           (column 1 conditions)
Column:
Program:
Detector:
Sample:
                              5% SP-1200/1,75* Bentone  34
                              50°C-2 Minutes,  68C/Min.  to  SO°C
                              Photoionization
                              0.40  |ig/L  Standard Mixture
         •      10      12      14

          RETENTION TIME (MINUTES)
                    It
II
20
22
                8020A - 12
                                Revision 1
                            September 1994

-------
                 Figure 2
Chromatogram of Aromatic  Volatile Orginics
           (column 2 conditions)
Column:     5% l,2,3-Tris(2-Cyanoethoxy)Propane on Chromosorb-¥
Program:    40"C-2 Minutes,  2"C/ttin. to lOO'C
Detector:    Photoionization
Sample:     2.0 pg/L Standard Mixture
           I       IS

          mi IMTION -ma OHNUT«)
                 8020A - 13
    Revision 1
September 1994
     \

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                                     METHOD 8020A
               AROMATIC VOLATILE OR6ANICS  BY GAS  CHROMATOGRAPHY
        Start
7.1 Introduce compound!
 into ge6 chrometogrnph
  by direct injection or
     purgo-and-trap
     (Method 5030)
      7.2 Sot gae
    chromatograph
      condition.
     7.3 Calibrate
 (refer to Method 8000)
    7.4.1 Introduce
  volatile compounds
into gas ehromatograph
 by purge-and-trap or
    direct injection.
 7.4.2 Follow Method
   8000 for analysis
    sequence, ate.
7.4,4 Record volume
 purged or injected
  and peak size*.
   7.4.1 Calculate
    concentration
(refer to Method 8000)
      7.4.6 Are
      analytical
    interferences
     •uapeeted?
                                            7.4.7
                                          raiponse for
                                             o peak
                                           off-scale?
                                                                    7.4.6 Analyze using
                                                                    eecond GC column.
                               7.4.7 Dilute second
                                aliquot of sample.
                                       8020A -14
                                            Revision  1
                                       September  1994

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                                 METHOD 8021A

               HALOGENATED VOLATILES  BY  GAS CHROMATOGRAPHY  USING
            PHOTOIONIZATION AND ELECTROLYTIC CONDUCTIVITY DETECTORS
                     IN SERIES:  CAPILLARY  COLUMN  TECHNIQUE
1.0   SCOPE AND APPLICATION

      1.1   Method 8021  is  used  to determine volatile organic  compounds  in a
variety of solid waste matrices.   This method  is applicable to nearly all types
of samples, regardless of water content, including ground water, aqueous sludges,
caustic  liquors,  acid  liquors,  waste  solvents,  oily wastes,
fibrous  wastes,  polymeric  emulsions,   filter  cakes,  spent
catalysts, soils, and sediments.   The following compounds can
this method:
                          mousses,  tars,
                          carbons,  spent
                         be determined by
Analyte
                                                  Appropriate Technique
CAS No.a   Purge-and-Trap
Direct
Injection
Benzene
Bromobenzene
Bromochl oromethane
Bromodichloromethane
Bromoform
Bromomethane
n- Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chlorodibromomethane
Chloroethane
Chloroform
Chi oromethane
2-Chlorotoluene
4-Chlorotoluene
l,2-Dibromo-3-chloropropane
1,2-Dibromoethane
Dibromomethane
1 , 2 -Di chl orobenzene
1 , 3 -Di chl orobenzene
1 , 4-Di chl orobenzene
Dichlorodifluoromethane
1,1-Dichloroethane
1,2-Di chloroethane
1 , 1 -Di chl oroethene
c i s - I , 2 ~Di chl oroethene
trans -1,2-Di chl oroethene
71-43-2
108-86-1
74-97-5
75-27-4
75-25-2
74-83-9
104-51-8
,135-98-8
98-06-6
56-23-5
108-90-7
124-48-1
75-00-3
67-66-3
74-87-3
95-49-8
106-43-4
96-12-8
106-93-4
74-95-3
95-50-1
541-73-1
106-46-7
75-71-8
75-34-3
107-06-2
75-35-4
156-59-4
156-60-5
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
PP
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
                                  8021A  -  1
                               Revision 1
                           September 1994

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Analyte
CAS No.'
  Appropriate Technique
                  Direct
Purge-and-Trap    Injection
1 , 2-Di chl oropropane
1,3-Dichloropropane
2, 2-Di chl oropropane
1 , 1 -Di chl oropropene
cis-l,3-dichloropropene
trans-l,3-dichloropropene
Ethyl benzene
Hexachlorobutadiene
I sopropyl benzene
p- I sopropyl tol uene
Methyl ene chloride
Naphthalene
n-Propyl benzene
Styrene
1 , 1, 1,2-Tetraehloroethane
1 , 1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1 , 1 , 1 -Tr i chl oroethane
1 , 1 , 2-Trichl oroethane
Trichloroethene
Tr i chl orof 1 uoromethane
1 ,2,3-Trichloropropane
1,2,4-Trimethylbenzene
1 , 3 , 5-Tr iniethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
78-87-5
142-28-9
590-20-7
563-58-6
10061-01-5
10061-02-6
100-41-4
87-68-3
98-82-8
99-87-6
75-09-2
91-20-3
103-65-1
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
87-61-6
120-82-1
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
95-63-6
108-67-8
75-01-4
95-47-6
108-38-3
106-42-3
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
a Chemical Abstract Services Registry Number.
b Adequate response by thi
pp Poor purging efficiency
s technique.
resulting in high EQLs.




       1.2    Method detection limits (MDLs) are compound dependent and vary with
purging  efficiency  and  concentration.    The MDLs  for selected  analytes  are
presented  in  Table  1.   The  applicable  concentration range  of  this method is
compound  and  instrument dependent  but  is  approximately  0.1  to 200  p,g/L.
Analytes that  are inefficiently purged  from water will not  be detected when
present at low concentrations,  but they can be measured  with acceptable accuracy
and  precision when  present  in sufficient  amounts.    Determination of some
structural isomers (i.e. xylenes) may be hampered by coelution.
                                   8021A -  2
                               Revision  1
                           September 1994

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       1.3    The  estimated  quantitation  limit  (EQL)  of Method  8021A  for an
individual  compound  is approximately  1  ^9/^9  Cwgt weight)  for  soil/sediment
samples, 0.1 mg/kg  (wet weight)  for wastes, and 1 ^g/L  for  ground water  (see
Table 3).  EQLs will be proportionately higher for sample extracts and samples
that require dilution or reduced sample size  to avoid saturation of the detector.

       1.4    This method is  recommended for  use only by analysts experienced in
the measurement of pyrgeable organics  at the  low  pg/L level  or by experienced
technicians under the close supervision of  a qualified analyst.

       1.5    The toxicity or carcinogenicity  of chemicals used  in this method has
not been  precisely  defined.  Each  chemical should be treated as  a potential
health  hazard,  and  exposure  to these  chemicals  should be  minimized.   Each
laboratory is responsible for maintaining awareness of OSHA regulations regarding
safe  handling  of chemicals used in  this   method.   Additional  references to
laboratory safety are available for the information of the  analyst (references
4 and 6).

       1.6    The following method analytes have  been tentatively  classified as
known or suspected human or mammalian carcinogens: benzene, carbon tetrachloride,
1,4-dichlorobenzene,    1,2-dichloroethane,    hexachloro-butadiene,    1,1,2,2-
tetrachloroethane,    1,1,2-trichloroethane,    chloroform,   1,2-dibromoetnane,
tetrachloroethene,  trichloroethene,  and vinyl chloride. Pure standard materials
and stock standard  solutions of  these  compounds  should be handled in a hood.  A
NIOSH/MESA approved  toxic gas respirator should be  worn when the analyst handles
high concentrations of these toxic  compounds.


2.0   SUMMARY OF METHOD

      2.1   Method   8021  provides  gas  chromatographic  conditions  for  the
detection of halogenated and aromatic volatile organic compounds.  Samples can
be analyzed using direct injection or purge-and-trap (Method  5030).  Ground water
samples must be analyzed using Method  5030  (where  applicable).   A temperature
program  is  used  in  the gas chromatograph  to  separate the organic  compounds.
Detection is achieved by a  photoionization  detector (PID)  and an electrolytic
conductivity detector (HECD) in series.

      2.2   Tentative identifications are obtained by  analyzing standards under
the same conditions used for samples and comparing  resultant GC retention times.
Confirmatory information can be gained by comparing the relative  response from
the two detectors.   Concentrations of  the identified components are measured by
relating the response produced for  that compound to the response  produced by a
compound that is used as an internal standard.


3.0   INTERFERENCES

      3.1    Refer to Methods 5030 and 8000.

      3.2   Samples  can be contaminated by  diffusion  of volatile  organics
(particularly chlorofluorocarbons and  methylene chloride)  through  the sample
container  septum  during shipment  and storage.   A trip blank  prepared  from


                                  8021A - 3                        Revision 1
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organic-free reagent water and carried  through sampling and  subsequent  storage
and handling can  serve  as a check on  such contamination.

       3.3    Sulfur dioxide is a potential interferant in the  analysis  for vinyl
chloride.
 4.0    APPARATUS  AND MATERIALS

       4.1    Sample  introduction  apparatus  -  Refer  to Method  5030  for the
 appropriate  equipment for sample introduction purposes,

       4.2    Gas  Chromatograph  - capable  of temperature programming; equipped
 with variable-constant differential flow controllers, subambient oven controller,
 photoionization  and  electrolytic conductivity detectors connected with a short
 piece  of uncoated  capillary tubing, 0.32-0.5 mm ID, and data system.

             4.2.1  Column -  60  m x 0.75 mm  ID VOCOL wide-bore capillary column
       with  1.5 urn  film  thickness  (Supelco Inc., or equivalent).

             4.2.2  Photoionization  detector  (PID)   (Tracer   Model   703,  or
       equivalent).

             4.2.3  Electrolytic conductivity detector  (HECD) (Tracer Hall Model
       700-A, or  equivalent).

       4.3    Syringes -  5 ml glass  hypodermic with  Luer-Lok tips.

       4.4    Syringe valves  - 2-way with Luer ends  (Teflon or Kel-F).

       4-5    Microsyringe -  25  ^L  with  a 2 in. x 0.006 in. ID,  22° bevel needle
 (Hamilton I702N  or equivalent).

       4.6    Microsyringes - 10, 100 pL.

       4.7    Syringes -  0.5, 1.0,  and 5  ml,  gas-tight  with shut-off valve.

       4.8    Bottles  - 15 ml, Teflon lined with screw-cap or crimp  top.

       4.     Analytical  balance - 0.0001 g.

       4.1C   Refrigerator.

       4.1i   Volumetric  flasks,  Class  A -  Appropriate sizes with ground glass
stoppers.


5.0    REAGENTS

       5.1    Reagent  grade  inorganic  chemicals shall be used  in  all  tests.
Unless otherwise indicated, it is intended that all  inorganic reagents shall
conform to  the specifications  of  the Committee on  Analytical  Reagents of the
American Chemical Society, where such specifications are available. Other grades


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may be used, provided it is first ascertained that the reagent is of sufficiently
high  purity  to  permit  its  use  without  lessening  the  accuracy  of  the
determination,

      5.2   Organic-free reagent water.  All  references to water  in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Methanol, CH3OH - Pesticide quality or equivalent, demonstrated to
be free of analytes.  Store away from other solvents.

      5,4   Vinyl chloride, (99.9% pure), CH2=CHC1.  Vinyl chloride is available
from  Ideal  Sas Products,  Inc., Edison,  New Jersey  and  from Matheson,  East
Rutherford, New Jersey, as well  as  from  other  sources.  Certified mixtures of
vinyl chloride in  nitrogen at  1.0 and  10.0  ppm  (v/v) are available from several
sources.

      5.5   Stock standards - Stock solutions may either be prepared from pure
standard materials or purchased as certified solutions.   Prepare stock standards
in methanol using  assayed  liquids  or  gases, as  appropriate.  Because  of the
toxicity of some of the organohalides, primary  dilutions of these materials of
the toxicity should be prepared in  a hood.

      NOTE: If direct injection  is  used,  the solvent  system of standards must
            match that  of the  sample.   It  is  not  necessary to  prepare  high
            concentration aqueous mixed standards when using direct injection.

            5.5,1 Place about 9.8 ml of methanol in a  10 ml tared ground glass
      stoppered volumetric flask.   Allow the flask  to  stand, unstoppered, for
      about 10 rainutes  until  all  alcohol-wetted surfaces have dried.  Weigh the
      flask to the nearest O.I mg.

            5.5.2 Add the assayed reference material,  as described below.

                  5.5.2.1     Liquids:  Using a 100 (j.L  syringe, immediately add
            two or more drops of assayed reference material  to the flask;  then
            reweigh.  The  liquid must fall directly into the  alcohol  without
            contacting the neck of the flask.

                  5.5.2.2     Gases:   To  prepare standards  for  any  compounds
            that   boil   below   30°C   (e.g.    bromomethane,    chloroethane,
            chloromethane,  dichlorodifluoromethane,   trichlorofluoromethane,
            vinyl  chloride),  fill   a  5 ml valved  gas-tight syringe with the
            reference standard  to the  5.0  ml mark.  Lower  the needle  to  5 mm
            above  the methanol  meniscus.   Slowly  introduce  the  reference
            standard above the  surface of the  liquid.  The heavy  gas  rapidly
            dissolves in the methanol.  This may also be accomplished by using
            a  lecture  bottle equipped with  a  Hamilton Lecture  Bottle Septum
            (#86600).  Attach  Teflon  tubing  to the side-arm relief  valve and
            direct a gentle stream of gas  into the methanol meniscus.

            5.5.3 Reweigh, dilute to volume,  stopper, and then mix by inverting
      the flask several times.   Calculate  the  concentration in  milligrams per
      liter (mg/L)  from the net gain in weight.  When compound purity is assayed


                                  8QZ1A -  5                         Revision 1
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                \

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       to  be 96%  or greater,  the  weight  may be  used without  correction to
       calculate the concentration of the stock standard.  .Commercially prepared
       stock standards may be used at any concentration if they  are certified by
       the manufacturer  or by an  independent  source.

            5.5,4 Transfer the  stock  standard solution  into  a  bottle  with a
       Teflon lined  screw-cap or  crimp  top.  Store, with minimal headspace, at
       -10°C to -20°C and protect  from light.

            5.5.5 Prepare fresh  stock standards for gases weekly or sooner if
       comparison  with check standards  Indicates a  problem.  Reactive compounds
       such as 2-chloroethyl  vinyl ether and styrene may need to  be prepared more
       frequently.  All other standards must be replaced after six months.  Both
       gas and  liquid  standards must be monitored  closely by comparison to the
       initial calibration curve and by  comparison to QC check standards.  It may
       be  necessary  to replace the  standards more frequently  if either check
       exceeds  a 20% drift.

       5.6   Prepare   secondary  dilution  standards,   using   stock  standard
solutions, in methanol,  as needed, that  contain the compounds of  interest, either
singly or mixed together.  The secondary dilution standards should be prepared
at concentrations such that the  aqueous calibration standards prepared in Sec.
5.7 will  bracket the working range of the analytical system.  Secondary dilution
standards should  be stored with  minimal  headspace  for volatiles and should be
checked frequently for signs of  degradation  or evaporation, especially just prior
to preparing calibration standards  from them.

       5.7   Cal ibration standards, at a minimum of five concentration levels are
prepared in organic-free reagent  water  from the secondary  dilution of the stock
standards.  One of the concentration levels should be at a concentration near,
but above, the method detection  limit.  The remaining concentration levels should
correspond to  the  expected range  of the concentrations  found in real  samples or
should define  the working range of the GC.   Standards  (one  or more)  should
contain each analyte for detection by this method.   In  order to prepare accurate
aqueous standard solutions,  the  following precautions must be observed.

       NOTE: Prepare calibration solutions for use with direct injection analyses
            in water at the concentrations required.

            5.7.1 Do  not inject more  than 20 jul  of  alcoholic standards  into
       100 ml of water.

            5.7.2 Use   a  25  jut Hamilton  702N  microsyringe  or  equivalent
       (variations  in  needle geometry   will  adversely  affect  the  ability  to
      deliver reproducible volumes  of methanolic standards into water).

            5.7.3 Rapidly  inject   the  alcoholic  standard  into  the  filled
      volumetric flask.  Remove the needle  as  fast  as possible after injection.

            5.7.4 Mix  aqueous  standards by inverting  the  flask three times.
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             5.7,5 Fill the sample syringe from the  standard solution contained
       in  the expanded area of the flask (do not use any solution contained  in
       the neck  of the flask).

             5.7.6 Never use pipets  to  dilute  or transfer  samples  or aqueous
       standards.

             5.7.7 Aqueous standards are not  stable and should be discarded after
       one hour,  unless properly sealed  and  stored.   The aqueous standards can
       be  stored  up to 12  hours,  if held in  sealed vials with zero headspace.

             5.7.8 Optionally calibration using a certified gaseous mixture can
       be  accomplished daily utilizing commercially available  gaseous analyte
       mixture  of  bromomethane,  chloromethane, chloroethane,  vinyl  chloride,
       dichlorodifluoromethane  and trichlorofluoromethane  in  nitrogen.  These
       mixtures  of documented  quality are  stable  for as  long as  six months
       without refrigeration.  (VOA-CYL III,  RESTEK  Corporation, Cat. #20194 or
       equivalent).

       5.8   Internal   standards  -   Prepare  a  spiking   solution  containing
fluorobenzene and 2-bromo-l-ehloropropane  in  methanol,  using  the  procedures
described  in Sees. 5.5 and 5.6.   It is recommended that the secondary dilution
standard  be  prepared  at a concentration of 5 mg/L of each  internal  standard
compound.   The  addition of  10  jtiL of such  a  standard to 5.0 ml of sample or
calibration standard would be equivalent to  10 /xg/L.

       5.9   Surrogate  standards  -   The  analyst   should   monitor   both  the
performance  of  the analytical   system and the effectiveness of the  method in
dealing with each  sample  matrix by spiking  each sample,  standard,  and reagent
blank with two or more surrogate compounds.   A  combination of 1,4-dichlorobutane
and bromochlorobenzene is recommended to encompass the range of the temperature
program used in  this method.   From stock standard solutions prepared as in Sec.
5.5, add  a volume to give 750  M9 of each  surrogate  to  45  ml  of  organic-free
reagent water contained in a 50 ml volumetric flask, mix, and dilute to volume
for a concentration of 15 ng/juL.  Add 10 juL  of this surrogate spiking solution
directly into the 5 mL syringe with every sample and reference standard analyzed.
If the internal  standard calibration  procedure is used, the surrogate compounds
may be added directly to the internal standard spiking solution (Sec. 5.8).


6.0    SAMPLE COLLECTION, PRESERVATION, AND  HANDLING

       6.1    See  the  introductory material   to  this  chapter.  Organic Analytes,
Sec. 4.1.
7.0   PROCEDURE

      7.1   Volatile compounds are Introduced into the gas chromatograph either
by direct injection or purge-and-trap  (Method  5030),  Method 5030 may be used
directly on ground  water samples or low-concentration  contaminated  soils and
sediments.   For medium-concentration  soils or sediments, methanolic extraction,
as described in Method  5030,  may  be necessary prior to purge-and-trap analysis.


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       7.2    Gas  chromatography conditions (Recommended)

             7.2.1  Set   up   the   gas   chromatograph   system   so   that   the
       photoionizatlon detector  (PID)  is  in  series  with   the electrolytic
       conductivity  detector  (HECD).

             7.2.2  Oven settings:

             Carrier gas  (Helium)  Flow  rate:     6 mt/min.
             Temperature  program
                   Initial  temperature:    10°C, hold for 8 minutes at
                   Program:                 10CC to 180°C at 4°C/min
                   Final  temperature:      180°C,   hold  until   all   expected
                                           compounds  have  eluted.

             7.2.3  The carrier gas  flow is augmented with an additional 24 ml of
       helium flow  before entering  the  photoionization detector.  This make-up
       gas  is  necessary to ensure optimal  response from both detectors.

             7.2.4  These  halogen-specific systems eliminate misidentifications
       due  to non-organohal ides which are  coextracted during the  purge step.  A
       Tracor Hall Model 700-A detector was used to gather the  single laboratory
       accuracy  and  precision  data presented in  Table  2.     The  operating
       conditions used to collect these data are:

             Reactor tube:                       Nickel, 1/16  in  00
             Reactor temperature:                8108C
             Reactor base temperature:           25Q°C
             Electrolyte:                        100% n-Propyl  alcohol
             Electrolyte  flow rate:              0.8 mL/min
             Reaction gas:                       Hydrogen at 40 mL/min
             Carrier gas  plus make-up gas:       Helium at 30 mL/min

             7.2.5  A sample chromatogram  obtained with  this column is presented
       in  Figure  5.   This  column was  used to develop the  method performance
       statements in  Sec. 9.0.   Estimated retention  times  and  MDLs that can be
       achieved under these conditions  are given in  Table  1.   Other columns or
       element specific detectors may be used if the requirements of Sec. 8.0  are
       met.

       7.3    Calibration  -   Refer   to   Hethod  8000  for  proper  calibration
techniques.   Use Table 1 and especially  Table 2 for guidance  on selecting  the
lowest point  on the  calibration curve.

             7.3.1  Calibration must take place  using the same sample introduction
       method  that will be used to analyze  actual samples  (see Sec. 7.4.1).

             7.3.2  The procedure for internal  or external calibration  may be
       used.  Refer to Method  8000 for a description of each of  these procedures.

       7.4    Gas chromatographic analysis
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             7.4.1  Introduce volatile compounds into the gas  chromatograph using
       either Method 5030 (purge-and-trap method)  or the direct  injection method
       (see Sec,  7.4.1.1).    If the  internal  standard  calibration technique  is
       used,  add  10 >j.l of internal  standard  to the  sample  prior to purging.

                   7.4.1.1     Direct injection -  In very  limited applications
             (e.g.  aqueous  process  wastes)  direct injection  of the sample into
             the  GC  system  with  a  10  pi  syringe may be  appropriate.   The
             detection limit  is very high (approximately 10,000 M9/U, therefore,
             it  is only permitted where concentrations  in excess of 10,000 (ug/L
             are  expected or  for water-soluble compounds that do not purge.  The
             system must be calibrated by direct injection  (bypassing the purge-
             and-trap  device).

             7.4.2  Follow  Sec.  7.6  in  Method 8000 for  instructions  on  the
       analysis  sequence,  appropriate dilutions,  establishing  daily  retention
       time windows,  and identification  criteria.   Include a mid-concentration
       standard after  each  group of  10 samples  in the analysis  sequence.

             7.4.3  Table 1  summarizes the estimated retention  times on the two
       detectors  for a number of organic  compounds analyzable using this method.

             7.4.4  Record the sample volume purged or injected and the resulting
       peak sizes (in  area  units or  peak heights).

             7.4.5  Calculation of  concentration is  covered in Method 8000.

             7,4.6  If analytical interferences are suspected, or for the purpose
       of  confirmation,  analysis using a second GC  column  is recommended.

             7.4.7  If the  response  for  a  peak is  off-scale,  i.e., beyond the
       calibration range of the standards,  prepare a dilution of the sample with
       organic-free reagent water.   The  dilution  must  be performed on  a second
       aliquot of the  sample  which has been properly sealed and  stored  prior to
       use.
8.0   QUALITY CONTROL

      8.1    Refer  to  Chapter One for specific quality  control  procedures and
Method 8000 for gas chromatographic procedures.  Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.

      8.2    Quality  control  required to validate  the GC  system  operation is
found in Method 8000.

             8.2.1  The  quality control  reference  sample (Method  8000)  should
      contain  each parameter of interest  at  a  concentration  of 10 mg/L in
      methanol.

             8.2.2  Table  2  gives  method  accuracy  and  precision as functions of
      concentration for the analytes of interest.
                                  8021A - 9                         Revision 1
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       8.3    Calculate surrogate standard recovery on all samples, blanks,  and
spikes.  Determine if recovery is within limits  (limits established by  performing
QC procedure cjtlined  in Method 8000).

             8.3.1 If recovery is not within limits,  the following  is required.

                   •    Check to be  sure  there are no errors in calculations,
                        surrogate solutions and internal standards.   Also check
                        instrument performance.

                   *    Recalculate the data and/or reanalyze the extract if  any
                        of the above checks reveal a problem.

                   •    Reextract and reanalyze the sample if none of the above
                        are  a   problem   or  flag   the  data  as   "estimated
                        concentration".
9.0   METHOD  PERFORMANCE

      9.1   Method detection limits for these analytes have been calculated from
data collected by spiking  organic-free reagent  water  at 0.1  M9/L.  These data
are presented in Table 1.

      9.2   This  method  was tested in a  single laboratory, using organic-free
reagent water spiked at 10 ^g/L.   Single laboratory  precision and  accuracy data
for each detector are presented for the method analytes in Table  2.


10.0  REFERENCES

1-    Volatile Organic Compounds  in Hater by Purqe-and-Trap Capi]larvalumn Gas
      Chromatography   with  Photolonization  and   Electrolytic   Conductivity
      Detectors  in  Series,  Method  502.2.  Rev.  2.0  f!989):  Methods  for  the
      Determination  of Organic  Compounds  in  Drinking  Water",   Environmental
      Monitoring Systems  Laboratory, Cincinnati, OH,  EPA/600/4-88/039, December,
      1988

2,    The Determination of Haloqenated Chemicals in  Mate*" by the Purge and Trap
      Method,  Method  502.1;  Environmental  Protection  Agency,   Environmental
      Monitoring  and  Support Laboratory:  Cincinnati,  Ohio  45268,  September,
      1986.

3.    Volatile Aromatic and Unsaturated Organic  Compounds in Water by Purge and
      Trap Gas Chroinatoqraphv, Method 503.1;  Environmental Protection Agency,
      Environmental   Monitoring  and  Support  Laboratory:  Cincinnati,  Ohio,
      September, 1986.

4.    Glaser, J.A.;  Forest, D.L.; McKee,  G.D.; Quave, S.A.; Budde, W.L. "Trace
      Analyses for Wastewaters"; Environ. Sci. Techno!.  1981, IS, 1426.
                                  8021A - 10
    Revision 1
September 1994

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5.    Bellar, T.A.;  Liehtenberg,  J.J.  The Determination of  Synthetic  Organic
      Compounds in Water by Purge and Sequential  Trapping Capillary Column Sas
      Chromatograptm  U.S.  Environmental  Protection  Agency,  Environmental
      Monitoring and Support Laboratory: Cincinnati, Ohio,  45268.
                                  8021A - 11                         Revision 1
                                                                September 1994

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                              TABLE  1.

CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (MDL)  FOR
  VOLATILE ORGANIC COMPOUNDS ON PHOTOIONIZATI ON DETECTION (PID) AND
      HALL  ELECTROLYTIC  CONDUCTIVITY DETECTOR  (HECD) DETECTORS
Analyte
Di ehl orodi f 1 uoromethane
Chl oromethane
Vinyl Chloride
Bromoroethane
Chloroethane
Trichl orofl uoromethane
1,1-Dichloroethene
Methyl ene Chloride
trans-l,2-Dichloroethene
1,1-Dichloroethane
2,2-Dichloropropane
ci s-1, 2 -Di chloroethane
Chloroform
Bromochl oromethane
1,1,1 -Tri chl oroethane
1,1-Dichloropropene
Carbon Tetrachloride
Benzene
1,2-Dichloroethane
Trichloroethene
1,2-Dichloropropane
Bromodi chl oromethane
Dibromomethane
Toluene
1,1,2-Trichl oroethane
Tetrachl oroethene
1,3-Dichloropropane
Dibromochl oromethane
1,2-Dibromoethane
Chlorobenzene
Ethyl benzene
1,1,1 , 2-Tetrachl oroethane
m-Xylene
p-Xylene
o-Xylene
Styrene
I sopropyl benzene
Broioform
1 , 1 , 2, 2-Tetrachl oroethane
1,2,3-Trichloropropane
PID
Ret. Time8
minute
_b
-
9.88
-
-
-
16.14
-
19.30
-
.
23.11
-
-
-
25.21
-
26.10
-
27.99
-
-
-
31.95
-
33.88
-
-
-
36.56
36.72
-
36.98
36.98
38.39
38.57
39.58
-
-
-
HECD
Ret. Time
minute
8.47
9.47
9.93
11.95
12.37
13.49
16.18
18.39
19.33
20.99
22.88
23.14
23.64
24.16
24.77
25.24
25.47
-
26.27
28.02
28.66
29.43
29.59
-
33.21
33.90
34.00
34.73
35.34
36.59
-
36.80
-
-
'
-
-
39.75
40.35
40.81
PID
MDL
MiA


0.02



NDC

0.05


0.02



0.02

0.009

0.02



0,01

0.05



0.003
0.005

0.01
0.01
0.02
0.01
0.05



HECD
MDL
M9/L
0.05
0.03
0.04
1.1
0.1
0.03
0.07
0.02
0.06
0.07
0.05
0.01
0.02
0.01
0.03
0.02
0.01

0.03
0.01
0.006
0.02
2.2

ND
0.04
0.03
0.03
0.8
0.01

0.005





1.6
0.01
0.4
                             8021A - 12
    Revision 1
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                                   TABLE  1.
                                  (Continued)
Analyte
   PID
Ret.  Time8
  minute
  HECD
Ret.  Time
 minute
PID
HDL
M9/L
                                                                        HECD
                                                                         MDL
n-Propylbenzene                   40.87
Bromobenzene                      40.99
1,3,5-Trimethylbenzene            41.41
2-Chlorotoluene                   41.41
4-Chlorotoluene                   41.60
tert-Butylbenzene                 42.92
1,2,4-Trimethylbenzene            42.71
sec-Butyl benzene                  43.31
p-Isopropyltoluene                43.81
1,3-Dichlorobenzene               44.08
1,4-Dichlorobenzene               44.43
n-Butylbenzene                    45.20
1,2-Dichlorobenzene               45.71
l,2-Dibromo-3-Chloropropane
1,2,4-Trichlorobenzene            51.43
Hexachlorobutadiene               51.92
Naphthalene                       52.38
1,2,3-Trichlorobenzene            53.34

Internal Standards
  Fluorobenzene                   26.84
  2-Bromo-l-chloropropane
                41.03

                41.45
                41.63
                44.11
                44.47

                45.74
                48,57
                51.46
                51.96

                53.37
                33.08
             0.004
             0.006
             0.004
             NO
             0.02
             0.06
             0.05
             0,02
             0.01
             0.02
             0.007
             0.02
             0.05

             0.02
             0.06
             0.06
             ND
          0.03

          0.01
          0.01
          0.02
          0.01

          0.02
          3.0
          0.03
          0.02

          0.03
    Retention  times determined  on  60 m x  0.75  mm ID VOCOL  capillary column.
    Program:  Hold at 10°C for 8 minutes, then program at 4°C/min to 180°C, and
    hold until  all  expected  compounds have  eluted.
b   Dash  (-}  indicates  detector  does  not  respond.

c   ND  =  Not  determined.
                                  8021A - 13
                                  Revision 1
                              September 1994

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                   TABLE 2.
SINGLE LABORATORY ACCURACY AND PRECISION DATA
   FOR VOLATILE ORGANIC COMPOUNDS IN WATER*
Photoionization
Detector
Analyte
Benzene
Bromobenzene
Bromochl oromethane
Bromodichl oromethane
Bromoform
Bromomethane
n- Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chi oromethane
2-Chlorotoluene
4-Chlorotoluene
1 ,2-Dibromo-3-chloropropane
Di bromochl oromethane
1,2-Dibrotnoethane
Dibromomethane
1 , 2 -Di chl orobenzene
1 , 3 -Di chl orobenzene
1 , 4 -Di chl orobenzene
Di chl orodi f 1 uoromethane
1,1 -Di chloroethane
1 , 2-Dichl oroethane
1,1-Dichloroethene
cis- 1,2 Dichloroethene
trans -1,2-Di chl oroethene
1,2-Di chl oropropane
1 , 3 -Di chl oropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachl orobutadi ene
I sopropyl benzene
p- I sopropyl toluene
Recovery,8
%
99
99
-
-
-
-
100
97
98
-
100
-
-
-
NDC
101
-
-
-
-
102
104
103
-
-
-
100
ND
93
-
-
-
103
101
99
98
98
Standard
Deviation
of Recovery
1.2
1.7
-
-
-
-
4.4
2.6
2.3
.
1.0
-
-
-
ND
1.0
-
-
-
-
2.1
1.7
2.2
-
-
-
2.4
ND
3.7
_
-
-
3.6
1.4
9.5
0.9
2.4
Hall Electrolytic
Conductivity Detector
Standard
Recovery,8 Deviation
% of Recovery
_b
97
96
97
106
97
-
-
-
92
103
96
98
96
97
97
86
102
97
109
100
106
98
89
100
100
103
105
99
103
100
105
103
-
98
-
-

2.7
3.0
2.9
5.5
3.7
-
-
-
3.3
3.7
3.8
2.5
8.9
2.6
3.1
9.9
3.3
2.7
7.4
1.5
4.3
2.3
5.9
5.7
3.8
2.9
3.5
3.7
3.8
3.4
3.6
3.4
-
8.3
-
-
                  8021A  -  14
    Revision 1
September 1994

-------
                                         TABLE 2.
                                        (Continued)
Analyte
                                  Photoionization
                                      Detector
                                  Recovery »
                                                            Hall  Electrolytic
                                            _               Conductivity  Detector
                                             Standard                      Standard
                                             Deviation      Recovery,*     Deviation
                                             of Recovery         %         of Recovery
Methyl ene chloride
Naphthalene
n-Propyl benzene
Styrene
1,1,1 , 2-Tetrachl oroethane
1 , 1 ,2, 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1 , 2 , 3-Tr ichl orobenzene
1,2, 4-Trichl orobenzene
1,1,1-Trichl oroethane
1,1, 2-Tr ichl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
1,2,3-Trichloropropane
1, 2, 4-Tri methyl benzene
1 ,3 , 5-Tri methyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
-
102
103
104
-
-
101
99
106
104
-
-
100
-
-
99
101
109
99
100
99
-
6.3
2.0
1.4
-
-
1.8
0.8
1.9
2.2
-
-
0.78
-
-
1.2
1.4
5.4
0.8
1.4
0.9
97
-
-
-
99
99
97
-
98
102
104
109
96
96
99
-
-
95
-
-
-
2.8
-
-
-
2.3
6.8
2.4
-
3.1
2.1
3.4
6.2
3.5
3.4
2.3
-
-
5.6

-
-
   Recoveries  and  standard deviations  were  determined from  seven  samples and spiked  at
   10 ng/l of each analyte.  Recoveries were determined by internal standard method.  Internal
   standards were: Fluorobenzene for PID, 2-Bromo-l-chloropropane for HECD.

   Detector does not respond.
ND = Not determined.

This method  was tested  in a  single  laboratory  using water  spiked at  10
reference 5).
                                                                                      (see
                                        8021A -  15
                                                                       Revision  1
                                                                   September  1994

-------
                      TABLE 3.
DETERMINATION OF ESTIMATED QUANTITATIQN LIMITS (EQL)
                FOR VARIOUS MATRICES8
  Matrix                              Factor
  Ground water                             10
  Low-concentration soil                   10
  Water miscible liquid waste             500
  High-concentration soil and sludge     1250
  Non-water nriscible waste               1250
  EQL = [Method detection limit (see Table 1)]  X [Factor  found  in
  this table].  For non-aqueous samples, the factor  is on  a  wet-
  weight basis. Sample EQLs are highly matrix-dependent.  The  EQLs
  listed herein are provided  for  guidance and may not always  be
  achievable.
                     8021A - 16                        Revision  1
                                                   September 1994

-------
    FIGURE  1.
 PURGING DEVICE
lMt£T 1M IM, O.O
        Z-WAT SYHMGC

        17 CM a &huG€ SI-WMGE

        8 MM 00 *UMKA StPTUM

              m oo.
                                 OO
                         /"" STAJNUESS STtfi
                            19
                            WOCECUUW sicvt
                            ^JRQC QAS FN.TCR
                             PUHQCOAS
   8021A  - 17
     Revision  1
September 1994

-------
                          FIGURE  2.
TRAP PACKINGS AND CONSTRUCTION TO  INCLUDE DESORB CAPABILITY
PACKING DETAIL


  ~"Ti- 5 MUOOS
                                 CONSTRUCTION CHETM.
                    moot
           rr CM SiUO Ga.

          '» CM
          •- • CM J% OV.1
        =r"
        \
                       8021A -  18
                                                    Revision  1
                                                September  1994

-------
                            FIGURE 3.
               PURGE-AND-TRAP SYSTEM - PURGE MODE
CAJWUBGAS
     CONTftOL
I- UQUK3 iHJfCTlON I«0«TS

        COLUMN OVfN
                                                  ANALYTICAL COLUMN
                               OPTIONAL 4^O«T OOUIMN
                               SiLfiCTION VALV1
                                                              COLUMN
                                                NOTE
                                                   UNCS BCTWf EM
                                                AMD QC SHCWLD K H€AT1D.
                                                TO arc.
                            8021A - 19
                                Revision 1
                           September 1994

-------
                            FIGURE 4.
        SCHEMATIC OF PURGE-AND-TRAP DEVICE -  OESORB  MODE
       GAS
R.OW CONTROL
PWISSURE
REGULATOR
PURGE GAS
FLOW CONTROL
SlEVf
LOJO INJlCnON PORTS

   r— CXXUMNOVEN
                                   UUl/V-
                                               OXFIRMATORY COLUMN
                                              TODCTfCTOR
   MOLECULAR
                             OPTIONAL 4^>ofrr COLUMN
                             SELfCTION VALVE
                                    /-TRAP INLET
                                     TRAP
                                     2QD-C
                                PURGING
                                OCVCC
             NOTE
             ALL UNES BETWEEN
             AMD GC SHOULD BE HEATED
             TOUTC.
                           8021A - 20
                            Revision 1
                        September 1994

-------
                              FIGURE 5.

                  GAS CHROMATOGRAM OF VOLATILE ORGAN ICS
COLUMNi 60 METER M 0.73 MM 1.0. VOCOL. CAPILLARY


PUNBt *MD T«*P MC'I HITH MAU. a PtQ IN SCHiKl"
     ss?   IB 8  sa  rs t
     ^M     •<  •!•!   i
sea a  s9

Kit i  83
      1
                                DU
                 J
         k
LjllJiL.

       =SiS«
                                                       . .
                                                       11
                        L PID
HECfi
                    A d

                    i !
                             8021A - 21
                          Revision 1

                       September 1994

-------
                                      METHOD  8021A
       HALOGENATED VOLATILES BY  SAS  CHROMATQGRAPHY USING  PHOTOION IZATION
                AND  ELECTROLYTIC CONDUCTIVITY  DETECTORS  IN SERIES:
                              CAPILLARY COLUMN TECHNIQUE
  f     Start     }
      7.2 Set
   chromatographic
     conditions.
    7.3 Refer to
  Method 8000 for
calibration techniques.
  7.4,1 Introduce
sample into GC using
  direct injection or
  purge-and-trap.
   7,4,4 Record
   sample volume
 introduced into GC
   and peak, sizes.
   7.4.5 Refer
to Method 8000 for
   calculations.
      7.4.6 Are
      analytical
    interferences
     •uspectsd?
                                      7.4,7 Is peak
                                      response off
                                         scale?
Reanalyze sample
using second GC
    column.
                             Dilute and reanalyze
                              second aliquot of
                                  sample.
                                       8021A  -  22
                                               Revision 1
                                          September  1994
                             \

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                                 METHOD 8030A

               ACROLEIN AND ACRYLONITRILE BY GAS CHROHATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   Method 8030 is used  to determine the concentration of the following
volatile organic compounds:
            Compound Name                                   CAS No.8


            Acrolein (Propenal)                             107-02-8
            Acrylonitrile                                   107-13-1


      8  Chemical  Abstract Services Registry Number.

      1.2   Table 1 lists  chromatographic conditions and method detection limits
for acrolein and acrylonitrile  in organic-free reagent water.  Table  2 lists the
estimated quantitation limit (EQL) for other matrices.


2.0   SUMMARY OF METHOD

      2.1   Method 8030 provides gas chromatographic conditions for the detection
of the target analytes.  Samples can be analyzed using direct injection or purge-
and-trap (Method  5030).   Tenax should  be  used as the trap  packing material.
Ground water samples must  be analyzed  using  Method 5030.  A temperature program
is used in the gas chromatograph to separate the organic compounds.   Detection
is achieved by a flame ionization detector  (FID).

      2.2   The method provides an optional  gas chromatographic column that may
be helpful  in resolving the analytes from co-eluting non-target compounds and for
analyte confirmation.


3.0   INTERFERENCES

      3.1   Refer to Methods 5030 and 8000.

      3.2   Samples  can   be  contaminated  by  diffusion  of   volatile  organics
(particularly chlorofluorocarbons  and methylene chloride) through  the  sample
container  septum  during  shipment  and  storage.   A  trip blank  prepared  from
organic-free reagent water and carried through sampling and  subsequent storage
and handling can serve as a check on such contamination.
                                   8030A  -  1                         Revision 1
                                                                     July 1992

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4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph

            4.1.1      Gas Chromatograph - Analytical  system complete with gas
      chromatograph suitable for on-column injections or purge-and-trap sample
      introduction and  all  required accessories,  including  detectors,  column
      supplies, recorder,  gases,  and syringes.  A data  system  for measuring peak
      height and/or peak area is recommended.

            4.1.2      Columns

                 4.1.2.1      Column 1  -  10 ft  x  2  mm ID stainless  steel  or
            glass packed with Porapak-QS (80/100 mesh) or equivalent.

                 4.1.2.2      Column 2  - 6  ft  x  0.1  in.  ID stainless steel  or
            glass packed with Chromosorb 101 (60/80 mesh) or equivalent.

            4.1.3      Detector - Flame ionization (FID).

      4.2   Sample  introduction apparatus  -  Refer   to  Method  5030 for  the
appropriate equipment for sample introduction purposes.

      4.3   Syringes - A  5  ml  Luer-lok glass hypodermic  and  a 5 ml, gas-tight
with shutoff valve.

      4.4   Volumetric  flasks,  Class  A - Appropriate  sizes  with  ground glass
stoppers.

      4.5   Microsyringes   -  10  and  25  p,i  with   a  0.006  in.  ID  needle
(Hamilton 702N, or equivalent) and a 100 p.1.

      4.6   Analytical balance - 0.0001 g.


5.0   REAGENTS

      5.1   Reagent grade chemicals shall  be used in all tests. Unless otherwise
indicated, it is intended that all  reagents  shall  conform to  the specifications
of the Committee on Analytical  Reagents of the  American Chemical Society, where
such specifications are available. Other grades may be  used, provided it is first
ascertained that the  reagent  is  of sufficiently high  purity to permit its use
without  lessening the accuracy of the determination.

      5.2   Organic-free reagent water:  All references to  water in  this method
refer to organic-free reagent water, as defined  in Chapter One.

      5.3   Hydrochloric  acid, HC1 - 1:1  (v/v).

      5.4   Sodium  hydroxide,  NaOH  -  ION  solution.   Dissolve  40 g  NaOH  in
organic-free reagent water  and dilute to  100 ml.

      5.5   Stock standards - Stock solutions may be prepared from  pure standard
materials  or  purchased as  certified  solutions.   Prepare stock  standards  in

                                   8030A - 2                        Revision  1
                                                                     July 1992

-------
organic-free  reagent  water  using  assayed  liquids.    Because  acrolein  and
acrylonitrile are lachrymators, primary dilutions of these compounds should be
prepared in a hood.

            5.5.1      Place  about  9.8  ml of organic-free reagent water in a 10
      ml tared ground-glass stoppered volumetric  flask.  For acrolein standards
      the water must be adjusted to pH  4-5 using  hydrochloric acid (1:1 v/v) or
      sodium hydroxide  (ION),  if necessary.    Weigh  the flask to  the nearest
      0.0001 g.

            5.5.2      Using  a  100 /zL syringe, immediately add two or more drops
      of assayed reference material  to the flask,  then  reweigh.  The liquid must
      fall directly into the  water without  contacting the neck of the flask.

            5.5.3      Reweigh, dilute  to  volume,  stopper,  and  then mix  by
      inverting  the flask  several times.    Calculate the  concentration  in
      milligrams per liter (mg/L)  from the net gain  in weight.   When compound
      purity is  assayed to be  96% or  greater, the weight may  be  used without
      correction  to  calculate  the  concentration  of  the  stock  standard.
      Commercially prepared stock standards may be used at any concentration, if
      they are certified by the manufacturer or by an independent source.

            5.5.4      Transfer the stock standard solution  into a bottle with
      a Teflon  lined screw-cap.   Store,  with minimal  headspace, at  4°C  and
      protect from light.

            5.5.5      Prepare  fresh standards daily.

      5.6   Secondary dilution  standards  - Prepare secondary dilution standards
as needed, in organic-free reagent water, from the stock standard solutions.  The
secondary dilution  standards must  contain the compounds of  interest,  either
singly or mixed together.   The secondary dilution standards  should be prepared
at concentrations such that the  aqueous calibration standards prepared in Section
5.7 will  bracket the working range of the  analytical system.  Secondary dilution
standards  should be  stored  with  minimal  headspace,  and  should be  checked
frequently for  signs of degradation or evaporation, especially just  prior to
preparing calibration standards from them.

      5.7   Calibration standards - Prepare calibration standards in organic-free
reagent water  from  the secondary  dilution  standards  at  a  minimum of  five
concentrations.  One of the concentrations should  be at  a concentration near, but
above,  the method  detection  limit.    The   remaining  concentrations  should
correspond to the  expected range of concentrations found in real  samples,  or
should define the working range of  the GC.   Each standard  should  contain each
analyte for detection  by  this method.   In  order to prepare  accurate aqueous
standard solutions, the following precautions must be observed.

            5.7.1      Use a  25 /zL  Hamilton  702N microsyringe,  or equivalent,
      (variations  in  needle  geometry  will  adversely affect  the ability  to
      deliver reproducible volumes of  standards into water).

            5.7.2      Never  use pi pets to dilute  or transfer samples or aqueous
      standards.
                                  8030A  - 3                         Revision 1
                                                                     July 1992

-------
            5.7.3      Standards must be prepared daily.

      5.8   Internal standards (if internal standard calibration is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to  the  compounds  of interest.   The analyst
must further demonstrate that the measurement  of the internal  standard is not
affected by method or  matrix  interferences.   Because of these limitations, no
internal standard can be suggested that is applicable to all samples.

            5.8.1      Prepare  calibration standards  at  a minimum of  five
      concentrations for each  parameter of interest,  as described in Section
      5.7.

            5.8.2      Prepare a spiking solution containing each of the internal
      standards, using the procedures described in Sections  5.5  and 5.6.  It is
      recommended  that  the  secondary dilution  standard   be   prepared  at  a
      concentration of 15 mg/L of each internal standard compound.  The addition
      of  10 p.1 of this  standard  to  5.0 ml of  sample  or calibration standard
      would be equivalent to 30 /*g/L.

            5.8.3      Analyze each calibration  standard according to Section
      7.0, adding 10 ^L  of  internal  standard  spiking solution directly to the
      syringe.

      5.9   Surrogate standards - The analyst should monitor both the performance
of the analytical  system and the effectiveness  of the method  in dealing with each
sample matrix by spiking each sample, standard, and organic-free reagent water
blank with one or two surrogate compounds  (e.g.  compounds similar in analytical
behavior to the analytes  of interest but which are not expected  to be  present in
the sample) recommended to encompass the range of the temperature program used
in this method.  From stock standard solutions prepared as  in Section 5.5, add
a volume to give 750 M9 of each surrogate to 45 ml of  organic-free reagent water
contained  in   a  50  ml volumetric  flask,   mix,  and  dilute to  volume  for  a
concentration  of 15 ng/pl.   Add  10  nl  of  this surrogate  spiking solution
directly into  the 5 ml syringe with every sample and reference standard analyzed.
If the internal standard  calibration  procedure is  used, the surrogate compounds
may be added directly to the internal  standard  spiking solution  (Section 5.8.2).


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See  the  introductory material  to  this chapter,  Organic Analytes,
Section 4.1.
7.0   PROCEDURE

      7.1   Volatile compounds are introduced into the gas chromatograph either
by direct injection or heated purge-and-trap (Method  5030).  Method 5030 may be
used directly on ground water samples or low-concentration contaminated soils and
sediments.  For high-concentration soils or sediments, methanolic extraction, as
described in Method 5030, may be necessary prior to  purge-and-trap analysis.
                                   8030A -  4                        Revision 1
                                                                     July 1992

-------
      7.2   Gas chromatographic conditions (Recommended)

            7.2.1      Column 1:

             Helium flow rate =                 30 ml/mln
             Temperature program:
                       Initial  temperature -    110°C,  hold for 1.5 minutes
                       Program =                 110°C  to  150°C,   heating  as
                                                rapidly as possible
                       Final  temperature =      150°C,  hold for 20 minutes.

            7.2.2      Column 2:

             Helium flow rate =                 40 mL/min
             Temperature program:
                       Initial  temperature -    80°C, hold for 4 minutes
                       Program =                 80°C to 120°C  at 50°C/min
                       Final  temperature -      120°C,  hold for 12 minutes.

      7.3   Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1  and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.

            7.3.1      Calibration  must  take place  using  the  same  sample
      introduction method  that will  be used  to  analyze actual  samples   (see
      Section 7.4.1).

            7.3.2      The  procedure for internal  or external calibration may be
      used.   Refer to Method 8000 for a description of each of these procedures.

      7.4   Gas chromatographic analysis

            7.4.1      Introduce  volatile compounds into the gas chromatograph
      using either Method 5030 (heated purge-and-trap method using Tenax as the
      trap packing material) or the direct  injection method.   If the internal
      standard calibration  technique is used, add 10 pL  of the internal standard
      to the sample prior to purging.

                 7.4.1.1      Direct  injection -  In  very limited applications
            (e.g. aqueous process wastes), direct injection of the sample  into
            the  GC system with  a  10  pi syringe  may  be  appropriate.   The
            detection limit is very high (approximately  10,000 /*g/L); therefore,
            it is only permitted when  concentrations in excess  of 10,000  ng/L
            are expected or for water-soluble  compounds that do not purge.  The
            system must be  calibrated  by direct injection  (bypassing the purge-
            and-trap device).

            7.4.2      Follow Method  8000  for Instructions  on  the  analysis
      sequence,  appropriate  dilutions,  establishing  daily  retention  time
      windows,  and  identification  criteria.     Include  a  mid-concentration
      standard after each group of  10 samples in the analysis sequence.

            7.4.3      Table  1 summarizes the estimated retention  times and
      detection limits for a number of organic compounds analyzable using this

                                  8030A - 5                         Revision 1
                                                                     July  1992

-------
      method.  Figure 1 illustrates the chromatographic separation of acrolein
      and of acrylonitrile using Column 1.

            7.4.4      Record  the  sample  volume  purged or  injected and  the
      resulting peak sizes (in area units  or peak heights).

            7.4.5      Calculation  of  concentration  is  covered  in  Method  8000.

            7.4.6      If analytical  interferences  are suspected, or for  the
      purpose  of  confirmation,  analysis   using  the   second   GC  column   is
      recommended.

            7.4.7      If the  response for  a  peak is  off-scale,  prepare  a
      dilution of the sample with organic-free reagent water.  The dilution must
      be performed on  a  second  aliquot of the sample  which  has been  properly
      sealed and stored prior to use.


8.0  QUALITY CONTROL

      8.1   Refer to Chapter  One for  specific quality  control  procedures  and
Method 8000 for gas chromatographic procedures.   Quality control  to ensure  the
proper operation of the purge-and-trap device is covered in  Method 5030.

      8.2   Procedures to check the GC  system operation are found in Method 8000,
Section 8.6.

            8.2.1      The quality control check sample concentrate  (Method 8000,
      Section 8.6)  should contain each parameter of  interest at a concentration
      of 25 mg/L in water.

            8.2.2      Table  3  indicates  the  calibration  and QC  acceptance
      criteria for this method.  Table  4 gives  single  laboratory  accuracy  and
      precision  for  the  analytes  of  interest.    The contents  of  both  Tables
      should be used to evaluate a  laboratory's ability to perform and generate
      acceptable data by this method.

      8.3   Calculate surrogate  standard recovery on all  samples,  blanks,  and
spikes.  Determine if recovery is within limits (limits established by performing
QC procedure outlined in Method 8000,  Section 8.10).

            8.3.1      If recovery is  not  within  limits,   the  following  is
      required.

            •    Check to be  sure that there  are no  errors  in  calculations,
                 surrogate  solutions   and  internal  standards.   Also,  check
                 instrument performance.

            •    Recalculate the data  and/or reanalyze the extract  if any of the
                 above checks reveal a problem.

            »    Reextract and reanalyze the sample if none  of the above are a
                 problem or flag the data  as "estimated concentration".


                                   8030A - 6                         Revision 1
                                                                     July 1992

-------
9.0   METHOD PERFORMANCE

      9.1   In  a  single  laboratory,  the  average  recoveries  and  standard
deviations presented in Table 4 were obtained using Method 5030,  Seven replicate
samples were analyzed at each spike concentration.

      9.2   The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique,  and by the calibration procedure used.


10.0  REFERENCES

1.    Bellar, T.A. and J.J. Lichtenberg,  J. Amer.  Water Works  Assoc., 66(12).
      pp. 739-744, 1974.

2.    Bellar, T.A. and J.J. Lichtenberg,  "Semi-Automated Headspace Analysis of
      Drinking Waters  and  Industrial  Waters for Purgeable Volatile Organic
      Compounds," in Van Hall, ed., Measurement of Organic Pollutants in Water
      and Wastewater, ASTM STP 686, pp. 108-129, 1979.

3.    Development and Application of Test  Procedures for Specific Organic Toxic
      Substances  in Wastewaters,  Category 11:  Purgeables  and Category  12:
      Acrolein,  Acrylonitrile,   and Dichlorodifluoromethane,  Report for  EPA
      Contract 68-03-2635 (in preparation).

4.    Going,  J.,  et  a!.,   Environmental  Monitoring Near  Industrial Sites  -
      Acrylonitrile, Office of Toxic Substances, U.S.  EPA, Washington, DC, EPA
      560/6-79-003, 1979.

5.    U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test  Procedures for the
      Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
      Final Rule and Proposed Rule," October 26, 1984.

6.    Kerns, E.H., et al. "Determination of Acrolein and Acrylonitrile in Water
      by Heated Purge and Trap Technique,"  U.S. Environmental  Protection Agency,
      Environmental Monitoring and Support Laboratory, Cincinnati,  Ohio 45268,
      1980.

7.    "Evaluation of Method 603," Final Report for EPA Contract 68-03-1760 (in
      preparation).
                                   8030A -  7                        Revision 1
                                                                     July 1992

-------
                             TABLE 1.
      CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
                        Retention time (min)             Method detection
Compound                Col. 1        Col.  2              limit8 (/ig/L)
Acrolein
Acrylonitrile
10.6
12.7
8.2
9.8
0.7
0.5
a  Based on using purge-and-trap, Method 5030.
                             TABLE 2.
              DETERMINATION  OF  ESTIMATED  QUANTITATION
                LIMITS (EQLs)  FOR VARIOUS MATRICES8
         Matrix                              Factorb
         Ground water                             10
         Low-concentration soil                   10
         Water mlsdble liquid waste             500
         High-concentration soil and sludge     1250
         Non-water miscible waste               1250
         Sample EQLs are highly matrix dependent.  The EQLs listed herein
         are provided for guidance and may not always be achievable.

         EQL =  [Method  detection  limit (Table 1)]  X [Factor (Table 2)].
         For non-aqueous samples, the  factor  is on a wet-weight basis.
                             8030A - 8                        Revision  1
                                                               July  1992

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                                   TABLE 3.
                    CALIBRATION  AND QC  ACCEPTANCE  CRITERIA8
Analyte
Acrolein
Acrylonitrile
Range
for Q
(M9A)
45.9 - 54.1
41.2 - 58.8
Limit
for S
(M9/L)
4.6
9.9
Range
for x
(M9/L)
42.9 - 60.1
33.1 - 69.9
Range
P> P8
(%)
88-118
71-135
Q     =     Concentration measured in QC check sample,  in M9/L.
S     =     Standard deviation of four recovery measurements,  in M9/L.
R     •     Average recovery for four recovery measurements,  in p.g/1.
P, P  =     Percent recovery measured.
      Criteria  from 40  CFR  Part  136  for  Method  603  and
      assuming a QC check sample concentration of 50 pg/L.
                                            were  calculated
                                   TABLE 4.
                   SINGLE LABORATORY ACCURACY AND PRECISION


Parameter
Acrolein





Acrylonitrile





AW
POTW
Spike
cone.
(M9/L)
5.0
50.0
5.0
50.0
5.0
100.0
5.0
50.0
20.0
100.0
10.0
100.0
ASTM Type
Average
recovery
(M9/L)
5.2
51.4
4.0
44.4
0.1
9.3
4.2
51.4
20.1
101.3
9.1
104.0
II water.
Prechlorination secon
Standard
deviation
(M9/L)
0.2
0.7
0.2
0.8
0.1
1.1
0.2
1.5
0.8
1.5
0.8
3.2

dary effluent
Average
percent
recovery
104
103
80
89
2
9
84
103
100
101
91
104

from a mui

Sample
matrix
AW
AW
POTW
POTW
IW
IW
AW
AW
POTW
POTW
IW
IW

nicipal sewage
IW
treatment plant.
Industrial  wastewater  containing  an unidentified
reactant.
acrolein
                                   8030A -  9
                                                  Revision 1
                                                   July 1992

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                   Figure  1
Gas Chromatogram of Acrolein  and  Acrylonitrlle
   Column; Por«p«k OS
   Program. 11 (PC for 1.S mm. rcpidly
          hoototf to 1WC
   Dotoctor: Flomo lonaaiien
    I
   1.8
 I
30
 i
45
 i
• 0
 I
75
 i
0.0
10.S
135  ISO
                  MITCNTlONTiMf. Mm.
                     8030A - 10
                                               Revision  1
                                                July  1992

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                         HETHOD  8030A
  ACROLEIN AND ACRYLONITRILE BY GAS CHROMATOGRAPHY
       Start
   7.1  Int roduce
compounds into gas
 chr ornmtograph by
direct  injaction or
  purge-and-trap
   [Method 5030J
    7.2  Set gas
   chromatograph
     condition
  7.3 Calibrate
(refer to Method
     8000)
  7  4.1 Introduce
volatile compounds
     into gas
 chromatograph by
 purge-and-trap or
 direct injection
7.4.2  Follow Method
 8000  for analysis
  s equence,  etc.
                             7 4,4 Record  volume
                             purged or injected
                              and peak sizes
                               7.45 Calculate
                               concentralion
                              (refer to Method
                                   8000)
                                                      7,4.6 Analyze using
                                                       second CC column
                                                     7.4.7 Dilute  second
                                                     aliquot of sample
                            8030A -  11
                                                                       Revision  1
                                                                        July  1992

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                                  METHOD 8031

                      ACRYLONITRILE BY GAS CHRONATOGRAPHY
 1.0    SCOPE AND APPLICATION

       I.I   Method 8031 is used to determine  the concentration of aeryHonitrlie
 in water.  This method may also be applicable to other matrices.  The following
 compound can be determined by this method:
      Compound Name                                         CAS No."
      Acrylonitrile                                         107-13-1
      *  Chemical Abstract Services Registry Number.

      1.2   The  estimated quantisation limit of Method 8031 for determining the
concentration of acrylonitrile in water is approximately 10 M9/L.

      1.3   This method  is  restricted to  use  by or under the  supervision of
analysts  experienced in  the use  of gas  chromatographs and  skilled  in  the
interpretation of gas chromatograms.   Each  analyst must demonstrate the ability
to generate acceptable results with this method.


2.0   SUMMARY OF METHOD

      2.1   A measured sample volume is micro-extracted with methyl tert-butyl
ether.   The extract  is  separated  by gas  chromatography and measured  with  a
Nitrogen/Phosphorus detector.


3.0   INTERFERENCES

      3.1   Method  interferences  may be caused  by contaminants  in  solvents,
reagents, glassware, and  other sample processing hardware that leads to discrete
artifacts and/or elevated baselines in gas chromatograms.  All of these materials
must be  routinely demonstrated to be free from interferences under the conditions
of the analysis  by running laboratory reagent blanks.

      3.2   Samples can be contaminated by diffusion of volatile organics around
the septum  seal  into the sample during handling and  storage.  A field blank
should  be  prepared from  organic-free reagent water  and carried  through  the
sampling and sample handling protocol to serve as  a  check  on such contamination.

      3.3   Contamination by carryover can occur whenever  high-concentration and
low-concentration samples are sequentially  analyzed. To  reduce  carryover,  the


                                   8031 -  1                         Revision 0
                                                                September 1994

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sample  syringe  must be rinsed  out between samples with  solvent.  Whenever an
unusually  concentrated  sample  is  encountered,  it  should be  followed  by the
analysis of solvent to check for cross contamination.


4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph system

            4.1.1 Gas  chromatograph,  analytical  system  complete  with  gas
      chromatograph  suitable   for  on-column   injections  and  all  required
      accessories, including detector, analytical  columns,  recorder, gases, and
      syringes.  A data system  for measuring peak heights and/or peak areas is
      recommended.

            4.1.2 Column:    Porapak Q  -  6 ft.,  80/10 Mesh, glass  column,  or
      equivalent.

            4.1.3 Nitrogen/Phosphorus detector,

      4.2   Materials

            4.2.1 Grab sample bottles - 40 ml VOA bottles.

            4.2.2 Mixing bottles - 90 ml bottle with a Teflon lined cap.

            4.2.3 Syringes - 10 /iL and 50 ^L.

            4.2.4 Volumetric flask (Class A) - 100 ml.

            4.2.5 Graduated cylinder - 50 mL.

            4.2.6 Pipet (Class A) - 5, 15, and 50 ml.

            4.2.7 Vials -  10 ml.

      4.3   Preparation

            4.3.1 Prepare  all materials to be used as described  in Chapter 4 for
      volatile organics.


5.0   REAGENTS

      5.1   Reagent grade  chemicals shall be used in all tests. Unless otherwise
indicated,  it is intended  that  all  reagents shall conform to the specifications
of the Committee on Analytical  Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first
ascertained that the reagent is of sufficiently  high  purity to permit its use
without lessening the accuracy of the determination.
                                   8031 - 2                         Revision 0
                                                                September 1994

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5.2   General

      5.2.1 Methanol, CH3OH - Pesticide quality,  or equivalent.

      5.2.2 Organic-free reagent water.  All references to water in this
method refer to organic-free reagent water, as defined in Chapter One.

      5.2.3 Methyl tert-butyl ether,  CH3Ot-C4H9  -  Pesticide  quality,  or
equivalent.

      5.2.4 Acrylonitrile, H2C:CHCN,  98%.

5.3   Stock standard solution

      5.3.1 Stock standard solutions  -  Can  be prepared from pure standard
materials  or  can be  purchased  as certified  solutions.    Prepare  stock
standards in organic-free reagent water using assayed liquids.

      5.3.2 The stock standard solution may  be prepared  by volume  or by
weight.  Stock  solutions  must  be replaced after one year,  or sooner if
comparison with the check standards indicates a problem.

      CAUTION:    Acrylonitrile is toxic.   Standard preparation should be
                  performed in a laboratory fume hood.

            5.3.2.1     To prepare the  stock  standard solution by volume:
      inject 10 pL of acrylonitrile (98%) into a 100 ml volumetric flask
      with a syringe.  Make up to volume with methanol,

            5.3.2.2     To prepare the  stock  standard solution by weight:
      Place  about  9.8 ml  of organic-free  reagent water  into a  10  mL
      volumetric flask before weighing the  flask and  stopper. Weigh the
      flask and record the weight to the nearest  0.0001 g.  Add two drops
      of pure acrylonitrile, using a  50  juL  syringe, to  the  flask.   The
      liquid must fall  directly  into the water, without  contacting the
      inside wall  of the  flask.   Stopper  the  flask and  then reweigh.
      Dilute to volume  with  organic-free reagent water.   Calculate the
      concentration from the net gain in weight.

5.4   Working standard solutions

      5.4.1 Prepare a minimum of 5 working standard solutions that cover
the range  of analyte concentrations expected  in the samples.   Working
standards of 20, 40,  60, 80, and 100 ^g/L may be prepared by injecting 10,
20, 30, 40,  and 50  /iL  of the  stock  standard solution prepared  in Sec.
5.3.E.I into 5 separate 90 ml mixing bottles  containing 40 ml of organic-
free reagent water.

      5.4.2 Inject 15  ml  of  methyl  tert-butyl  ether  into  each  nixing
bottle, shake vigorously,  and let  stand 5  minutes,  or  until  layers have
separated.
                             8031 - 3                         Revision 0
                                                          September 1994

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            5.4.3 Remove 5 ml of top layer by  pipet, and place in a 10 ml vial.

            5,4,4 Keep all standard solutions below 4°C  until  used.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory material to this chapter, Organic  Analytes,
Sec.  4.1.


7.0   PROCEDURE

      7.1   Sample Extraction

            7.1.1 Pour 40 mL  of the sample into a 90 mL mixing bottle.  Pipet 15
      ml of Methyl tert-butyl ether  into  the  mixing bottle.   Shake  vigorously
      for about 2 min.  and let stand  for about 5 min.  Remove about 5 mL of the
      top layer and store in  a 10 mL vial.

      7.2   Chromatographic Conditions (Recommended)

      Carrier Gas (He)  flow rate:   35 mL/min.
      Column Temperature:           180° C,  Isothermal
      Injection port temperature;   250° C
      Detector temperature:         250° C
      Detector Current  (DC):         18 volts
      Gases:                        Hydrogen,  3  mL/min;  Air,  290  mL/min.
                                                                                    \
      7.3   Calibration of GC                                                        \

            7.3.1 On a  daily basis,  inject  3 fj,L  of  methyl  tert-butyl  ether
      directly into the  GC to  flush the  system.   Also  purge  the system  with
      methyl tert-butyl  ether injections  between injections of standards  and
      samples.

            7.3.2 Inject 3 ML  of a  sample  blank (organic-free reagent  water
      carried through the sample storage  procedures and extracted with  methyl
      tert-butyl  ether).

            7.3,3 Inject 3 yl of at  least five  standard solutions:  one  should
      be near the detection limit;  one should  be near, but  below,  the expected
      concentrations of the analyte; one should be near, but above,  the expected
      concentrations  of  the  analyte.    The   range  of  standard   solution
      concentrations used should  not  exceed the working range of the  GC system.

            7.3.4 Prepare  a  calibration   curve  using  the  peak areas  of  the
      standards (retention time  of acrylonitrile under the conditions of  Sec.
      7.2 is  approximately 2.3  minutes).    If the  calibration curve  deviates
      significantly from a straight line,  prepare a new  calibration  curve  with
      the existing standards, or, prepare new standards and a new calibration
      curve.   See  Method  8000,  Sec.  7.4.2,   for  additional   guidance  on
      calibration by the external  standard method.


                                   8031 -  4                          Revision 0
                                                               September  1994

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      7.4   Sample Analysis

            7.4.1 Inject  3   jsiL  of  the  sample  extract,   using   the  same
      chromatographic conditions used to prepare the standard curve.  Calculate
      the concentration of acrylonitrile in the extract, using the area of the
      peak, against the calibration curve prepared in Sec. 7.3.4.


8.0   QUALITY CONTROL

      8.1   Refer to Chapter  One  and  Method  8000  for  specific quality control
procedures.

      8.2   Prior  to  preparation of  stock  solutions,   methanol  and  methyl
tert-butyl ether reagents should be analyzed gas chromatographically under the
conditions described in Sec. 7.2, to determine possible interferences with the
acrylonitrile peak.   If the solvent blanks show contamination, a different batch
of solvents should be used.
9.0   METHOD PERFORMANCE

      9.1   Method 8031 was tested  in a single laboratory over a period of days.
Duplicate samples and one spiked sample were run for each calculation.   The GC
was calibrated daily.  Results are presented in Table 1.


10.0  REFERENCES

1.    K.L. Anderson,  "The  Determination  of Trace Amounts of Acrylonitrile in
      Water by Specific Nitrogen Detector Gas Chromatograph", American  Cynamid
      Report No. WI-88-13, 1988.
                                   8031 - 5                         Revision 0
                                                                September 1994

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                        TABLE  1

         SINGLE LABORATORY METHOD PERFORMANCE
                  CONCENTRATION
  SAMPLE          SPIKE (/jg/L)        % RECOVERY
      A                 60                100
      B                 60                105
      C                 40                 86
      D                 40                100
      E                 40                 88
      F                 60                 94

Average                                    96
                       8031  -  6                         Revision 0
                                                    September 1994
                               \

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            METHOD 8031
ACRYLONITRILE BY GAS CHROMAT06RAPHY
            C
Start
7.1.1 Extract 40 mL
of sample with methyl
t-butyl ether in 90 mL
bottle.
^
f
7.2 Set
Chromatographic
conditions.
^
r
7.3.1 Rush GC
system with 30 uL
methyl t-butyl ether.
i
r
7.3.2 Analyze 3 uL
of sample blank.
^
r
7.3.3 - 7.3.4 Establish
calibration curve with
at least 5 stds.
i
r
7.4 Sample Analysis
1
r
                   Stop

              8031 - 7
                              Revision 0
                          September 1994

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                                  METHOD 8032

                       ACRYLAHIDE BY GAS CHROHATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   Method 8032 Is used to determine trace amounts of acrylamide monomer
in  aqueous  matrices.   This method  may  be applicable to  other  matrices.   The
following compound can be determined by this method:
      Compound Name                             CAS No."


      Acrylamide                                79-06-01


      a  Chemical  Abstract Services Registry Number.

      1,2   The method detection limit (MOL) in clean water is 0,032

      1.3   This method is  restricted  to  use  by,  or  under the supervision of,
analysts  experienced  in  the use  of  gas  chromatographs  and  skilled  in  the
interpretation of gas  chromatograms.   Each analyst must demonstrate the ability
to generate acceptable results with this method.


2.0   SUMMARY OF METHOD

      2.1   Method 8032 is based on bromination of the acrylamide double bond.
The reaction product  (2,3-dibromopropionamide)  is extracted  from the reaction
mixture with ethyl  acetate,  after salting out with sodium sulfate.  The extract
is cleaned up using a Florisil column, and analyzed by gas chromatography with
electron capture detection (GC/ECD).

      2.2   Compound  identification  should  be  supported by   at  least  one
additional qualitative technique.  Analysis using a second gas chromatographic
column  or  gas  chromatography/mass  spectrometry  may  be used  for  compound
confirmation.


3.0   INTERFERENCES

      3.1   No interference  is observed from sea water or in the presence of 8.0%
of ammonium  ions  derived from  ammonium  bromide.   Impurities  from potassium
bromide are removed by the Florisil clean up procedure.
                                   8032 - 1                         Revision 0
                                                                September 1914

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4.0   APPARATUS AND HATERIALS
      4.1   Gas chromatographic System
            4.1.1 Gas chromatograph suitable for on-column injections with all
      required accessories,  including detector,  analytical  columns,  recorder,
      gases, and syringes. A data system for measuring peak heights and/or peak
      areas is recommended.
            4.1.2 Column:   2  m  x 3 mm glass column, 5%  FFAP  (free  fatty acid
      polyester) on 60-80 mesh acid washed Chromosorb W,  or equivalent.
            4.1.3 Detector:  electron capture detector.
      4.2   Kuderna-Danish  (K-D) apparatus.
            4.2.1 Concentrator tube -  10 ml graduated (Kontes K-570050-1025 or
      equivalent).  A  ground  glass stopper is used to prevent  evaporation of
      extracts.
            4.2.2 Evaporation  flask -    500  ml  (Kontes   K-570001-5QO    or
      equivalent).   Attach to  concentrator  tube  with   springs,  clamps,  or
      equivalent.
            4.2.3 Snyder  column  -   Three  ball  macro (Kontes  K-503000-0121 or
      equivalent).
            4.2.4 Snyder  column  -   Two  ball  micro  {Kontes K-569001-0219 or
      equivalent).
            4.2.5 Springs -  1/2 inch (Kontes  K-662750  or equivalent).
      4.3   Separatory funnel  - 150 ml.
      4.4   Volumetric flask  (Class  A)  -   100 ml,  with  ground  glass  stopper;
25 ml, amber,  with ground glass stopper.
      4.5   Syringe - 5 mi.
      4.6   Hicrosyringes - 5 /uL, 100 /iL.
      4.7   Pipets (Class A).
      4.8   Glass column  (30 cm x 2 cm).
      4.9   Mechanical  shaker.

5.0   REAGENTS
      5.1   Reagent grade chemicals shall be used in all tests.  Unless otherwise
indicated, it  is  intended that all reagents shall conform to the  specifications
of the Committee  on  Analytical Reagents of the American Chemical  Society, where

                                   8032  -  2                         Revision 0
                                                                September 1994

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such  specifications  are  available.  Other grades may  be useds provided  it  is
first ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.

      5.2   Organic-free reagent water.  All  references to water in this method
refer to organic-free reagent water, as defined  in Chapter One.

      5.3   Solvents

            5.3.1 Ethyl acetate, C2H5C02C2H5.   Pesticide qua!ity,  or equivalent.

            5.3.2 Diethyl ether,  C2H5OC2H5.   Pesticide quality, or equivalent.
      Must  be  free  of  peroxides  as  indicated  by test strips  (EM Quant,  or
      equivalent).   Procedures  for removal  of peroxides are provided with the
      test strips.  After cleanup, 20 ml of ethyl alcohol preservative must  be
      added to each liter of ether.

            5.3.3 Methanol, CH3OH.  Pesticide quality, or equivalent.

            5.3.4 Benzene, C5H5.  Pesticide  quality,  or equivalent.

            5.3.5 Acetone, CH3COCH3.   Pesticide quality, or equivalent.

      5.4   Saturated bromine water.   Prepare by shaking organic-free reagent
water with bromine and allowing to stand for  1 hour,  in  the  dark,  at 4°C.  Use
the aqueous phase.

      5.5   Sodium sulfate (anhydrous, granular), Na2S04,   Purify  by heating  at
400°C  for 4 hours in a shallow tray, or by precleaning the sodium  sulfate with
methylene chloride.   If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed,  demonstrating  that there is no interference from
the sodium sulfate.

      5.6   Sodium thiosulfate, Na2S203!  1 M aqueous  solution.

      5.7   Potassium bromide, KBr, prepared  for infrared analysis.

      5.8   Concentrated hydrobromic acid, H8r,  specific gravity  1.48.

      5.9   Acrylamide  monomer,  H2C:CHCONH2,   electrophoresis  reagent  grade,
minimum 95% purity.

      5.10  Dimethyl phthalate, C6H4{COOCH3)2, 99.0%  purity.

      5.11  Florisil (60/100 mesh):  Prepare Florisil by activating at 130°C for
at least 16 hours.  Alternatively, store Florisil in an  oven at  130"C.  Before
use, cool the Florisil in a  desiccator.   Pack  5 g of  the  Florisil,  suspended  in
benzene, in a glass column (Sec. 4.8).

      5.12  Stock standard solutions

            5.12.1      Prepare a stock standard  solution of  acrylamide monomer
      as specified in Sec.  5.12.1.1.   When compound purity is assayed to be 96%

                                   8032 - 3                          Revision 0
                                                                September  1994

-------
      or greater, the  weight  can be used without  correction  to calculate the
      concentration of the stock standard.  Commercially prepared standards can
      be used at any concentration  if they are certified by the manufacturer or
      by an independent source,

                  5.12,1.1    Dissolve  105.3  mg  of  acrylamide  monomer  in
            organic-free reagent water in a 100 ml  volumetric flask, and dilute
            to the mark with organic-free reagent water. Dilute the solution of
            acrylamide monomer  so  as to obtain standard  solutions containing
            0.1 - 10 mg/L of acrylamide monomer.

      5.13  Calibration standards

            5.13.1      Dilute the  acrylamide stock solution  with organic-free
      reagent water to produce  standard solutions  containing 0.1-5  rag/L of
      acrylamide.  Prior to injection the calibration standards are reacted and
      extracted in the same manner  as environmental samples (Sec. 7).

      5.14  Internal standards

            5.14.1      The suggested internal  standard is dimethyl phthalate.
      Prepare a  solution  containing 100 mg/L  of  dimethyl phthalate  in  ethyl
      acetate.  The concentration of dimethyl phthalate in the sample  extracts
      and calibration standards should be 4 mg/L.


6.0   SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

      6.1   See the  introductory material to this chapter, Organic Analytes,
Sec.  4.1.
7.0   PROCEDURE

      7.1   Bromination

            7.1.1 Pipet 50 ml of  sample  into a 100 ml  glass  stoppered  flask.
      Dissolve 7.5 g of potassium bromide into the sample, with stirring.

            7.1.2 Adjust the pH of the solution with  concentrated  hydrobromic
      acid until  the pH is between 1  and  3.

            7.1.3 Wrap the flask with aluminum foil  in order to exclude  light.
      Add 2.5  ml  of saturated bromine water,  with stirring. Store the flask and
      contents in the dark, at 0°C, for at least 1 hour.

            7.1.4 After reacting the solution for at  least an  hour,  decompose
      the excess  of bromine by adding  1 M  sodium thiosulfate solution,  dropwise,
      until  the color of the solution is  discharged.

            7.1.5 Add 15 g of sodium sulfate, using a magnetic stirrer to effect
      vigorous stirring.
                                   8032 - 4                         Revision 0
                                                                September 1994
                                                          \

-------
      7,2   Extraction

            7.2.1 Transfer the solution into a 150 ml separatory funnel.  Rinse
      the reaction flask three times with  1  ml  aliquots of organic-free reagent
      water.  Transfer the rinsings into the separatory funnel.

            7.2.2 Extract the aqueous solution with two 10 ml portions of ethyl
      acetate for 2 min each, using a mechanical shaker (240 strokes per min).
      Dry the organic phase with 1 g of sodium sulfate.

            7.2.3 Transfer the  organic phase  into  a 25  ml amber  volumetric
      flask.   Rinse  the sodium  sulfate with  three  1.5  ml portions  of ethyl
      acetate and combine the rinsings with the organic  phase.

            7.2.4 Add exactly 100 ^9 of dimethyl phthalate to the flask and make
      the solution  up to  the 25 ml  mark  with  ethyl  acetate.   Inject 5  yl
      portions of this solution into the gas chromatograph.

      7.3   Florisil  cleanup:  Whenever  interferences are observed, the samples
should be cleaned up as follows.

            7.3.1 Transfer the dried extract  into a  Kuderna-Danish  evaporator
      with  15  ml of  benzene.   Evaporate the  solvent  at  70°C under  reduced
      pressure, and concentrate the solution to about 3  ml.

            7.3.2 Add 50 ml  of benzene and subject  the solution to  Florisil
      column chromatography at a  flow rate of  3 mL/min.  Elute the column first
      with 50 ml of diethyl ether/benzene  (1:4) at a flow rate of 5 mL/min,  and
      then with  25  ml of  acetone/benzene (2:1) at  a flow  rate of 2  mL/min.
      Discard all of  the first eluate and the initial  9 ml portion of the second
      eluate,  and  use the remainder  for  the  determination,  using  dimethyl
      phthalate (4 mg/L) as an internal standard.

            NOTE: Benzene  is  toxic,  and   should be only  be  used  under  a
                  ventilated laboratory hood.

      7.4   Gas chromatographic conditions:

      Nitrogen carrier gas flow rate:     40 mL/min
      Column temperature:                  165°C.
      Injector temperature:               180°C
      Detector temperature:               185°C.
      Injection volume:                    5 ^L

      7.5   Calibration:

            7.5.1 Inject  5 /iL of a  sample  blank (organic-free  reagent water
      carried through all  sample storage,  handling,  bromination and  extraction
      procedures),

            7.5.2 Prepare standard  solutions of acrylamide as described in Sec.
      5.13.1.   Brominate  and extract each  standard  solution  as  described  in
      Sees,  7.1 and 7.2.


                                   8032 -  5                         Revision 0
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            7.5.2.1     Inject 5 pi of each of a minimum of five standard
      solutions: one  should  be near the detection  limit;  one should be
      near, but  below,  the expected concentrations of the  analyte; one
      should  be near,  but above,  the expected  concentrations  of the
      analyte.

            7.5.2.2     Prepare a calibration curve using the peak areas
      of the standards.  If the calibration curve deviates significantly
      from  a  straight line,  prepare  a new  calibration  curve  with the
      existing standards,  or,  prepare  new standards  and a new calibration
      curve.   See  Method  8000,  Sec.  7.4.3,  for additional  guidance on
      calibration by the internal standard method.

            7.5,2.3     Calculate the response factor for  each standard
      according to Equation 1.

                  (P.)  (MJ
                                          Equation 1
                  (PJ ("A)

            RF    =     Response factor
            Ps    =     Peak height of acryl amide
            Mis    =     Amount of internal  standard injected (ng)
            Pjs    -     Peak height of internal  standard
            MA    =     Amount of acryl amide  injected {ng}

      7.5.3 Calculate the mean response factor according to Equation 2.
                                                Equation 2
            RF    =     Mean response factor
            RF    =     Response   factors   from    standard    analyses
                        (calculated in Equation 1)
            n     =     Number of analyses

7.6   Gas chromatographic analysis:

      7.6.1 Inject  5  pi.  portions of each  sample  (containing  4  mg/L
internal  standard)  into  the  gas chromatograph.    An  example  EC/ECD
chromatogram is shown  in Figure 1.

      7.6.2 The concentration of acrylamide monomer in the sample is given
by Equation 3.

               (PA)  (HJ
                                          Equation  3
             (PJ  (RF) (V,) (VJ

      [A]   =     Concentration of acrylamide monomer in sample (rag/L)

                             8032 - 6                         Revision 0
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            PA    =     Peak height of acrylamide monomer
            Mis    =     Amount of internal  standard injected  (ng)
            V5    =     Total volume of sample  (ml)
            P^    =     Peak height of internal standard
            RF    =     Mean response factor from Equation 2
            V|    =     Injection volume  (fj.1}


8.0   QUALITY CONTROL

      8.1   Refer to Chapter One  and  Method 8000  for specific quality control
procedures.


9.0   METHOD  PERFORMANCE

      9.1   The  following  performance  data  have  been generated  under  the
conditions described in this method:

            9.1.1 The calibration curve for  Method 8032 is linear over the range
      0-5 /jg/L of aery 1 amide monomer.

            9.1.2 The limit of detection  for an  aqueous solution  is 0.032 M9/L.

            9.1.3 The yields of the  brominated compound are 85.2 ± 3,3% and 83.3
      + 0.9%,  at  fortification concentrations of 1.0  and 5.0 jug/L, respectively.

      9.2   Table 1  provides  the  recoveries of acrylamide monomer  from river
water, sewage effluent,  and sea water.

      9.3   The recovery of the bromination  product  as a  function of the amount
of  potassium  bromide and  hydrobromic acid added  to the  sample is  shown  in
Figure 2.

      9.4   The effect of the reaction time on the recovery of the bromination
product is shown  in  Figure 3.  The yield was  constant when the  reaction time was
more than 1 hour.

      9.5   Figure 4 shows the recovery of the bromination product as a function
of the initial pH from 1  to  7.35.  The yield was constant within  this pH range.
The use of conventional  buffer solutions, such as  sodium acetate - acetic acid
solution or phosphate solution, caused a significant decrease in yield.


10.0  REFERENCES

1.    Hashimoto,   A.,  "Improved  Method  for the  Determination  of  Acrylamide
      Monomer in Water by Means of Gas-Liquid Chromatography with an Electron-
      capture Detector,"  Analyst,  101:932-938,  1976.
                                   8032 - 7                         Revision 0
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                                                  TABLE 1

                               RECOVERY OF ACRYLAMIDE FROM WATER SAMPLES AS
                                        .  2,3-DIBROMOPROPIONAMIDE
Sample
Matrix
Standard
River Water
Sewage
Effluent
Sea Water
Acryl amide
Monomer
Spiked//Lig
0.05
0.20
0.25
0.20
0.20
0.20
Amount of 2
Calculated
0.162
0.649
0.812
0.649
0.649
0.649
,3-DBPAa/jug
Found6
0.138
0.535
0.677
0.531
0.542
0.524
Overall
Bromination
Recovery
%b
85.2
82.4
83.3
81.8
83.5
80.7
Recovery of
Acryl amide
Monomer, %b
—
99.4
101.3
98.8
Coefficient
of
Variation
3.3
1.0
0.9
2.5
3.0
3.5
"  2,3-Dibromopropionamide

b  Mean of five replicate determinations
                                                  8032 - 8
    Revision 0
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                                    Figure 1
                ft
                I
                                                          B
                                •    •   10   12

                                   TilTH/fTlirt
14   16
Typical  gas chromatograms  of the  bromination  product  obtained  from  aqueous
acrylamide monomer solution:

   A.   Untreated
   B.   With Florisil  cleanup
   BL.   Chromatogram of blank, concentrated five-fold before gas chromatographic
        analysis.

Peaks:

   1.       2,3-Dibroraopropionamide
   2.       Dimethyl  phthalate
   4-7.     Impurities from potassium bromide

Sample size = 100 ml;  acrylamide monomer - 0,1 pg
                                   8032 - 9
                  Revision 0
              September 1994

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                                   Figure 2
                         o     i    10    is    2a    21
                             Amount of KSr/g pir SO ml

                         0     2    *     6     I    10
                            Amount of H§r/ml otr SO ml
Effect of  (A)  potassium  bromide  and  (B)  hydrobromic  acid on  the  yield of
bromination,   Sample  size  = SO ml; acrylamide monomer =  0.25 ^9
                                  8032  -  10
    Revision  0
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                                                                          \

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                                   Figure 3
                      100
                                                     24
Effect of reaction time on the bromination.  Reaction conditions:

   50 ml of sample;
   0.25 jig of acrylamide monomer;
   7.5 g of potassium bromide;
   2.5 mL of saturated bromine water

Extraction conditions:

   15 g of sodium sulfate;
   extraction at  pH  H;
   solvent = 10 ml of ethyl  acetate (12)
                                  8032  - 11
    Revision 0
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                                  Figure 4
                  100
                I"
                        i    1
                    012345*71

                                      PH
Effect of initial pH on the bromination.  Reaction and extraction conditions as
in Figure 3.  The pH was adjusted to below 3 with concentrated hydrobromic acid,
and to 4-5 with dilute hydrobromic acid.  Reaction at pH 6 was  in  distilled
water. pH 7.35  was achieved  by careful addition of dilute sodium  hydroxide
solution. The broken line shows the result obtained by the use of sodium acetate
- acetic  acid  buffer  solution.
                                 8032 - 12
    Revision 0
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             METHOD 8032
ACRYLAMIDE BY  GAS CHROMATOGRAPHY
{ Start )
7.1 Breminaten
*
7.1 ,1 Dissolve 7.5 g KBr into
50 ml sample in flask.
1
7.1 .2 Adjust sola pH with
concentrated HBr to between
1 and 3.
i
7.1 ,3 Wrap soln. flask with
aluminum. Add 2.5 ml sstd.
bromine water, stir, store at
0 C tori hr.
1
7.1 .4 Add 1 M sodium
thiosulfate dropwise to flask to
decompose excess bromine.
I
7.1 .5 Add iSg sodium
sutfate, and stir
,



I
7.2 Extraction
*
7.2.1 Transfer task soln. to
sep. funnel along wifri rinses.
I
7.2.2 Extract soln, twice w/ethyl
acetate. Dry organic phase
using sodium sulfate
;
7.2.3 Transfer organic phase
and rinses into amber
glass flask.
,
7.2.4 Add 100 «e dimethyl
pfithalate to flask, dilute to
mark. Inject 5 uL into GC.
1
7.3 Rorisil Cleanup
1
7.3.1 Transfer dried extract to
K-D assembly w/benzene.
Concentrate to 3 ml at 70 C
under reduced pressure.
                                       7.3.2 Add 50 ml benzene to
                                       solution. Pass soln. through
                                       Flonsil column. Bute with
                                       diethyi ether/benzene, then
                                       acetone/benzene. Collect
                                       the second elution train (less
                                       initial 9 ml} for analysis.
              8032  - 13
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            METHOD  8032
              continued
        7.4 GC Conditions
        7.5 Calibration
   7.5.1 Inject 5 uL sample Walk,
  7.5,2 Braminate and extract std.
  solrts. similar to the samples.
  .1 Inject 5 uL of each of the
    minimum 5 stds
  .2 Plot peak are vs. [ ].
  .3 Calculate response factor
    (RF) for each {].
   7.5.3 Calculate mean RF bam
   eqn. 2.
        7.6 GC Analysis
 7.6.1 Inject 5 ul sample containing
 internal std into GC
7.6.2 Calculate acr/larrude monomer
concentrator! in sample using
eqn.3
              8032  -  14
      Revision 0
September  1994

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                                 METHOD 8040A

                         PHENOLS  BY  GAS  CHROMATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   Method  8040  is  used to  determine the  concentration  of  various
phenolic compounds.  The following compounds can be determined by this method:
Compound Name
             Appropriate Technique

CAS No.8   3510   3520    3540  3550  3580
2-sec-Butyl-4,6-dinitrophenol
  (DNBP, Dinoseb)
4-Chloro-3-methylphenol
2-Chlorophenol
Cresols (methyl phenols)
2-Cyclohexyl-4,6-dinitrophenol
2,4-Dichlorophenol
2,6-Dlchlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
Tetrachlorophenols
Trichlorophenols
2,4,6-Trichlorophenol
   J-85-7   X
59-50-7
95-57-8
1319-77-3
131-89-5
120-83-2
87-65-0
105-67-9
51-28-5
534-52-1
88-75-5
100-02-7
87-86-5
108-95-2
25167-83-3
25167-82-2
88-06-2
X
X
X
X
X
X
X
X
X
X
X
X
DC (28)
X
X
X
ND

X
X
ND
ND
X
ND
X
X
X
X
X
X
X
ND
X
X
ND    ND
                        X
                        X
                        ND
                        ND
                        X
                        ND
                        X
                        X
                        X
                        X
                        X
                        X
                        X
                        ND
                        X
                        X
      X
      X
      ND
      ND
      X
      ND
      X
      X
      X
      X
      X
      X
      X
      ND
      X
      X
X
X
X
LR
X
X
X
X
X
X
X
X
X
X
X
X
a      Chemical Abstract Services Registry Number.
DC -   Unfavorable distribution coefficient  (number  in  parenthesis is percent
       recovery).
LR =   Low response.
ND =   Not determined.
X  =   Greater than 70 percent recovery by this technique.

       1.2  Table 1 lists the method  detection  limit  for the target analytes in
water.  Table 2 lists the estimated quantitation limit (EQL) for all matrices.
2.0    SUMMARY OF METHOD

       2.1  Method 8040 provides gas chromatographic conditions for the detection
of phenolic  compounds.   Prior  to analysis,  samples  must be  extracted using
appropriate techniques (see Chapter Two  for  guidance).   Both neat  and diluted
organic  liquids  (Method  3580,  Waste Dilution)  may  be  analyzed  by  direct
                                   8040A  -  1
                               Revision 1
                                July 1992

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injection.  A 2 to I pi  sample  is  injected  into  a gas  chromatograph using the
solvent flush technique,  and compounds in the GC effluent are detected by a flame
ionization detector (FID).

       2.2  Method 8040 also provides  for the preparation of pentafluorobenzyl-
bromide  (PFB)  derivatives,  with  additional  cleanup  procedures for  electron
capture gas  chromatography.   This  is to lower  the  detection limits of  some
phenols and to aid the analyst in the elimination of interferences.


3.0    INTERFERENCES

       3.1  Refer to Methods 3500,  3600, and 8000.

       3.2  Solvents, reagents,  glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms.  All of these materials must  be  demonstrated  to be free
from interferences, under the conditions of the analysis, by analyzing reagent
blanks.    Specific  selection  of  reagents  and  purification of  solvents  by
distillation in all-glass systems may be required.

       3.3  Interferences coextracted from samples will vary considerably from
source to  source,  depending upon  the  waste  being sampled.   Although general
cleanup techniques are recommended as  part of this  method,  unique  samples may
require additional cleanup.

       3.4  The decomposition of some analytes under basic extraction conditions
has been demonstrated.  Specifically, phenols may react  to form tannates.  These
reactions increase with increasing  pH, and are decreased by the shorter reaction
times available in Method 3510.

       3.5  The flame  ionization detector  (FID)  is very susceptible  to false
positives caused by the presence of hydrocarbons  commonly found in samples from
waste sites.  The problem may be minimized by applying acid-base cleanup (Method
3650) and/or  alumina column chromatography (Method 3611) prior to 6C/FID analysis
or  using  the derivatization  technique  and  analyzing  by  GC/electron  capture
detector.  Initial  site investigation should always be performed utilizing GC/MS
analysis to  characterize the site  and detenine  the feasibility of utilizing
Method 8040 with a GC/FID.


4.0    APPARATUS AND MATERIALS

       4.1  Gas chromatograph

            4.1.1 Gas  Chromatograph   -  Analytical  system complete with  gas
       chromatograph  suitable  for  on-column   injections  and  all  required
       accessories, including detectors, column supplies, recorder,  gases, and
       syringes.  A data system  for measuring peak areas  and/or peak heights is
       recommended.

            4.1.2 Columns

                  4.1.2.1     Column for underivatized  phenols - 1.8 m x 2.0 mm

                                   8040A - 2                         Revision I
                                                                     July 1992

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            ID glass column packed with 1% SP-1240DA on Supelcoport 80/100 mesh,
            or equivalent.

                  4.1.2.2     Column for derlvatized  phenols - 1.8 m x 2 mm ID
            glass column  packed with  5% OV-17 on  Chromosorb  W-AW-DMCS  80/100
            mesh, or equivalent.

            4.1.3 Detectors -  Flame ionization (FID) and electron capture (ECD).

       4.2  Reaction vial - 20 ml,  with Teflon lined  screw-cap or crimp top.

       4.3  Volumetric flask,  Class  A  -  Appropriate sizes with  ground-glass
stoppers.

       4.4  Kuderna-Danish (K-D)  apparatus

            4.4.1 Concentrator tube -  10 ml, graduated (Kontes K-570050-1025 or
       equivalent).    Ground-glass  stopper is  used to prevent evaporation  of
       extracts.

            4.4.2 Evaporation  flask   -  500  ml   (Kontes   K-570001-500   or
       equivalent).    Attach  to  concentrator tube  with  springs,  clamps  or
       equivalent.

            4.4.3 Snyder  column  -  Three  ball  macro  (Kontes  K-503000-0121  or
       equivalent).

            4.4.4 Snyder  column  -  Two ball  micro  (Kontes  K-569001-0219  or
       equivalent).

            4.4.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).

       4.5  Boiling chips - Solvent extracted,  approximately 10/40 mesh (silicon
carbide or equivalent).

       4.6  Water  bath  - Heated,  with  concentric   ring   cover,  capable  of
temperature control  (± 5°C).   The  bath should  be  used in  a  hood.

       4.7  Microsyringe  - 10 pi.

       4.8  Syringe - 5 ml.

       4.9  Balance - analytical,  0.0001 g.


5.0    REAGENTS

       5.1  Reagent grade chemicals shall be used  in all tests. Unless otherwise
indicated, it is  intended that all  reagents shall  conform to the specifications
of the Committee  on  Analytical Reagents of the American Chemical Society, where
such specifications  are available. Other grades may  be used,  provided it is first
ascertained that the  reagent  is of sufficiently  high  purity to permit its use
without lessening the accuracy of the determination.


                                   8040A - 3                         Revision 1
                                                                     July 1992

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       5.2  Organic-free reagent water -  All  references to water in this method *
refer to organic-free reagent water, as defined In Chapter One.

       5.3  Hexane, CH3(CH2)4CH3 - Pesticide quality or equivalent.

       5.4  2-Propanol, (CH3)2CHOH  -  Pesticide  quality or equivalent.

       5.5  Toluene, C6H5CH3 - Pesticide quality or equivalent.

       5.6  Derivatization reagent - Add  1  ml pentafluorobenzyl bromide and 1 g
18-crown-6-ether  to  a  50  ml  volumetric  flask  and  dilute  to  volume  with
2-propanol.  Prepare  fresh weekly.   This operation  should  be carried out in a
hood.  Store at 4°C and protect from light.

            5.6.1 Pentafluorobenzyl  bromide  (alpha-Bromopentafluorotoluene),
       C6F5CH2Br.  97% minimum purity.

            NOTE:  This chemical Is a lachrymator.

            5.6.2 18-crown-6-ether  (1,4,7,10,13,16-Hexaoxaeyclooctadecane)  -
       98% minimum purity.

            NOTE;  This chemical is highly toxic.

       5.7  Potassium carbonate (Powdered), K2C03.

       5.8  Stock standard solutions

            5.8.1 Prepare  stock  standard  solution  at  a  concentration  of
       1000 mg/L  by  dissolving  0.0100  g  of  assayed  reference  material  in
       2-propanol and diluting to volume in  a  10  ml volumetric flask.  Larger
       volumes can  be  used  at the convenience of the  analyst.   When compound
       purity is assayed  to be  96%  or greater,  the  weight  can be  used without
       correction  to  calculate  the  concentration  of  the  stock  standard.
       Commercially prepared stock standards can be used at  any concentration if
       they are certified by the manufacturer or by an independent source.

            5.8.2 Transfer the stock standard solutions into bottles with Teflon
       lined screw-caps or  crimp tops.  Store at  4°C  and  protect  from light.
       Stock standards should be checked  frequently  for signs of degradation or
       evaporation, especially  just prior to  preparing  calibration standards
       from them.

            5.8.3 Stock standard solutions must be replaced after one year, or
       sooner if comparison with check standards indicates a problem.

       5.9  Calibration standards -  Prepare  calibration standards at a minimum
of five concentrations through dilution of  the  stock standards with 2-propanol.
One  of  the concentrations should be  at  a concentration near,  but  above, the
method detection limit.   The remaining concentrations should correspond to the
expected  range  of concentrations found  in real  samples or  should  define the
working  range  of the  GC.  Calibration  solutions  must be  replaced  after six
months, or sooner,  if comparison with check  standards indicates a problem.


                                   8040A  -  4                         Revision 1
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       5.10 Internal standards (if internal standard calibration is used) - To
use this approach, the analyst must select one or more internal  standards that
are similar in analytical behavior to the  compounds  of interest.   The analyst
must further demonstrate that the measurement  of  the internal  standard is not
affected by method or matrix  interferences.   Because of these limitations, no
internal standard can be suggested that is applicable to all  samples.

            5.10.1      Prepare  calibration  standards  at  a  minimum  of  five
       concentrations for each analyte as described in Section 5.9.

            5.10.2      To  each  calibration  standard,  add  a  known  constant
       amount of one or more  internal standards,  and dilute  to  volume with 2-
       propanol.

            5.10.3      Analyze each calibration standard according to Section
       7.0.

       5.11 Surrogate standards - The analyst  should  monitor the performance of
the  extraction,   cleanup  (if  necessary),  and  analytical   system  and  the
effectiveness of the method in dealing with each sample matrix by spiking each
sample, standard, and organic-free reagent  water blank with phenolic surrogates
(e.g. 2-fluorophenol  and 2,4,6-tribromophenol)  recommended to encompass the range
of the temperature program used in this method.  Method 3500 details instructions
on the preparation of acid surrogates. Deuterated analogs of analytes should not
be used as  surrogates for gas chromatographic analysis due to coelution problems.


6.0    SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

       6.1   See  the  introductory material  to this chapter,  Organic  Analytes,
Section 4.1.   Extracts must be stored under refrigeration and analyzed within 40
days of extraction.


7.0    PROCEDURE

       7.1   Extraction

            7.1.1 Refer to Chapter Two for  guidance on choosing the appropriate
       extraction procedure.   In  general, water samples are  extracted  at a pH of
       less than  or  equal to 2 with methylene chloride,  using either Method 3510
       or 3520.   Solid samples are extracted using either Method 3540 or 3550,
       and  non-aqueous  samples  using Method  3580.    Extracts  obtained  from
       application  of  either  Method 3540  or 3550  should undergo  Acid-Base
       Partition  Cleanup, using Method 3650.

            7.1.2 Prior to gas chromatographic analysis, the extraction solvent
       must be exchanged to 2-propanol.   The exchange is performed as follows:

                  7.1.2.1     Following concentration  of the extract  to  1 mL
            using the macro-Snyder column,  allow the apparatus  to cool  and drain
            for at least 10 minutes.
                                  8040A  -  5                         Revision 1
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                  7.1.2.2     Remove the micro-Snyder column and rinse its lower
            joint  into  the  concentrator  tube  with  a  minimum  amount of  2-
            propanol.   Adjust  the  extract  volume  to  1.0 ml.   Stopper  the
            concentrator  tube  and  store  refrigerated  at  4°C  if  further
            processing will not be performed immediately.  If the extract will
            be stored longer than two days,  it should be transferred to a vial
            with a Teflon  lined  screw-cap or crimp top.  If the extract requires
            no   further   derivatization   or   cleanup,   proceed   with   gas
            chromatographic analysis.

       7.2  Gas chromatographic conditions (Recommended)

            7.2.1 Column for underivatized phenols -

            Carrier gas (N2)  flow rate:    30 mL/min
            Initial temperature:          80°C
            Temperature program:          80°C to 150°C  at 8°C/min
            Final Temperature:            150°C,  hold until  all compounds have
                                          eluted.

            7.2.2 Column for derivatized phenols -

            Carrier gas (5% methane/95% argon)
            flow rate:                          30 mL/min
            Initial temperature:                200°C
            Temperature program:                isothermal,  hold   until   all
                                                compounds have eluted.

       7.3  Calibration -  Refer to Method 8000 for proper  calibration techniques.
Use Table 1  and especially Table 2 for guidance on selecting  the lowest point on
the calibration curve.

            7.3.1 The procedure for  internal or external  calibration  may be used
       for the underivatized  phenols.  Refer to Method 8000  for  a description of
       each of these procedures.   If derivatization of the phenols is required,
       the method of external calibration should  be  used by injecting  five or
       more concentrations of calibration standards  that  have also undergone
       derivatization and cleanup prior to instrument calibration.

       7.4  Gas chromatographic analysis

            7.4.1 Refer to Method 8000.   If the internal standard calibration
       technique is used,  add 10 jut  of internal  standard to  the sample prior to
       injection.

            7.4.2 Phenols  are to be determined on a gas chromatograph equipped
       with a flame ionization detector according to the conditions listed for
       the 1% SP-1240DA column  (Section 7.2.1).   Table  1 summarizes estimated
       retention times and sensitivities that should  be  achieved by this method
       for  clean water  samples.    Estimated  quantitation  limits   for  other
       matrices are list in Table 2.

            7.4.3 Method  8000 provides  instructions  on  the analysis sequence,
       appropriate  dilutions,  establishing  daily retention  time  windows, and

                                  8040A - 6                        Revision  1
                                                                     July 1992

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 *         Identification criteria.  Include a mid-concentration standard after each
•          group of 10 samples in the  analysis  sequence.

                7.4.4 An example of a GC/FID chromatogram for certain  phenols  is
           shown in Figure  1.   Other  packed or capillary  (open- tubular)  columns,
           chromatographic conditions, or detectors may be used if the requirements
           of Section 8.2 are met.

                7,4.5 Record the sample volume injected and the resulting peak sizes
           (in area units or peak heights).

                7.4.6 Using either the Internal or external  calibration procedure
           (Method 8000),  determine the identity and quantity  of each component peak
           in the sample chromatogram which corresponds to the compounds  used for
           calibration purposes.  See  Method 8000  for calculation  equations.

                7.4.7 If peak detection using the SP-1240DA  column with the  flame
           ionization detector is prevented by interferences,  PFB derivatives of the
           phenols  should  be  analyzed  on   a  gas  chromatograph  equipped with  an
           electron capture detector according  to  the conditions  listed  for the 5%
           OV-17 column (Section 7.2.2).  The derivatization  and  cleanup procedure
           is outlined in Sections 7.5 through 7.6.   Table 3 summarizes estimated
           retention times for derivatives  of some phenols  using  the  conditions of
           this method.

                7.4.8 Figure 2  shows  a  GC/ECD  chromatogram of PFB derivatives  of
           certain phenols.

                7.4.9 Record the sample volume injected and the resulting peak sizes
           (in area units or peak heights).

                7.4.10      Determine  the identity and quantity of each component
           peak in the sample chromatogram  which corresponds  to  the compounds used
           for calibration purposes.   The method of external  calibration should be
           used (see Method 8000 for guidance).  The concentration of the individual
           compounds in the sample is  calculated as follows;


                Concentration
           where:
                A     -     Mass of underivatized phenol represented by area of peak
                            in  sample  chromatogram,  determined  from  calibration
                            curve (see Method 8000), ng.

                Vt    -     Total amount of column eluate or combined fractions from
                            which V{.  was taken,  pi.

                B     -     Total volume of hexane added in Section 7.5.5,  ml.

                D     =     Total   volume   of   2-propanol   extract   prior   to
                            derivatization,  ml.

                                      8040A  - 7                         Revision 1
                                                                         July 1992

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            V,-     =     Volume injected, /iL.

            X     =     Volume of water extracted,  ml, or weight of nonaqueous
                        sample extracted, g, from Section 7.1.   Either the dry
                        or wet weight  of the  nonaqueous sample may  be  used,
                        depending upon the specific application of the data.

            C     =     Volume of hexane sample solution added to cleanup column
                        (Method 3630),  ml.

            E     =     Volume   of   2-propanol    extract   carried   through
                        derivatization in Section 7.5.1, mL.

       7.5  Derivatization - If interferences prevent measurement of peak area
during analysis  of the extract  by flame  ionization gas  chromatography,  the
phenols must be derivatized and analyzed by electron capture gas chromatography.

            7.5.1 Pipet a 1.0 ml aliquot  of the  2-propanol   stock  standard
       solution or of  the  sample extract  into a glass  reaction vial.  Add 1.0 ml
       derivatization   reagent (Section 5.3).    This  amount   of  reagent  is
       sufficient to derivatize a solution whose total  phenolic content does not
       exceed 300 mg/L.

            7.5.2 Add  approximately  0.003  g  of potassium  carbonate to  the
       solution and shake  gently.

            7.5.3 Cap the  mixture and heat it  for 4 hours at 80°C  in a hot water
       bath.

            7.5.4 Remove the solution from  the hot water bath  and  allow it to
       cool.

            7.5.5 Add 10 ml  hexane to the reaction vial and shake vigorously for
       1 minute.   Add  3.0 ml organic-free reagent  water to the reaction vial and
       shake for 2 minutes.

            7.5.6 Decant the organic layer into a  concentrator tube and cap with
       a glass stopper.  Proceed  with  cleanup procedure.

       7.6  Cleanup

            7.6.1 Cleanup of the derivatized extracts takes place using Method
       3630 (Silica Gel Cleanup),  in which specific instructions for cleanup of
       the derivatized phenols appear.

            7.6.2 Following column cleanup,  analyze the samples  using GC/ECD, as
       described starting  in Section 7.4.7.


8.0    QUALITY CONTROL

       8.1  Refer  to   Chapter  One  for   specific  quality  control  procedures.
Quality control to validate sample extraction is  covered in Method 3500 and  in


                                   8040A - 8                        Revision  1
                                                                     July 1992

-------
 *  the  extraction method used.  If extract cleanup was performed,  follow the QC in
*   Method  3600  and  in  the  specific  cleanup  method.

           8.2   Procedures to check the GC system operation are found in Method 8000,
    Section 8.6.

                8.2.1 The  quality control check  sample concentrate  (Method  8000,
           Section 8.6)  should  contain each  analyte of interest  at  a  concentration
           of 100 mg/L  in 2-propanol.

                8.2.2 Table  4  indicates  the  calibration and  QC acceptance criteria
           for  this  method.   Table  5  gives  method  accuracy  and  precision  as
           functions of concentration for the analytes.  The contents of both tables
           should be used to evaluate a laboratory's ability to perform and generate
           acceptable data by this method.

           8.3   Calculate  surrogate  standard recovery on all samples,  blanks,  and
    spikes.   Determine  if  the recovery  is  within limits  (limits established  by
    performing QC procedures outlined in Method 8000,  Section 8.10).

                8.3.1 If recovery  is  not within limits,  the  following is  required.

                •     Check  to be sure that  there  are no errors in  calculations,
                     surrogate solutions and  internal  standards.    Also,  check
                     instrument  performance.

                •     Recalculate  the data and/or reanalyze the extract  if  any of
                     the above checks reveal a problem.

                •     Reextract and reanalyze the sample if none of the above are a
                     problem  or  flag the  data as  "estimated concentration."


    9.0     METHOD PERFORMANCE

           9.1   The method was  tested by 20 laboratories using  organic-free reagent
    water,  drinking water,  surface water,  and three industrial wastewaters spiked at
    six  concentrations  over  the range 12 to  450 M9/L-   Single operator precision,
    overall  precision,  and method accuracy were found to be directly related to the
    concentration of  the analyte  and  essentially  independent of  the  sample matrix.
    Linear  equations to describe these relationships for a flame ionization detector
    are  presented in  Table 5.

           9.2   The  accuracy and  precision obtained will  be  affected  by the sample
    matrix,  sample-preparation  technique,  and calibration  procedures  used.


    10.0   REFERENCES

    1.      Development and Application of Test Procedures for Specific Organic Toxic
           Substances  in Wastewaters.  Category  3  -  Chlorinated Hydrocarbons  and
           Category  8   -  Phenols.    Report  for  EPA  Contract   68-03-2625  (in
           preparation).


                                      8040A - 9                         Revision 1
                                                                         July 1992

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U.S. EPA 40 CFR  Part  136,  "Guidelines Establishing Test Procedures for
the Analysis  of  Pollutants Under  the Clean Water Act;  Final  Rule and
Interim Final  Rule and Proposed Rule," October 26, 1984.

"Determination of Phenols  in  Industrial  and  Municipal  Wastewaters,"
Report for EPA Contract 68-03-2625 (in preparation).

"EPA Method Validation Study Test Method 604 (Phenols)," Report for EPA
Contract 68-03-2625 (in preparation).

Kawahara,  F.K.  "Microdetermination  of  Derivatives  of  Phenols  and
Mercaptans by Means of Electron Capture Gas Chromatography," Analytical
Chemistry, 40, 1009, 1968.

Burke, J.A.  "Gas Chromatography  for Pesticide  Residue  Analysis; Some
Practical Aspects," Journal  of the  Association  of Official  Analytical
Chemists, 48,  1037, 1965.
                           8040A  -  10                         Revision  1
                                                               July  1992

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                                   TABLE 1.
                FLAME IONIZATION GAS CHROMATOGRAPHY OF PHENOLS*
Analyte
Retention time
(minutes)
Method
Detection
limit (pg/L)
2-sec-Butyl-4,6-dinitrophenol (DNBP)
4-Chloro-3-methylphenol
2-Chlorophenol
Cresols (methyl phenols)
2-Cyclohexyl-4,6-dinitrophenol
2,4-Dichlorophenol
2,6-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
Tetrachlorophenols
Trichlorophenols
2,4,6-Trichlorophenol
 7.50
 1.70
 4.30

 4.03
10.00
10.24
 2.00
24,25
12,42
 3.01
 6.05
   0.36
   0.31
   0.39

   0.32
  13.0
  16.0
   0.45
   2.8
   7.4
   0.14
   0.64
8 - 1% SP-1240DA on Supelcoport 80/100 mesh column.
                                   TABLE 2.
                    DETERMINATION  OF  ESTIMATED QUANTITATION
                      LIMITS (EQLs)  FOR VARIOUS MATRICES*
   Matrix
                Factor
Ground water                                                     10
Low-concentration soil by sonication with GPC cleanup           670
High-concentration soil and sludges by sonication            10,000
Non-water miscible waste                                    100,000
a  Sample EQLs are highly matrix-dependent.  The EQLs listed  herein are provided
   for guidance and may not always be achievable.

b  EQL -  [Method  detection limit (Table  1)]  X [Factor (Table  2)].   For non-
   aqueous samples, the factor is on a wet-weight basis.
                                  8040A - 11
                        Revision 1
                         July 1992

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                                 TABLE 3.
          ELECTRON CAPTURE GAS CHROMATOGRAPHY  OF  PFB DERIVATIVES8


Parent compound
4-Chl oro-2-methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2, 4-Dimethyl phenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2 , 4, 6-Tri chl orophenol
Retention
time
(rain)
4.8
3.3
5.8
2.9
46.9
36.6
9.1
14.0
28.8
1.8
7.0
Method
detection
limit (MQ/L)
1.8
0.58
0.68
0.63


0.77
0.70
0.59
2.2
0.58
- 5% OV-17 on Chromosorb W-AW-DMCS 80/100 mesh column,
                                8040A - 12                        Revision  1
                                                                   July  1992

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                                   TABLE 4.
                            QC ACCEPTANCE CRITERIA8

Analyte
4-Chl oro-3 -methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2, 4-Dimethyl phenol
4, 6-Dinitro-2-methyl phenol
2,4-Dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Test
cone.
(M9/L)
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
Range
for x
Recovery
Range
(MA) (M9/L) (%)
16
27
25
33
25
36
22
19
32
14
16
.6
.0
.1
.3
.0
.0
.5
.0
.4
.1
.6
56.
54.
59.
50.
42.
31.
56.
22.
56.
32.
60.
7-113.
1-110.
7-103.
4-100.
4-123.
7-125.
6-103.
7-100.
7-113.
4-100.
8-110.
4
2
3
0
6
1
8
0
5
0
4
99-122
38-126
44-119
24-118
30-136
12-145
43-117
13-110
36-134
23-108
53-119
s   - Standard deviation of four recovery measurements, in /*g/L.

x   = Average recovery for four recovery measurements, in jug/L.

a   Criteria from  40  CFR Part 136  for  Method 604.    These  criteria are based
    directly upon the method performance data in Table 5.  Where necessary, the
    limits for  recovery have  been  broadened to  assure applicability  of the
    limits to concentrations below those used to develop Table 5.
                                  8040A - 13
Revision 1
 July 1992

-------
                                   TABLE 5.
         METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION8
Analyte
4-Chloro-3-methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethyl phenol
4, 6-Dinitro-2-methyl phenol
2,4-Dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2 , 4, 6-Tri chl orophenol
Accuracy, as
recovery, x'
(M9/L)
0.87C-1.97
0.83C-0.84
0.81C+0.48
0.62C-1.64
0.84C-1.01
0.80C-1.58
0.81C-0.76
0.46C-I-0.18
Q.83C+2.07
0.43C+0.11
0.86C-0.40
Single analyst
precision, s '
(M9/L)
O.llx-0.21
O.lSx+0.20
0.17X-0.02
0.30X-0.89
O.lSx+1.25
0.27X-1.15
O.lSx+0,44
0.17X+2.43
0.22X-0.58
0.20X-0.88
O.lOx+0.53
Overal 1
precision,
S' (Mfl/L)
0.16X+1.41
0.21X+0.75
O.lSx+0.62
0.25X+0.48
0.19X+5.85
0.29X+4.51
0.14X+3.84
0.19X+4.79
0.23X-I-O.S7
0.17X+0.77
O.lSx+2.40
X'
S'


C

x
Expected  recovery  for  one  or  more  measurements  of  a  sample
containing a concentration of C,  in p,g/L,

Expected single  analyst  standard deviation of measurements  at an
average concentration of x, in M9/L.

Expected interlaboratory standard  deviation  of  measurements  at an
average concentration found of x, in pg/L.

True value for the concentration, in jug/L,

Average recovery found for measurements of samples  containing a
concentration of C, in /ag/L.
'From 40 CFR Part 136 for Method 604.
                                  8040A - 14
                                                        Revision  1
                                                         July  1992

-------
           Figure 1
 Gas Chromatogram  of Phenols
   Column: 1% SP-12400A on Suotieooort
   Program: 80°C 0 Minum 8°/Mmut« to 150°C
   Ocuctor: Flam* formation
S      12      18      20
 RETENTION TIME (MINUTES)
24
21
          8040A  -  15
                Revision 1
                 July 1992

-------
                     Figure 2
     Gas Chromatogram of PFB Derivatives of Phenols
JU
                   Column: 8% OV*1? on Qiromouxt W-AW
                   TMnfMrmm: 200°C
                   Dtttctsr: liMtren
                                  •b
                                 A_
I     12     II    20     24     21
   KITINTION TIMI (MINUTQ)
                                                  32
                      8040A - 16
                                        Revision 1
                                         July 1992

-------
                        METHOD 8040A
              PHENOLS  BY GAS CHROMATOGRAPHY
     Sid
 1 1.1 Choose
  appcoprxate
  BM traction
 method  (refer
 to Chapter 2)
     7.1-2
   Enchange
  extraction
  so 1vent t o
  2 -propanol
  7,2  Set gas
chromatography
  conditions
 7,3  Refer to
  Method 8000
  for  proper
  calibratian
  techniques
                      7.3-1 Inject at
                          least S
                      concent rations
                      of  calibra tion
                         s tandards
                                |No
 7.4  Perform
 CC analysis
 (gee Method
   8000]
 ?  4 analyze
using CC/FID
                        8040A  - 17
                                         Revision  1
                                          July  1992

-------
          METHOD 8040A
           (Continued)
                           7.5 Prepare
                           derivativet
7.4.9 Record
sample volume
injected and
 peak sizea
                           7,6 Cleanup
                           jsing Method
                              3630
    7.4.10
Identitify and
quantitate each
component pesk
                          7.4.7 Analyze
                              PFB
                          der x va 11 ve>
                          u»ing CC/ECD
    7.4.10
   Calculate
 concentration
     Stop
            8040A  -  18
                                                       Revision 1
                                                        July 1992

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                                 METHOD 8060

                              PHTHALATE ESTERS
1.0  SCOPE AND APPLICATION

     1.1  Method 8060  is  used  to  determine  the  concentration  of various
phthalate esters.  Table 1 indicates  compounds that may be determined by this
method and lists  the  method  detection  limit  for  each compound in reagent
water.   Table  2  lists  the  practical  quantisation  limit  (PQL) for other
matrices.
2.0  SUMMARY OF METHOD

     2.1  Method  8060  provides   gas   chromatographic  conditions  for  the
detection of ppb levels of  phthalate  esters.    Prior to use of this method,
appropriate sample extraction techniques must be  used.  Both neat and diluted
organic liquids  (Method  3580,  Waste  Dilution)  may  be  analyzed by direct
Injection.  A 2-  to  5-uL  aliquot  of  the  extract  is  injected into a gas
chromatograph (GC) using the solvent flush  technique, and compounds in the GC
effluent are  detected  by  an  electron  capture  detector  (ECD)  or a flame
ionization detector (FID).  Ground water samples should be determined by ECD.

     2.2  The method provides a second  gas chromatographic column that may be
helpful in resolving the analytes  from  interferences  that may occur and for
analyte confirmation.


3.0  INTERFERENCES

     3.1  Refer to Methods 3500, 3600, and 8000.

     3.2  Phthalate esters contaminate many  types  of products commonly found
in the  laboratory.  The  analyst  must  demonstrate that no phthalate residues
contaminate the sample or  solvent  extract  under the conditions of analysis.
Plastics, 1n particular, must be  avoided because phthalates are commonly used
as plastidzers and  are  easily  extracted  from  plastic materials.  Serious
phthalate contamination may result at  any  time if consistent quality control
is not  practiced.

     3.3  Solvents, reagents, glassware, and  other sample processing hardware
may   yield   discrete    artifacts    and/or    elevated   baselines   causing
misinterpretation  of  gas  chromatograms.     All  these  materials  must   be
demonstrated to  be  free  from  interferences,  under  the  conditions of the
analysis, by analyzing  method  blanks.    Specific   selection of reagents and
purification of solvents by distillation in all-glass  systems may be required.

     3.4  Interferences coextracted from  samples  will vary considerably from
source  to source, depending upon  the  waste  being sampled.  Although general
cleanup techniques are recommended as part  of this method, unique  samples may
require additional cleanup.


                                  8060 - 1
                                                         Revision      0
                                                         Date  September 1986

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TABLE 1.  RETENTION TIME AND DETECTION LIMIT INFORMATION FOR PHTHALATE ESTERS ,j-

                                Retention time (m1n)      Method detection
                                                            limit (ug/L)
Compound                         Col. la    Col. 2b        ECD        FID
Benzyl butyl phthalate
B1 s (2-ethy 1 hexy 1 ) phthal ate
D1-n-butyl phthalate
D1 ethyl phthalate
Dimethyl phthalate
D1-n-octyl phthalate
*6.94
*8.92
8.65
2.82
2.03
*16.2
**5.11
**10.5
3.50
1.27
0.95
**8.0
0.34
2.0
0.36
0.49
0.29
3.0
15
20
14
31
19
31
     aColumn 1:  Supelcoport 100/120  mesh  coated with 1.5% SP-2250/1.95% SP-
     2401 packed 1n a 180-cm x 4-mrn  I.D,  glass column with carrier gas at 60
     mL/m1n flow rate.  Column temperature  1s 180*C, except where * Indicates
     220*C.  Under these conditions the  retention  time of Aldrln 1s 5.49 m1n
     at 180*C and 1.84 min at 220*C.

     ^Column 2:  Supelcoport 100/120 mesh with 3% OV-1 1n a 180-cm x 4-mm I.D.
     glass column with carrier gas at 60 mL/m1n flow rate.  Column temperature
     Is 200*C, except where **  Indicates  220*C.   Under these conditions the
     retention time of Aldrln 1s 3.18 m1n at 200*C and 1.46 m1n at 220*C.
 TABLE  2.   DETERMINATION  OF  PRACTICAL QUANTITATION LIMITS  (PQL) FOR VARIOUS
           MATRICES3


     Matrix                                                    Factorb


 Ground water                                                     10
 Low-level  soil  by sonlcation  with  GPC  cleanup                    670
 High-level soil  and  sludges by sonlcatlon                     10,000
 Non-water  mlsdble waste                                    100,000


      aSaiple PQLs are highly   matrix-dependent.     The  PQLs listed  herein  are
      provided for guidance and may not always  be achievable.

      bPQL  = [Method  detection limit (Table 1)]  X [Factor (Table  2)].  For non-
      aqueous samples, the factor 1s on a wet-weight basis.
                                   8060 - 2
                                                          Revision
                                                          Date  September 1986

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    APPARATUS AND MATERIALS

    4.1  Gas chromatograph;

         4.1,1   Gas  chromatograph:    Analytical  system  complete  with gas
    chromatograph  suitable   for   on-column   Injections  and  all  required
    accessories. Including detectors,  column  supplies, recorder, gases, and
    syringes.   A data  system for  measuring peak areas and/or peak heights 1s
    recommended.

         4.1.2   Columns:

              4.1.2.1   Column 1:  1.8-m  x  4-mm  I.D. glass column packed with
         1.5%   SP-2250/1.95%   SP-2401   on   Supelcoport    100/120  mesh  or
         equivalent.

              4.1.2.2   Column 2:  1.8-m  x  4-mm  I.D. glass column packed with
         3% OV-1 on Supelcoport 100/120  mesh or  equivalent.

         4.1.3   Detectors:   Flame 1on1zat1on  (FID) or electron  capture  (ECD).

    4.2  Volumetric flask;   10-,  50-, and  100-mL, ground-glass  stopper.

    4.3  Kuderna-Danlsh (K-D) apparatus;

         4.3.1   Concentrator tube:   10-mL, graduated  (Kontes K-570050-1025 or
    equivalent).  Ground-glass stopper  is  used  to  prevent  evaporation of
    extracts

         4.3.2   Evaporation    flask:      500-mL   (Kontes   K-570001-500  or
    equivalent).  Attach  to  concentrator tube with springs.

         4.3.3   Snyder eoluwu   Three-ball  macro   (Kontes K-503000-0121 or
    equivalent).

         4.3.4   Snyder  column:    Two-ball  micro   (Kontes  K-569001-0219 or
    equivalent).

    4-4  Boiling chips;  Solvent  extracted,  approximately  10/40 mesh (silicon
carbide or  equivalent).

     4.5 Waterbath;     Heated,  with   concentric   ring  cover,   capable  of
temperature control (+5*C).  The bath should  be  used  1n  a hood.

     4.6  H1crosyr1nge;  10-uL.

     4.7  Syr1nge;   5-mL.

     4'8  il§]l:  Glass, 2- and 20-mL capacity with  Teflon-Hned screw cap.
                                  8060 - 3
                                                         Revision
                                                         Date  September1986

-------
5.0  REAGENTS                                                                V

     5-1  Solvents;    Hexane,   acetone,  Isooctane  (2,2,4-trimethylpentane)
(pesticide quality or equivalent).

     5.2  Stock standard solutions;

          5.2.1  Prepare stock standard solutions  at  a concentration of 1.00
     ug/uL by dissolving 0.0100 g  of  assayed reference material  1n Isooctane
     and diluting to volume 1n a  10-mL  volumetric flask.  Larger volumes can
     be used at the  convenience  of  the  analyst.    When compound purity 1s
     assayed to be 96% or greater,  the  weight can be used without correction
     to calculate  the  concentration  of  the  stock  standard.  Commercially
     prepared stock standards can  be  used  at  any concentration 1f they are
     certified by the manufacturer or by an Independent source.

          5.2.2  Transfer  the  stock  standard  solutions  Into Teflon-sealed
     screw-cap bottles.  Store at 4*C and protect from light.  Stock standards
     should be checked  frequently  for  signs  of degradation or evaporation,
     especially just prior to preparing  calibration standards from them.

          5.2.3  Stock standard solutions must be  replaced after one year, or
     sooner if comparison with check standards Indicates a problem.

     5.3  Calibration standards;  Calibration  standards  at a minimum of five
concentrationlevelsshouldbe  prepared  through  dilution  of  the  stock
standards with Isooctane.   One  of  the concentration  levels should be at a
concentration near, but  above,  the  method  detection  limit.  The remaining
concentration levels should correspond to the expected range of concentrations
found   1n  real  samples  or  should  define  the  working  range  of  the GC.
Calibration  solutions  must  be   replaced  after  six  months,  or  sooner If
comparison with check standards Indicates a problem.

     5.4  Internal  standards  (1f  Internal  standard  calibration 1s used):  To
use this  approach,  the analyst must select one or more Internal standards that
are similar  1n analytical behavior to  the compounds of Interest.  The analyst
must further demonstrate that the measurement  of the Internal standard  is not
affected  by method or matrix  Interferences.   Because of these limitations, no
internal  standard  can be suggested that  1s applicable to all samples.

          5.4.1  Prepare  calibration    standards   at   a   minimum  of five
     concentration levels  for   each  analyte  of  interest  as  described in
     Paragraph 5.3.

          5.4.2  To each calibration standard, add  a known constant amount of
     one  or more Internal standards, and dilute to  volume with Isooctane.

          5.4.3  Analyze each calibration  standard  according to Section  7.0.

      5.5  Surrogate standards;   The  analyst   should monitor the performance of
 the extractlon,  cleanup(when   used),   and   analytical   system and the  effec-
 tiveness  of  the  method   1n  dealing  with  each   sample matrix by  spiking  each


                                   8060 - 4
                                                          Revision      0
                                                          Date  September 1986

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•^sample, standard, and reagent water  blank  with  one or two surrogates (e.g.,
 phthalates that are not expected to be 1n the sample) recommended to encompass
 the range of  the  temperature  program  used  in  this  method.  Method 3500,
 Section 5.3.1.1,  details  Instructions  on  the  preparation  of base/neutral
 surrogates.  Deuterated analogs of  analytes  should not be used as surrogates
 for gas chromatographlc analysis due to coelutlon problems.


 6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See the Introductory  material  to  this  chapter, Organic Analytes,
 Section 4.1.  Extracts must be  stored under refrigeration and analyzed within
 40 days of extraction.


 7.0  PROCEDURE

      7.1   Extraction;

            7.1.1   Refer to  Chapter Two for guidance on choosing the appropriate
      extraction  procedure.    In  general,  water  samples  are  extracted at  a
      neutral, or as  1s, pH with  methylene chloride, using either Method 3510
      or 3520.   Solid samples  are extracted using either Method 3540 or  3550.

            7.1.2  Prior to  gas chromatographlc analysis, the extraction  solvent
      must be  exchanged to  hexane.    The  exchange 1s performed during  the  K-D
      procedures listed 1n  all of   the  extraction  methods.   The exchange 1s
      performed  as follows.

                 7.1.2.1  Following  K-D of the methylene chloride extract to
            1 mL  using the macro-Snyder column,   allow the apparatus to cool  and
            drain for  at least  10 mln.

                 7A.2,2  Momentarily remove the  Snyder  column,   add  50 mL of
            hexane, a  new boiling  chip,  and  reattach the  macro-Snyder  column.
            Concentrate the  extract  using 1  mL   of  hexane  to prewet the Snyder
            column. Place the   K-D   apparatus  on  the  water  bath so that  the
            concentrator tube  1s partially  Immersed   1n  the hot water.  Adjust
            the vertical position of  the apparatus and the water  temperature, as
            required,  to complete concentration In 5-10 mln.  At  the proper rate
            of  distillation  the balls of  the  column will actively chatter,  but
            the chambers will  not  flood.    When the apparent volume of liquid
            reaches 1  mL, remove the   K-D  apparatus  and  allow  1t to drain  and
            cool  for at least  10 mln.   The extract will be handled differently
            at  this point, depending  on  whether  or  not cleanup 1s needed.  If
            cleanup is not required,  proceed  to  Paragraph  7.1.2.3.  If  cleanup
            is  needed, proceed  to Paragraph 7.1.2.4.

                 7.1.2.3  If cleanup  of the extract  is not  required, remove  the
            Snyder column and   rinse   the  flask  and  Its   lower joint into  the
            concentrator tube   with   1-2  mL  of  hexane.    A  5-mL  syringe 1s
            recommended for  this operation.  Adjust the extract volume to


                                    8060  - 5
                                                          Revision      0
                                                          Date   September 1986

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          10.0 ml.  Stopper  the  concentrator  tube and store refrigerated at,'
          4*C 1f  further processing will not be performed Immediately.  If the
          extract will  be  stored   longer   than  two  days,  1t  should  be
          transferred  to a  Teflon-sealed  screw-cap  vial.   Proceed with gas
          chromatographlc analysis.

              7.1.2.4 If cleanup  of  the  extract  1s  required, remove the
          Snyder  column and  rinse  the  flask  and  Its  lower Joint Into the
          concentrator tube with  a minimum  amount  of hexane.  A 5-mL syringe
          1s recommended for this operation.   Add a clean boiling chip to the
          concentrator tube and attach a two-ball mlcro-Snyder column.  Prewet
          the column by adding about  0.5 ml  of  hexane to the top.  Place the
          m1cro-K-D  apparatus  on  the   water   bath    (80*C)  so  that  the
          concentrator tube 1s partially  Immersed  1n  the  hot water.  Adjust
          the vertical position of the apparatus and the water temperature, as
          required,  to complete concentration  1n 5-10 m1n.   At the proper rate
          of distillation  the balls of  the  column will  actively chatter, but
          the chambers will not   flood.    When  the apparent volume of liquid
          reaches 0.5  ml,  remove  the  K-D  apparatus  and  allow 1t to drain and
          cool  for at  least 10 m1n.

               7.1.2.5  Remove  the mlcro-Snyder column  and  rinse the flask and
          Its  lower joint  Into  the  concentrator  tube  with 0.2 ml of hexane.
          Adjust the extract  volume to  2.0  ml and proceed with either Method
          3610  or 3620.

     7.2  Gas   chromatpgraphy  conditions  (Recommended);     The   analysis  for
phthalate esters maybeconductedusing   eitheraflame  1on1zat1on  or  an
electron capture detector.  The ECD  may,  however, provide substantially better
sensitivity.

          7.2.1  Column 1:  Set 5%  methane/95%  argon  carrier  gas  flow  at  60
     mL/m1n flow rate.  Set column temperature at 180*C Isothermal.

          7.2.2  Column 2:  Set 5%  methane/95%  argon  carrier  gas  flow at 60
     mL/m1n flow rate.  Set column temperature at 200*C Isothermal.

     7.3  Calibration;    Refer   to   Method   8000  for  proper  calibration
techniques"^  Use Table 1 and especially  Table 2 for guidance on selecting the
lowest point on  the calibration curve.

          7.3.1  The  procedure for  Internal  or  external   calibration may be
     used.    Refer   to  Method  8000  for  a  description  of  each  of these
     procedures.

          7.3.2  If cleanup 1s performed  on  the  samples, the analyst should
     process a series  of  standards  through  the  cleanup procedure and then
     analyze the samples by GC.    This  will  confirm elutlon patterns and the
     absence of  Interferents from the reagents.
                                  8060 - 6
                                                         Revision
                                                         Date  September 1986

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     7.4  Gas chromatographlc analysis;

         7.4.1   Refer to Method 8000.     If the Internal standard calibration
     technique Is used, add  10  uL of  Internal standard to the sample prior to
     Injection.

         7.4.2   Follow Section 7.6   1n  Method  8000  for Instructions on the
     analysis sequence,  appropriate  dilutions,  establishing dally retention
     time windows,  and Identification criteria.   Include a mid-level standard
     after  each  group of 10  samples 1n the analysis sequence.

         7.4.3   Examples of GC/ECD  chromatograms  for  phthalate esters are
     shown  1n Figures 1 and  2.

         7.4.4   Record the  sample   volume  Injected  and  the resulting peak
     sizes  (1n area units or peak heights).

         7.4,5   Using either the  Internal  or external calibration procedure
     (Method 8000),  determine the Identity and  quantity of each analyte peak
     1n  the  sample chromatogram.    See Section  7.8  of  Method  8000 for
     calculation equations.

         7,4,6   If peak detection  and   Identification  are  prevented due to
     interferences,  the hexane  extract may undergo cleanup using either Method
     3610 or 3620.

     7,5  Cleanup;

         7.5.1   Proceed with   either Method  3610  or  3620,  using the 2-mL
     hexane extracts obtained  from  Paragraph 7.1.2.5,

          7.5.2    Following cleanup,  the extracts  should be  analyzed by 6C, as
     described  1n the previous  paragraphs and  1n Method 8000.


8.0  QUALITY  CONTROL

     8.1   Refer  to  Chapter  One  for  specific   quality   control  procedures.
Quality control  to validate sample  extraction  1s  covered  1n  Method 3500  and  1n
the extraction  method utilized.  If  extract  cleanup was performed,  follow  the
QC In Method  3600 and 1n the specific cleanup  method,

     8.2  Procedures to check  the   GC  system  operation   are found 1n  Method
8000, Section 8.6.

          8.2.1   The quality control   check  sample  concentrate  (Method 8000,
     Section  8.6) should contain  each  analyte  of  Interest at  the following
     concentrations 1n acetone:    butyl  benzyl   phthalate,   10  ug/mL,«  b1s(2-
     ethylhexyl) phthalate, 50 ug/mL; d1-n~octyl   phthalate,  50 ug/mL;  and  any
     other phthalate, 25 ug/mL.
                                  8060 - 7
                                                         Revision
                                                         Date  September 1986

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           Column:  1.5%SP-2250+
                   1Ji% SP-2401 on Supdcoport
           Ttmptratur*: 180°C
           DttKtor: Eltctron Capture
          S  S
          i  1
          I 1
              Q>
             5
      0    2    4   S    S   10   12

         RETENTION TIME (MINUTES)


Figure 1. Gas chromatogram of phthalates (txample 1).
        8060 - 8
                                 Revision       Q
                                 Date  September 1986

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     Column: 13% SP-2250+
             US% SP-2401 on Supclcoport
     Ttmptraturt: 1SO°C
     Dtttctor: Electron Capture
                     s

                     I
                     s
                 "•   i
                 1   I
                 I   S
                 >•   M
|
                                    e
                                   5
                 i
                  u
                               *	i
           4       8       12      16

           RETENTION TIME (MINUTES)
       18
Figure 2. Gas chromatogram of phthalates (example 2).
                    8060 - 9
                                             Revision      o
                                             Date   September  1986

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          8.2.2  Table 3 Indicates the  calibration and QC acceptance criteria-
     for this  method.    Table  4  gives  method  accuracy  and  precision as
     functions of concentration for the analytes of Interest.  The contents of
     both Tables should be used to  evaluate a laboratory's ability to perform
     and generate acceptable data by this method.

     8.3  Calculate surrogate standard  recovery  on  all  samples, blanks, and
spikes.  Determine If  the  recovery  1s  within limits (limits established by
performing QC procedures outlined 1n Method 8000, Section 8.10).

          8.3.1  If recovery 1s not within limits, the following 1s required.

                •  Check to  be  sure  there  are  no  errors  1n calculations,
                  surrogate solutions  and  Internal  standards.   Also, check
                  Instrument performance.
                  Recalculate the data and/or reanalyze
                  the above checks reveal a problem.
the extract 1f any of
                  Reextract and reanalyze the sample  1f none of the above are
                  a problem or flag the data as "estimated concentration."
9.0  METHOD PERFORMANCE

     9.1  The method  was  tested  by  16  laboratories  using  reagent water,
drinking water, surface water, and  three Industrial wastewaters spiked at six
concentrations over the range  0.7  to  106  ug/L.  Single operator precision,
overall precision, and method accuracy  were  found  to be directly related to
the concentration of the  analyte  and  essentially  Independent of the sample
matrix.    Linear  equations  to  describe  these  relationships  for  a flame
1on1zat1on detector are presented 1n Table 4.

     9.2  The accuracy and precision obtained will be determined by the sample
matrix, sample-preparation technique, and calibration procedures used.


10.0  REFERENCES

1.  Development and Application of Test  Procedures for Specific Organic Toxic
Substances 1n Wastewaters.  Category 1  - Phthalates.  Report for EPA Contract
68-03-2606 (1n preparation).

2.  "Determination of  Phthalates  1n  Industrial  and Municipal Wastewaters,"
EPA-600/4-81-063,   U.S.   Environmental   Protection   Agency,  Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio 45268, October  1981.

3.  Burke, J.A.   "Gas  Chromatography  for   Pesticide  Residue  Analysis; Some
Practical  Aspects,"  Journal  of   the  Association  of  Official  Analytical
Chemists, 48,  1037, 1965.
                                   8060 - 10
                                                          Revision      0
                                                          Date  September 1986

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4.  "EPA Method Validation Study  16,  Method  606 (Phthalate Esters)," Report
for EPA Contract 68-03-2606 (1n preparation).

5.  U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act,» Final Rule and  Interim Final
Rule and Proposed Rule," October 26, 1984.

6.  Provost, UP. and R.S.  Elder,   "Interpretation of Percent Recovery Data,"
American Laboratory, lj>, pp. 58-63,  1983.
                                   8060 - 11
                                                          Revision      0
                                                          Date  September 1986

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TABLE 3.  QC ACCEPTANCE CRITERIA3


Parameter
B1 s (2-ethyl hexyl ) phthal ate
Butyl benzyl phthal ate
D1-n-butyl phthal ate
Di ethyl phthal ate
Dimethyl phthal ate
D1-n-octyl phthal ate
Test
cone.
(ug/L)
50
10
25
25
25
50
Limit
for s
(ug/L)
38.4
4.2
8.9
9.0
9.5
13.4
Range
for 7
(ug/L)
1.2-55.9
5.7-11.0
10.3-29.6
1.9-33.4
1.3-35.5
D-50.0
Range
P, PS
(%)
D-158
30-136
23-136
D-149
D-156
D-114
     s = Standard deviation of four recovery measurements, 1n ug/L.

     X = Average recovery for four recovery measurements, in ug/L.

     P, Ps » Percent recovery measured.

     D = Detected; result must be greater than zero.

     3Cr1teria  from 40 CFR Part  136 for  Method 606.  These criteria are based
directly upon the method performance  data  1n  Table 4.  Where necessary, the
limits for recovery have been broadened  to assure applicability of the limits
to  concentrations below those used to develop Table 4.
                                   8060 - 12
                                                          Revision
                                                          Date   September 1986

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TABLE 4.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Bis(2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di ethyl phthalate
Dimethyl phthalate
Dl-n-octyl phthalate
Accuracy, as
recovery, x'
(ug/L)
0.53C+2.02
0.82C+0.13
0.79C+0.17
0.70C+0.13
0.73C+0.17
0.35C-0.71
Single analyst
precision, sr'
(ug/L)
0.807-2.56
0.267+0.04
0.237+0.20
0.277+0.05
0.267+0.14
0.387+0.71
Overal 1
precision,
S1 (ug/L)
0.737-0.17
0.257+0.07
0.297+0,06
0.457+0.11
0.447+0.31
0.627+0.34
     x1  = Expected  recovery  for  one  or  more  measurements  of  a  sample
           containing a concentration of C, 1n ug/L.

     sr' = Expected single analyst  standard  deviation  of measurements at an
           average concentration of 7, in ug/L.

     S1  = Expected interlaboratory standard  deviation  of measurements at an
           average concentration found of 7, in ug/L.

     C   = True value for the concentration, in ug/L.

     7   = Average recovery found for measurements of samples containing a
           concentration of C, in ug/L.

     aCriteria from 40 CFR Part 136 for Method 606.
                                  8060 -  13
                                                         Revision      0
                                                         Date  September 1986

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                                        METHOD 8060

                                     PHTHALATE ESTERS
c
7.1.1
                                                       o
       Choose
    appropriate
    extract Ion
     procedure
(Gee Chapter 2)
7.1.2
                                                    7.4
                                                       Perform GC
                                                     analysis (see
                                                      Method BOOO)
       Exchange
       extract-
 Ion advent to
       nexonc
   during micro
 K-O procedures
 7.2
                                                                            7.5.1
    Set gas
 chromatography
  conditions
                                                                                 Cleanup
                                                                               using Method
                                                                              3610 or 3620)
7.

3
HI
fc
Cl
t«
Refer to
ithod BOOO
»r proper
il ioratlon
sehnlques
                         7.3.81 Proce»«
                         I. i Hi	J a series
                            of standards
                         through cleanup
                             procedure:
                           analyze by GC
                                    8060 - 14
                                                               Revision       o
                                                               Date  September 1986

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                                  METHOD 8061

               PHTHALATE  ESTERS BY CAPILLARY GAS CHROMATOGRAPHY
                   WITH ELECTRON  CAPTURE DETECTION  (GC/ECD)
 1.0   SCOPE AND APPLICATION

      1.1   Method 8061 is used to determine the  identities and concentrations
 of various phthalate esters in  liquid, solid and sludge matrices.  The following
 compounds can be determined  by this method:
      Compound Name                                           CAS No."
      Benzyl benzoate  (I.S.)                                 120-51-4
      Bis(2-ethylhexyl) phthalate                             117-81-7
      Butyl benzyl phthalate                                   85-68-7
      Di-n-butyl phthalate                                     84-74-2
      Diethyl phthalate                                        84-66-2
      Dimethyl phthalate                                      131-11-3
      Di-n-octyl phthalate                                    117-84-0


      "  Chemical  Abstract Services Registry Number.

      1.2   Table  1  lists the  method detection  limits  (MDL)  for  the  target
analytes in a water matrix.  The MDLs for the components of a specific sample may
differ  from those listed  in Table 1 because  MDLs  depend  on  the nature  of
interferences in the sample  matrix.   Table 2 lists the estimated quantitation
limits (EQL) for other matrices.

      1.3   When this method  is used to  analyze for any  or  all  of the  target
analytes, compound identification should be supported by at least one additional
qualitative technique.  This  method describes  conditions for parallel  column,
dual electron capture detector  analysis which  fulfills the above requirement.
Retention time information obtained on two megabore  fused-silica open tubular
columns is given in Table  1.  Alternatively, gas  chromatography/mass spectrometry
could be used for compound confirmation.

      1.4   The  following  compounds,  bis(2-n-butoxyethyl)  phthalate,  bis(2-
ethoxyethyl) phthalate, bis(2-methoxyethyl)  phthalate, bis(4-methyl -2-pentyl)
phthalate,  diatnyl  phthalate,   dicyclohexyl   phthalate,   dihexyl   phthalate,
diisobutyl phthalate, dinonyl phthalate,  and hexyl  2-ethylhexyl  phthalate can
also be analyzed by this method and may be used as surrogates.

      1.5   This method  is  restricted to  use  by or under the  supervision  of
analysts  experienced  in  the  use  of gas  chromatographs  and  skilled  in  the
interpretation of gas chromatograms.  Each  analyst must demonstrate the ability
to generate acceptable results with this  method.
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                                                                September 1994

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2.0   SUMMARY OF METHOD

      2.1   A measured  volume  or weight of sample  (approximately  1  liter for
liquids,  10  to 30  grams for  solids  and sludges)  is  extracted by  using the
appropriate sample extraction technique specified in Methods 3510,  3540, 3541,
and 3550.  Method 3520 is not recommended for the extraction of aqueous samples
because the longer chain esters (dihexyl  phthalate, bis(2-ethylhexyl) phthalate,
di-n-octyl phthalate, and dinonyl phthalate) tend to adsorb to the glassware and
consequently, their extraction recoveries are <40 percent.  Aqueous samples are
extracted at a  pH of 5 to 7, with methylene chloride,  in a separatory funnel
(Method 3510).  Alternatively, particulate-free aqueous samples could be filtered
through membrane disks that contain C18-bonded silica.  The phthalate esters are
retained by the silica and,  later eluted with  acetonitrile.  Solid  samples are
extracted with  hexane/acetone  (1:1)  or methylene chloride/acetone  (1:1)  in a
Soxhlet extractor  (Methods 3540/3541) or with an  ultrasonic extractor (Method
3550).   After  cleanup,  the extract  is analyzed  by  gas  chromatography  with
electron capture detection (GC/ECD).

      2.2   The  sensitivity  of Method  8061  usually depends on the  level  of
interferences rather than on instrumental limitations.  If  interferences prevent
detection of the analytes, cleanup of  the sample extracts  is necessary.  Either
Method 3610 or 3620 alone or  followed by Method 3660,  Sulfur Cleanup, may be used
to eliminate interferences in the analysis.  Method 3640,  Gel Permeation Cleanup,
is applicable for samples that contain high amounts of lipids and waxes.


3.0   INTERFERENCES

      3.1   Refer to Methods 3500,  3600, and 8000.

      3.2   Interferences coextracted from the samples  will  vary considerably
from waste to waste.  While general cleanup techniques are referenced or provided
as part of this method, unique samples  may require additional cleanup approaches
to achieve desired sensitivities for  the target  analytes.

      3.3   Glassware  must   be  scrupulously clean.    All  glassware  require
treatment in a muffle furnace at 400 *C for  2 to 4 hrs, or thorough rinsing with
pesticide-grade solvent,  prior  to  use.   Refer to  Chapter 4, Sec.  4.1.4,  for
further details  regarding the cleaning  of glassware.  Volumetric glassware should
not be heated in a muffle furnace.

      If Soxhlet extractors  are baked  in the muffle  furnace, care must be taken
to ensure that  they  are  dry  (breakage may  result if any  water  is  left  in the
side-arm).  Thorough  rinsing with hot tap water, followed by deionized water and
acetone is  not  an adequate decontamination procedure.   Even after  a Soxhlet
extractor was refluxed with  acetone for three days, with daily solvent changes,
the concentrations of  bis(2-ethylhexyl)  phthalate  were  as high  as  500  ng per
washing.  Storage of glassware  in the  laboratory introduces contamination,  even
if the glassware is  wrapped  in  aluminum foil.  Therefore, any glassware used in
Method 8061 should be cleaned immediately prior  to use.

      3.4   Florisil  and alumina may be contaminated with phthalate  esters and,
therefore,  use   of   these materials  in sample  cleanup   should  be  employed


                                   8061 -  2                         Revision 0
                                                                September 1994

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 cautiously.  If these materials are used, they must be obtained packaged in glass
 (plastic  packaging will  contribute  to contamination  with  phthalate  esters).
 Washing  of these materials prior to use with  the  solvent(s) used for elution
 during extract cleanup was found helpful, however, heating at 320 °C for Florisil
 and  210  *C  for alumina  is  recommended.    Phthalate  esters  were detected  in
 Florisil  cartridge method blanks  at  concentrations ranging  from  10 to 460 ng,
 with  5  phthalate esters in the 105 to  460  ng  range.   Complete removal of the
 phthalate esters from Florisil cartridges  does  not seem possible,  and  it  is
 therefore desirable  to  keep the  steps involved  in  sample  preparation  to  a
 minimum.

      3.5   Paper thimbles and filter paper must be exhaustively washed with the
 solvent that will be used in  the sample extraction.   Soxhlet  extraction of paper
 thimbles  and filter paper  for 12 hrs with fresh solvent should be repeated for
 a minimum of three times.   Method  blanks  should  be obtained before any of the
 precleaned thimbles or filter papers are used.  Storage of precleaned thimbles
 and  filter  paper   in  precleaned  glass jars  covered  with  aluminum  foil   is
 recommended,

      3.6  Glass  wool  used  in  any step  of  sample  preparation  should be  a
 specially treated  pyrex  wool,  pesticide grade, and  must  be  baked  at 400°C for
 4 hrs. immediately prior to use.

      3.7   Sodium sulfate must be obtained packaged in  glass  (plastic packaging
 will contribute to contamination with phthalate esters), and  must be purified by
 heating at 400 °C for  4  hrs.  in a shallow tray,  or by precleaning with methylene
 chloride  (Sec. 5.3).  To avoid recontamination, the  precleaned material must be
 stored in glass-stoppered glass bottles, or glass bottles covered with precleaned
 aluminum  foil.   The storage period should not exceed  two weeks.   To minimize
 contamination, extracts should be  dried directly in  the glassware  in which they
 are collected  by adding  small amounts  of  precleaned  sodium  sulfate  until  an
 excess of free flowing material is noted.

      3.8   The  presence  of  elemental  sulfur will  result  in large peaks  which
often mask the  region of the compounds eluting before dicyclohexyl  phthalate
 (Compound No. 14)  in  the  gas  chromatograms  shown in Figure  1.   Method 3660 is
 suggested for removal of sulfur.

      3,9   Waxes  and  lipids  can  be removed by Gel  Permeation Chromatography
 (Method 3640).   Extracts containing high concentrations of lipids  are viscous,
and may even solidify at room temperature.


4.0   APPARATUS AND MATERIALS

      4.1   Gas Chromatography

            4.1.1 Gas  chromatograph,   analytical   system  complete  with  gas
      chromatograph suitable  for on-column  and split/splitless injections  and
      all  required   accessories,  including   detector,   analytical   columns,
      recorder, gases, and syringes,   A data system for measuring  peak heights
      and/or peak areas is recommended.
                                   8061 - 3                         Revision 0
                                                                September 1994

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                  4.1,1.1     Eight inch injection tee  (Supelco, Inc., Catalog
            No. 2-3665, or equivalent) or glass Y splitter for rnegabore columns
            (J&M Scientific,-"press-fit", Catalog No,  705-0733, or equivalent).

            4.1.2 Columns

                  4.1.2.1     Column 1, 30 m x 0.53 mm ID, 5% phenyl/95% methyl
            silicone fused-silica open tubular column  (DB-5, J&W Scientific, or
            equivalent), 1.5 pm film  thickness.

                  4.1.2.2     Column  2,  30  m x  0.53  mm ID,  14%  cyanopropyl
            phenyl  silicone fused-silica  open  tubular column  (DB-1701,  J&W
            Scientific, or equivalent), 1.0 pm  film thickness.

            4.1.3 Detector - Dual  electron capture detector (ECD)

      4.2   Glassware, see Methods 3510, 3540, 3541,  3550, 3610, 3620, 3640, and
3660 for specifications.

      4.3   Kuderna-Danish (K-D) apparatus.

            4.3.1 Concentrator tube - 10 ml graduated (Kontes K-570050-1025 or
      equivalent).  A  ground  glass  stopper is  used to  prevent  evaporation of
      extracts.

            4.3.2 Evaporation flask  -  500 ml  {Kontes  K-570001-5QO  or equiva-
      lent).  Attach to concentrator tube with springs, clamps,  or equivalent.

            4.3.3 Snyder column  - Three  ball  macro  (Kontes  K-503000-0121 or
      equivalent).

            4.3.4 Snyder  column   -  Two  ball  micro  (Kontes  K-569001-0219  or
      equivalent).

            4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).

      4.4   Boiling chips,  approximately  10/40 mesh.  Heat to 400  °C for 30 min,
or Soxhlet-extract with methylene chloride prior to use.

      4.5   Water  bath,  heated,   with  concentric  ring  cover,  capable  of
temperature control  (± 2*C).


5.0   REAGENTS

      5.1   Reagent grade chemicals shall  be used in all tests.  Unless otherwise
indicated,  it  is intended that all reagents shall conform to the specifications
of the Committee on  Analytical Reagents of the American  Chemical  Society,  where
such specifications are  available.   Other grades may be used, provided  it is
first ascertained that  the  reagent is  of  sufficiently high purity to permit its
use without lessening the accuracy of the determination.
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       5.2    Organic-free  reagent water.  All references to water in this  method
 refer to organic-free  reagent  water,  as  defined  in  Chapter One.

       5.3    Sodium  sulfate  (granular, anhydrous), Na2SQ4.   Purify by heating  at
 400  °C for 4 hours  in a shallow trays  or by precleaning the sodium sulfate  with
 methylene chloride.  If the sodium sulfate is precleaned with methylene chloride,
 a method blank must  be analyzed, demonstrating that there is no interference  from
 the  sodium sulfate,

       5.4    Solvents:

             5.4.1 Hexane, C6H14 -  Pesticide quality,  or equivalent.

             5.4.2 Methylene chloride,  CH2C12 - Pesticide quality,  or equivalent.

             5.4.3 Acetone, CH3COCH3 -  Pesticide quality,  or equivalent.

             5.4.4 Acetonitrile, CH3CN - HPLC grade.

             5.4.5 Methanol, CH3OH - HPLC grade.

             5.4.6 Diethyl Ether,  C2H5OC2H5  - Pesticide quality, or  equivalent.
      Must be  free of peroxides,  as  indicated  by  test strips  (EN Quant,  or
      equivalent).  Procedures for removal of peroxides are provided with the
      test strips.  After cleanup, 20 ml of ethyl alcohol preservative must  be
      added to each liter of ether.

      5.5   Stock standard solutions:

            5.5.1 Prepare  stock  standard  solutions  at   a concentration   of
      1000 mg/L by dissolving 0.0100 g of assayed reference  material  in hexane,
      and diluting to volume in a  10 ml  volumetric flask.  When compound purity
      is assayed to be 96 percent or greater, the  weight  can  be used without
      correction  to  calculate  the  concentration  of  the  stock  standard.
      Commercially  prepared  stock standard   solutions  can  be  used at  any
      concentration  if  they   are  certified  by  the  manufacturer  or  by   an
      independent source.

            5.5.2 Transfer the  stock  standard  solutions  into glass vials with
      Teflon lined  screw-caps  or  crimp tops.   Store at 4  "C and protect from
      light.    Stock standard  solutions should be checked  periodically  by gas
      chromatography for  signs  of  degradation  or evaporation,  especially just
      prior to preparation of calibration  standards.

            5.5.3 Stock standard solutions must be replaced after 6 months,  or
      sooner if comparison with check standards indicates a problem.

      5.6   Calibration  standards:  Calibration  standards  are  prepared at  a
minimum of five concentrations for each parameter of interest through dilution
of the stock standard solutions with hexane.  One of the concentrations should
be at a concentration near, but above,  the method detection limit.  The remaining
concentrations should correspond to the expected range of concentrations found
in real samples, or should define the  working range of the GC.   Calibration


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solutions must  be  replaced after 1 to 2 months,  or sooner if comparison with
calibration verification standards indicates a problem.

      5,7   Internal standards  (if internal standard calibration is used):  To
use this approach, the analyst  must select one or more internal standards that
are similar in  analytical  behavior  to the  compounds of interest.   The analyst
must further  demonstrate that  the  measurement  of the internal standard is not
affected by method or matrix interferences.  Benzyl benzoate has been tested and
found appropriate for Method 8061.

            5.7.1 Prepare  a spiking  solution of benzyl  benzoate  in  hexane at
      5000 mg/L.  Addition  of 10 ^L of this solution to 1 ml of sample extract
      is recommended. The  spiking concentration of the  internal standard should
      be kept constant  for all  samples and  calibration  standards.   Store the
      internal  standard  spiking solution at 4  "C in glass  vials  with Teflon
      lined screw-caps  or  crimp tops.  Standard  solutions  should  be replaced
      when ongoing QC (Sec. 8)  indicates a problem.

      5.8   Surrogate standards: The analyst should monitor the performance of
the extraction,  cleanup  (when used), analytical  system,  and the effectiveness of
the method in  dealing with  each  sample matrix by spiking each sample,  standard,
and blank with surrogate compounds.  Three surrogates may be used for Method 8061
in  addition  to  those   listed   in  Sec.  1.4:  diphenyl  phthalate,   diphenyl
isophthalate,  and dibenzyl  phthalate.  However,  the compounds listed in Sec. 1.4
are recommended.

            5.8.1 Prepare  a surrogate standard spiking  solution,  in  acetone,
      which contains 50  ng//iL of each compound.   Addition of 500 juL  of this
      solution to 1  L of water or 30 g solid sample is equivalent to 25 ^g/L of
      water or  830  /jg/kg of solid  sample.   The spiking concentration  of the
      surrogate standards may be adjusted accordingly,  if  the final  volume of
      extract is  reduced  below 2 ml  for  water  samples or  10 ml for  solid
      samples.  Store the surrogate spiking solution at  4 °C  in glass vials with
      Teflon lined  screw-caps  or crimp tops.   The solution must  be  replaced
      after 6 monthSj or sooner if ongoing QC (Sec. 8)  indicates  problems.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to this  chapter,  Organic  Analytes,
Sec.  4.1.
7.0   PROCEDURE

      7.1   Extraction:

            7.1.1 Refer to Chapter Two  for guidance on choosing the appropriate
      extraction procedure.  In general, water  samples are extracted at a pH of
      5 to 7  with methylene  chloride  in  a  separatory  funnel  (Method  3510).
      Method  3520  is not  recommended  for the  extraction  of  aqueous  samples
      because  the longer  chain esters  (dihexyl  phthalate  bis(2-ethylhexy1)
      phthalate, di-n-octyl phthalate,  and dinonyl phthalate) tend to adsorb to


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the  glassware   and  consequently,   their  extraction   recoveries   are
<40 percent.  Solid samples  are extracted with  hexane/acetone  (1:1)  or
methylene  chloride/acetone  (1:1)   in  a   Soxhlet   extractor  (Methods
3540/3541) or with  an ultrasonic extractor (Method  3550).   Immediately
prior  to  extraction,  spike  500 pi  of the  surrogate standard  spiking
solution (concentration = 50  ng/juL)  into 1  L aqueous  sample or 30 g solid
sample.

      7.1.2 Extraction   of   particulate-free   aqueous   samples   using
C18-extraction disks (optional):

            7.1.2.1     Diskpreconditioning: Place the C18-extraction disk
      into the filtration apparatus  and  prewash the disk with 10 to 20  ml
      of acetonitrile. Apply vacuum to pull  the solvent through the disk.
      Maintain vacuum to  pull air through for 5 min.   Follow with 10 ml  of
      methanol.   Apply vacuum and pull  most of the methane!  through the
      disk.   Release vacuum before the disk gets  dry.  Follow with 10  ml
      organic-free reagent water.  Apply vacuum and pull most of the water
      through the disk.  Release the vacuum before the disk gets  dry.

            7.1.2.2     Sample preconcentration: Add 2.5 ml of methanol  to
      the 500 ml  aqueous sample in  order  to  get reproducible  results.
      Pour the sample into the  filtration  apparatus.  Adjust vacuum  so
      that it takes  approximately 20 min  to process  the entire  sample.
      After all  of the sample has passed through  the  membrane  disk,  pull
      air through the disk for 5 to 10 min.  to remove  any  residual  water.

            7.1.2,3     Sample elution:  Break the vacuum and place the tip
      of the filter base into the test tube that  is contained  inside the
      suction flask.  Add 10  ml  of acetonitrile  to the graduated  funnel,
      making sure to rinse  the  walls of the graduated  funnel with the
      solvent.  Apply vacuum to pass  the  acetonitrile through the membrane
      disk.

            7.1.2.4     Extract  concentration (if necessary): Concentrate
      the extract to  2 ml or less, using either  the  micro  Snyder  column
      technique   (Sec.  7.1.2.4.1)  or  nitrogen blowdown  technique  (Sec.
      7.1.2.4.2).

                  7.1,2.4.1   Micro  Snyder  Column Technique

                        7.1.2.4.1.1  Add  one or two clean boiling  chips  to
                  the concentrator tube and attach a two ball micro Snyder
                  column.  Prewet the column by  adding  about 0.5 ml  of
                  acetonitrile to the top  of the column.    Place the K-D
                  apparatus in a hot water bath (15-20°C above the  boiling
                  point of the solvent)  so  that the concentrator  tube  is
                  partially immersed  in the hot water  and the entire lower
                  rounded surface of the flask is bathed  with  hot  vapor.
                  Adjust the  vertical position  of the apparatus and the
                  water  temperature,  as   required,   to   complete  the
                  concentration  in 5-10 minutes.   At the proper rate  of
                  distillation  the  balls  of .the column  will actively


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                        chatter, but  the  chambers will  not flood.   When the
                        apparent volume of liquid reaches 0,5 ml,  remove the K-D
                        apparatus from the water bath  and allow it to drain and
                        cool for at least 10 minutes.  Remove the Snyder column
                        and rinse  the flask and  its  lower joints  with  about
                        0,2 ml  of  solvent  and  add  to the  concentrator  tube.
                        Adjust the final volume to 1.0-2.0 ml with solvent.

                        7.1.2.4.2   Nitrogen Slowdown Technique

                              7.1.2.4,2.1  Place the concentrator  tube in a warm
                        water  bath  (approximately  35 °C)   and  evaporate  the
                        solvent volume  to  the  required  level  using a  gentle
                        stream of clean, dry nitrogen (filtered through a column
                        of activated carbon).

                              CAUTION:   Do not use plasticized tubing between
                                         the  carbon trap and the sample.

                              7.1.2.4.2.2 The  internal wall  of the tube must be
                        rinsed down several  times with acetonitrile during the
                        operation.  During evaporation, the solvent level in the
                        tube must be positioned to prevent water from condensing
                        into the sample  (i.e.,  the solvent level should be below
                        the level  of the water  bath).  Under  normal  operating
                        conditions, the extract  should not be allowed to become
                        dry.

      7.2   Solvent Exchange:  Prior to Florisil  cleanup  or gas  chromatographic
analysis, the methylene chloride and methylene chloride/acetone extracts obtained
in Sec.  7.1.1  must be exchanged to hexane,  as  described  in  Sees.  7.2.1  through
7.2.3.    Exchange  is not  required  for  the  acetonitrile  extracts obtained  in
Sec.  7.1.2.4.

            7.2.1  Add one or two clean boiling chips to  the flask and  attach a
      three ball Snyder column.  Concentrate the extract as described  in  Sec.
      7.1.2.4.1, using  1  ml of methylene chloride  to prewet the  column,  and
      completing the concentration  in 10-20  minutes.   When  the  apparent volume
      of liquid  reaches  1-2 ml, remove the K-D  apparatus from the water bath and
      allow it to  drain and cool for at least  10 minutes.

            7.2.2  Momentarily  remove the Snyder column,  add 50  ml of hexane, a
      new boiling chip, and attach  the macro  Snyder column.  Concentrate the
      extract  as described in Sec. 7.1.2.4.1,  using 1 ml of hexane to prewet the
      Snyder column,  raising the temperature of the water bath, if necessary, to
      maintain proper distillation, and completing the concentration  in  10-20
      minutes.  When the apparent volume of liquid reaches  1-2 ml,  remove the
      K-D apparatus and allow  it to drain and  cool  for at  least  10  min.

            7.2.3  Remove the Snyder column and  rinse  the flask  and  its  lower
      joint into the  concentrator tube with  1  to 2 ml hexane. A 5 ml syringe is
      recommended  for this operation.   Adjust  the extract  volume to 2 ml for
      water samples,  using either  the micro  Snyder column  technique  (Sec.


                                   8061 - 8                          Revision 0
                                                                September  1994

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7,1.2,4.1) or nitrogen blowdown technique (Sec. 7.1.2.4.2), or 10 ml for
solid samples.  Stopper the concentrator tube and store at 4 "C  if further
processing will be performed immediately.  If the extract will be stored
for two days  or longer,  it should  be transferred  to a glass vial with a
Teflon lined screw-cap or crimp top.  Proceed with  the  gas chromatographic
analysis,

7.3   Cleanup/Fractionation:

      7,3.1 Cleanup may not be necessary  for extracts from a relatively
clean  sample   matrix.    If   polychlorinated   biphenyls   (PCBs)   and
organochlorine pesticides are known to be present in the sample, use the
procedure outlined in  Methods 3610  or 3620.   When using column cleanup,
collect  Fraction   1  by  eluting  with 140 ml  (Method  3610)   or  100 ml
(Method 3620) of  20-percent diethyl  ether in hexane.   Note that,  under
these  conditions,   bis(2-methoxyethyl)   phthalate,  bis(Z-ethoxyethyl)
phthalate, and bis(2-n-butoxyethyl) phthalate are not recovered from the
Florisil  column.  The elution patterns and compound recoveries are given
in Table 3.

      7,3.2 Methods 3610 and 3620  also describe   procedures  for sample
cleanup  using  Alumina and  Florisil  Cartridges.    With  this  method,
bis(2-methoxyethyl)   phthalate,    bis(2-ethoxyethyl)   phthalate,    and
bis(2-n-butoxyethyl)  phthalate  are recovered quantitatively.

7.4   Gas chromatographic conditions (recommended):

      7.4.1 Column 1  and  Column 2 (Sec. 4.1.2):

      Carrier gas  (He) =             6 mL/min.
      Injector temperature  =         250 °C.
      Detector temperature  =         320 °C.
      Column temperature:
            Initial temperature =   150 °C,  hold for 0.5 min.
            Temperature program =   150  "C   to  220  °C  at  5  °C/min.,
                                    followed by 220  'C  to  275 °C  at  3
                                    "C/min.
            Final  temperature =     275 °C hold for 13 min.

      7,4.2 Table   1  gives the retention  times  and  MDLs  that can  be
achieved  by this method for the 16  phthalate esters.   An example of the
separations achieved  with the DB-5 and DB-1701 fused-silica open tubular
columns is shown in Figure  1.

7.5   Calibration:

      7.5.1 Refer  to  Method 8000  for proper calibration techniques.   Use
Tables 1  and  2  for guidance  on  selecting the lowest  point on  the
calibration curve.

      7.5.2 The procedure  for  internal or  external calibration may  be
used.    Refer  to   Method 8000  for  the  description  of  each  of  these
procedures.


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      7.6   Gas chromatographic  analysis:

            7.6,1 Refer  to  Method  8000.   If the internal standard calibration
      technique is  used,  add 10 t±L of internal standard solution at 5000 mg/L
      to the sample prior to injection.

            7,6.2 Follow Method 8000 for instructions on  the analysis sequence,
      appropriate  dilutions, establishing  daily  retention time  windows,  and
      identification criteria.

            7.6.3 Record  the sample  volume injected  and  the  resulting  peak
      areas.

            7.6.4 Using  either  the  internal  or  the  external  calibration
      procedure (Method 8000), determine the identity and the quantity of each
      component  peak  in the  sample chromatogram  which  corresponds  to  the
      compounds used for calibration purposes.

            7.6.5 If the  response  of a peak exceeds  the working  range of the
      system, dilute the extract and reanalyze.

            7.6.6 Identify  compounds  in  the sample  by comparing the retention
      times of the peaks in  the  sample chromatogram with those of the peaks in
      standard  ehromatograms.    The  retention  time  window  used  to  make
      identifications  is based  upon measurements  of  actual   retention  time
      variations over the course of 10 consecutive injections.  Three times the
      standard deviation of  the retention time  can be  used  to calculate  a
      suggested window size.


8.0   QUALITY CONTROL

      8.1   Refer  to Chapter One  for  specific  quality control  procedures.
Quality control to validate  sample extraction  is covered in Method 3500 and in
the extraction method utilized.   If extract cleanup was performed,  follow the QC
specified in Method 3600 and  in the specific cleanup method.

      8.2   Quality control  required to evaluate the GC system operation  is found
in Method 8000.

            8.2.1 The quality control  check sample  concentrate  (Method  8000)
      should contain the test compounds at  5 to 10 ng/jiL.

      8,3   Calculate the recoveries of the surrogate compounds for all samples,
method blanks,  and method spikes.  Determine if the recoveries are within limits
established by performing QC procedures outlined in Method 8000.

            8.3.1 If the recoveries  are not within  limits, the  following  are
      required:

                  8.3.1.1     Make sure  there  are no errors  in calculations,
            surrogate solutions and internal standards.   Also check instrument
            performance.


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                  8.3.1.2     Recalculate the data and/or reanalyze the extract
             if  any  of the  above checks reveal a problem.

                  8.3.1.3     Reextract and reanalyze the sample if none  of the
             above are a problem, or flag  the data  as  "estimated concentration."

      8.4    An  internal  standard  peak area  check must  be performed  on all
samples.  The internal  standard must be evaluated  for acceptance by determining
whether  the  measured area  for the  internal  standard deviates  by more than 30
percent  from the average  area for  the  internal  standard  in  the calibration
standards.   When the internal  standard  peak area is outside  that limit, all
samples  that fall outside  the QC criteria must be reanalyzed.

      8.5    GC/MS confirmation: Any compounds confirmed  by two columns may also
be confirmed by GC/MS if the concentration  is sufficient  for detection by GC/MS
as determined by the laboratory-generated detection limits.

             8.5.1 The GC/MS would normally require a minimum concentration of 10
      ng//iL  in  the  final extract for each single-component compound.

             8.5.2 The sample extract and  associated blank should be analyzed by
      GC/MS  as  per  Sec.  7.0  of  Method  8270.   Normally,  analysis of a blank is
      not required  for confirmation analysis, however,  analysis for phthalates
      is a  special  case because of the  possibility for sample contamination
      through septum punctures, etc.

            8.5.3 A reference standard of the compound must  also be analyzed by
      GC/MS.    The   concentration  of  the   reference  standard  must  be  at  a
      concentration that would demonstrate  the ability to  confirm the phthalate
      esters identified by GC/ECD.

      8.6    Include a mid-concentration calibration standard after each group of
20 samples   in   the analysis  sequence.     The  response   factors  for  the
mid-concentration calibration must  be within ± 15  percent  of the average values
for the multiconcentration calibration.

      8.7   Demonstrate  through  the analyses of  standards that  the Florisil
fractionation scheme is reproducible.  When using the fractionation  schemes given
in Methods 3610  or  3620,  batch-to-batch  variations  in  the  composition  of the
alumina  or  Florisil material may  cause  variations  in  the recoveries of the
phthalate esters.


9.0   METHOD PERFORMANCE

      9.1   The MDL is defined in Chapter One. The MDL concentrations listed in
Table 1  were obtained  using  organic-free  reagent water.   Details on  how  to
determine MDLs are given in Chapter One.   The MDL actually achieved in a given
analysis will vary,  as  it  is  dependent  on  instrument  sensitivity  and  matrix
effects.

      9.2   This method has been tested in a single laboratory by using different
types of aqueous samples and  solid  samples  which  were  fortified with the test


                                   8061 - 11                         Revision 0
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compounds at two concentrations.  Single-operator precision, overall precision,
and  method  accuracy  were found to be  related to  the concentration  of the
compounds and  the type  of matrix.   Results of the  single-laboratory method
evaluation are presented  in Tables 4 and 5.

      9.3   The  accuracy and precision  obtained  is determined by  the sample
matrix,  sample  preparation  technique,  cleanup  techniques,  and  calibration
procedures used,


10.0  REFERENCES

1.    Glazer, J.A.;  Foerst,  S.D.;  McKee, G.D.; Quave,  S.A.,  and  Budde, W.L.,
      "Trace Analyses  for Wastewaters,"  Environ. Sci.  and  Techno!.  15: 1426,
      1981.

2.    Lopez-Avila, V,,  Baldin,  E,, Benedicto,  J.,  Milanes, J.,  and  Beckert,
      W.F.,  "Application of Open-Tubular Columns to SW-846 6C Methods", EMSL-Las
      Vegas, 1990.

3.    Beckert,  W.F. and Lopez-Avila, V.,  "Evaluation of SW-846 Method 8060 for
      Phthalate  Esters",  Proceedings  of  Fifth  Annual Testing  and  Quality
      Assurance Symposium, USEPA, 1989.
                                  8061 - 12
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                                        TABLE  1.
GAS CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS FOR THE PHTHALATE ESTERS"

Compound
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
IS
SU-1
SU-2
SU-3


Compound name
Dimethyl phthalate
Diethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-pentyl ) phthalate
Bis(2-methoxyethyl ) phthalate
Diamyl phthalate
Bis(2-ethoxyethyl) phthalate
Hexyl 2-ethylhexyl phthalate
Dihexyl phthalate
Butyl benzyl phthalate
Bis(2-n-butoxyethyl) phthalate
Bis(2-ethylhexyl) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate
Benzyl benzoate
Diphenyl phthalate
Diphenyl isophthalate
Dibenzyl phthalate
Chemical
Abstract
Registry
No.
131-11-3
84-66-2
84-69-5
84-74-2
146-50-9
117-82-8
131-18-0
605-54-9
75673-16-4
84-75-3
85-68-7
117-83-9
117-81-7
84-61-7
117-84-0
84-76-4
120-51-4
84-62-8
744-45-6
523-31-9
Retention time8
(min)

Column 1
7.06
9.30
14.44
16.26
18.77
17.02
20.25
19.43
21.07
24.57
24.86
27.56
29.23
28.88
33.33
38.80
12.71
29.46
32.99
34.40

Column 2
6.37
8.45
12.91
14.66
16.27
16.41
18.08
18.21
18.97
21.85
23.08
25.24
25.67
26.35
29.83
33.84
11.07
28.32
31.37
32.65
MDLb
Liquid
(ng/L)
640
250
120
330
370
510
110
270
130
68
42
84
270
22
49
22
c
c
c
c
                                        8061 - 13
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                                     Table 1. (continued)

Column 1 is a 30 m x 0.53 mm ID DB-5 fused-silica open tubular column (1.5 /zm film thickness).
Column 2 is a 30 m 0.53 mm ID DB-1701 fused-silica open tubular column (1.0 urn film thickness).
Temperature program is 150°C (0.5 min hold) to 220°C at 5'C/min, then to 275'C (13 min hold) at
3°C/min.  An 8-in Supelco injection tee or a J&W Scientific press fit glass inlet splitter is used
to connect the two columns to the injection port of a gas chromatograph.  Carrier gas helium at
6 mL/min; makeup gas nitrogen at 20 mL/min; injector temperature 250"C; detector temperature
320°C.

MDL is the method detection limit.  The MDL was determined from the analysis of seven replicate
aliquots of organic-free reagent water processed through the entire analytical method (extraction,
Florisil cartridge cleanup, and GC/ECD analysis using the single column approach:  DB-5 fused-
silica capillary column).  MDL = t(rv1 099, x SO where t(rv1 099)  is  the  student's  t value  appropriate
for a 99 percent confidence interval and a standard deviation with n-1 degrees of freedom, and SD
is the standard deviation of the seven replicate measurements.  Values measured were not corrected
for method blanks.

Not applicable.
                                           8061 - 14                                        Revision  0
                                                                                        September  1994

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                             TABLE 2.
     ESTIMATED QUANTITATION LIMITS (EQL) FOR VARIOUS MATRICES*
Matrix                                                Factor
Groundwater                                                10
Low-concentration soil by ultrasonic extraction           670
  with GPC cleanup
High-concentration soil and sludges by ultrasonic      10,000
  extraction
Non-water miscible waste                              100,000
EQL = [Method detection limit (see Table 1)] X [Factor found in this
table].  For non-aqueous samples, the factor is on a wet-weight basis.
Sample EQLs are highly matrix-dependent.  The EQLs determined herein are
provided for guidance and may not always be achievable.
                            8061  -  15                         Revision 0
                                                          September 1994

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                                   TABLE  3.
    AVERAGE RECOVERIES OF METHOD 8061 COMPOUNDS USING METHODS 3610 AND 3620
Compound
Dimethyl phthalate
Diethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-pentyl) phthalate
Bis(2-methoxyethyl) phthalate
Diamyl phthalate
Bis(2-ethoxyethyl) phthilate
Hexyl 2-ethylhexyl phthalate
Dihexyl phthalate
Benzyl butyl phthalate
B1s(2-n-butoxyethyl) phthalate
B1s(2-ethylhexy1) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate
Alumina
col umn8
64.5
62.5
77.0
76.5
89.5
70.5
75.0
67.0
90.5
73.0
87.0
62.5
91.0
84.5
108
71.0
Florisil
col umn*
40.0
57.0
80.0
85.0
84.5
0
81.5
0
105
74.5
90.0
0
82.0
83.5
115
72.5
Alumina
cartridgeb
101
103
104
108
103
64. r
103
111
101
108
103
108
97.6
97.5
112
97.3
Florisil
cartridge**
89.4
97.3
91.8
102
105
78.3*
94.5
93.6
96.0
96.8
98.6
91.5
97.5
90.5
97.1
105
8 2 determinations; alumina and Florisil chromatography performed according
  to Methods 3610 and 3620, respectively.

b 2 determinations, using 1 g alumina cartridges; Fraction 1 was eluted with
  5 ml of 20-percent acetone in hexane.  40 #g of each component was spiked
  per cartridge.

c 36.8 percent was recovered by elution with an additional 5 ml of
  20-percent acetone in hexane.

d 2 determinations, using 1 g Florisil cartridges; Fraction 1 was eluted
  with 5 ml of 10-percent acetone in hexane,  40 ^g of each component was
  spiked per cartridge,

8 14.4 percent was recovered by elution with an additional 5 ml of
  10-percent acetone in hexane.
                                   8061  -  16                         Revision 0
                                                                September 1994

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                                                        TABLE  4.
                              ACCURACY AND  PRECISION  DATA FOR  METHOD  3510  AND  METHOD 8061"
                                               Spike  Concentration
                                                    (20 uq/L)
                                                       Spike Concentration
                                                            (60 ug/L)
Estuarine
Compound
water
Leachate
Estuarine
Groundwater
water
Leachate
Groundwater
Dimethyl phthalate
Diethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-pentyl) phthalate
Bis(2-methoxyethyl) phthalate
Diamyl phthalate
Bis(2-ethoxyethyl) phthalate
Hexyl 2-ethylhexyl phthalate
Dihexyl phthalate
Benzyl butyl phthalate
Bis(2-n-butoxyethyl)  phthalate
Bis(2-ethylhexyl) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate

Surrogates:
84.0 (4.1)
71.2 (3.8)
76.0 (6.5)
     (6.5)
     (2.6)
73.8 (1.0)
78.2 (7.3)
     (3.3)
     (5.3)
               98.9
               82.8
83
78
         95.
         97.
         87
         87,
         92
75.6
84.7
79.8 (7.2)
84.
78.
81
   1
   ,5
   .4
77.4
74.9
(6.4)
(3.5)
(4.1)
(6.5)
(4.9)
 90.8
 91.1
102
105
 92.3
 93.0
               88.
               87,
59.5 (6.1)     77.3
(19.6)
(19.3)
(16.9)
(22.3)
(18.2)
(21.7)
(21.5)
(22.4)
(27.5)
(21.5)
(20.5)
(16.1)
(15.0)
(13.2)
(18.7)
 (4.2)
                       87
                       88
                            92.7
                            82.4
                            88.8
      (8.1)
     (15.3)
     (17.1)
91.0 (10.7)
92.6 (13.7)
      (4.4)
      (7.5)
      (5.8)
     (17.6)
      (7.6)
      (6.1)
      (3.6)
      (4.9)
     (15.2)
      (3.7)
      (8.0)
86
81
90
89
89
90
91
87
                            67.2
 87.1
 71.0
 99.1
 87.0
 97
 82
 89
 88
107
 90.1
 92.7
 86.1
 86.5
 87.7
 85.1
 97.2
 (7.5)
 (7.7)
(19.0)
 (8.0)
(15.0)
 (5.5)
 (2.8)
 (4.9)
(16.8)
 (2.4)
 (5.6)
 (6.2)
 (6.9)
 (9.6)
 (8.3)
 (7.0)
112
88.5
100
106
107
99.0
112
109
117
109
117
107
108
102
105
108
(17.5)
(17.9)
(9.6)
(17.4)
(13.3)
(13.7)
(14.2)
(14.6)
(11.4)
(20.7)
(24.7)
(15.3)
(15.1)
(14.3)
(17.7)
(17.9)
                                                           90,
                                                           75,
                                                           83
                                                           87
                                                           87
                                                           76.9
                                                           92.5
                                                  (4.5)
                                                  (3.5)
                                                  (3.3)
                                                  (2.7)
                                                  (2.9)
                                                  (6.6)
                                                  (1.8)
84.8 (5.9)
   1 (4.1)
   9 (2.4)
   0 (2.0)
     (0.6)
     (3.0)
     (2.4)
     (2.0)
     (1.1)
80.
88,
93.
92.
91.
                                                           71.9
                                                           90.4
                                                           90.1
Diphenyl phthalate
Diphenyl isophthalate
Dibenzyl phthalate
98.5 (2.6)
95.8 (1.9)
93.9 (4.4)
113
112
112
(14.9)
(11.7)
(14.0)
110
109
106
(3.3)
(3.3)
(3.8)
110
104
111
(12.4)
(5.9)
(5.9)
95.1
97.1
93.3
(7.2)
(7.1)
(9.5)
107
106
105
(2.4)
(2.8)
(2.4)
   The number of determinations was 3.
   the average recoveries.
    The values given  in  parentheses  are the  percent  relative  standard  deviations  of
                                                        8061 - 17
                                                                           Revision 0
                                                                       September 1994

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                                                          TABLE 5.
                                ACCURACY AND PRECISION DATA FOR METHOD 3550 AND METHOD 80618
Spike Concentration
(1 mq/kq)
Compound
Dimethyl phthalate
Diethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-pentyl) phthalate
Bis(2-methoxyethyl) phthalate
Diamyl phthalate
Bis(2-ethoxyethyl) phthalate
Hexyl 2-ethylhexyl phthalate
Dihexyl phthalate
Benzyl butyl phthalate
Bis(2-n-butoxyethyl) phthalate
Bis(2-ethylhexyl) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate
Estuarine
sediment
77.9
68.4
103
121
108
26.6
95.0
c
c
103
113
114
c
36.6
c
c
(42.8)
(1.7)
(3.1)
(25.8)
(57.4)
(26.8)
(10.2)


(3.6)
(12.8)
(21.1)

(48.8)


Municipal
sludge
52.1
68.6
106
86.3
97.3
72.7
81.9
66.6
114
96.4
82.8
74.0
76.6
65.8
93.3
80.0
(35.5)
(9.1)
(5.3)
(17.7)
(7.4)
(8.3)
(7.1)
(4.9)
(10.5)
(10.7)
(7.8)
(15.6)
(10.6)
(15.7)
(14.6)
(41.1)
Sandy loam
soil
c
54.7
70.3
72.6
c
0
81.9
c
57.7
77.9
56.5
c
99.2
92.8
84.7
64.2

(6.2)
(3.7)
(3.7)


(15.9)

(2.8)
(2.4)
(5.1)

(25.3)
(35.9)
(9.3)
(17.2)
Spike Concentration
(3 uq/q)
Estuarine
sediment
136
60.2
74.8
74.6
104
19.5
77.3
21.7
72.7
75.5
72.9
38.3
59.5
33.9
36.8
c
(9.6)
(12.5)
(6.0)
(3.9)
(1.5)
(14.8)
(4.0)
(22.8)
(11.3)
(6.8)
(3.4)
(25.1)
(18.3)
(66.1)
(16.4)

Municipal
sludge
64.8
72.8
84.0
113
150
59.9
116
57.5
26.6
80.3
76.8
98.0
85.8
68.5
88.4
156
(11.5)
(10.0)
(4.6)
(5.8)
(6.1)
(5.4)
(3.7)
(9.2)
(47.6)
(4.7)
(10.3)
(6.4)
(6.4)
(9.6)
(7.4)
(8.6)
Sandy loam
soil
70.2 (2.0)
67.0 (15.1)
79.2 (0.1)
70.9 (5.5)
83.9 (11.8)
0
82.1 (15.5)
84.7 (8.5)
28.4 (4.3)
79.5 (2.7)
67.3 (3.8)
62.0 (3.4)
65.4 (2.8)
62.2 (19.1)
115 (29.2)
115 (13.2)
a  The number of determinations was 3.  The values given in parentheses are the percent relative standard deviations of the
   average recoveries.  All samples were subjected to Florisil cartridge cleanup.

b  The estuarine sediment extract (Florisil, Fraction 1) was subjected to sulfur cleanup (Method 3660 with
   tetrabutylammonium sulfite reagent).

c  Not able to determine because of matrix interferant.
                                                          8061 - 18
    Revision 0
September 1994

-------
                                     Figure 1
                                                               06-5
                                                               30 m x 0.53 mm ID
                                                                     Fim
                         IS
            11    12 SU-1  SU-Z SU-3
                                 8    *

                                   5
     O
     UJ
     -3
                       is
                                        10
                                                                OB-1701
                                                                30 m x 0.53 mm ID
                     w *• «#wr if


             12  SU-1 15  I 1 16
t

N
U
uu
U
a,
JL
M)JuM
i i
                     10
    20

TIME (min)
                                                                      40
GC/ECD chromatograms of a composite phthalate esters standard  (concentration
10 ng/jiL  per compound) analyzed on a  DB-5  and a DB-1701 fused-silica  open
tubular column.   Temperature program: 150°C (0.5 min  hold)  to 220°C at
     >in>  then to  275°C  (13 min hold)  at  3°C/nrin- .
                                    8061 - 19
                                      Revision 0
                                  September 1994

-------
                                  METHOD  8061
     PHTHALATE  ESTERS BY  CAPILLARY  GAS  CHROMATOGRAPHY
           WITH  ELECTRON  CAPTURE  DETECTION  (GC/ECD)
             Stan
         7 1 Extraction
  '. 1.1  Refer to Chapter 2 tor
      guidance on choosing
      an extraction procedure.
      Recommendaaorc given.
 7.1.2 Determine spite sample
     recovery and detector limit
     (of each new sample matrix
     and a given extraction
     procedure.
 7.t.3 Aqueous sampleextraction
      with C18 disks:
      .1 Precondition disks using
        solvent tain.
      .2 Concentrate sample
        anaiytas on (Ask.
      .3 Bute sample anatyns
        witn acetonmle
     A Concentrate extract:
        1 Micro-Snyder Column
         Technique
        .2 Nitrogen Slowdown
         Technique
         .1 Evaporate solvent no
           desired level
         2 Rinse tube walls
           frequently and avoid
           evaporating to dryness.
 7.2 Solvent Exchange to Heiaria
 7.2.1 Evaporate extract volume to
 1 -2 nL using K-D assembly
72.2 Add nexane to K-D assembly
and evaporate to 1 -2 ml
 7 2.3 Rinse K-D components and
 adjust volume to desired level.
                                                                        '3 Cleanup/Eracnonatinn
 7.3,1 Cleanup may not be
      necessary tor extracts with
      dean sample matrices
      Fraction collection and
      methods outlined tor other
      ccmpd. groups of interest
7.3,2 Fiona! Cartridge Cleanup
     1 Crwc* each lot of Florist!
       cartridges for analyte
       recovery by eMng and
       analyzing a composite srd
     .2 Wash and adjust solvent
       flow through cartridges,
     .3 Place culture tubes or S ml
       va  flasks tor eJuate
       collection
     .4 Transfer appropriate extract
       volume on cartridge
     5 Bun aw cartridges and
      dilute to made on flask.
      Transfer eluate to glass
      vials-lor concentration.
7 3.3 Collect 2 Iraclions if PCBs
    and organochtorine pesticides
    are Known to be present
                                                                        7 4 Gas Cnromatograpn
                                                                   I 7 4 1 Set GC operating parameters
                                                                    7.42 Table 1 and Figure 1 show
                                                                         MOLs and analytB reran oon
                                                                         cmes
                                   8061  -  20
                    Revision 0
             September  1994

-------
     METHOD  8061
      (CONTINUED)
         7.5 Calibration
  7.5,1  S«e Metiod 8000 for
       calibration tsc*inique
  7,5.2 Refer to Method 8000 for
      inumavextemal std.
      procsoure.
        •6 3C Analysis
  7 6.1 Rater to Manx) 8000.
 7.6.2 Fallow Serion 7.6 in
      Method 6000 far
      mstrjctons on analysts
    '  sequence, dilutions.
      retention time windows,
      and lOonndcaBon criteria.
 7.6.3 Ftaoord irpdion volume
      and sampte peak areas.
 764  dentrty and quanmy sacn
     component peak iraing the
     internal or external std.
     DroceOure.
 76.S Dtlu» extracts *nk*
      show anajye tevets
      outside of the calibration
	range.     	
 7.6.6  identity compounds ;n me
      sample by comparing
      retention times in tie
      sample and aw standard
      crifonatograms.
        ("  Stop ")
      8081  -  21
      Revision  0
September  1994

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                                 METHOD 8070

                      NITROSAMINES  BY GAS CHROMATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   This method covers the determination of certain nitrosamines.   The
following compounds can be determined by this method:


                                        	Appropriate Technique	
Compound Name               CAS No.a    3510    3520    3540    3550    3580
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
62-75-9
86-30-6


N-Nitrosodi-n-propylamine 621-64-7
a Chemical Abstract Services Registry
X Greater than 70 percent
recovery
by
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Number.
this
preparation

technique.

      1.2   This  is  a  gas  chromatographic  (GC)  method  applicable  to  the
determination  of the  parameters  listed  above  in municipal  and  industrial
discharges.  When this method is used to analyze unfamiliar samples for any or
all of the compounds above, compound identifications  should be supported by at
least one additional qualitative technique.   This  method describes analytical
conditions for a second gas chromatographic column  that can be used to confirm
measurements  made  with  the  primary  column.     Method   8270  provides  gas
chromatograph/mass  spectrometer   (GC/MS)   conditions  appropriate   for  the
qualitative    and    quantitative    confirmation     of    results    for
N-nitrosodi-n-propylamine.      In    order   to   confirm   the   presence   of
N-nitrosodiphenylamine, the cleanup procedure specified in Section  7.3.3 or 7.3.4
must be used.   In order to confirm the presence of N-nitrosodimethylamine by
GC/MS, chromatographic column 1 of this method must be substituted  for the column
recommended  in  Method  8270.   Confirmation  of these   parameters  using  GC-high
resolution mass spectrometry or a  Thermal  Energy Analyzer  is  also recommended
practice.

      1.3   The method detection limit  (MDL)  for each parameter  is  listed in
Table 1.   The MDL  for a  specific wastewater may differ  from  those  listed,
depending upon the nature of  interferences  in  the sample matrix.  Table 2 lists
the Estimated Quantitation Limits (EQLs) for various  matrices.

      1.4   The toxicity or carcinogenicity of each reagent used in this method
has not  b.een precisely  defined.   However, each chemical  compound  should be
treated as a potential health hazard.   From this viewpoint, exposure to these
chemicals must be reduced to the lowest possible  concentration  by whatever means
available.  The laboratory is responsible  for maintaining  a current awareness
file of OSHA regulations regarding  the safe  handling of the chemicals specified
in this method.  A reference file of material  data  handling sheets should also

                                   8070  -  1                         Revision 0
                                                                     July 1992

-------
be made available to all personnel involved in the chemical  analysis.

      1.5   These nitrosamines are known carcinogens.   Therefore,  utmost care
must be exercised  in  the handling of these materials.   Nitrosamine reference
standards and standard solutions  should  be  handled and prepared in a ventilated
glove box within a properly ventilated room.

      1.6   N-Nitrosodiphenylamine  is  reported  to  undergo  transnitrosation
reactions.  Care must  be exercised in  the heating or concentrating of solutions
containing this compound in the presence of reactive amines,


2.0   SUMMARY OF METHOD

      2.1   A measured  volume  of aqueous sample, approximately  one liter,  is
solvent  extracted  with  methylene chloride using  a  separatory  funnel.   The
methylene chloride  extract is  washed with  dilute  HC1 to remove free amines,
dried, and  concentrated to a  volume  of 10 ml  or less.  Gas  chromatographic
conditions  are  described which permit  the separation and  measurement  of the
compounds in the extract after it has been exchanged to methanol.

      2.2   Method 8070 provides gas chromatographic conditions for the detection
of ppb concentrations  of nitrosamines.  Prior to use  of this method, appropriate
sample extraction techniques must be used.  Both neat and  diluted organic liquids
(Method 3580, Waste Dilution) may be analyzed  by direct  injection.  A 2 to 5 pi
aliquot of  the extract  is  injected  into  a gas  chromatograph (GC)  using the
solvent flush  technique, and  compounds in  the  GC effluent  are  detected by a
nitrogen-phosphorus detector (NPD) or a Thermal Energy Analyzer and the reductive
Hall detector.


3.0   INTERFERENCES

      3.1   Refer to Methods 3500, 3600, and 8000.

      3.2   Matrix  interferences  may  be   caused   by  contaminants  that  are
coextracted  from the  sample.   The extent  of matrix interferences  will vary
considerably from source to source, depending upon the nature and diversity of
the  industrial  complex  or  municipality  being  sampled.  The  cleanup procedures
(Methods 3610 or 3620) can be used to  overcome many of these interferences, but
unique samples  may require additional  cleanup  approaches to achieve  the MDL
listed in Table  1.

      3.3   Nitrosamines contaminate many types of products commonly found in the
laboratory.    The   analyst must  demonstrate that   no  nitrosamine  residues
contaminate  the sample or solvent extract under the conditions of analysis.
Plastics, in particular, must be  avoided because nitrosamines are commonly used
as  plasticizers and  are easily  extracted from  plastic materials.   Serious
nitrosamine contamination may result at any time if consistent quality control
is not practiced.

      3.4   The sensitive and selective Thermal Energy Analyzer and the reductive
Hall  detector  may  be used  in  place  of the nitrogen-phosphorus  detector when

                                   8070 - 2                         Revision 0
                                                                     July 1992

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interferences are encountered.  The Thermal Energy Analyzer offers the highest
selectivity of the non-mass spectrometric detectors.

      3,5   Solvents, reagents,  glassware,  and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms.  All  these materials  must be demonstrated to be free from
interferences, under the conditions of the analysis, by analyzing reagent blanks.
Specific selection of reagents and purification of solvents by distillation in
all-glass systems may be required.

      3.6   Interferences coextracted from samples will vary considerably from
source to  source,  depending upon the waste being sampled.   Although general
cleanup techniques are recommended as part of this  method,  unique samples may
require additional  cleanup.


4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph - An analytical system complete with temperature
programmable gas chromatograph suitable for on-column injection and all required
accessories including syringes,  analytical  columns, gases, detector, and strip-
chart recorder.  A data system is recommended for measuring peak areas.

            4.1.1 Column 1  - 1.8 m x 4 mm ID Pyrex glass, packed with Chromosorb
      W AW, (80/100 mesh)  coated  with 10%  Carbowax  20 M/2% KOH  or equivalent.
      This  column  was used  to  develop the method  performance  statements  in
      Section 9.0.   Guidelines for the  use of alternate column  packings are
      provided in Section 7.3.2.

            4.1.2 Column  2  -  1.8  m  x 4 mm  ID  Pyrex  glass,  packed  with
      Supelcoport (100/120 mesh) coated with 10% SP-2250,  or equivalent.

            4.1.3 Detector  -  Nitrogen-Phosphorus,  reductive  Hall  or Thermal
      Energy Analyzer. These  detectors have proven effective in the analysis of
      wastewaters for the parameters listed in the scope.  A nitrogen-phosphorus
      detector was  used to  develop the method performance statements in Section
      9.0.   Guidelines  for the  use  of alternate  detectors  are  provided  in
      Section 7.3.2.

      4.2   Kuderna-Danish  (K-D) apparatus

            4.2.1 Concentrator tube -  10 ml, graduated  (Kontes K-570050-1025 or
      equivalent).   Calibration must  be checked at the volumes employed in the
      test.  A ground glass stopper  is used to prevent evaporation of extracts.

            4.2.2 Evaporation   flask   -  500  ml   (Kontes   K-570001-0500  or
      equivalent).     Attach to  concentrator tube  with  springs,   clamps,  or
      equivalent.

            4.2.3 Snyder column  - Three ball  macro  (Kontes  K-503000-0121  or
      equivalent).

            4.2.4 Snyder  column  -  Two ball  micro  (Kontes  K-569001-0219  or

                                   8070 - 3                         Revision 0
                                                                     July 1992

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      equivalent).

            4.2.5 Springs -  1/2 inch (Kontes K-662750 or equivalent).

      4.3   Boiling chips - Approximately 10/40 mesh.  Heat to 400°C for
30 minutes or Soxhlet extract with methylene chloride.

      4.4   Water  bath  -  Heated,  with  concentric  ring  cover,  capable  of
temperature control (± 2°C).   The bath should be used in a hood.
top.
      4.5   Balance - Analytical, 0.0001 g.

      4.6   Vials - 10 to 15 ml, amber glass with Teflon lined screw-cap or crimp
      4.7   Volumetric  flasks,  Class A,  Appropriate  sizes with  ground glass
stoppers.


5.0   REAGENTS

      5.1   Reagent grade inorganic chemicals shall be  used  in all tests.  Unless
otherwise indicated, it is intended that all inorganic  reagents  shall conform to
the  specifications  of  the  Committee on  Analytical  Reagents  of  the  American
Chemical Society, where such specifications are available.  Other grades may be
used, provided it is first ascertained that the reagent  is  of sufficiently high
purity to permit its use without lessening the accuracy of the determination.

      5.2   Organic-free reagent water - All references  to  water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Methanol, CH3OH - Pesticide quality or equivalent.

      5,4   Isooctane,  (CH3)3CCH2CH(CH3)2 - Pesticide quality  or equivalent.

      5.5   Methylene chloride, CH2C12 - Pesticide quality  or equivalent.

      5.6   Stock standard solutions (1000 mg/L) - Stock standard solutions can
be prepared from pure standard materials or purchased as certified solutions.

            5.6.1 Prepare  stock  standard  solutions  by   accurately  weighing
      0.1000 ± 0.0010 g of pure  material.   Dissolve the material in pesticide
      quality  methanol  and  dilute  to  volume  in  a  100 ml  volumetric  flask.
      Larger volumes can be used  at the convenience of the  analyst.  If compound
      purity  is  certified at 96% or greater,  the weight  can  be  used without
      correction  to  calculate  the  concentration  of  the   stock  standard.
      Commercially prepared stock standards can be used  at  any  concentration if
      they are certified  by the manufacturer or by an independent source.

            5.6.2 Transfer the stock standard solutions into bottles with Teflon
      lined screw-caps  or crimp tops.   Store at 4°C and  protect from light.
                                   8070 - 4                         Revision 0
                                                                     July 1992

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      Stock  standard solutions  should  be checked  frequently  for signs  of
      degradation or evaporation, especially just prior to preparing calibration
      standards from them.

            5.6.3 Stock standard solutions must be replaced after six months, or
      sooner if comparison with check standards indicates a problem.

      5.7   Calibration standards - A minimum of five concentrations should be
prepared through dilution  of the stock standards with isooctane.   One of the
concentrations should be at a concentration  near, but above,  the method detection
limit.  The remaining concentrations should correspond  to the expected range of
concentrations found in real samples or should define the working range of the
GC.   Calibration solutions  must  be replaced after  six  months, or sooner if
comparison with check standards indicates a problem.

      5.8   Internal standards (if internal standard calibration is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical  behavior  to  the  compounds  of interest.  The analyst
must further demonstrate that the measurement of  the internal  standard is not
affected by method or matrix interferences.   Because of  these  limitations, no
internal standard can be suggested that is applicable to all samples.

            5.8.1 Prepare   calibration   standards   at   a   minimum  of  five
      concentrations for each analyte of interest, as described in Section 5.7.

            5.8.2 To each calibration standard,  add a known constant amount of
      one or more internal standards, and dilute to volume with isooctane.

            5.8.3 Analyze each calibration standard according to Section 7.0.

      5.9   Surrogate standards - The analyst  should monitor the performance of
the extraction, cleanup  (when used), and analytical  system and the effectiveness
of  the  method in  dealing  with  each  sample  matrix by  spiking each  sample,
standard, and reagent blank with one or two surrogates (e.g. nitrosamines that
are not expected  to be  in  the sample) recommended to encompass the range of the
temperature program used in this method.  Method 3500 details instructions on the
preparation of base/neutral surrogates.  Deuterated analogs of analytes should
not be  used  as surrogates  for  gas  chromatographic analysis due to coelution
problems.


6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1   See the  introductory material  to this chapter,  Organic Analytes,
Section 4.1.   Extracts  must be  stored  at  4°C and analyzed within  40  days of
extraction.
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7.0   PROCEDURE

      7.1   Extraction

            7.1.1 Refer to Chapter Two  for guidance on choosing the appropriate
      extraction  procedure.    In  general,  water  samples are  extracted at  a
      neutral, or as  is, pH with methylene chloride, using either Method 3510 or
      3520.  Solid samples are extracted using either Method 3540 or 3550.

            7.1.2 Prior to gas chromatographic analysis,  the extraction solvent
      must be exchanged to methanol.   The exchange is performed during the K-D
      procedures  listed  in all of the extraction methods.   The  exchange  is
      performed as follows.

                  7.1.2.1     Following K-D of the methylene  chloride extract to
      1 ml using the macro-Snyder  column, allow the apparatus to cool and drain
      for at least 10 minutes.

                  7.1.2.2     Momentarily remove the Snyder column, add 50 ml of
            methanol, a new boiling chip, and reattach the macro-Snyder column.
            Concentrate the extract using 1 ml of methanol to prewet the Snyder
            column.   Place the K-D  apparatus  on the  water bath  so  that  the
            concentrator tube  is  partially immersed  in  the  hot water.  Adjust
            the vertical  position  of the apparatus and the water temperature, as
            required, to complete  concentration in 5-10 minutes.  At the proper
            rate of distillation the  balls of the column  will actively chatter,
            but the chambers will  not flood.  When the apparent volume of liquid
            reaches  1 ml,  remove  the K-D apparatus and  allow  it  to  drain and
            cool  for at  least  10  minutes.    The  extract will  be  handled
            differently at this point, depending on  whether or not cleanup is
            needed.  If cleanup is  not required, proceed to Section  7.1.2.3.  If
            cleanup  is needed, proceed to Section 7.1.2.4,

                  7.1.2.3      If cleanup of the extract  is not required, remove
            the Snyder column and  rinse the flask and its lower joint into the
            concentrator  tube with  1-2  ml  of methanol,   A  5 ml  syringe  is
            recommended  for this  operation.   Adjust the  extract volume  to
            10.0 ml.  Stopper  the  concentrator tube  and store  refrigerated at
            4°C if further processing will not be  performed immediately.  If the
            extract  will  be  stored  longer  than   two  days,  it  should  be
            transferred to a  vial  with  a Teflon  lined screw-cap or crimp top.
            Proceed with gas chromatographic analysis.

                  7.1.2.4      If cleanup of the extract  is required, remove the
            Snyder column  and rinse the  flask and  its  lower joint  into  the
            concentrator tube with a  minimum amount of methylene chloride.  A 5
            ml syringe is recommended for this operation.  Add a clean boiling
            chip  to  the  concentrator tube and attach a  two ball  micro-Snyder
            column.   Prewet the  column  by adding about 0.5 ml  of  methylene
            chloride to the top.   Place the micro K-D  apparatus  on  the water
            bath  (80°C)  so that the concentrator  tube is partially immersed in
            the hot  water.  Adjust the vertical  position of the apparatus and
            the water temperature, as required, to complete  concentration in 5-

                                   8070 - 6                         Revision 0
                                                                     July 1992

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      10 minutes.   At  the proper rate of distillation  the  balls of the
      column will actively chatter, but the chambers will not flood.  When
      the  apparent volume  of liquid  reaches  0.5 ml,  remove  the  K-D
      apparatus and allow it to drain and cool for at least 10 minutes.

            7.1.2.5     Remove the micro-Snyder column and rinse the flask
      and  its  lower joint  into   the  concentrator tube  with  0.2 ml  of
      methylene chloride.   Adjust  the extract volume to 2.0 ml and proceed
      with either Method 3610, 3620,  or 3640.

      7.1.3 If   N-nitrosodiphenylamine   is  to   be  measured   by   gas
chromatography, the analyst must  first use a cleanup column to eliminate
diphenylamine   interference   (Methods    3610   or   3620).      If   N-
nitrosodiphenylamine is of no interest,  the analyst may proceed directly
with gas chromatographic analysis (Section 7.3).

7.2   Cleanup

      7.2.1 Cleanup procedures may not be necessary for a relatively clean
sample matrix.   The cleanup procedure recommended  in this method has been
used for the analysis of various clean waters and industrial effluents. If
particular  circumstances  demand the  use   of  an  alternative  cleanup
procedure, the analyst  must determine the elution profile and demonstrate
that  the  recovery  of  each compound of  interest   is  no less  than  85%.
Diphenylamine,  if present  in the  original sample extract must be separate
from  the  nitrosamines  if  N-nitrosodiphenylamine is to  be determined by
this method.

      7.2.2 Proceed with  either   Method  3610 or  3620,  using  the 2  ml
methylene chloride extracts obtained from Section  7.1.2.5.

      7.2.3 Following cleanup, the extracts should be analyzed by GC, as
described in the previous paragraphs and in Method 8000.

7.3   Gas Chromatography

      7.3.1 N-nitrosodiphenylamine completely reacts to form diphenylamine
at the normal operating temperatures of a GC injection port (200  to 250°C).
Thus,   N-nitrosodiphenylamine   is  chromatographed   and  detected   as
diphenylamine.   Accurate determination depends on removal of diphenylamine
that  may  be present in the original  extract prior to GC  (see  Section
7.1.3),

      7.3.2 Table  1 summarizes the recommended  operating conditions  for
the gas  chromatograph.  This table includes retention  times and MDLs that
were  obtained   under   these  conditions.     Examples  of  the  parameter
separations achieved by these columns are shown in  Figures 1 and 2.  Other
packed columns, chromatographic conditions,  or  detectors  may  be  used if
the requirements of Section 8.2 are met.  Capillary  (open-tubular) columns
may  also  be used  if the  relative standard deviations  of responses  for
replicate  injections   are  demonstrated  to  be  less  than  6% and  the
requirements of Section 8.2 are met.


                             8070 -  7                         Revision 0
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      7.4   Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1  and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.

            7.4.1 The procedure  for internal  or external  calibration  may  be
      used.   Refer to  Method 8000 for a description of each of these procedures.

            7.4.2 If  cleanup  is  performed on the  samples, the  analyst should
      process a  series of  standards  through  the  cleanup  procedure  and  then
      analyze the  samples by  GC.   This will  confirm elution  patterns and the
      absence of interferents from the reagents.

      7.5   Gas chromatographic analysis

            7.5.1 Refer to Method 8000.   If the internal  standard calibration
      technique is used, add 10 ^L of internal standard to the sample prior to
      injection.

            7.5.2 Method 8000 provides instructions on  the  analysis sequence,
      appropriate  dilutions,  establishing  daily  retention  time  windows,  and
      identification criteria. Include a mid-concentration check standard after
      each group of 10 samples in the analysis sequence.

            7.5.3 Examples of GC/NPD chromatograms for nitrosamines are shown in
      Figures 1 and 2.

            7.5.4 Record the sample  volume injected and the resulting peak sizes
      (in area units or peak heights).

            7.5.5 Using either the  internal  or external  calibration procedure
      (Method 8000), determine the identity  and quantity of each analyte peak in
      the sample chromatogram.  See Method 8000 for calculation equations.

            7.5.6 If  peak  detection and  identification  are prevented  due  to
      interferences, the hexane extract may  undergo cleanup using either Method
      3610 or 3620.
8.0   QUALITY CONTROL

      8.1   Refer  to Chapter  One  for specific  quality control  procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized.  If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.

      8.2   Procedures to check the GC system operation are found in Method 8000,
Section 8.6.

            8.2.1 The quality control (QC)  reference sample concentrate (Method
      8000, Section 8.6) should contain each analyte of interest at 20 mg/L.

            8.2.2 Table 3 indicates the calibration and QC acceptance criteria
      for this method.  Table 4 gives method accuracy and  precision as functions

                                   8070 - 8                         Revision 0
                                                                     July 1992

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      of concentration  for the  analytes  of interest.   The contents  of both
      Tables should be used to  evaluate  a laboratory's  ability to perform and
      generate acceptable data by this method.

      8.3   Calculate surrogate  standard  recovery on  all  samples, blanks, and
spikes.   Determine if the  recovery is  within  limits  (limits  established  by
performing QC procedures outlined in Method 8000, Section 8.10).

            8.3.1 If recovery is not within limits,  the following is required.

            *     Check to be  sure  that  there are no errors  in calculations,
                  surrogate  solutions  and  internal  standards.   Also,  check
                  instrument performance.

            •     Recalculate the data and/or reanalyze the extract if any of
                  the above checks reveal a problem.

            *     Reextract and reanalyze the sample  if  none of the  above are a
                  problem or flag the data as "estimated concentration.


9.0   METHOD PERFORMANCE

      9.1   This method has been tested  for linearity of recovery from spiked
organic-free reagent water and  has  been  demonstrated  to be applicable for the
concentration range from 4 x MDL to 1000 x MDL.

      9.2   In a single laboratory (Southwest Research Institute), using spiked
wastewater samples, the average recoveries presented in Table 2 were obtained.
Each spiked sample was  analyzed in triplicate on  three separate occasions.  The
standard deviation of the percent recovery is also included in Table 2.


10.0  REFERENCES

1.    Fed. Regist. 1984, 49, 43234; October 26.

2.    "Determination of Nitrosamines in Industrial and Municipal Wastewaters";
      Report for EPA Contract 68-03-2606, in preparation.

3.    Burgess,  E.M.;  Lavanish,  J.M.   "Photochemical   Decomposition  of  N-
      nitrosamines"; Tetrahedron Letters 1964,  1221.

4.    Methods  for  Chemical  Analysis of  Water  and Wastes;  U.S.  Environmental
      Protection  Agency.  Office  of Research  and Development.  Environmental
      Monitoring and Support Laboratory.  ORD Publication Offices of Center for
      Environmental Research Information:  Cincinnati, OH,  1979; EPA-600/4-79-
      020.

5.    "Method Detection Limit and Analytical Curve Studies EPA Methods 606, 607,
      608"; U.S. Environmental  Protection Agency. Environmental Monitoring and
      Support Laboratory,  Cincinnati, OH, special letter report  for EPA Contract
      68-03-2606.

                                   8070 - 9                         Revision 0
                                                                     July 1992

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                                   TABLE 1.
            CHROMAT06RAPHIC CONDITIONS AND METHOD DETECTION LIMITS
Analyte
  Retention Time
     (minutes)	
Column 1    Column 2
                  Method
               Detection Limit
                  (WI/L)
N-Ni trosodimethyl ami ne
N-Nitrosodi-n-propylamine
N-N1 trosodi phenylamine11
4.1
12.1.
12. 8b
0.88
4.2
6.4e
0.15
0.46
0.81
Column 1 conditions:
   Carrier gas (He) flow rate:
   Column temperature:
Column 2 conditions:
   Carrier gas (He) flow rate:
   Column temperature:
  40 mL/min
  Isothermal,
  indicated.
  40 mL/min
  Isothermal,
  indicated.
at  110°C,   except  as  otherwise
at  120°C,   except  as  otherwise
a  Measured as diphenylamine.
b  Determined isothermally at 220°C.
c  Determined isothermally at 210°C.
                                   TABLE 2.
                    SINGLE OPERATOR ACCURACY AND PRECISION
                             Average   Standard    Spike
                             Percent   Deviation   Range
                              Number
                                of     Matrix
Analyte
Types
N-Nitrosodimethylamine
N-Ni trosodi phenyl ami ne
N-Ni trosodi -n-propyl ami ne
Recovery

32
79
61
%

3.7
7.1
4.1
(MBA)

0.8
1.2
9.0
Analyses

29
29
29


5
5
5
                                   8070  -  10

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                                   TABLE 3.
                            QC ACCEPTANCE CRITERIA
                                   Test      Limit       Range      Recovery
                                   Cone.      for s       for X        Range
 Analyte                           ([ig/L)
 N-Nitrosodimethyl amine              20        3.4       4.6-20.0     13-109

 N-Nitrosodiphenylamine              20        6.1       2.1-24.5      D-139

 N-Nitrosodi-n-propylamine           20        5.7      11.5-26.8     45-146


s     =     Standard deviation for four recovery measurements,  in  ng/L.

X     =     Average recovery  for four recovery measurements,  in  ng/L.

D     =     Detected, result  must be greater than zero.
                                   8070 - 11                         Revision 0
                                                                     July  1992

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                                   TABLE 4.
         METHOD  ACCURACY AND  PRECISION  AS  FUNCTIONS  OF  CONCENTRATION
Analyte
N-Nitrosodi methyl ami ne
N-Ni trosodi phenyl ami ne
N-Nitroso-n-propylamine
Accuracy, as
recovery, X'
(ng/L)
0.37C+0.06
0.64C+0.52
0.96C-0.07
Single
analyst
precision,
s/ (ng/L)
0.25X-0.04
0.36X-1.53
0.15X+0.13
Overall
precision,
S' (ng/L)
0.25X+0.11
0.46X-0.47
0.21X+0.15
c

X
Expected  recovery  for  one  or  more  measurements  of  a  sample
containing a concentration of C, in [ig/L.

Expected single  analyst  standard deviation of measurements  at an
average concentration found of X, in |ig/L.

True value for the concentration, in |ig/L.

Average recovery found for measurements  of samples  containing a
concentration of C, in [ig/L.
                                   8070 - 12
                                                        Revision 0
                                                         July 1992

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             FIGURE  1.
GAS CHROMATOGRAM OF NITROSAMINES
    Column 10% Cirbowex 20M + 2%
           KOH on Chromotorb W-AW
    Tempertturt: t tO°
    Dettctor: Phosphorus/Nitrogen
       2   4   6   8  10  12  14

         Retention time, minute*
            8070 - 13
Revision 0
 July  1992

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                           FIGURE 2.
GAS CHROMATOGRAM OF  N-NITROSOOIPHENYLAMINE AS DIPHENYLAMINE
               Column: 1O% Cirbowix 20M - 2% KQH on
                      Chromotoro W-AW
               TtmptrMurt: 220"C.
               Qitietor: Phoaphorus/Nilrogtn
                                          I
              0  2   4   S   8  10  12  14  16  19

                                tim*. minun*
                            8070  -  14
Revision  0
 July  1992

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                             METHOD 8070
               NITROSAMINES BY GAS  CHROMATOGRAPHY
  7.1,2.4 P.cforn
•uero-K-D procedure
  utliig Rt«thyl«n«
 ehlorid*: p»rfors
  M«thod 3610 at
3620; Pro=..d »ith
   CC *n*ly«i«
I Start I


71.1 Choo**
•pprpriit*
procedure



• 01 v»n t *n chang*
u* ing M»t Hanoi
/ 7-1-2 2 N.
/I* cUanwp of \
-( the wMtraet J
\ r«q«ir»d? /
v
71.23 Ad, u.i
•itraet volunc and
tnannar


713 Perform
co 1 IUBII ci •anup
using M.thod 3610
or 3620

73.2 R*f*r to
T*bl« i for
condi Liana for th*
GC
..
7 4 R«f«r to Method
8000 for pr op*r
eal ibratian
tachniqu**

7 SI R*f*r to
M«thod 8000 for


7 5 4/7 S 5 H«cord
tanpl* volua*
in]*ci«d and
ruaultmg p*ak
»ix«/p»rf orm
appropr ia t*
calculation* { r*f«r
to Hvthod 8000)

                               8070  -  15
Revision 0
 July 1992

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                                 HETHOD 8080A

           OR6ANOCHLORINE  PESTICIDES AND  POLYCHLORINATED BIPHENYLS
                             BY GAS CHROMATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   Method 8080  is  used  to  determine  the  concentration  of  various
organochlorine pesticides and polychlorinated biphenyls (PCBs),   The  following
compounds can be determined by this method:
      Compound Name
CAS No."
Aldrin
a-BHC
jS-BHC
5-BHC
7-BHC (Lindane)
Chlordane (technical)
4,4'-DDD
4,4'-DDE
4, 4' -DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
4,4'-Methoxychlor
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
309-00-2
319-84-6
319-85-7
319-86-8
58-89-9
12789-03-6
72-54-8
72-55-9
50-29-3
60-57-1
959-98-8
33212-65-9
1031-07-8
72-20-8
7421-93-4
76-44-8
1024-57-3
72-43-5
8001-35-2
12674-11-2
1104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
a  Chemical  Abstract Services Registry Number.

      1,2   Table 1  lists the  method detection  limit for  each  compound  in
organic-free reagent water.  Table 2 lists the estimated  quantitation limit (EQL)
for other matrices.
                                  8080A - 1
                  Revision 1
              September 1994

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2.0   SUMMARY OF METHOD

      2.1   Method 8080 provides gas chromatographic conditions for the detection
of ppb concentrations of certain organochlorine pesticides and PCBs.  Prior to
the use of this method, appropriate sample extraction techniques must be used.
Both neat  and diluted organic  liquids (Method 3580,  Waste Dilution)  may be
analyzed by  direct injection.   A  2  to 5  nl sample  is  injected  into  a  gas
chromatograph (6C) using the  solvent  flush  technique,  and compounds in the SC
effluent are detected by an electron capture detector (ECO) or an electrolytic
conductivity detector (HECD).

      2.2   The sensitivity of Method  8080 usually depends on the concentration
of interferences  rather  .than on  instrumental  limitations.   If interferences
prevent detection of the  analytes,  Method 8080 may also be performed on samples
that have undergone cleanup.   Method 3620,  Florisil Column  Cleanup, by itself or
followed by Method 3660,  Sulfur Cleanup, may be used to eliminate interferences
in the analysis.


3.0   INTERFERENCES

      3.1   Refer to Methods  3500, 3600, and 8000.

      3.2   Interferences  by  phthalate esters  can  pose  a  major  problem  in
pesticide  determinations  when  using  the  electron  capture  detector.    These
compounds  generally  appear in the  chromatogram as  large  late-eluting  peaks,
especially in  the 15% and  50% fractions  from  the  Florisil cleanup.   Common
flexible plastics contain varying amounts  of phthalates.   These phthalates  are
easily extracted or leached from  such materials during laboratory operations.
Cross contamination of clean glassware  routinely occurs when plastics  are handled
during extraction  steps, especially when  solvent-wetted  surfaces are handled.
Interferences from phthalates  can best be minimized by avoiding contact with any
plastic materials.  Exhaustive cleanup of reagents and glassware may  be required
to  eliminate background  phthalate  contamination.     The contamination  from
phthalate  esters  can  be  completely  eliminated  with a  microcoulometric  or
electrolytic conductivity detector.


4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph

            4.1.1 Gas  Chromatograph:    Analytical   system  complete with  gas
      -hroraatograph  suitable  for  on-column   injections  and   all  required
      accessories, including  detectors, column  supplies,  recorder,  gases,  and
      syringes.   A data system for measuring peak heights and/or peak areas is
      recommended.

            4.1.2 Columns

                  4.1.2.1     Column 1:  Supelcoport  (100/120 mesh)  coated with
            1.5% SP-2250/1.95% SP-2401 packed in a 1.8 m x 4 mm ID glass column
            or equivalent.


                                   8080A -2                        Revision 1    \
                                                                September 1994     v

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                  4.1.2.2     Column 2:  Supelcoport (100/120 mesh) coated with
            3% OY-1 in a 1.8 m x 4 mm  ID glass column or equivalent.

            4.1.3 Detectors:     Electron   capture   (ECD)  or   electrolytic
      conductivity detector (HECD).

      4.2   Kuderna-Danish (K-D) apparatus:

            4.2.1 Concentrator tube:  10 mL, graduated  (Kontes K-570050-1025 or
      equivalent).  A ground-glass stopper is used  to  prevent  evaporation of
      extracts.

            4.2,2 Evaporation   flask:      500   ml   (Kontes  K-570001-500   or
      equivalent).    Attach  to  concentrator   tube  with  springs,  clamps,  or
      equivalent.

            4.2.3 Snyder column:   Three ball  macro {Kontes K-503000-Q121  or
      equivalent).

            4,2.4 Snyder  column:    Two  ball  micro  (Kontes K-5690Q1-0219  or
      equivalent).

            4.2.5 Springs -  1/2 inch  (Kontes K-662750 or equivalent).

      4.3   Boiling chips:  Solvent extracted,  approximately 10/40 mesh (silicon
carbide or equivalent),

      4.4   Water  bath:    Heated,  with  concentric  ring   cover,  capable  of
temperature control (±5°C).   The bath should be used in a hood.

      4.5   Volumetric flasks, Class A:  sizes  as appropriate with ground-glass
stoppers.

      4.6   Microsyringe:  10 /iL.

      4.7   Syringe:  5 ml.

      4.8   Vials:  Glass, 2, 10, and 20 ml capacity with Teflon-lined screw caps
or crimp tops.

      4.9   Balances:   Analytical,  0.0001 g and Top loading, 0.01 g.


5.0   REAGENTS

      5.1   Reagent grade chemicals shall be used in all  tests. Unless otherwise
indicated, it is  intended that all  reagents shall conform to the specifications
of the Committee  on Analytical  Reagents of  the American Chemical  Society, where
such specifications are available. Other grades  may be used,  provided it is first
ascertained that the  reagent  is of sufficiently  high purity to  permit its  use
without lessening the accuracy of the determination.
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      5,2   Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5,3   Solvents

            5,3,1 Hexane, C6H14  -  Pesticide  quality or  equivalent.

            5,3.2 Acetone,  CH3COCH3 -  Pesticide quality or  equivalent.

            5.3.3 Toluene, C6HSCH3 -  Pesticide  quality  or equivalent.

            5.3.4 Isooctane, (CH3)3CCH2CH(CH3)Z - Pesticide quality or equivalent,

      5.4   Stock standard solutions:

            5.4.1 Prepare  stock  standard  solutions   at  a  concentration  of
      1000 mg/L  by  dissolving  0.0100  g  of  assayed   reference  material  in
      isooctane  and  diluting  to volume in a 10 ml volumetric  flask.   A small
      volume of  toluene may be necessary to put  some  pesticides  in  solution.
      Larger  volumes can be  used at  the convenience  of  the analyst.   When
      compound purity is assayed  to  be  96%  or  greater, the  weight can be used
      without correction to calculate the concentration of the stock standard.
      Commercially prepared stock standards  can be used at any concentration if
      they are certified by the manufacturer or by an  independent source.

            5.4.2 Transfer the stock standard solutions into vials with Teflon-
      lined screw  caps  or crimp  tops.   Store  at 4°C  and protect  from light.
      Stock standards should be checked frequently for signs of degradation or
      evaporation, especially just prior to preparing calibration standards from
      them.

            5.4.3 Stock standard solutions must be replaced after one year, or
      sooner if  comparison with check standards indicates a problem.

      5.5   Calibration standards:  Calibration standards at a minimum of five
concentrations for each parameter of interest are prepared through dilution of
the stock standards  with isooctane.  One  of the concentrations should be at a
concentration  near,  but  above,  the method detection  limit.   The  remaining
concentrations should correspond to the expected range of concentrations found
in real  samples  or  should  define the working  range  of the GC.   Calibration
solutions must be replaced after six months,  or  sooner,  if comparison with check
standards indicates a problem.

      5.6   Internal standards (if internal  standard calibration is used):  To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds  of interest.   The analyst
must further demonstrate that the  measurement  of  the  internal  standard is not
affected by method or matrix  interferences.  Because of these limitations, no
internal standard can be suggested that is applicable to all samples.

            5.6.1 Prepare   calibration   standards  at  a   minimum   of  five
      concentrations for each analyte of interest as described in Sec, 5.5.
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            5.6.2 To each calibration standard, add a known constant amount of
      one or more internal standards, and dilute to volume with isooctane.

            5,6.3 Analyze each calibration standard according to Sec. 7.0.

      5.7   Surrogate standards:   The analyst should monitor the performance of
the extraction,  cleanup (when used), and analytical  system and the effectiveness
of  the  method  in  dealing with  each  sample  matrix by  spiking each  sample,
standard,  and organic-free  reagent  water  blank  with  pesticide  surrogates.
Because GC/ECD data are much more  subject to interference than GC/MS, a secondary
surrogate is  to  be  used  when sample  interference  is apparent..  Two surrogate
standards (tetrachloro-m-xylene (TCMX) and decachlorobiphenyl)  are added to each
sample;  however,  only one need  be  calculated  for recovery.   Proceed  with
corrective action when both surrogates are out of limits for a sample (Sec. 8.3).
Method 3500 indicates the proper procedure for preparing  these surrogates.


6.0   SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1   See  the introductory material  to this chapter, Organic Analytes, Sec.
4.1.  Extracts must be stored under refrigeration  and analyzed within 40 days of
extraction.
7.0,  PROCEDURE

      7.1   Extraction:

            7.1,1 Refer  to Chapter Two  for guidance on choosing the appropriate
      extraction procedure.    In  general,  water  samples are  extracted at  a
      neutral,  or as  is,  pH with methylene chloride, using either Method 3510 or
      3520.   Solid  samples are extracted using Method 3540,  3541,  or 3550.

            7.1.2 Prior  to gas chromatographic analysis, the extraction solvent
      must be exchanged  to  hexane.   The exchange is performed during  the  K-D
      procedures listed   in all of  the extraction methods.   The  exchange  is
      performed as  follows.

                  7.I.E.I     Following K-D of the methylene chloride extract to
            1 mL using the macro-Snyder column, allow the apparatus to cool  and
            drain for at least 10 min.

                  7.1.2.2     Increase the temperature of the hot water bath to
            about 90°C.    Momentarily  remove  the  Snyder  column,  add 50 mL  of
            hexane,  a new boiling chip,  and  reattach the macro-Snyder column.
            Concentrate  the extract using 1 mL of hexane to  prewet the Snyder
            column.   Place  the K-D apparatus  on the water  bath   so that  the
            concentrator tube is partially immersed  in the hot water.   Adjust
            the vertical position of the apparatus and the water temperature, as
            required, to complete concentration in 5-10 min.  At the proper rate
            of  distillation the balls of the  column  will  actively  chatter,  but
            the chambers will  not  flood.   When the apparent  volume  of liquid
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            reaches  1 ml,  remove the K-D apparatus and  allow  It  to drain and
            cool for at least 10 min.

                  7.1.2.3     Remove the Snyder column and rinse the flask and
            its lower joint  into the  concentrator tube with 1-2 mL of hexane.
            A  5 ml  syringe  is   recommended  for this  operation.    Adjust the
            extract volume to 10.0 mL.  Stopper the concentrator tube and store
            refrigerated at  4°C»  if  further processing  will not  be performed
            immediately.  If the extract will be stored longer than  two days, it
            should be transferred to a vial with a Teflon-lined  screw cap or
            crimp top.   Proceed with gas chromatographic  analysis if further
            cleanup is not required.

      7.2   Sas chromatography conditions (Recommended):

            7.2.1 Column 1:

            Carrier gas (5% methane/95% argon) flow rate:   60 mL/min
            Column temperature:                              200°C  isothermal

            When analyzing  for   the  low molecular weight  PCBs (PCB  1221-PCB
      1248), it is advisable to  set the oven temperature to 160°C.

            7.2.2 Column 2:

            Carrier gas (5% methane/95% argon) flow rate:   60 mL/min
            Column temperature:                              200°C  isothermal

            When analyzing  for   the  low molecular weight  PCBs (PCB  1221-PCB
      1248), it is advisable to  set the oven temperature to 14Q°C.

            7.2.3 When analyzing for most or all of the analytes in this method,
      adjust the oven  temperature and  column  gas flow  to  provide sufficient
      resolution for accurate quantitation of the  analytes.  This will normally
      result 1n a retention time of 10 to 12 minutes for  4,4'-DDT,  depending on
      the packed column used.

      7.3   Cal ibration: Refer to Method 8000 for proper calibration techniques.
Use Table 1  and especially Table  2 for guidance on  selecting  the lowest point on
the calibration curve.

            7.3.1 The procedure  for  internal  or  external  calibration may  be
      used.  Refer to Method 8000 for a description of  each of these procedures.

            7.3.2 Because  of the low  concentration   of pesticide  standards
      injected on a GC/ECD, column adsorption may be a problem when the GC has
      not been  used  for  a  day.   Therefore,  the GC column  should  be primed or
      deactivated by injecting a  PCB or pesticide standard mixture approximately
      20 times  more concentrated than  the mid-concentration standard.   Inject
      this prior to beginning initial or daily calibration.
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7,4   Gas chromatographic analysis:

      7.4.1 Refer to Method 8000.   If the internal  standard calibration
technique is used, add 10 pL of internal standard to the sample prior to
injection.

      7.4.2 Method 8000 provides  instructions  on  the analysis sequence,
appropriate dilutions,  establishing daily  retention time  windows,  and
identification criteria.   Include  a mid-concentration standard after each
group of 10 samples in the analysis sequence.

      NOTE: A 72 hour sequence is not required with this method.

      7.4.3 Examples of GC/ECD chromatograms for  various pesticides and
PCBs are shown in Figures 1 through 5.

      7.4.4 Prime the column as per Sec. 7.3.2.

      7.4.5 DDT and endrin are easily degraded  in  the  injection port if
the injection  port or front of the column is dirty.  This  is  the result of
buildup  of high  boiling  residue from sample  injection.    Check  for
degradation problems by injecting  a mid-concentration standard containing
only 4,4'-DDT and endrin.  Look for the degradation products of 4,4'-DDT
(4,4'-DDE and 4,4'-ODD) and endrin  (endrin  ketone  and  endrin aldehyde).
If degradation of  either DDT or endrin exceeds 20%, take corrective action
before proceeding  with calibration, by following the 6C system maintenance
outlined in of Method 8000.  Calculate percent breakdown as follows;

                          Total DDT degradation peak area (DDE + ODD)
      % breakdown       =	— x 100
      for 4,4'-DDT          Total  DDT peak area (DDT + DDE + ODD)

                          Total endrin degradation peak area
                          (endrin aldehyde + endrin ketone)
      % breakdown       = 	:	   x 100
      for Endrin           Total  endrin peak area (endrin +
                           endrin aldehyde + endrin ketone)

      7.4.6 Record the sample volume injected and the  resulting peak sizes
(in area units or peak heights).

      7.4.7 Using either the internal or  external  calibration procedure
(Method 8000), determine  the identity  and quantity of each component peak
in the  sample  chromatogram which  corresponds to the compounds  used for
calibration purposes,

      7.4.8 If peak  detection  and identification  are  prevented  due to
interferences, the hexane  extract may need to undergo  cleanup using Method
3620.   The  resultant  extract(s)  may  be analyzed  by GC  directly or may
undergo further cleanup to remove sulfur using Method 3660,
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7,5   Cleanup:

      7.5.1 Proceed with  Method  3620,  followed by, if necessary, Method
3660, using the 30 ml hexane  extracts obtained from Sec. 7.1.2.3.

      7.5.2 Following cleanup, the extracts should be analyzed by GC, as
described in the previous  sections and  in Method 8000.

      7.5.3 If  only  PCBs  are  to  be  measured in a  sample,  the sulfuric
acid/permanganate  cleanup  (Method   3665),  followed  by Silica  Cleanup
(Method 3630) or Florisil  Cleanup (Method 3620), is recommended.

7.6   Calculations (excerpted  from U.S. FDA, RAM):

      7.6.1 Calculation of Certain Residues:  Residues which are mixtures
of two or more components present problems  in measurement.  When they are
found  together,  e.g.,  toxaphene  and DDT,  the problem  of  quantisation
becomes even more difficult.   In  the following sections suggestions are
offered for  handling toxaphene,  chlordane,  PCB,  DDT,  and  BHC.   A 10%
DC-200 stationary phase column was  used to obtain  the  chromatograms in
Figures 6-9.

      7.6.2 Toxaphene:  Quantitative  calculation of toxaphene or Strobane
is difficult,  but reasonable  accuracy  can be  obtained.  To  calculate
toxaphene on 6C/ECD:   (a)  adjust sample size so  that toxaphene major peaks
are  10-30% full-scale deflection  (FSD);  (b)  inject a toxaphene standard
that is estimated to  be within ±10  ng  of the  sample;  (c)  construct the
baseline of standard toxaphene between  its extremities; and (d) construct
the baseline under the sample, using  the distances  of the peak troughs to
baseline on the standard as a guide (Figures 7,  8, and 9).  This procedure
is made difficult by the fact that the relative heights and widths of the
peaks in the  sample  will  probably not be identical to  the  standard.   A
toxaphene standard that has been passed through a  Florisil  column  will
show a shorter retention time  for peak X and an enlargement of peak Y.

      7.6.3 Toxaphene and  DDT:  If  DDT is present,  it  will  superimpose
itself on toxaphene peak V.  To determine the approximate baseline of the
DDT,  draw a line connecting the trough of peaks U and  V with the trough of
peaks W and X and  construct another line parallel to this line which will
just cut the top of peak  W (Figure 61).   This  procedure was  tested  with
ratios of standard toxaphene-DDT mixtures from 1:10 to 2:1 and the results
of added and calculated DDT and toxaphene by the "parallel  lines" method
of baseline  construction  were within  10% of  the  actual values  in all
cases.

            7.6.3.1     A   series  of   toxaphene  residues   have  been
      calculated using total peak area for comparison to the standard and
      also using  area of  the last   four peaks  only in  both  sample and
      standard.  The  agreement between the results obtained  by  the two
      methods  justifies the  use  of  the  latter method  for  calculating
      toxaphene  in  a  sample  where  the  early eluting  portion   of the
      toxaphene chromatogram is interfered with by other substances.
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            7.6;3.2     The  baseline for  methoxychlor superimposed  on
      toxaphene (Figure 8b) was constructed by overlaying the samples on
      a toxaphene standard of approximately the same concentration (Figure
      8a) and viewing the charts against a lighted background.

      7.6.4 Chlordane  is  a  technical  mixture  of  at least  11  major
components  and  30   or  more   minor  ones.     Gas  chromatography-mass
spectrometry  and  nuclear magnetic resonance  analytical techniques have
been applied  to  the  elucidation of the chemical  structures  of  the many
chlordane constituents.  Figure 9a  is  a chromatogram of standard chlor-
dane.  Peaks  E and F  are responses  to  trans-  and cis-chlordane,  respec-
tively.  These are the two major  components of technical  chlordane,  but
the exact percentage of each  in the technical  material is  not completely
defined and is not consistent from batch to batch.  Other labelled peaks
in  Figure  9a  are thought  to represent:   A,  monochlorinated adduct  of
pentachlorocyclopentadiene   with   cyclopentadiene;   B,   coelution   of
heptachlor and a-chlordene; C,  coelution of jS-chlordene and  y-chlordene;
D, a chlordane analog; G, coelution of cis-nonachlor and "Compound K," a
chlordane isomer.  The  right "shoulder" of peak F is   caused by trans-
nonachlor.

            7.6.4.1     The GC pattern of a chlordane residue may differ
      considerably from that  of the  technical  standard.  Depending on the
      sample substrate and  its  history,  residues of chlordane can consist
      of  almost   any  combination  of  constituents   from  the technical
      chlordane,   plant  and/or  animal   metabolites,  and  products  of
      degradation caused  by  exposure to  environmental factors   such  as
      water and sunlight.  Only limited  information is available  on which
      residue GC patterns are likely to  occur  in which samples types,  and
      even this information may not be applicable to a situation where the
      route of exposure  is unusual.  For example,  fish exposed to  a recent
      spill of  technical  chlordane  will  contain a  residue  drastically
      different from  a  fish  whose chlordane  residue was  accumulated  by
      ingestion of  smaller  fish  or of vegetation,  which  in turn  had
      accumulated  residues  because  chlordane  was  in the  water  from
      agricultural runoff.

            7.6.4.2     Because of this inability to predict a chlordane
      residue GC  pattern, it  is  not  possible to prescribe a single method
      for the  quantitation  of chlordane  residues.  The analyst must judge
      whether or not the residue's GC pattern  is sufficiently similar to
      that of a technical chlordane reference  material  to  use the latter
      as a reference standard for quantitation.

            7.6.4.3     When  the  chlordane residue  does  not  resemble
      technical chlordane,  but instead consists primarily  of individual,
      identifiable peaks,  quantitate each peak separately  against  the
      appropriate reference materials and report the individual residues.
      (Reference  materials  are  available  for  at   least  11 chlordane
      constituents, metabolites or degradation  products which may occur in
      the residue.)
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            7.6.4.4     When the GC pattern of the residue resembles that
      of technical chlordane, quantitate chlordane residues by comparing
      the total area of the chlordane  chromatogram from peaks A through F
      (Figure  9a)  in the  sample versus the  same  part of  the standard
      chromatogram.  Peak 6 may be obscured in a sample by the presence of
      other  pesticides.    If  G  is  not  obscured,   include  it   in  the
      measurement for both standard  and sample.  If the heptachlor epoxide
      peak is relatively small,  include it  as  part of the total chlordane
      area  for  calculation  of   the   residue.    If  heptachlor  and/or
      heptachlor  epoxide  are much  out of  proportion  as in  Figure  6j»
      calculate these separately  and subtract  their areas from total area
      to give a corrected chlordane area,   (Note that octachlor epoxide,
      a metabolite  of chlordane, can  easily  be mistaken  for heptachlor
      epoxide on a nonpolar GC column.)

            7.6.4.5     To  measure the total  area  of  the  chlordane
      chromatogram,  proceed  as  in  Sec. 7.6.2 on  toxaphene.   Inject  an
      amount  of  technical  chlordane  standard  which  will  produce  a
      chromatogram in which peaks E  and F are  approximately the same size
      as  those in  the sample chromatograms.   Construct the  baseline
      beneath the standard from the  beginning of peak A to the end of peak
      F as shown in Figure 9a,  Use the distance from the trough between
      peaks E and F  to the baseline in  the chromatogram of the standard to
      construct the baseline in the chromatogram of the sample.  Figure 9b
      shows  how the  presence of  toxaphene  causes  the  baseline  under
      chlordane to take an upward angle.  When the  size  of peaks E and F
      in standard and sample chromatograms are the same, the distance from
      the  trough  of  the  peaks  to  the  baselines  should  be  the  same.
      Measurement of chlordane area should be done  by total  peak area if
      possible.

            NOTE: A  comparison  has been  made  of  the  total   peak  area
                  integration method  and  the  addition  of peak  heights
                  method for several  samples  containing  chlordane.   The
                  peak  heights A,  B,   C, D,   E, and  F were measured  in
                  millimeters from peak maximum of each  to  the baseline
                  constructed under  the total chlordane area and were then
                  added together.   These  results  obtained  by the  two
                  techniques are  too close  to  ignore this method of "peak
                  height addition"  as  a means of calculating chlordane.
                  The technique has  inherent difficulties because not all
                  the peaks are symmetrical and not all are present in the
                  same ratio in standard and in sample.  This method does
                  offer a  means  of calculating results  if no means  of
                  measuring total area is practical.

      7.6.5 Polychlorinated biphenyls  {PCBs}:  Quantitation of residues of
PCB involves problems similar to  those  encountered in the quantitation of
toxaphene, Strobane, and chlordane.  In each case, the  chemical  is made up
of numerous compounds.   So the chromatograms are multi-peak.  Also in each
case, the chromatogram of  the residue  may not  match that of the standard.

            7.6.5.1     Mixtures  of  PCBs of various chlorine contents were
      sold for  many years  in  the  U.S.  by the Monsanto Co.  under  the

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                    tradename Aroclor (1200 series and 1016).  Though these Aroclors are
                    no  longer marketed, the  PCBs  remain  in  the environment  and are
                    sometimes found as residues in foods, especially fish.

                          7.6.5.2     PCS residues are quantitated by comparison to one
                    or more of the Aroclor materials, depending on the chromatographic
                    pattern of the residue.  A choice must be made as to which Aroclor
                    or mixture of Aroclors will produce a chromatogram most similar to
                    that of the residue.   This may  also involve a judgment about what
                    proportion of  the different  Aroclors to  combine  to  produce the
                    appropriate reference material.

                          7.6.5.3     Quantitate PCS residues by comparing total area or
                    height  of residue peaks  to  total  area of  height  of  peaks  from
                    appropriate Aroclor(s) reference materials,  Heasure total area or
                    height  response  from common baseline  under all peaks.   Use  only
                    those   peaks   from  the   sample   that   can  be   attributed  to
                    chlorobiphenyls.    These  peaks  must  also  be  present  in  the
                    chromatogram of the reference materials.  Mixtures  of Aroclors may
                    be required to provide the best match of 6C patterns of sample and
                    reference.

                    7.6.6 DDT:  DDT found  in  samples often  consists of  both o,p'- and
              p,p'-DDT,   Residues  of DDE  and  ODD  are also frequently  present.   Each
              isomer of  DDT and  its metabolites  should be  quantitated  using  the  pure
              standard of that compound and reported as such.

                    7.6.7 Hexachlorocyclohexane   {BHC,  from the  former name,  benzene
              hexachloride):  Technical  grade BHC is a cream-colored  amorphous  solid
\            with a very  characteristic musty odor; it consists of a  mixture of six
  %           chemically distinct isomers and one or more heptachloro-cyclohexanes and
              octachloro-cyclohexanes.

                          7.6.7.1     Commercial   BHC  preparations   may show  a  wide
                    variance  in  the percentage  of   individual  isomers  present.    The
                    elimination rate of the isomers  fed  to rats was 3 weeks for the a-,
                    7-,  and  5-isomers  and 14 weeks for the /3-isomer.   Thus it may be
                    possible to have any combination of the various isomers in different
                    food commodities.  BHC found in dairy products usually has a large
                    percentage of /S-isomer.

                          7.6.7.2     Individual  isomers (a, /3,  7, and s) were injected
                    into   gas   chromatographs  equipped   with   flame   ionization,
                    raicrocoulometric, and electron capture detectors.  Response for the
                    four isomers is  very nearly  the same whether flame ionization or
                    microcoulometric GLC is used.  The a-, 7-, and 5-isomers show equal
                    electron  affinity.   /3-BHC shows a  much weaker  electron  affinity
                    compared to the other isomers.

                          7.6.7.3     Quantitate  each  isomer   (a,   /S,  7,   and  5)
                    separately against a standard of the respective pure isomer,  using
                    a GC column which separates all  the isomers from one another.
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8.0   QUALITY CONTROL

      8.1   Refer  to Chapter  One  for specific  quality  control  procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized.   If extract cleanup was performed,  follow the QC
in Method 3600 and in the specific cleanup method.

      8.2   Quality control  required to evaluate the GC system operation is found
in Method 8000.

            8.2.1 The quality  control  check sample  concentrate  (Method  8000)
      should  contain  each  single-component  parameter  of  interest  at  the
      following  concentrations   in  acetone  or  other water  miscible  solvent:
      4,4'-DDD, 10 mg/L; 4,4'-DDT, 10 mg/L; endosulfan II,  10 rag/L; endosulfan
      sulfate,  10  mg/L;  endrin,  10  mg/L;  and   any  other  single-component
      pesticide, 2 mg/L.  If this method is only to be used  to analyze for PCBs,
      chlordane, or  toxaphene, the  QC  check sample concentrate should contain
      the most representative multi-component parameter at a concentration of 50
      mg/L in acetone.

            8.2.2 Table 3 indicates  the QC  acceptance criteria for this method.
      Table 4 gives method accuracy  and precision as  functions of concentration
      for the analytes of interest.  The contents of  both Tables should be used
      to evaluate a laboratory's  ability to perform and generate acceptable data
      by this method.

      8,3   Calculate surrogate  standard recovery  on all samples, blanks,  and
spikes.   Determine  if  the  recovery is within  limits (limits established  by
performing QC procedures outlined in Method 8000).

            8.3.1 If recovery is not within limits, the following is required.

                  *     Check to  be sure there  are no  errors in  calculations,
                        surrogate solutions and  internal standards. Also, check
                        instrument performance.

                  •     Recalculate the data and/or reanalyze the extract if any
                        of the above checks reveal  a problem.

                  •     Reextract and  reanalyze the sample  if none of the above
                        are  a   problem  or  flag   the  data  as  "estimated
                        concentration".

      8.4   GC/HS confirmation;   Any compounds confirmed by  two columns may also
be confirmed by GC/MS if the concentration  is sufficient for detection by GC/MS
as determined by the laboratory generated detection limits.

            8.4.1 The GC/MS would normally require a minimum concentration of 10
      ng/^L in the final extract, for each single-component compound.

            8.4.2 The pesticide extract and  associated blank should be analyzed
      by GC/MS as per Sec. 7.0 of Method 8270.
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            8.4.3 The  confirmation  may be  from  the  GC/MS  analysis  of the
      base/neutral-acid extractables extracts  (sample and blank).  However,  if
      the  compounds are  not  detected  in  the  base/neutral-acid  extract even
      though the concentration is high enough,  a GC/MS analysis of the pesticide
      extract should be performed.

            8.4.4 A reference standard of the compound must  also be analyzed  by
      GC/MS.  The  concentration of the reference  standard  must be  at a  level
      that  would  demonstrate  the  ability  to  confirm  the  pesticides/PCBs
      identified by fiC/ECD,


9.0   METHOD PERFORMANCE

      9.1   The method was tested by 20  laboratories  using organic-free reagent
water, drinking water,  surface water, and three industrial wastewaters spiked  at
six concentrations.  Concentrations used in the study ranged  from 0,5 to 30 ng/l
for single-component pesticides and from 8.5  to  400 fj.g/1  for multi-component
parameters.  Single operator precision, overall precision,  and method accuracy
were  found  to  be directly related to  the concentration of  the  parameter and
essentially independent of the sample matrix. Linear equations to describe these
relationships for an electron capture detector are presented in Table 4.

      9.2   The accuracy and precision obtained will be determined by the sample
matrix,  sample-preparation   technique,  optional   cleanup   techniques,   and
calibration procedures used.


10.0  REFERENCES

\,    U.S.   EPA,  "Development  and Application  of  Test Procedures  for Specific
      Organic Toxic Substances  in Wastewaters,  Category  10: Pesticides and
      PCBs," Report for EPA Contract 68-03-2605.

2.    U.S.   EPA,  "Interim Methods  for  the  Sampling  and Analysis of Priority
      Pollutants in  Sediments and Fish Tissue,"  Environmental Monitoring and
      Support Laboratory, Cincinnati, OH 45268, October 1980.

3.    Pressley,  T.A.,  and J.E.  Longbottom,  "The Determination of Organohalide
      Pesticides and PCBs in Industrial and Municipal Wastewater:  Method 617,"
      U.S.  EPA/EMSL, Cincinnati, OH, EPA-600/4-84-006,  1982.

4.    "Determination  of  Pesticides and  PCB's  in  Industrial  and  Municipal
      Wastewaters,    U.S.   Environmental  Protection Agency,"   Environmental
      Monitoring and Support Laboratory, Cincinnati, OH 45268, EPA-600/4-82-023,
      June 1982.

5.    Goerlitz,  D.F. and L.M.  Law,  Bulletin  for Environmental Contamination and
      Toxicology, 6, B, 1971.

6.    Burke, J.A.,  "Gas Chromatography for Pesticide  Residue Analysis;  Some
      Practical  Aspects,"  Journal of the  Association  of  Official  Analytical
      Chemists,  48, 1037, 1965.


                                  8080A - 13                        Revision 1
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7.    Webb, R.G.  and A.C.  McCall,  "Quantitative  PCB  Standards  for  Electron
      Capture Gas Chromatography," Journal of Chromatographic Science, H, 366,
      1973.

8.    Millar,  J.D.,  R.E.  Thomas  and  H.J. Schattenberg, "EPA Method  Study 18,
      Method 608: Organochlorine Pesticides  and PCBs,"  U.S.  EPA/EMSL,  Research
      Triangle Park, NC, EPA-600/4-84-061,  1984.

9.    U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
      Analysis of Pollutants Under the Clean Water Act;  Final  Rule and Interim
      Final Rule and Proposed Rule,"  October 26,  1984.

11.    U.S. Food and Drug Administration, Pesticide Analytical Manual,  Vol.  1,
      June 1979.

12.    Sawyer,  L.D., JAOAC, 56, 1015-1023 (1973),  61 272-281  (1978),  61 282-291
      (1978).

13.    Stewart, 0.  "EPA Verification Experiment  for Validation of  the SQXTEC® PCB
      Extraction Procedure";  Oak Ridge  National  Laboratory, Oak Ridge,  TN,
      37831-6138; October 1988.
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                                   TABLE 1.
                   GAS CHROMATOGRAPHY OF PESTICIDES AND RGBs'
Analyte
Aldrin
a-BHC
/3-BHC
5-BHC
-y-BHC (Lindane)
Chlordane (technical)
4, 4' -ODD
4,4'-DDE
4, 4' -DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Methoxychlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Retention
Col. 1
2.40
1.35
1,90
2,15
1.70
e
7.83
5.13
9.40
5.45
4.50
8.00
14.22
6.55
11.82
2.00
3.50
18.20
e
e
e
e
e
e
e
e
time din)
Col, 2
4.10
1.82
1.97
2.20
2.13
e
9.08
7.15
11.75
7.23
6.20
8.28
10.70
8.10
9.30
3.35
5.00
26.60
e
e
e
e
e
e
e
e
Method
Detection
limit (MiA)
0.004
0.003
0.006
0.009
0.004
0.014
0.011
0.004
0.012
0.002
0.014
0.004
0.066
0.006
0.023
0.003
0.083
0.176
0.24
nd
nd
nd
0.065
nd
nd
nd
"U.S.  EPA.   Method  617.   Organochlorine  Pesticides and PCBs.
Monitoring and Support Laboratory, Cincinnati, Ohio 45268.

e  =  Multiple peak response.

nd = not determined.
 Environmental
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                                  TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQLs) FOR VARIOUS MATRICES"
        Matrix                                                Factor
        Ground water                                               10
        Low-concentration soil  by sonication with GPC cleanup     670
        High-concentration soil  and sludges by sonication      10,000
        Non-water miscible waste                              100,000
           EQL =  [Method detection limit (see Table 1)]  X [Factor found in this
           table].   For  non-aqueous  samples, the  factor  is on  a  wet-weight
           basis.  Sample EQLs are highly matrix-dependent.  The EQLs listed
           herein are  provided for guidance  and  may not always  be achievable.
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                                   TABLE 3.
                            QC ACCEPTANCE CRITERIA8
Analyte
                        Test
                        cone.
Limit
for s
Range
for x
Range
P, Ps
Aldrin
a-BHC
j8-BHC
S-BHC
7-BHC
Chlordane
4,4'-DDD
4,4'-DDE
4,4f-DDT
Dieldrin
Endosulfan
Endosulfan
Endosulfan
Endrin
Heptachlor
Heptachlor
Toxaphene
PCB-10I6
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
s ^
X
P> P8 =
D
2.0
2.0
2.0
2.0
2.0
50
10
2.0
10
2.0
I 2.0
II 10
Sulfate 10
10
2.0
epoxide 2.0
50
50
50
50
50
50
50
50
0.42
0.48
0.64
0.72
0.46
10.0
2.8
0.55
3.6
0.76
0.49
6.1
2.7
3.7
0.40
0.41
12.7
10.0
24.4
17.9
12.2
15.9
13.8
10.4
1.08-2.24
0,98-2.44
0.78-2.60
1.01-2.37
0.86-2.32
27.6-54.3
4.8-12.6
1.08-2.60
4.6-13.7
1.15-2.49
1.14-2.82
2.2-17.1
3.8-13.2
5.1-12.6
0.86-2.00
1.13-2.63
27.8-55.6
30.5-51.5
22.1-75.2
14.0-98.5
24.8-69.6
29.0-70.2 t
22.2-57.9
18.7-54,9
Standard deviation of four recovery measurements, in
Average recovery for four
Percent recovery measured
Detected; result must be
42-122
37-134
17-147
19-140
32-127
45-119
31-141
30-145
25-160
36-146
45-153
D-202
26-144
30-147
34-111
37-142
41-126
50-114
15-178
10-215
39-150
38-158
29-131
8-127
M9/L.
recovery measurements, in fj,g/l.
-
greater than

zero.


"Criteria from 40 CFR Part 136 for Method 608.  These criteria are based directly
upon the method performance  data in  Table 4.   Where necessary, the limits for
recovery  have  been  broadened  to  assure  applicability  of  the  limits  to
concentrations below those used  to develop Table 4.
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                                   TABLE 4.
         METHOD ACCURACY AND  PRECISION AS  FUNCTIONS OF CONCENTRATION*
Analyte
Aldrin
a-BHC
jS-BHC
5-BHC
-y-BHC
Chlordane
4, 4' -ODD
4, 4' -DDE
4, 4' -DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrin
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Accuracy, as
recovery, x'
(Mfl/L)
0.81C+0.04
0.84C+0.03
0.81C+0.07
0.81C+0.07
0.82C-0.05
0.82C-0.04
0.84C+0.30
0.85C+0.14
0.93C-0.13
0.90C4Q.02
0.97C+0.04
0.93C+0.34
0.89C-0.37
0.89C-0.04
0.69C+0.04
0.89C+0.10
0.80C+1.74
0.81C+0.50
0.96C40.65
0.91C+10.79
0.91C+10.79
0.91C+10.79
0.91C+10.79
0.91C+10.79
Single analyst
precision, sr'
(M9/L)
O.lSx-0.04
0.13X40.04
0.22X40.02
0.18X4-0.09
0.12X+0.06
0.13X+0.13
0.20X-0.18
0.13X+0.06
0.17x+0.39
0.12X+0.19
O.lOx+0.07
0.41X-0.65
O.lSx+0.33
0.20X+0.25
0.06X+0.13
O.lBx-0.11
0.09X+3.20
0.13X+0.15
0.29X-0.76
0.21X-1.93
0.21X-1.93
0.21X-1.93
0.21X-1.93
0.21X-1.93
Overal 1
precision,
S' (M9/L)
0.20X-0.01
0.23X-0.00
0.33X-0.95
0.25X+0.03
0.22X+0.04
O.lSx+0.18
0.27X-0.14
0.28X-0.09
O.Slx-0.21
0.16X+0.16
0.18X+0.08
0.47X-0.20
0. 24X+0.35
0.24X+0.25
0.16X+0.08'
0.25X-0.08
0.20X40.22
0.15X+0.45
0.35X-0.62
O.Slx+3.50
O.Slx+3.50
0.31X+3.50
0.31X43.50
0.31x43.50
*/

S'

c

x
Expected  recovery  for  one  or  more  measurements  of  a  sample
containing concentration C, in M9/L.

Expected single  analyst  standard deviation of measurements  at an
average concentration of x, in M9/L.

Expected inter!aboratory standard deviation of measurements  at an
average concentration found of x, in j*g/L.

True value for the concentration, in /*g/L.

Average recovery  found for measurements  of samples containing a
concentration of C, in
                                  8080A - 18
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                Figure 1
      Gas Chromatogram of  Pesticides
Column:    1.5% SP-2250+
           1.95% SP-2401 on Supelcoport
Temperature: 200°C
Detector:  Electron Capture
              I        13
       ftfTfNTION TIME (MINUTtS)
II
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            Figure 2
  Gas Chromatogram of Chlordane
Column:    1.5% SF-2250+
           1.95% SP-2401  on Supelcoport
Temperature:  200°C
Detector:  Electron Capture •
 4         •

HtTiNTIOM TIMf
                       12
II
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         Figure 3
Sas Chromatogram of Toxaphene
          Column:    1.5% SP-2250+
                     1.95% SP-2401  on Supelcoport
          Temperature:  200°C
          Detector:  Electron Capture
10
            14       It

               (MlNUTfJ)
22
2t
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                 Figure 4
      Gas  Chromatogram of Aroclor 1254
Column:    1.5* SP-2250-t-
           1.95* SP-2401 on Supelcoport
Temperature: 200°C
Detector:  Electron Capture
2         I        l§        M

            MfTIMTlON TMfll
                                     It
  22
                8080A - 22
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                     Figure 5
           Gas Chromatogram of Aroclor 1260
Column:    1.5% SP-2250+
           1.95% SP-2401  on Supelcoport
Temperature:  200°C
Detector:  Electron Capture
  10       14
RfTfNTlON T1MI
                                II
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                             Figure 6
         J..L
Fig.6--Baseline construction for some typical gas chromotagraphic peaks.
a: symmetrical separated flat baseline; b and c:  overlapp flat baseline;
d: separated (pen does not return to baseline between peaks);  e: separated
sloping baseline; €: separated (pen. goes below baseline between peaks);
g: a- and 7-BHC  sloping baseline;  h: a-,ft- and 7-BHC sloping  baseline;
i: chlordane flat baseline; j: heptachlor and heptachlor epoxide super-
imposed on chlordane; k: chair-shaped peaks,  unsymmetrical peak;
1: p,p'-DDT superimposed on toxaphene.
                           8080A - 24
    Revision 1
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                               Figure  7
 Fig.- 7a -- Baseline construction for multiple residues with standard
                              toxaphene.
Fig.- 7b -- Baseline construction for multiple residues with toxaphene,
                      DDE and o,p' -, and p,p'-DDT
                               8080A  - 25
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                                  Figure 8
  fig.- 8a -- Baseline construction for multiple residues: standard toxaphene,
Pig,- 8to -- Baselina construction for multiple rasidusBs tics fcran with BHC,
                     toxaphene, DOT, and methoxychlor.
                               8080A -  26
    Revision 1
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                               Figure 9
Fig.- 9a -- Baseline construction for multiple residues;  standard ehlordane
Fig.- 9b -- Baseline construction for multiple residues: rice bran with
                     ehlordanei toxaph«ne, and DDT.
                              8030A - 27
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                                METHOD 3080A
       OR6ANOCHLORINE  PESTICIDES AND POLYCHLORINATED BIPHEMYLS
                           BY GAS CHROMATOGRAPHY
       Stan
J
     7.1.1 Choose
appropriate extraction
      procedure.
   7.1.2 Exchange
 extraction solvent
     to hsxane.
       7.2 Set
  chromatooraphic
      conditions.
     7.3 Refer to
   Method 8000 for
  proper calibration
     techniques.
                        7.3.2 Prime or
                       deactivate the GC
                        column prior to
                       daily calibration.
                         7.4 Perform
                         GC analysis.
                            7.4.8
                           is peak
                         detection and
                         identification
                          prevented?
                           7.6.1  Do
                         residues  Have
                          two or  more
                         components?
   7.5.1  Cleanup
 using Method 3620
or 3660 if necessary.
    7.6 Calculate
   concentrations.
                                S080A -  28
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                                  METHOD 8081

             ORGANOCHLORINE PESTICIDES  AND PCBs  AS  AROCLORS  BY  GAS
                  CHROHAT06RAPHY: CAPILLARY COLUMN TECHNIQUE
1.0   SCOPE AND APPLICATION

      1.1   Method  8081  is used  to determine  the  concentrations of  various
organochlorine pesticides and polychlorinated biphenyls (PCBs) as Aroclors, in
extracts from solid and liquid matrices.  Open-tubular, capillary columns were
employed with  electron capture detectors  (ECO) or electrolytic  conductivity
detectors (ELCD).  When compared to the packed columns, these fused-silica, open-
tubular  columns  offer  improved  resolution,   better  selectivity,  increased
sensitivity, and faster analysis.  The list below is annotated to show whether a
single- or dual-column analysis system was used to identify each target analyte.
            Compound Name
CAS Registry No.
AldrinB-b
Aroclor-1016"'b
Aroclor-1221*-"
Aroclor-iaSZ8-6
Aroclor-I242a'b
Aroclor-1248"'b
Aroclor-1254a'b
Aroclor-1260°'b
a-BHC*"
/3-BHCa>b
-y-BHC (Lindane)"-"
S-BHCa'b
Chlorobenzilateb
a-Chlordaneb
7-Chlordane"'b
DBCPb
4,4'-DDDa'b
4»4'-DDE*-b
4,4'-DDTa>b
Diallateb
Dieldrina'b
Endosulfan I"'b
Endosulfan II"'b
Endosulfan sulfatea-b
Endrina-b
Endrin aldehyde"'b
Endrin ketoneb
309-00-2
12674-11-2
1104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
319-84-6
319-85-7
58-89-9
319-86-8
510-15-6
5103-71-9
5103-74-2
96-12-8
72-54-8
72-55-9
50-29-3
2303-16-4
60-57-1
959-98-8
33213-65-9
1031-07-8
72-20-8
7421-93-4
53494-70-5
                                   8081  -  1
                          Revision 0
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            Compound Name                  CAS  Registry No.
              Heptachlora-b                      76-44-8
              Heptachlor epoxide8'"            1024-57-3
              Hexachlorobenzeneb               118-74-1
              Hexachlorocyclopentadi eneb        77-47-4
              Isodrin"                         465-73-6
              Kepone"                          143-50-0
              Methoxychlor"-"                    72-43-5
              Toxaphenea'b                     8001-35-2
                Single-column analysis
                Dual-column analysis
      1,2   The analyst must select columns, detectors and calibration procedures
most  appropriate  for the specific  analytes  of interest in  a  study.   Matrix-
specific performance data must be established and the stability of the analytical
system and instrument calibration must be established for each analytical matrix
(e.g., hexane solutions from sample extractions, diluted oil samples, etc.).

      1.3   Although  performance  data  are  presented for  many  of  the listed
chemicals,  it  is  unlikely that  all of them  could  be determined  in  a single
analysis.   This limitation results because the chemical  and chromatographic
behavior  of many  of  these  chemicals can  result  in  co-elution.    Several
cleanup/fractionatlon  schemes are  provided  in  this  method  and in Method 3600.
Any chemical is a potential method  interference when it is not a target analyte.

      1.4   Several multi-component mixtures (i.e.,  Aroclors  and  Toxaphene) are
listed as target compounds.  When  samples  contain more than one multi-component
analyte, a  higher  level  of analyst expertise is  required to attain acceptable
levels of qualitative  and  quantitative analysis.   The  same  is true of multi-
component analytes  that  have been subjected to environmental  degradation or
degradation by  treatment  technologies.  These result  in "weathered" Aroclors (or
any other multi-component mixtures) that may have significant differences in peak
patterns than those of standards.   In these cases, individual congener analyses
may be preferred over total mixture analyses.

      1.5   Compound identification based on  single column analysis should be
confirmed on a second column,  or should  be  supported  by  at  least  one other
qualitative technique.  This method describes analytical  conditions for a second
gas chromatographic column that can be used to confirm the measurements made with
the primary column.   GC/MS Method 8270 is also recommended  as a confirmation
technique if sensitivity permits (Sec.  8).

      1.6   This method  describes  a dual  column option.   The  option  allows a
hardware configuration of two analytical  columns joined to a  single injection
port.  The  option  allows one injection to  be used for  dual column analysis.

                                   8081 -  2                         Revision 0
                                                                 September 1994

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Analysts are cautioned that the dual column option may not be  appropriate  whin
the instrument is subject to mechanical stress, many samples  are to be run  in  a
short period, or when contaminated samples are analyzed.

      1.7   This method  is restricted to  use by or  under the supervision of
analysts  experienced  in  the  use  of  a  gas  chromatograph  (GC)  and  in   the
interpretation of gas chromatograms. Each  analyst must demonstrate the  ability
to generate acceptable results with this method.

      1.8   Extracts suitable for analysis by this method may  also be analyzed
for organophosphorus pesticides  (Method  8141).   Some  extracts may  also be
suitable for triazine herbicide  analysis,  if low recoveries  (normally  samples
taken  for triazine analysis must be preserved) are not a problem.
      1.9
           •"             *         ,._-.-- ,     _

The following compounds lay also be determined using this method:
            Compound Name
                              CAS Registry No,
             Alachlor8-"
             Captafol"
             Captanb
             Chloronebb
             Chloropropylateb
             Chlorothalonil"
             DCPAb
             Dichloneb
             Dicofolb
             Etridiazoleb
             Halowax-1000"
             Halowax-1001b
             Halowax-1013b
             Halowax-1014b
             Halowax-1051b
             Halowax-1099b
             Mirexb
             Nitrofenb
             PCNBb
             Perthaneb
             Propachlorb
             Strobaneb
             trans-Nonachlorb
             tra/is-Permethrinb
             Trifluralinb
                                15972-60-8
                                2425-06-1
                                 133-06-2
                                2675-77-6
                                99516-95-7
                                1897-45-6
                                1861-32-1
                                 117-80-6
                                 115-32-2
                                2593-15-9
                                58718-66-4
                                58718-67-5
                                12616-35-2
                                12616-36-3
                                2234-13-1
                                39450-05-0
                                2385-85-5
                                1836-75-5
                                  82-68-8
                                  72-56-0
                                1918-16-17
                                8001-50-1
                                39765-80-5
                                51877-74-8
                                1582-09-8
               Single-column  analysis
               Dual-column  analysis
                                   8081  -  3
                                                        Revision 0
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2.0   SUMMARY OF METHOD

      2.1   A measured volume or weight of sample (approximately 1 L for liquids,
2 g  to  30 g for solids)  is extracted  using the  appropriate sample extraction
technique.  Liquid samples are extracted at neutral pH with methylene chloride
using either  a  separator^ funnel  (Method 3510) or a continuous liquid-liquid
extractor (Method 3520).  Solid samples are  extracted with hexane-acetone (1:1)
or  methylene  chloride-acetone (1:1)  using  either Soxhlet  extraction  (Method
3540), Automated Soxhlet (Method  3541), or Ultrasonic Extraction  (Method 3550).
A variety of cleanup steps may be  applied to the extract, depending on (1) the
nature  of the coextracted latrix  interferences  and (2) the  target analytes.
After cleanup, the extract  is  analyzed by  injecting a  l-yl sample into  a gas
chromatograph with  a narrow-   or  wide-bore  fused   silica capillary column  and
electron  capture  detector (GC/ECD)  or an  electrolytic  conductivity  detector
(GC/ELCD).


3.0   INTERFERENCES

      3.1   Refer to Methods 3500  (Sec. 3,  in particular),  3600, and 8000.

      3.2   Sources of  interference  in this method can  be  grouped into  three
broad categories:  contaminated  solvents, reagents or sample processing hardware;
contaminated GC carrier gas, parts, column surfaces or detector surfaces; and the
presence  of coeluting compounds  in  the sample matrix  to  which the ECO  will
respond. Interferences coextracted from the  samples will vary considerably from
waste to waste.   While general  cleanup  techniques are referenced or provided as
part of this method, unique samples may require  additional cleanup approaches to
achieve desired degrees of discrimination and quantitation.

      3.3   Interferences  by  phthalate  esters   introduced   during   sample
preparation can  pose  a  major problem  in  pesticide  determinations.    These
materials may  be removed  prior  to  analysis  using  Gel  Permeation Cleanup  -
pesticide option  (Method  3640) or as  Fraction  III of the  silica  gel  cleanup
procedure (Method 3630).  Common  flexible plastics contain  varying amounts of
phthalate esters which are easily  extracted or leached from such materials during
laboratory operations.  Cross-contamination  of clean glassware routinely occurs
when plastics are handled during extraction steps, especially when solvent-wetted
surfaces are handled.  Interferences from phthalate esters can best be minimized
by avoiding contact with  any  plastic materials and checking  all  solvents  and
reagents for phthalate contamination.   Exhaustive cleanup of solvents,  reagents
and  glassware  may  be  required  to  eliminate  background  phthalate  ester
contamination.

      3.4   Glassware must be scrupulously cleaned.  Clean all glassware as soon
as possible after use  by  rinsing with the  last solvent  used.   This should be
followed by detergent  washing  with hot  water,  and rinses  with  tap water  and
organic-free reagent  water.  Drain  the  glassware and dry in  an oven  at 130°C for
several  hours  or  rinse with methanol  and drain.  Store dry glassware in a clean
environment.

      3.5   The presence  of elemental  sulfur will  result in  broad peaks  that
interfere with the detection of early-eluting organochlorine  pesticides.  Sulfur
                                                   i

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contamination should be expected with sediment samples.  Method 3660 is suggested
for removal  of  sulfur.  Since the recovery  of Endrin  aldehyde (using the TBA
procedure)  is drastically reduced,  this compound  must  be  determined  prior to
sulfur cleanup.

      3.6   Waxes, lipids, and other high molecular weight co-extractables can
be removed  by Gel-Permeation Cleanup (Method 3640).

      3.7   It  may  be difficult to  quantitate Aroclor  patterns  and  single
component  pesticides together.   Some  pesticides  can  be removed  by  sulfuric
acid/permanganate cleanup (Method 3665)  and  silica  fractionation (Method 3630).
Guidance on the identification of PCBs is given in Sec. 7.

      3.8   The following target  analytes coelute using single column analysis:

            DB 608      Trifluralin/Dial!ate isomers
                        PCNP/Dichlone/Isodrin
                        DDD/Endosulfan II

            DB 1701     Captan/Chlorobenzilate
                        Captafol/Mirex
                        DDD/Endosulfan II
                        Methoxychlor/Endosulfan sulfate

            3.8.1 Other  halogenated  pesticides  or  industrial  chemicals  may
      interfere  with   the   analysis   of  pesticides.     Certain  co-eluting
      organophosphorus  pesticides  are  eliminated  by  the  Gel   Permeation
      Chromatography  cleanup  -  pesticide  option  (Method  3640),    Co-eluting
      chlorophenols are eliminated by Silica gel (Method 3630), Florisil (Method
      3620), or Alumina (Method 3610)  cleanup.

      3.9   The following compounds coelute using the dual column analysis.  Two
temperature programs are provided for the same pair of columns as  option 1 and
option Z for dual  column analysis.  In general, the DB-5 column resolves fewer
compounds that the DB-1701:

            3.9.1 DB-5/DB-1701, thin  film,  slow ramp:  See  Sec. 7  and  Table 6.

                  DB-5  trans-Permethrin/Heptachlor epoxide
                        Endosulfan I/er-Chlordane
                        Perthane/Endrin
                        Endosulfan II/Chloropropylate/Chiorobenzi1 ate
                        4,4'-DDT/Endosulfan sulfate
                        Methoxychlor/Dicofol

            Perthane/Endrin  and  Chiorobenzilate/Endosulfan  II/Chloropropylate
      will   also co-elute  on  DB-5  after   moderate  deterioration  in  column
      performance.
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                  DB-1701     Chlorothalonil/B-BHC
                              d-BHC/DCPA/trans-Permethrin
                              o-Chlordane/trans-Nonachlor
                              Captan/Dieldrin
                              Chlorobenzilate/Chioropropylate

            Chlorothalonil/B-BHC and 
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      methylpolysiloxane  (DB  608,  SPB 608, or equivalent),  25 pm
      coating thickness, 1 fitn film thickness.

            4.1.1.1.3   Narrow bore columns should be installed in
      split/split!ess (Grob-type) injectors.

      4.1.1,2     Wide-bore columns

            4.1.1.2.1   Column 1 - 30  m x 0.53 ran ID fused silica
      capillary  column  chemically bonded  with  35  percent phenyl
      methylpolysiloxane (DB 608, SPB 608, RTx-35, or equivalent),
      0.5 fj,m or 0.83 Mm film thickness.

            4.1.1.2.2   Column 2 - 30  m x 0.53 mm ID fused silica
      capillary  column  chemically bonded  with  50  percent phenyl
      methylpolysiloxane  (DB  1701,  or  equivalent),  1.0  pm  film
      thickness.

            4.1.1.2.3   Column 3 - 30  m x 0.53 mm ID fused silica
      capillary column chemically bonded with SE-54 (DB 5, SPB 5,
      RTx5, or equivalent), 1.5 pm film  thickness.

            4.1.1.2.4   Wide-bore columns should be installed in 1/4
      inch injectors, with  deactivated  liners designed specifically
      for use with these columns.

4.1.2 Dual Column Analysis:

      4.1.2.1     Column pair  1:

            4.1.2.1.1   J&W Scientific press-fit  Y-shaped glass 3-
      way union splitter (J&W  Scientific, Catalog no. 705-0733) or
      Restek Y-shaped fused-silica connector  (Restek,  Catalog no.
      20405), or equivalent.

            4.1.2.1.2   30 m x  0.53 re ID DB-5   (J3AI Scientific),
      1.5 ^m film thickness,  or equivalent.

            4.1.2.1,3   30 m x 0.53 mm  ID DB-1701  (J&W Scientific),
      1.0 pm film thickness,  or equivalent.

      4.1.2.2     Column pair  2:

            4.1.2.2.1    Splitter  2 -  Supelco 8 in. glass injection
      tee,  deactivated   (Supelco,   Catalog  no.   2-3665H),   or
      equivalent.

            4.1.2.2.2   30 m x  0.53 m ID DB-5   (J&W Scientific),
      0.83 Mm film thickness,  or equivalent.

            4.1.2.2.3   30 m x 0.53 mm  ID DB-1701  (J&W Scientific),
      1.0 fim film thickness,  or equivalent.
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            4.1.3 Column  rinsing  kit:  Bonded-phase  column  rinse  kit  (J&W
      Scientific, Catalog no. 430-3000 or equivalent).

      4.2   Glassware  (see  Hethods 3510, 3520, 3540,  3541,  3550,  3630, 3640,
3660, and 3665 for specifications).

      4.3   Kuderna-Danish (K-D) apparatus. See extraction methods for specifics.


5.0   REAGENTS

      5.1   Reagent or  pesticide  grade chemicals shall be used  in  all  tests.
Unless otherwise indicated,  it is  intended  that  all  reagents shall  conform to
specifications of the Committee on Analytical  Reagents  of the American Chemical
Society, where such  specifications are available.   Other grades may  be used,
provided it is first ascertained that the reagent  is of  sufficiently high purity
to permit its use without lessening the accuracy of the determination.

      NOTE: Store  the  standard  solutions   (stock,   composite,  calibration,
            internal, and surrogate) at 4°C  in Teflon-sealed  containers in the
            dark.  When a lot of standards is prepared, it is recommended that
            aliquots of that lot be stored in individual small  vials.  All stock
            standard  solutions must  be replaced  after one  year or  sooner  if
            routine  QC (Sec.  8)   indicates  a problem.   All  other  standard
            solutions must be replaced after six months or sooner if routine QC
            (Sec. 8) indicates a problem.

      5.2   Solvents and reagents:  As  appropriate for  Method 3510,  3520, 3540,
3541, 3550,  3630,   3640,  3660, or 3665: n-hexane,  diethyl   ether,  methylene
chloride, acetone,  ethyl acetate,  and isooctane (2,2,4-trimethylpentane).  All
solvents should  be  pesticide quality  or  equivalent, and each lot of  solvent
should be determined to be phthalate free. Solvents must be exchanged to hexane
or isooctane prior to analysis.

            5.2.1 Organic-free reagent water:  All references to water in this
      method refer to organic-free reagent water as  defined  in Chapter One.

      5.3   Stock standard  solutions  (1000  mg/L): Can be prepared from pure
standard materials  or can be purchased as certified  solutions.

            5.3.1 Prepare stock standard  solutions by accurately weighing about
      0.0100 g of pure compound.   Dissolve the compound in isooctane  or hexane
      and dilute  to volume in a 10-mL volumetric  flask   If  compound  purity  is
      96 percent  or  greater,  the  weight can be usec without  correction  to
      calculate the concentration  of the  stock standard solution.  Commercially
      prepared stock standard solutions can be used at any concentration if they
      are certified by the manufacturer or by an  independent  source.

            5.3.2 8-BHC,  Dieldrin,  and  some  other  standards may  not  be
      adequately  soluble  in  isooctane.   A small  amount of acetone or  toluene
      should be used to dissolve  these compounds  during the  preparation of the
      stock standard solutions.
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      5.4   Composite  stock  standard: Can  be  prepared from  individual  stock
solutions.  For composite  stock standards  containing less than 25 components,
take exactly 1 ml of each individual stock solution at 1000 mg/L, add solvent,
and mix the solutions in a 25-mL volumetric flask.  For example, for a composite
containing 20 individual standards, the resulting concentration of  each component
in the mixture, after the volume is adjusted to 25 ml, will be  1 mg/25 ml.  This
composite solution can be further diluted to obtain the desired concentrations.
For composite stock  standards containing more than 25  components,  use volumetric
flasks of the appropriate volume  (e.g.,  50 ml,  100 ml).

      5,5   Calibration  standards should  be  prepared  at a  minimum of  five
concentrations by dilution  of  the composite stock standard with isooctane or
hexane.    The  concentrations   should  correspond  to  the expected  range  of
concentrations found in real  samples  and should bracket the linear range of the
detector.

            5.5.1 Although all  single component  analytes  can  be  resolved  on a
      new  35  percent  phenyl   methyl  silicone   column   (e.g.,  DB-608),   two
      calibration mixtures should be  prepared for the  single component analytes
      of this method.

            5.5.2 This  procedure  is  established  to  (1)  minimize  potential
      resolution and quantitation problems on confirmation columns or on older
      35  percent  phenyl methyl silicone  (e.g.  DB-608)  columns  and  (2)  allow
      determination of  Endrin and DDT breakdown for method QC (Sec.  8).

            5.5.3 Separate calibration standards  are  required for each  multi-
      component target  analyte, with  the exception of Aroclors 1016  and 1260,
      which can be run  as a mixture.

      5.6   Internal standard (optional):

            5.6.1 Pentachloronitrobenzene is suggested as an internal  standard
      for the single column analysis, when it is not considered to be a  target
      analyte.    l-Bromo-2-nitrobenzene  is  a  suggested  option.   Prepare  the
      standard to complement the concentrations found in Sec.  5.5.

            5.6.2 Hake  a solution of 1000 mg/L  of  l-bromo-2-nitrobenzene  for
      dual-column analysis.   Dilute  it  to 500 ng/^l for spiking, then use a
      spiking volume of 10 pi/ml  of extract.

      5.7   Surrogate  standards:   The  performance  of the  method  should  be
monitored  using  surrogate  compounds.   Surrogate standards  are  added to  all
samples, method blanks, matrix spikes, and calibration standards.

            5.7.1 For the single column analysis,  use decachlorobiphenyl  as the
      primary surrogate. However, if recovery is  low,  or late-eluting compounds
      interfere with  decachlorobiphenyl,  then tetrachloro-m-xylene  should be
      evaluated  as  a  surrogate.   Proceed  with  corrective  action  when  both
      surrogates are out of limits for a sample (Sec. 8.2).  Method  3500,  Sec.
      5, indicates the proper procedure  for preparing these surrogates.
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            5.7.2 For the dual column analysis make a solution of 1000 rag/L of
      4-chloro-3~nitrobenzotr1fluoride and dilute to 500 ng/^L.  Use a spiking
      volume of 100 ^L  for  all aqueous sample.   Store the spiking solutions
      at 4°C in Teflon-sealed containers  in the dark.
6.0   SAMPLE COLLECTION, PRESERVATION AND HANDLING

      6.1 "  See Chapter 4, Organic Analytes, Sec. 4.

      6.2   Extracts must be stored under refrigeration in the dark and analyzed
within 40 days of extraction.


7.0   PROCEDURE

      7.1   Extraction:

            7.1.1 Refer to Chapter Two  and Method 3500 for guidance in choosing
      the appropriate  extraction procedure.   In  general,  water samples  are
      extracted at a neutral  pH with methylene chloride as a  solvent  using a
      separatory funnel  (Hethod  3510)  or a  continuous liquid-liquid extractor
      (Method 3520).   Extract  solid samples with hexane-acetone (1:1) using one
      of the Soxhlet extraction (Method 3540 or 3541) or ultrasonic  extraction
      (Method 3550) procedures.

            NOTE: Hexane/acetone (1:1)  may be more effective as  an  extraction
                  solvent  for  organochlorine  pesticides  and  PCBs  in  some
                  environmental   and  waste   matrices  than   is   methylene
                  chloride/acetone (1:1).    Use of hexane/acetone  generally
                  reduces the  amount  of co-extracted interferences and improves
                  signal/noise.

            7.1.2 Spiked samples are used to verify the applicability  of  the
      chosen extraction technique to each new  sample type.  Each sample  type
      must be spiked with  the compounds  of interest to determine the  percent
      recovery and the  limit of detection for that  sample (Sec.  5).  See Method
      8000 for guidance on demonstration  of  initial method  proficiency as  well
      as guidance on matrix spikes for  routine  sample analysis.

      7.2   Cleanup/Fractionation:

            7.2.1 Cleanup procedures  may not be  necessary for a relatively clean
      sample matrix,  but most extracts from environmental and waste samples will
      require additional  preparation before analysis.   The specific  cleanup
      procedure used will  depend on the nature of the sample to be analyzed and
      the data quality  objectives for  the measurements.  General  guidance  for
      sample extract cleanup is provided  in  this section and in Method 3600.

                  7.2.1.1     If a sample is of biological  origin, or contains
            high molecular weight materials, the use  of GPC  cleanup/pesticide
            option  (Method 3640)  is  recommended.    Frequently,  one  of  the
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            adsorption chromatographic cleanups may also be required following
            the GPC cleanup,

                  7.2.1,2     If only PCBs are to be measured in a sample, the
            sulfuric  acid/permanganate  cleanup (Method 3665}  is recommended.
            Additional cleanup/fractionation by Alumina Cleanup  (Method 3610),
            Silica-Sel Cleanup (Method 3630), or Florisil Cleanup  (Method 3620),
            may be necessary,

                  7.2.1,3     If both PCBs and  pesticides are to  be measured in
            the sample, isolation of the  PCB fraction by Silica Cleanup (Method
            3630) is recommended.

                  7.2.1.4     If only pesticides are to be measured, cleanup by
            Method 3620 or Method 3630 is recommended.

                  7.2.1.5     Elemental   sulfur,  which  may  appear  in  certain
            sediments  and  industrial  wastes,   interferes  with  the  electron
            capture gas chromatography of certain pesticides.  Sulfur should be
            removed by the technique described  in  Method  3660,  Sulfur Cleanup.

      7.3   SC Conditions:     This method allows the analyst to choose between
a single column or  a  dual column configuration in the injector  port.   Either
wide- or narrow-bore columns may be  used.   Identifications based on retention
times from  a  single column must  be confirmed  on a  second  column or  with an
alternative qualitative technique.

            7.3.1 Single Column Analysis:

                  7.3.1.1     This capillary GC/ECD method allows  the  analyst
            the option of using  0.25-0.32 mm ID capillary columns  (narrow-bore)
            or 0.53 mm ID capillary columns (wide-bore).   Performance data are
            provided   for  both  options.     Figures   1-6  provide   example
            chromatograms.

                  7.3.1.2     The use of narrow-bore columns is recommended when
            the analyst  requires greater chromatographic  resolution.  Use of
            narrow-bore columns  is  suitable for relatively clean samples or for
            extracts that have been  prepared with one or more  of the clean-up
            options referenced in the method.   Wide-bore columns  (0.53  mm) are
            suitable for more complex environmental  and waste matrices.

                  7,3.1.3     For the single column method of  analysis,  using
            wide-bore capillary columns,  Table  1  lists  average retention  times
            and method detection limits (MOLs) for the target analytes in  water
            and soil matrices.   For the single column method of analysis,  using
            narrow-bore capillary columns, Table 2 lists average retention times
            and method detection limits (MDLs) for the target analytes in  water
            and soil matrices.  The MDLs  for the components of a specific sample
            may differ from  those  listed in Tables  1  and  2 because they are
            dependent  upon the  nature of interferences  in the sample  matrix.
            Table 3 lists the  Estimated  Quantitation Limits (EQLs)  for  other
            matrices.   Table 4 lists  the  GC operating conditions for the single
            column method of analysis.

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      7.3.2 Dual Column Analysis:

            7.3.2.1     The dual-column/dual-detector  approach involves
      the use of two 30 m x 0.53 mm ID fused-silica open-tubular columns
      of different  polarities,  thus  different selectivities towards the
      target compounds. The columns are connected to an injection tee and
      ECD detectors.  Retention times for the organochlorine analytes on
      dual columns  are  in Table  5.   The  GC  operating conditions for the
      compounds in  Table  5  are in Table 6.   Multicomponent mixtures of
      Toxaphene and Strobane were  analyzed  separately  (Figures 7  and 8)
      using the GC operating conditions found in Table 7.  Seven Aroclor
      mixtures and six  Halowax mixtures were analyzed under the conditions
      outlined in Table 7 (Figures 9 through 21).  Figure 22 is a sample
      chrornatogram  for a  mixture of  organochlorine  pesticides.    The
      retention times  of the  individual components  detected  in  these
      mixtures are given in Tables 8 and 9.

                  7.3.2.1.1    Operating  conditions  for  a  more  heavily
            loaded DB-5/DB-1701 pair are given  in Table  7.   This  column
            pair   was   used   for  the   detection   of   multi component
            organochlorine compounds.

                  7.3.2.1.2   Operating  conditions   for  a  DB-5/DB-1701
            column pair with thinner  films,  a different type of splitter,
            and a  slower  temperature programming  rate are  provided  in
            Table  6.    These   conditions gave  better  peak shapes  for
            compounds such as  Nitrofen  and  Dicofol.   Table  5  lists the
            retention  times for the compounds  detected on  this  column
            pair.

7.4   Calibration:

      7.4.1  Prepare calibration standards using  the procedures in Sec. 5.
Refer to Method 8000 (Sec.  7)  for proper calibration techniques for both
initial   calibration  and calibration  verification.    The procedure  for
either  internal or external  calibration may  be used,  however, in  most
cases external standard calibration  is  used with Method 8081.  This is
because  of  the sensitivity  of  the  electron capture  detector and  the
probability  of  the internal  standard  being affected  by  interferences.
Because  several of the pesticides  may co-elute  on any single  column,
analysts should use two calibration mixtures (see Sec. 3.8).  The specific
mixture should be  selected to  minimize  the problem of peak overlap.

      NOTE:  Because of the sensitivity  of the electron  capture detector,
            the Injection  port and column should always be cleaned  prior
            to performing  the  initial  calibration.

            7.4.1.1     Method  8081   has  many  multi-component  target
      analytes.    For   this  reason,  the   target  analytes  chosen  for
      calibration   should  be  limited to  those  specified in  the  project
      plan.    For  instance,  some  sites  may  require  analysis for  the
      organochlorine pesticides only or the  PCBs only.   Toxaphene  and/or
      technical Chlordane nay  not be  specified at  certain sites.   In
      addition, where PCBs are specified in the project  plan, a mixture of

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      Aroclors 1016 and 1260 will suffice for the initial calibration of
      all  Aroclors,  since  they  include  all congeners  present  in  the
      different regulated Aroclors.  A mid-point calibration standard of
      all Aroclors (for Aroclor  pattern recognition)  must  be  included with
      the  initial calibration so  that  the  analyst  is familiar with each
      Aroclor pattern and retention times on each column,

            7.4.1.2     For calibration verification  (each  12  hr shift)
      all  target analytes required  in  the  project  plan  must be injected
      with the  following exception  for  the Aroclors.   For  sites  that
      require PCB analysis,  include only the Aroclors that are expected to
      be found at the site.  If PCBs are required, but  it  is unknown which
      Aroclors may be  present,  the  mid-concentration Aroclors  1016/1260
      mixture only, may be  injected.   However,  if  specific  Aroclors  are
      found at the site during the initial screening,  it  is required that
      the  samples containing Aroclors be reinjected with the proper mid-
      concentration Aroclor standards.

      7.4.2 Because of the  low  concentration  of  pesticide  standards
injected on a GC/ECD,  column adsorption may be a problem when the GC  has
not been  used for a day  or more.   Therefore,  the  GC column  should  be
primed or  deactivated  by  injecting  a PCB or pesticide  standard mixture
approximately  20 times  more  concentrated   than  the  mid-concentration
standard.  Inject this standard mixture prior to beginning  the initial
calibration or calibration verification.
      CAUTION:
Several analytes, including Aldrin, may be observed in
the  injection  just  following  this  system  priming.
Always  run  an acceptable  blank  prior to  running  any
standards or samples.
      7.4.3 Retention time windows:

            7.4.3.1      Before establishing the  retention  time  windows,
      make sure the gas chromatographic system is within optimum operating
      conditions.  The width of the retention time window should be based
      upon actual retention times of standards measured over the course of
      72 hours.   See Method 8000 for details.

            7.4.3.2      Retention time windows shall be defined as plus or
      minus three  times  the standard deviation of the absolute  retention
      •frimes for each  standard.   However,  the experience of  the analyst
      should weigh heavily  in  the interpretation of the  chromatograms.
      For multicomponent standards (i.e., PCBs), the analyst should  use
      the  retention  time  window  but should  primarily  rely on  pattern
      recognition.   Sec. 7.5.4 provides guidance on the  establishment of
      absolute retention time  windows.

            7.4.3.3      Certain analytes, particularly Kepone, are subject
      to changes in  retention  times.   Dry Kepone  standards  prepared in
      hexane or isooctane can  produce gaussian peaks.   However,  Kepone
      extracted  from  samples or standards exposed to water or methanol  may
      produce peaks  with broad tails  that elute  later than the  standard
      (0-1 minute).   This  shift is presumably the result  of the  formation

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      of  a  hemi-acetal  from the  ketone functionality.   Method  8270 is
      recommended for Kepone.

7.5   Gas chromatographic analysis:

      7.5.1 Set up the GC system using the conditions described in Tables
4, 6, or 7.  An  initial oven temperature at or below 140-150°C is required-
to resolve  the  four BHC  isomtrs,   A  final  temperature  of 240-27Q°C is
required  to  elute  decachlorobiphenyl.     Use  of  injector  pressure
programming will improve the chromatography of late eluting peaks.

      7.5.2 Verify calibration each 12 hour shift by injecting calibration
verification standards prior to  conducting any analyses.  See Sec. 7.4.1.2
for special guidance on calibration verification of PCBs.  A calibration
standard must also be  injected  at  intervals  of not less  than  once every
twenty  samples  (after  every 10 samples is  recommended  to  minimize the
number of samples requiring re-injection when  QC  limits are exceeded) and
at the  end  of the analysis sequence.   The calibration  factor  for each
analyte to be quantitated must  not exceed a  ±15 percent  difference when
compared  to  the  initial  calibration  curve.   When  this criterion  is
exceeded, inspect the gas  chromatographic system to determine  the cause
and perform whatever maintenance is necessary  before verifying calibration
and proceeding  with  sample analysis.   If routine maintenance  does not
return the instrument performance to meet the QC requirements  (Sec. 8.2)
based on the last initial calibration, then a  new initial calibration must
be performed.

            7.5.2.1     Analysts should use high and low concentrations of
      mixtures of single-component analytes  and multi-component analytes
      for calibration verification.

      7.5.3 Sample injection may continue for as long as  the calibration
verification standards and  standards  interspersed  with the  samples meet
instrument QC  requirements.   It  is  recommended that standards be analyzed
after every 10  (required  after every 20 samples), and at the end of a set.
The sequence  ends  when  the set of samples   has  been  injected or when
qualitative and/or quantitative QC criteria are exceeded.

            7.5.3.1     Each sample  analysis  must be  bracketed with an
      acceptable initial calibration, calibration verification standard(s)
      (each 12 hr shift), or calibration standards interspersed within the
      samples.   All  samples that were  injected  after  the standard that
      last met the QC criteria must be reinjected,

            7.5.3.2     Although analysis of  a  single  mid-concentration
      standard (standard  mixture or multi-component analyte) will satisfy
      the minimum  requirements,  analysts are  urged  to use  different
      calibration   verification    standards    during    organochlorine
      pesticide/PCB analyses.   Also,  multi-level  standards  (mixtures or
      multi-component analytes)  are highly  recommended  to ensure that
      detector  response  remains  stable  for  all  analytes   over  the
      calibration range.
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       7.5.4  Establish  absolute retention time windows for each  analyte.
Use the  absolute retention  time  for each  analyte  from standards  analyzed
during that 12  hour  shift  as  the midpoint  of  the window.   The  daily
retention  time window  equals the midpoint  + three  times  the  standard
deviations.

             7.5.4.1     Tentative identification of an analyte occurs when
       a  peak froi a sample  extract falls  within the daily retention time
       window.

             7.5.4.2     Validation   of   gas   chromatographic    system
       qualitative  performance:  Use  the  calibration  standards  analyzed
       during the sequence to evaluate retention time stability.  If any of
       the  standards fall outside their daily retention time windows, the
       system is  out  of control. Determine the cause  of  the problem and
       correct  it.

       7.5.5  Record the  volume injected to  the  nearest  0.05  fj.1 and the
resulting  peak size  in  area units.   Using  either the  internal  or the
external calibration procedure  {Method 8000), determine the identity and
the quantity of each  component peak  in  the sample  chromatogram which
corresponds  to the compounds  used for calibration purposes.

             7.5.5.1     If  the responses  exceed the calibration range of
       the  system,  dilute   the  extract   and  reanalyze.   Peak   height
       measurements  are  recommended   over  peak   area  integration when
       overlapping peaks cause errors in area integration.

             7.5.5.2     If  partially overlapping  or coeluting peaks are
       found, change  columns or  try GC/MS quantitation,  see  Sec.  8 and
       Method 8270.

             7.5.5.3     If  the  peak response  is  less  than  2.5 times the
       baseline noise  level,  the validity of the quantitative  result  may be
       questionable.  The  analyst should  consult with the  source of the
       sample to determine whether further concentration of the sample is
       warranted.

       7.5.6  Identification of mixtures  (i.e.  PCBs  and Toxaphene)  is based
on  the  characteristic  "fingerprint"  retention  time and  shape  of the
indicator  peak(s);  and  quantitation   is  based  on the  area  under the
characteristic  peaks  as compared  to  the area  under the  corresponding
calibration  peak(s) of the  same  retention time and shape generated using
either internal or external calibration procedures.

       7.5.7  Quantitation of the target  compounds  is based  on:    1}   a
reproducible response of the ECD  or ELCD within the calibration  range; and
2)  a  direct proportionality  between  the magnitude of  response of the
detector to  peaks  in  the sample extract  and  the  calibration  standards.
Proper quantitation requires the appropriate  selection of a baseline from
which the area  or height of the characteristic peak(s) can be determined.
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      7.5.8 If compound identification or quantitation is  precluded due to
interference  (e.g.,  broad,  rounded  peaks  or ill-defined  baselines  are
present) cleanup of the extract or replacement of the capillary column or
detector  is  warranted.    Rerun the sample  on  another  instrument  to
determine if  the  problem results from  analytical  hardware  or the sample
matrix.  Refer to Method 3600  for the procedures to be followed in sample
cleanup.

7.6   Quantitation of Multiple Component Analytes:

      7.6.1 Multi-component analytes present  problems   in  measurement.
Suggestions are offered in the following sections for handing Toxaphene,
Chlordane, PCBs, DDT, and BHC.

      7.6.2 Toxaphene:  Toxaphene is manufactured by the  chlorination of
camphenes, whereas Strobane results  from the chlorination of a mixture of
camphenes and pinenes.  Quantitative calculation of Toxaphene or Strobane
is difficult,  but reasonable  accuracy  can be  obtained.  To  calculate
Toxaphene on  GC/ECD:   (a)   adjust  the sample size  so  that the  major
Toxaphene peaks are  10-70% of full-scale deflection (FSD);  (b)   inject a
Toxaphene standard that is estimated to be within  +10 ng of  the  sample;
(c)  quantitate  using  the  five major  peaks  or  the total  area  of  the
Toxaphene pattern.

            7.6.2.1     To measure  total area,  construct  the  baseline of
      standard  Toxaphene  between  its  extremities;  and  construct  the
      baseline under the sample, using the distances of the peak  troughs
      to baseline  on the  standard  as a guide.   This procedure  is  made
      difficult by the fact that the relative heights and  widths of the
      peaks in the sample will  probably  not be identical  to the standard.

            7.6.2.2     A  series   of   Toxaphene  residues  have   been
      calculated using the  total peak area for comparison  to the standard
      and also using the area  of the  last four peaks only, in  both sample
      and standard.  The agreement between  the results obtained by the two
      methods justifies  the use of the  latter  method   for  calculating
      Toxaphene  in  a  sample  where  the early  eluting   portion  of  the
      Toxaphene chromatogram  shows  interferences from other  substances
      such as DDT.

      7.6.3 Chlordane  is  a  technical  mixture  of at  least  11  major
components and 30 or more minor components.   Trans- and cis-Chlordane (a
and 7, respectively), are the two major components of technical Chlordane.
However, the exact  percentage  of each  in  the technical   material  is  not
completely defined, and is not consistent  from  batch to batch.

            7.6.3.1     The GC pattern of  a Chlordane residue may differ
      considerably from that of the  technical  standard.  Depending on the
      sample substrate and  its  history,  residues of Chlordane can  consist
      of almost  any combination of:    constituents  from the  technical
      Chlordane,  plant  and/or  animal  metabolites,  and   products  of
      degradation  caused  by exposure to  environmental  factors  such  as
      water and sunlight.
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            7.6.3.2     Whenever possible, when a Chlordane residue does
      not resemble technical  Chlordane,  the analyst should quantitate the
      peaks of o-Chlordane, 7-Chlordane, and Heptachlor separately against
      the  appropriate  reference  materials,  and  report the  individual
      residues.

            7.6,3.3     When the GC pattern of the residue resembles that
      of  technical  Chlordane,   the analyst  may  quantitate  Chlordane
      residues by comparing the total area of the Chlordane chromatogram
      using the five major  peaks or the total area.   If the Heptachlor
      epoxide peak is relatively small, include  it  as part  of the total
      Chlordane  area  for calculation of the residue.  If Heptachlor and/or
      Heptachlor  epoxide  are much  out of  proportion,   calculate  these
      separately and subtract their areas from the total  area to  give a
      corrected   Chlordane  area.    (Note  that  octachloro  epoxide,   a
      metabolite  of  Chlordane,   can  easily be  mistaken for  Heptachlor
      epoxide on a nonpolar GC column.)

            7.6.3,4     To  measure  the total  area  of  the  Chlordane
      chromatogram, inject an amount of technical Chlordane standard which
      will  produce  a  chromatogram  in  which  the  major  peaks  are
      approximately the same size as those in  the sample chromatograms.

      7.6.4 Polychlorinated biphenyls (PCBs):  Quantitation of residues of
PCBs involves problems similar to those encountered in  the quantitation of
Toxaphene, Strobane,  and Chlordane.  In each case, the  material is made up
of numerous compounds which generate multi-peak chromatograms.  Also,  in
each case,  the  chromatogram of  the  residue  may not  .match  that of  the
standard.

             7.6.4.1     Mixtures of PCBs of various chlorine contents were
      sold for many years  in  the  U.S. by the Monsanto Co. under the trade
      name Aroclor (1200 series and 1016).  Although these Aroclors are no
      longer  marketed,  the  PCBs  remain   in  the  environment  and  are
      sometimes  found as residues in foods,  especially  fish.  The Aroclors
      most commonly found  in the environment  are  1242, 1254, and 1210.

            7.6.4.2     PCB  residues   are   generally   quantitated   by
      comparison to the most similar Aroclor  standard.  A choice must  be
      made as to which Aroclor is most similar to that of the residue and
      whether that standard  is  truly  representative  of the PCBs  in  the
      sample.

            7.6.4.3     PCB  Quantitation option  #1-  Quantitate the  PCB
      residues by comparing  the  total  area of the chlorinated  biphenyl
      peaks to  the total   area  of  peaks  from the  appropriate Aroclor
      reference  material.  Measure the total area or height response from
      the  common baseline  under all the peaks.  Use only those peaks from
      the  sample that can  be attributed  to  chlorobiphenyls.   These peaks
      must also  be present  in the  chromatogram of the reference materials.
      Option #1  should not be used if there are interference  peaks  within
      the  Aroclor  pattern,  especially  if they overlap  PCB congeners.
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                  7.6.4.4     PCB  Quantitatlon  option #2-  Quantitate  the PCB
            residues by comparing  the  responses  of 3  to  5 major peaks in each
            appropriate  Aroclor  standard  with  the  peaks  obtained  from the
            chlorinated biphenyls in the sample extract.   The  amount of Aroclor
            is calculated using  an  individual  response factor for each of the
            major peaks.  The results of the 3 to S determinations are averaged.
            Major peaks are  defined as  those peaks in the  Aroclor standards that
            are at least 25% of the height of the largest Aroclor peak.  Late-
            eluting  Aroclor  peaks  are  generally the   most stable  in  the
            environment.

                  7.6.4.5     When  samples  appear to  contain weathered  PCBs,
            treated PCBs,  or mixtures of Aroclors,  the use of  Aroclor standards
            is not appropriate.  Several diagnostic peaks  useful for identifying
            non-Aroclor PCBs are  given in Table  10.   Analysts should examine
            chromatograms containing these peaks carefully, as  these samples may
            contain PCBs.   PCB  concentrations may  be estimated  from specific
            congeners by adding the concentration of the congener peaks listed
            in fable 11.  The congeners are analyzed as single  components.  This
            approach will  provide reasonable accuracy  for Aroclors 1016,  1232,
            1242 and 1248 but will  underestimate  the concentrations of Aroclors
            1254,  1260 and  1221.    It  is  highly recommended  that  heavily
            weathered,  treated,  or  mixed  Aroclors be  analyzed using  GC/MS  if
            concentration permits,

            7.6.5 Hexachlorocyclohexane  (BHC,  from the  former name,  benzene
      hexachloride);   Technical  grade BHC is a  cream-colored amorphous  solid
      with a very  characteristic  musty odor; it consists of  a mixture of six
      chemically distinct isomers and  one or more heptachlorocyclohexanes and
      octachlorocyclohexanes.    Commercial   BHC  preparations  may  show a  wide
      variance in the  percentage  of individual   isomers  present.    Quantitate
      each isomer  (a,   0,  7,  and  S) separately  against  a  standard of the
      respective pure isomer.

            7.6.6 DDT:   Technical DDT consists primarily of a  mixture of 4,4'-
      DDT  (approximately  75%)  and  2,4'-DDT  (approximately   25%).    As  DDT
      weathers, 4,4'-DDE,  2,4'-DDE, 4,4'-ODD, and  2,4'-DDD  are formed.   Since
      the 4,4'-isomers  of  DDT,  DDE,  and  ODD predominate in  the  environment,
      these  are  the  isomers  normally regulated  by  US  EPA and  should  be
      quantitated against  standards of the respective  pure isomer.

      7.7  Suggested chromatography maintenance:  Corrective measures may require
any one or more of the  following remedial  actions.

           7.7.1 Splitter connections: For  dual columns which are  connected
      using a  press-fit Y-shaped  glass  splitter  or  a  Y-shaped  fused-silica
      connector (J&W Scientific or  Restek),  clean  and deactivate  the splitter
      port insert or replace with a cleaned and deactivated splitter.  Break off
      the first few inches (up to one  foot)  of the injection  port  side of the
      column.    Remove   the  columns  and solvent backflush according  to  the
      manufacturer's instructions.  If  these procedures  fail  to eliminate the
      degradation problem,  it may be necessary to deactivate the metal  injector
      body and/or replace  the  columns.


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                   7.7.1.1      GC  injector ports  can be  of  critical concern,
            especially  in  the analysis of DDT and Endrin.  Injectors that  are
            contaminated,   chemically   active,   or  too  hot  can   cause   the
            degradation ("breakdown") of the  analytes.  Endrin and DDT breakdown
            to Endrin aldehyde, Endrin  ketone, DDD, or DDE. When  such breakdown
            is observed, clean and  deactivate the injector port, break off at
            least  0.5 M of the  column  and  remount  it.   Check the injector
            temperature  and lower  it  to 205DC,  if required.   Endrin  and  DDT
            breakdown is less of a problem when  ambient  on-column injectors  are
            used.

            7.7.2  Metal  injector body:    Turn  off  the  oven  and  remove   the
      analytical columns when  the oven has cooled.   Remove the glass injection
      port insert  (instruments with on-column injection).  Lower  the injection
      port temperature  to  room temperature.   Inspect  the injection port  and
      remove any.noticeable foreign material.

                   7.7.2.1      Place a  beaker beneath the injector port inside
            the oven.  Using a wash  bottle, serially  rinse the entire inside  of
            the  injector port with acetone and then toluene;  catch the rinsate
            in the beaker.

                   7.7.2.2      Prepare a solution of a deactivating agent (Sylon-
            CT or  equivalent)  following  manufacturer's  directions.   After all
            metal surfaces  inside the injector body have been thoroughly coated
            with  the deactivation  solution,  rinse  the  injector   body  with
            toluene, methanol, acetone,  then hexane.   Reassemble the injector
            and replace the columns.

            7.7.3 Column rinsing:   The  column  should be rinsed with  several
      column  volumes of  an  appropriate solvent.   Both  polar  and nonpolar
      solvents are recommended.  Depending on the  nature of the sample residues
      expected,  the  first  rinse might  be  water,   followed  by  methanol  and
      acetone; methylene chloride is a  good final rinse and in some cases may  be
      the  only  solvent  required.   The  column  should then  be filled  with
      methylene  chloride  and  allowed  to stand  flooded  overnight to  allow
      materials within the  stationary  phase  to migrate  into  the  solvent.   The
      column is then flushed with fresh methylene chloride, drained, and dried
      at room temperature with a stream of ultrapure nitrogen.


8.0   QUALITY CONTROL

      8.1   Refer to Chapter One  for  specific quality control  (QC)  procedures
including matrix spikes, duplicates and blanks.  Quality control to validate
sample  extraction  is covered in  Hethod 3500  and  in  the  extraction  method
utilized.  If  an  extract cleanup was performed, follow the QC  in Method 3600 and
in the specific cleanup method.

      8.2   Quality control  requirements for the GC system,  including calibration
and corrective  actions,  are found  in  Method 8000.   The following  steps  are
recommended as additional method QC.
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            8.2.1 The  QC  Reference  Sample  concentrate  (Method  3500}  should
      contain the organochlorine  pesticides  at  10  mg/L for water samples.  If
      this  method  is  to  be  used  for  analysis  of  Aroclors, Chlordane,  or
      Toxaphene  only,  the  QC   Reference  Sample  should  contain  the  most
      representative multi-component mixture  at a  concentration of 50 mg/L in
      acetone.  The frequency of analysis of the QC  reference sample analysis is
      equivalent to a minimum of  1 per 20 samples or 1  per batch if less than 20
      samples.  If the recovery of any compound found in the QC  reference sample
      is  less  than 80 percent or greater than 120 percent of the  certified
      value, the laboratory performance is  judged to be out  of  control, and the
      problem must be corrected.  A new set of  calibration standards should be
      prepared and analyzed.

            8.2.2 Calculate surrogate standard recovery on all  samples, blanks,
      and  spikes.    Determine  if   the  recovery   is   within   limits  (limits
      established by performing QC procedures outlined  in Method 8000).

            If recovery is not within limits, the following are required:

                  8.2.2.1     Confirm that  there are no errors  in calculations,
            surrogate solutions and  internal  standards.  Also, check instrument
            performance.

                  8.2.2.2     Examine chromatograms for interfering  peaks and
            for integrated areas.

                  8.2.2.3     Recalculate the data  and/or  reanalyze the extract
            if any of the above checks reveal a problem.

                  8.2.2.4     Reextract and reanalyze  the  sample if none of the
            above are a problem or flag the data as "estimated concentration."

            8.2.3 Include a calibration  standard after  each group of 20 samples
      (it is recommended  that a calibration standard be  included after every 10
      samples to  minimize the number  of repeat  injections)   in  the  analysis
      sequence as a  calibration check.  The  response factors  for the calibration
      should  be  within  15 percent  of  the  initial calibration.   When  this
      continuing calibration is out of this  acceptance window, the  laboratory
      should stop analyses and take  corrective action.

            8.2.4 Whenever  quantitation  is   accomplished using  an  internal
      standard,   internal  standards  must  be  evaluated for  acceptance.    The
      measured area of the internal  standard must  be no  more  than  50 percent
      different from the  average area calculated during calibration.   When the
      internal standard peak area is outside  the limit, all  samples  that fall
      outside the QC criteria must be reanalyzed.

      8.3   DDT and Endrin are  easily degraded in the injection  port.  Breakdown
occurs when the injection port  liner is contaminated high boiling residue from
sample injection  or when  the  injector  contains  metal  fittings.   Check for
degradation problems by injecting a standard containing only 4,4'-DDT and Endrin.
Presence of 4,4'-DDE, 4,4'-ODD, Endrin ketone or Endrin  indicates breakdown.  If
degradation of either DDT or Endrin  exceeds 15%, take  corrective action before
proceeding with calibration.

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            8.3.1 Calculate percent breakdown as follows:

            % breakdown    Total DDT degradation peak area  (DDE + ODD)
            for 4,4'-DDT = 	  x  100
                                    peak areas (DDT + DDE + ODD)

                              Total endrin degradation peak area
            % breakdown       (Endrin aldehyde + Endrin ketone)
            for Endrin   =     	•	       x 100
                              peak areas (Endrin + aldehyde + ketoneJ

            8.3.2 The  breakdown  of DDT and  Endrin should  be  measured before
      samples are analyzed and at the beginning of each 12 hour  shift.  Injector
      maintenance and  recalibration  should  be  completed if the  breakdown is
      greater than 15% for either compound (Sec. 8.2.3).

      8.4   GC/MS confirmation  may be  used  for single  column analysis.   In
addition,  any compounds  confirmed  by two columns  should  also  be  confirmed by
GC/HS if the concentration is sufficient for detection by GC/MS.

            8.4.1 Full-scan GC/MS will  normally  require a minimum concentration
      near  10 ng/^tL  in the final extract  for each single-component compound.
      Ion  trap  or selected  ion monitoring  will  normally  require  a  minimum
      concentration near 1 ng/^L.

            8.4.2 The  GC/MS  must  be  calibrated  for  the  specific  target
      pesticides when it is used for quantitative analysis.

            8.4.3 GC/HS may  not  be used  for single column  confirmation  when
      concentrations are below 1 ng/fj.1.

            8.4.4 GC/MS confirmation  should  be  accomplished by  analyzing  the
      same extract used for GC/ECD analysis and the associated blank.

            8.4.5 Use of the base/neutral-acid extract and associated blank may
      be used if the surrogates and internal  standards do not interfere and it
      is demonstrated that the analyte  is stable during acid/base partitioning.
      However,  if the  compounds are  not detected  in  the  base/neutral-acid
      extract even though the concentrations are high enough, a GC/MS analysis
      of the pesticide extract should be performed.

            8.4.6 A QC reference  sample of the compound must  also be analyzed by
      GC/MS.  The concentration  of the  QC  reference standard must demonstrate
      the ability to confirm the pesticides/Aroclors identified by GC/ECD.

      8.5   Whenever silica gel  (Method  3630) or Florisil  (Method 3620) cleanup
is  used,   the  analyst  must  demonstrate  that   the fractionation  scheme  is
reproducible.  Batch to  batch variation in the composition  of the  silica  gel
material or overloading the  column  may  cause  a  change in the  distribution
patterns of the organochlorine pesticides and PCBs.   When  compounds are found 1n
two fractions, add the concentrations  in the fractions, and corrections for any
additional  dilution.
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9.0   METHOD PERFORMANCE

      9.1   The MDL is defined in Chapter One.  The MDL concentrations listed  in
Tables  1  and  2 were obtained  using  organic-free reagent water and  sandy loam
soil.

      9.2   The chroraatographic  separations  in this method have been tested  in
a  single  laboratory  by using  clean hexane  and liquid and solid waste extracts
that  were spiked with the test  compounds  at three  concentrations.  Single-
operator  precision,  overall  precision, and  method accuracy were  found  to  be
related to the concentration of  the  compound  and the  type of matrix.

      9.3   This method has been  applied in a variety of commercial  laboratories
for environmental  and waste matrices.   Performance  data were  obtained  for a
limited number of target analytes  spiked into sewage  sludge and dichloroethene
still bottoms at high  concentration  levels.  These data are provided in Tables
12 and  13.

      9.4   The accuracy and precision obtainable with this method depend on the
sample  matrix, sample  preparation technique,  optional cleanup techniques, and
calibration procedures used.

      9.5   Single laboratory  accuracy data  were  obtained  for organochlorine
pesticides  in  a clay  soil.    The spiking  concentration was  500   ^tg/kg.   The
spiking solution was  mixed  into the soil and then immediately transferred to the
extraction device and immersed in the extraction solvent.  The  spiked  sample was
then extracted by Method 3541  (Automated Soxhlet).  The  data represent a single
determination.   Analysis  was   by  capillary  column gas chromatography/electron
capture detector following  Method 8081 for the organochlorine pesticides.  These
data are listed in Table 14 and were  taken from Reference 14.

      9.6   Single laboratory  recovery data were obtained for PCBs in clay and
soil.     Oak Ridge  National   Laboratory  spiked  Aroclors 1254 and 1260   at
concentrations of  5 and 50  ppm  into portions  of clay and  soil  samples and
extracted these  spiked samples  using the  procedure  outlined  in  Method  3541.
Multiple extractions  using two different extractors were performed.   The extracts
were analyzed by Method 8081.  The data are listed in Table  15 and were taken
from Reference 15.

      9.7   Multi-laboratory accuracy and precision data were obtained for PCBs
in soil.  Eight laboratories spiked Aroclors 1254 and 1260 into three portions
of 10 g of Fuller's Earth on three non-consecutive days, followed by immediate
extraction using Method 3541.   Six of the laboratories spiked each Aroclor at 5
and 50 mg/kg and  two  laboratories spiked each Aroclor  at 50 and  500 mg/kg.  All
extracts were analyzed by  Oak  Ridge  National  Laboratory,  Oak  Ridge,  TN,  using
Method 8081.  These data are listed in Table 16 and were taken from Reference 13.
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 10.0  REFERENCES

 1.    Lopez-Avila,  V.;  Baldin,  E.; Benedicto, J; Milanes,  J.;  Beckert. W. F.
      Application of Open-Tubular Columns to SW-846 GC Methods";  final report to
      the  U.S.  Environmental Protection Agency on  Contract  68-03-3511; Mid-
      Pacific Environmental  Laboratory,  Mountain View, CA,  1990.

 2.    Development and Application of Test Procedures  for Specific Organic Toxic
      Substances in Wastewaters.   Category 10 - Pesticides and PCB Report for
      the U.S. Environmental Protection  Agency on Contract 68-03-2606.

 3.    Goerlitz, D.F.;  Law,  L.M.  "Removal of Elemental Sulfur Interferences from
      Sediment Extracts for Pesticide Analysis"; Bull. Environ. Contam. Toxicol.
      1971, 6, 9.

 4.    Ahnoff, M.; Josefsson, B.  "Cleanup  Procedures for PCB Analysis on River
      Water Extracts"; Bull. Environ. Contain. Toxicol. 1975, 135 159.

 5.    Jensen, $.; Renberg,  L.; Reutergardth, L.  "Residue Analysis of Sediment
      and  Sewage Sludge  for  Organochlorines  in  the  Presence of  Elemental
      Sulfur"; Anal. Chen.  1977, 49, 316-318.

 6.    Wise, R.H.; Bishop, D.F.; Williams, R.T.; Austern, B.M.   "Gel Permeation
      Chromatography  in the GC/MS  Analysis of  Organics  in   Sludges";  U.S.
      Environmental  Research Laboratory.  Cincinnati, OH  45268.

 7.    Pionke, H.B.;  Chesters, G.;  Armstrong,  D.E.   "Extraction  of Chlorinated
      Hydrocarbon Insecticides from Soil"; Agron. J.  1968, 60,  289.

8.    Burke, J.A.; Mills, P.A.; Bostwick, D.C.  "Experiments  with Evaporation of
      Solutions of Chlorinated Pesticides"; J. Assoc.  Off.  Anal.  Chem. 1966, 49,
      999.

9.    Glazer, J.A.,  et al.   "Trace  Analyses for Wastewaters"; Environ. Sci. and
      Techno!. 1981, 15, 1426.

10.   Marsden, P.J., "Performance Data for SW-846 Methods 8270, 8081, and 8141,"
      EMSL-LV, EPA/600/4-90/015.

11.   Marsden, P.J., "Analysis of PCBs", EMSL-LV, EPA/600/8-90/004

12.   Erickson,  M.  Analytical  Chemistry of PCBs, Butterworth  Publishers,  Ann
      Arbor Science  Book (1986).

13.   Stewart, J.  "EPA Verification Experiment for Validation of the SOXTEC* PCB
      Extraction Procedure";  Oak  Ridge  National Laboratory,  Oak Ridge,  TN,
      37831-6138; October 1988.

14.   Lopez-Avila,  V.  {Beckert,  W., Project Officer), "Development of a Soxtec
      Extraction Procedure  for Extracting Organic   Compounds  from Soils  and
      Sediments",  EPA  600/X-91/14Q,  US   EPA,  Environmental  Monitoring  Systems
      Laboratory-Las Vegas,  October 1991.
                                  8081  -  23                         Revision 0
                                                                September 1994

-------
15.    Stewart,  J.H.;  Bayne, C.K.; Holmes, R.L.; Rogers, W.F.; and  Haskarinec,
      M.P.,  "Evaluation of a Rapid Quantitative Organic Extraction System  for
      Determining the Concentration of PCB in Soils",  Proceedings of  the  USEPA
      Symposium on Waste Testing  and  Quality Assurance,  Oak Ridge  National
      Laboratory,  Oak Ridge,  TN 37831-6131;  July 11-15,  1988.
                                  8081 - 24                        Revision 0
                                                               September 1994

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                           TABLE 1

  GAS CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION
LIMITS FOR THE ORGANOCHLORINE PESTICIDES AND PCBs AS  AROCLORS
              USING WIDE-BORE CAPILLARY  COLUMNS
              SINGLE COLUMN METHOD  OF  ANALYSIS

Compound
Aldrin
O-BHC
B-BHC
<5-BHC
7-BHC (Lindane)-*
o-Chlordane
7-Chlordane
4,4' -ODD
4,4'-DDE
4, 4 '-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Methoxychlor
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Retention
DB 608b
11.84
8.14
9.86
11.20
9.52
15.24
14.63
18.43
16.34
19.48
16.41
15.25
18.45
20.21
17.80
19.72
10.66
13.97
22.80
MR
MR
MR
MR
MR
MR
MR
MR
Water = Organic- free reagent
Time (min)
DB 1701b
12.50
9.46
13,58
14.39
10.84
16,48
16.20
19.56
16.76
20.10
17.32
15.96
19.72
22.36
18.06
21.18
11.56
15.03
22.34
MR
MR
MR
MR
MR
MR
MR
MR
water.
MDLa Water
(M9/D
0.034
0.035
0.023
0.024
0.025
0.008
0.037
0.050
0.058
0.081
0.044
0.030
0.040
0.035
0.039
0.050
0.040
0.032
0.086
NA
0.054
NA
NA
NA
NA
NA
0.90

MDLa Soil
(/*gAg)
2.2
1.9
3.3
1.1
2.0

1.5
4.2
2.5
3.6
NA
2.1
2.4
3.6
3.6
1.6
2.0
2.1
5.7
NA
57.0
NA
NA
NA
NA
NA
70.0

Soil = Sandy loam soil.
MR - Multiple
NA = Data not
peak responses.
available.



MDL  is  the method detection  limit.   MDL was determined  from the
analysis  of seven  replicate  aliquots  of  each matrix  processed
through  the  entire  analytical  method  (extraction,  silica  gel
cleanup, and GC/ECD analysis). MDL = t{n-l,  0.99) x SD, where  t(n-
1, 0.99) is the Student's  t  value appropriate for a 99%  confidence
interval and a standard deviation with n-1  degrees  of freedom, and
SD is the standard deviation of the seven replicate measurements.
See Table 4 for GC operating conditions.
                       8081  -  25
    Revision 0
September 1994

-------
                                TABLE  2

        GAS CHROMATQGRAPHIC RETENTION TIMES AND METHOD DETECTION
      LIMITS FOR THE ORGANOCHLORINE  PESTICIDES AND  PCBs AS  AROCLORS
                  USING NARROW-BORE CAPILLARY COLUMNS
                    SINGLE COLUMN METHOD OF ANALYSIS
Compound
Retention Time (min)
  DB 608"    DB 5b
MDL" Water MDL" Soil
 (M9A)     (M9/kg)
Aldrin
ff-BHC
6-BHC
£-BHC
f-BHC (Lindane)
or-Chlordane
p-Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosul fan sul fate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Methoxychlor
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
14.51
11.43
12.59
13.69
12.46

17.34
21.67
19.09
23.13
19.57
18.27
22.17
24.45
21.37
23.78
13.41
16.62
28.65
MR
MR
MR
MR
MR
MR
MR
MR
14.70
10.94
11.51
12.20
11.71

17.02
20.11
18.30
21.84
18.74
17.62
20.11
21.84
19.73
20.85
13.59
16.05
24.43
MR
MR
MR
MR
MR
MR
MR
MR
0.034
0,035
0.023
0.024
0.025

0.037
0.050
0.058
0.081
0.044
0.030
0.040
0.035
0.039
0.050
0.040
0.032
NA
0.086
NA
0.054
NA
NA
NA
NA
0.90
2.2
1.9
3.3
1.1
2.0

1.5
4.2
2.5
3.6
NA
2.1
2.4
3.6
3.6
1.6
2.0
2.1
NA
5.7
NA
57.0
NA
NA
NA
NA
70.0
Water = Organic- free reagent water.
Soil - Sandy loam soil.
MR = Multiple
NA = Data not
peak responses
available.
.





                            8081 - 26
                                        Revision  0
                                    September 1994

-------
                          TABLE  2
                         (Continued)

MDL is  the method detection limit.   MDL was determined  from the
analysis  of seven  replicate aliquots  of  each matrix  processed
through  the entire  analytical  method  (extraction,  cleanup,  and
GC/ECD analysis).  MDL = t(n-l,  0.99) x SD,  where  t(n-l,  0.99) is
the Student's t value appropriate for a 99% confidence interval and
a standard  deviation with n-1  degrees of  freedom,  and SD  is the
standard deviation of the seven  replicate measurements.

30 m x 0.25 mm ID DB-608 1  pm film  thickness,  see Table  4  for GC
operating conditions.

30 m x  0.25 mm  ID DB-5  1 ^irt film  thickness,  see Table  4  for GC
operating conditions.
                      8081 - 27                         Revision 0
                                                    September 1994

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                                  TABLE 3

DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQLs} FOR VARIOUS MATRICES"



    Matrix                                                   Factor
    Ground water                                                  10
    Low-concentration soil by sonication with GPC cleanup        670
    High-concentration soil and sludges by sonication         10,000
    Non-water miscible waste                                 100,000
    EQL = [Method detection limit for water  (see Table 1 or Table 2} wide-
    bore or narrow-bore options] x [Factor found in this table].  For
    nonaqueous samples, the factor is on a wet-weight basis.  Sample EQLs
    are highly matrix-dependent.  The EQLs to be determined herein are
    provided for guidance and may not always be achievable.
                                8081  -  28                         Revision 0
                                                              September 1994

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                                   TABLE 4
             GC OPERATING CONDITIONS FOR ORSANOCHLORINE COMPOUNDS
                             SINGLE  COLUHN ANALYSIS
      Narrow-bore  columns:

Narrow-bore Column 1 - 30 m x 0.25 or 0.32 mm  internal diameter  (ID)  fused
silica capillary column chemically bonded with  SE-54  (DB-5 or  equivalent),  1
im  film  thickness.
      Carrier  gas  (He)
      Injector temperature
      Detector temperature
      Initial  temperature
      Temperature  program

      Final temperature
16 psi
225°C
300°C
100°C, hold 2 minutes
100°C to 160°C at  15°C/nnn, followed
by 160°C to 270°C  at,5°C/min
270°C
Narrow-bore Column 2 - 30 m x 0.25 mm  ID fused silica capillary column
chemically bonded with 35 percent phenyl methylpolysiloxane  (DB-608, SPfi-608,
or equivalent), 25 pm coating thickness, 1  pm film thickness
      Carrier gas  (N2)
      Injector temperature
      Detector temperature
      Initial temperature
      Temperature  program
      Final temperature
20 psi
225°C
300°C
160°C, hold 2 minutes
160°C to 290°C  at 50C/min
290°C, hold 1 min
      Wide-bore columns:

Wide-bore Column 1 - 30 ra x 0.53 mm ID fused silica capillary column
chemically bonded with 35 percent phenyl methylpolysiloxane  {DB-608, SPB-608,
RTx-35,  or equivalent), 0.5 pm or 0.83 pim  film thickness.

Wide-bore Column 2 - 30 ra x 0.53 mm ID fused silica capillary column
chemically bonded with 50 percent phenyl methylpolysiloxane  (DB-1701, or
equivalent), 1.0 urn film thickness.
      Carrier gas  (He)
      Makeup gas
      argon/methane  (P-5 or P-10) or N2
      Injector temperature
      Detector temperature
      Initial temperature
      Temperature program
      Final temperature
5-7 mL/minute

30 raL/min
250°C
290°C
150°C,  hold 0.5 minute
150°C to 270°C  at  5°C/min
270°C,  hold 10  min
                                                                    (continued)
                                   8081  -  29
                          Revision 0
                      September 1994

-------
                             TABLE 4   (Continued)
             SC  OPERATING CONDITIONS  FOR ORGANOCHLORINE COMPOUNDS
                            SINGLE COLUHN ANALYSIS
Wide-bore Columns (continued)

Wide-bore Column 3 - 30 m x 0.53 ran ID fused silica capillary column
chemically bonded with SE-54 (DB-5, SPB-5, RTx-5, or equivalent),  1.5  p,m film
thickness.

      Carrier gas (He)                    6 mL/minute
      Makeup gas
      argon/methane  (P-5 or P-10)  or N2   30 tnL/min
      Injector temperature                2Q5°C
      Detector temperature                290°C
      Initial temperature                 140°C,  hold 2 min
      Temperature program                 140°C  to 240°C at 10DC/min,
                                          hold  5 minutes  at 240°C,
                                          240°C  to 265°C at 5°C/min
      Final temperature                   265°C,  hold 18 min
                                   8081  -  30                         Revision  0
                                                                September  1994

-------
                    TABLE 5
RETENTION TIMES OF THE ORGANOCHLORINE PESTICIDES"
         DUAL COLUMN METHOD  OF  ANALYSIS
Compound
DBCP
Hexachl orocycl opentadi ene
Etridiazole
Chloroneb
Hexachl oro benzene
Dial! ate
Propachlor
Trifluralin
a-BHC
PCNB
7-BHC
Heptachlor
Aldrin
Alachlor
Chlorothalonil
Alachlor
/3-BHC
Isodrin
DCPA
.S-BHC
Heptachlor epoxide
Endosulfan-I
•y-Chlordane
a-Chlordane
trans-Nonachlor
4,4'-DDE
Dieldrin
Captan
Perthane
Endrin
Chloropropylate
Chi orobenzi late
Nitrofen
4, 4' -ODD
Endosulfan II
4, 4' -DDT
Endrin aldehyde
Mi rex
Endosulfan sulfate
CAS No.
96-12-8
77-47-4
2593-15-9
2675-77-6
118-74-1
2303-16-4
1918-16-17
1582-09-8
319-84-6
82-68-8
58-89-9
76-44-8
309-00-2
15972-60-8
1897-45-6
15972-60-8
319-85-7
465-73-6
1861-32-1
319-86-8
1024-57-3
959-98-8
5103-74-2
5103-71-9
39765-80-5
72-55-9
60-57-1
133-06-2
72-56-0
72-20-8
99516-95-7
510-15-6
1836-75-5
72-54-8
33213-65-9
50-29-3
7421-93-4
2385-85-5
1031-07-8
DB-5
RT(min)
2.14
4.49
6.38
7.46
12.79
12.35
9.96
11.87
12.35
14.47
14.14
18.34
20.37
18.58
15.81
18.58
13.80
22.08
21.38
15.49
22.83
25.00
24.29
25.25
25.58
26.80
26.60
23.29
28.45
27.86
28.92
28.92
27.86
29.32
28.45
31.62
29.63
37.15
31.62
DB-1701
RT(min)
2.84
4.88
8.42
10.60
14.58
15.07
15.43
16.26
17.42
18.20
20.00
21.16
22.78
24.18
24.42
24.18
25.04
25.29
26.11
26.37
27.31
28.88
29.32
29.82
30.01
30.40
31.20
31.47
32.18
32.44
34.14
34.42
34.42
35.32
35.51
36.30
38.08
38.79
40.05
                                                     continued
                   8081  -  31
    Revision 0
September 1994

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Compound
Methoxychlor
Captafol
Endnn ketone
trans- Permethr in
Kepone
Dicofol
Dichlone
o,o'-Dibromo-m-xy1ene
2-Broiobiphenyl
TABLE 5
(Continued)

CAS No.
72-43-5
2425-06-1
53494-70-5
51877-74-8
143-50-0
115-32-2
117-80-6




DB-5
RT(min)
35.33
32.65
33.79
41.50
31.10
35.33
15.17
9.17
8.54


DB-1701
RT(min)
40.31
41.42
42.26
45.81
b
b
b
11.51
12.49
aThe GC operating conditions were as follows:  30-m x 0.53-mm ID DB-5
 (0.83-Mm film thickness) and 30-m x 0.53-mm ID DB-1701  (l.Q-pm  film
 thickness)  connected to an 8-in injection tee (Supelco  Inc.).  Temperature
 program:  140°C  (2-rain  hold)  to  270°C  (1-min  hold)  at   H.8°C/min; injector
 temperature 250°C;  detector temperature 320°C; helium carrier gas  6 mL/min;
 nitrogen  makeup gas 20 mL/min.
     detected at 2 ng per injection.
                                  8081  - 32                         Revision 0
                                                                September 1994

-------
Column  1:
                                    TABLE 6
              GC OPERATING CONDITIONS FOR ORGANOCHLORINE PESTICIDES
                       FOR DUAL  COLUMN METHOD OF ANALYSIS
                          LOW TEMPERATURE, THIN FILM
            Type:  DB-1701  (J&W) or equivalent
            Dimensions:  30 m x 0,53 mm  ID
            Film Thickness  (^m):   1.0
Column 2:
            Type:  DB-5  (J&W) or equivalent
            Dimensions:  30 m x 0.53 mm  ID
            Film Thickness (urn):   0.83
Carrier gas flowrate (mL/min):  6  (Helium)
Makeup gas flowrate (mL/min):  20  (Nitrogen)
Temperature program:  140°C (2 min hold) to 270°C  {1  min  hold)  at 2.8°C/min
Injector temperature:  25Q°C
Detector temperature:  320°C
Injection volume:  2 /jL
Solvent:  Hexane
Type of injector:  Flash vaporization
Detector type:  Dual ECD
Range:  10
Attenuation:  64 (DB-1701)/32 (DB-5)
Type of splitter:  Supelco 8 in injection tee
                                   8081  -  33                         Revision 0
                                                                September 1994

-------
Column  1:
                                    TABLE  7
              GC  OPERATING CONDITIONS FOR  ORGANOCHLORINE PESTICIDES
                     FOR THE DUAL  COLUMN HETHOD  OF  ANALYSIS
                          HIGH TEMPERATURE,  THICK FILM
            Type:  DB-1701  (J&W)  or equivalent
            Dimensions:   30 m  x  0.53 mm  ID
            Film Thickness:  1.0  m
Column 2:
            Type:  DB-5  (J&W)  or  equivalent
            Dimensions:   30 m  x 0.53 mm  ID
            Film Thickness:  1.5  pm
Carrier gas flowrate  (mL/min):  6 (Helium)
Makeup gas flowrate  (mL/min):  20 (Nitrogen)
Temperature program:   150°C (0.5 min hold) to 190°C (2 min hold)  at  12°C/min
                       then to  275°C (10 min hold) at 4°C/imn-
Injector temperature:  250°C
Detector temperature:  320°C
Injection volume:  2 Mi-
Solvent:  Hexane
Type of injector:  Flash  vaporization
Detector type:  Dual ECD
Range:  10
Attenuation:  64 (DB-1701)/64  (DB-5)
Type of splitter:  J&W Scientific  press-fit Y-shaped  inlet splitter
                                   8081  -  34                        Revision 0
                                                                September 1994

-------
              TABLE 8   SUMMARY OF  RETENTION TIMES  (MIN) OF AROCLORS
                                ON  THE DB-5 COLUMN8
                              DUAL  SYSTEM OF ANALYSIS
Peak
Mo.b
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41

42
43
44
45
46
47
48

49
50
51
52
53
54
55
Aroclor
1016


8.41
8,77
8.98
9.71
10.49
10.58
10.90
11.23
11.88
11.99
12.27
12.66
12.98
13.18
13.61
13.80
13.96
14.48
14.63
14.99
15.35
16.01

16.27































Aroclor-
1221
5.85
7.63
8.43
8.77
8.99

10.50
10.59

11.24


12.29
12.68
12.99










































ft roe I or
1232
5.85
7.64
8.43
8.78
9.00

10.50
10.59
10.91
11.24
11.90
12.00
12.29
12.69
13.00
13.19
13.63
13.82
13.97
14.50
14.64
15.02
15.36

16.14
16.29

17.04
17.22
17.46



18.41
18.58

18.83
19.33


20.03





21.18










Aroclor
1242

7.57
8.37
8.73
8.94
9.66
10.44
10.53
10.86
11.18
11.84
11.95
12.24
12.64
12.95
13.14
13.58
13.77
13.93
14.46
14.60
14.98
15.32
15.96
16.08
16.26


17.19
17.43

17.92
18.16
18.37
18.56

18. 80
19.30


19.97


20.46

20.85
21.14



2Z.08






Aroclor
1248




8.95

10.45

10.85
11.18
11.85

12.24
12.64
12.95
13.15
13.58
13.77
13.93
14.45
14.60
14.97
15.31

16.08
16.24

16.99
17.19
17.43
17.69
17.91
18.14
18.36
18.55

1S.78
19.29


19.92


20.45

20.83
21.12
21.36


22.05






Aroctor
1254
















13.59
13.78
13.90
14.46

14.98
15.32

16.10
16.25
16.53
16.96
17.19
17.44
17.69
17.91
18.14
18.36
18.55

18.78
19.29
19.48
19.81
19.92

20.28

20.57
20.83
20,98
21.38
21.78

22.04
22.38
22.74
22.96
23.23

23.75
Aroclor
1260
















13,59








16.26

16.97
17.21




18.37

18.68
18.79
19.29
19.48
19.80


20.28

20.57
20.83

21.38
21.78

22.03
22.37
22.73
22.95
23.23
23.42
23.73
Pesticide eluting at same
retention time









Chtorothalonil (11.18)















Captan (16.21)

gamna-Chlordane (16.95)





4,4' -DDE (18.38)
Dieldrin (18.595





Chloropropylate (19.91)
Endosulfan II (19.91)


%

Kepone (20.99)

4,4'-OOT (21.75)
Endosulfan sulfate (21.75)


Captafol (22.71)



Endrin ketone (23.73)
"The GC operating conditions are given in Table 7.
                                                                            (continued)
                                     8081  - 35
    Revision 0
September 1994

-------
                                     TABLE 8   CONTINUED
Peak
No.
56
57
58

59
60
61
62
63
64
65
66
67
68
69
Aroclor Aroctor Aroclor Aroclor Aroclor Aroclor
1016 1221 1232 1242 1248 1254
23.99

24.27


24.61
24.93

26.22






Aroclor Pesticide eluting at same
1260 retention time
23.97
24.16
Hethoxychtor (24.29)
OJcofot (24.29)
24.45
24.62
24.91
25.44
26.19 Mirex (26.19)
26.52
26.75
27.41
28.07
28.35
29.00
"The GC operating conditions are given in Table 7.
"These are sequentially numbered from elution order and are not isomer numbers
                                          8081  - 36
     Revision  0
September 1994

-------
              TABLE 9   SUMMARY OF RETENTION TIMES  (MIN) OF AROCLORS
                               ON THE DB-1701 COLUMN'
                              DUAL SYSTEM OF ANALYSIS
Peak
No,.
1
2
3
4
5
6
7
B
9
10
11
12
13
14
15
16
17
18
19
20 •
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
Aroctor Aroclor
1016 1221
4.45
5.38
5.78
5.86
6.33 6.34
6.78 6.78
6.96 6.96
7.64
8.23 8.23
8.62 8.63
8.88
9.05 9.06
9.46
9.77 9.79
10.27 10.29
10.64 10.65

11.01
11.09
11.98
12.39

12.92
12.99
13.14

13.49
13.58


























Aroclor
1232
4.45
5.86
6.34
6.79
6.96

8.23
8.63
8.89
9.06
9.47
9.78
10.29
10.66

11.02
11.10
11.99
12.39
12.77

13.00
13.16

13.49
13.61

14.08
14.30

14.49


15.38
15.65
15.78
16.13




16.77
17.13









Aroclor
1242
6.28
6.72
6.90
7.S9
8. 15
8.57
8.83
8.99
9.40
9.71
10.21
10.59
10.96
11.02

11.94
12.33
12.71
12.94
13.09


13.44
13.54
13.67
14.03
14.26

14.46


15.33
15.62
15.74
16.10




16.73
17.09

17.46
17.69

18.48


19.13

Aroclor
1248


6.91

8.16

8.83
8.99
9.41
9.71
10.21
10.59
10.95
11.03

11.93
12.33
12.69
12.93
13.09


13.44
13.54

14.03
14.24
14.39
14.46

15.10
15.32
15.62
15.74
16.10




16.74
17.07

17.44
17.69
18.19
18.49


19.13

Aroctor
1254












10.95


11.93
12.33


13.10

13.24

13.51
13.68
14.03
14.24
14.36

14.56
15.10
15.32
15.61
15.74
16.08

16.34
16.44
16.55
16.77
17.07
17.29
17.43
17.68
18.17
18.42
18.59
18.66
19.10
19.42
Aroclor Pesticide eluting at same
1260 retention time


Triflurslin (6.96)




















13.52

14.02
14.25


14.56

Chlordane (15.32)
16.61 4,4' -DDE (15.67)
15.79

16.19
16.34
16.45

16.77 Perthane (16.71;
17,08
17.31
17.43
17.68
18.18
18.40

18.86
19.09 Endosylfan M C 19.05)
19.43
"The 6C operating conditions are given in Table 7.
                                                                            (continued)
                                     8081  - 37
    Revision 0
September  1994

-------
                                     TABLE 9   CONTINUED
Peak
No.
55
56
5?
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
Aroclor Aroclor Aroclor Aroclor Aroctor Aroclor
1016 1221 1232 1242 1248 1254
19.55
20.20
20.34

20.57 20.55
20.62
20.88

21.53
21.83
23.31








Aroclor Pesticide elating at sane
1260 retention time
19.59 4,4'-DDT (19.54)
20.21

20.43

20.66 Endrin aldehyde (20.69)
20.87
21.03
21.53
21.81
23.27
23.85
24.11
24.46
24.59
24.87
25.85
27.05
27.72
*Th* GC operating  conditions are given in Table 7.
"These are sequentially timbered from elution order and are not  isomer numbers
                                          8081  -  38
     Revision  0
September 1994

-------
                                   TABLE 10
            PEAKS DIAGNOSTIC OF PCBs OBSERVED IN 0.53 mm ID COLUMN
                            SINGLE COLUMN ANALYSIS
Peak          RT  on      RT on                           Elution
 No.c       DB 60S8   DB 1701' Aroc1orb                  Order

I             OO        Ol  1ZZ1'                  Before TCmX

II            7.15        6.98  1221, 1232, 1248         Before a-BHC

III           7.89        7.65  1061,1221., 1232, 1242,  Before a-BHC

IV            9.38        9.00  1016, 1232, 1242, 1248,  just after a-BHC  on
                                                        DB-1701;just before
                                                        7-BHC on  DB-608

V           10.69       10.54  1016, 1232, 1242.        1248 a-BHC and
                                                        heptachlor on  DB-1701;
                                                        just after heptachlor
                                                        on DB-608

VI          14.24       14.12  1248, 1254               7-BHC and heptachlor
                                                        epoxide on DB-1701;
                                                        heptachlor epoxide  and
                                                        7-Chlordane  on DB-608

VII         14.81       14.77  1254                     Heptachlor epoxide  and
                                                        7-Chlordane  on
                                                        DB-1701; a-  and
                                                        7-Chlordane  on DB-608

VIII        16.71       16.38  1254                     DDE and Dieldrin  on
                                                        DB-1701; Dieldrin and
                                                        Endrin on DB-608

IX          19.27       18.95  1254, 1260               Endosulfan II  on
                                                        DB-1701; DDT on DB-608
                                                       Continued
                                   8081  - 39                         Revision 0
                                                                September 1994

-------
                             TABLE 10 (Continued)
            PEAKS DIAGNOSTIC OF PCBs OBSERVED IN 0.53 mm ID COLUMN
                            SINGLE  COLUMN  ANALYSIS
Peak         RT on      RT on                            Elution
 No.        DB 608°   DB 1701"    Aroclor"              Order
X           21.22       21.23       1260                 Endrin aldehyde  and
                                                        Endosulfan  sulfate on
                                                        DB-1701;  Endosulfan
                                                        sulfate and
                                                        Methoxychlor on
                                                        on  DB-608

XI          22.89       22.46       1260                 Just  before endrln
                                                        ketone on DB-1701;
                                                        after endrin ketone on
                                                        DB-608
   Temperature program:  Ts = 150°C, hold 30 seconds; increase temperature at
               to  275°C.
b  Underlined Aroclor indicates the largest peak in the pattern.

c  These are sequentially numbered from slut ion order and are not isomer
   numbers
                                  8081 - 40                         Revision 0
                                                                September 1994

-------
                 TABLE 11  SPECIFIC PCB CONGENERS IN AROCLORS
Congener
IUPAC number
                  Aroclor
1016  1221  1232  1242  1248  1254  1260
Biphenyl
2CB
23DCB
34DCB
244'TCB
22'35'TCB
23'44'TCB
233'4'6PCB
23'44'5PCB
22'44'55'HCB
22'344'5'HCB
22'344'55'HpCB
22'33'44'SHpCB

1
5
12
28*
44
66*
110
118*
153
138
180
170
X
XXX
XXX
X X
X X
X








X
X
X
X
X









X
X
X
X
X










X
X
X
X
X










X

X
X
X
X
X
*apparent co-elution of two major peaks:

      28 with 31 (2,4',5 trichloro)
      66 with 95 (2,2',3,5',6 pentachloro)
      118 with 149 (2,2',3,4'f5',6 hexachloroj
                                  8081 - 41
                                                  Revision 0
                                             September  1994

-------
                 TABLE 12  ANALYTE RECOVERY FROM SEWAGE SLUDGE
Compound
Sonication
Soxhlet

Hexachloroethane
2-Chloronapthalene
4-Bromodiphenyl ether
a-BHC
y-BHC
Heptachlor
Aldrin
iS-BHC
<5-BHC
Heptachlor epoxide
Endosulfan I
7-Chlordane
a-Chlordane
DDE
Dieldrin
Endrin
Endosulfan II
DDT
Endrin aldehyde
DDD
Tetrachl oro-nt-xyl ene
Decachl orobi pheny 1
^Recovery
80
50
118
88
55
60
92
351
51
54
52
50
49
52
89
56
52
57
45
57
71
26
%RSD
7
56
14
25
9
13
33
71
11
11
11
9
8
11
19
10
10
10
6
11
19
23
^Recovery
79
67
nd
265
155
469
875
150
57
70
70
65
66
74
327
92
88
95
42
99
82
28
%RSD
1
8

18
29
294
734
260
2
3
4
1
0
1
7
15
11
17
10
8
1
48
Concentration spiked in the sample:  500-1000 ng/g
Three replicates/sample

Extraction solvent, Method 3540 - methylene chloride
Extraction solvent, Method 3550 - methylene chloride/acetone (1:1)

Cleanup - Method 3640

GC column - DB-608, 30M X 0.53 mm ID
                                  8081  - 42
                                   Revision 0
                               September 1994

-------
               TABLE 13  ANALYTE RECOVERY FROM DCE STILL BOTTOMS
Compound
Sonlcation
Soxhlet

Hexachloroethane
2-Chloronapthal ene
4-Bromodiphenyl ether
a-BHC
/3-BHC
Heptachlor
Aldrin
0-BHC
S-BHC
Heptachlor epoxide
Endosulfan I
7-Chlordane
a-Chlordane
DDE
Dieldrin
Endrin
Endosulfan II
DDT
Endrin aldehyde
ODD
Tetrachloro-m-xylene
Decachlorobiphenyl
%Recovery
70
59
159
55
43
48
48
51
43
47
47
48
45
45
45
50
49
49
40
48
49
17
%RSD
2
3
14
7
6
6
5
7
4
6
4
5
5
4
5
6
5
4
4
5
2
29
^Recovery
50
35
128
47
30
55
200
75
119
66
41
47
37
70
58
41
46
40
29
35
176
104
%RSD
30
35
137
25
30
18
258
42
129
34
18
13
21
40
24
23
17
29
20
21
211
93
Concentration spiked in the sample:  500-1000 ng/g
Three replicates/sample

Extraction solvent, Method 3540 - methylene chloride
Extraction solvent, Method 3550 - methylene chloride/acetone (1:1)

Cleanup - Method 3640

GC column - DB-608, 30M X 0.53 ran ID
                                   8081  - 43
                                   Revision 0
                               September 1994

-------
                                   TABLE  14
             SINGLE LABORATORY ACCURACY DATA FOR THE EXTRACTION OF
        ORGANOCHLORINE PESTICIDES FROM SPIKED CLAY SOIL BY METHOD 3541
                              (AUTOMATED SOXHLET}'
Compound Name
a-BHC
J3-BHC
Heptachlor
Aldrin
Heptachlor epoxide
trans-Chlordane
Endosulfan I
Dieldrin
Endrin
Endosulfan II
4,4'~DDT
Mi rex
Spike Level
M9A9
500
100
500
500
500
500
500
500
500
500
500
500
% Recovery
DB-5
89
86
94
b
97
94
92
b
111
104
b
108

DB-1701
94
b
95
92
97
95
92
113
104
104
b
102
a     The  operating  conditions  for the  automated Soxhlet  were as  follows:
      immersion time 45 nrin; extraction time  45 win;  the  sample  size was 10 g
      clay soil, extraction solvent, 1:1 acetone/hexane.  No equilibration time
      following spiking.

b     Not able to determine because of interference.

Data taken from Reference 14.
                                   8081  - 44                         Revision 0
                                                                September 1994

-------
                         TABLE 15
     SINGLE LABORATORY RECOVERY  DATA FOR EXTRACTION OF
PCBS FROM CLAY AND SOIL BY METHOD 3541* (AUTOMATED  SOXHLET)
Matrix Compound Spike Level
(ppm)
Clay Aroclor-1254 5





Clay Areclor-1254 50





Clay Aroclor-1260 5





Clay Aroclor-1260 50





Soil Aroclor-1254 5




Soil Aroclor-1254 50





Trial
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
6
1
2
3
4
5
1
2
3
4
5
6
Percent
Recovery13
87.0
92.7
93.8
98.6
79.4
28.3
65.3
72.6
97.2
79.6
49.8
59.1
87.3
74.6
60.8
93.8
96.9
113.1
73.5
70.1
92.4
88.9
90.2
67.3
69.7
89.1
91.8
83.2
62.5
84.0
77.5
91.8
66.5
82.3
61.6
                                            (continued)
                         8081  -  45
    Revision 0
September 1994

-------
                                   TABLE 15
                                  (continued)
Matrix Compound Spike Level
(ppm)
Soil Aroclor-1260 5






Soil Aroclor-1260 50





Trial
1
2
3
4
5
6
7
1
2
3
4
5
6
Percent
Recovery*"
83.9
82.8
81.6
96.2
93.7
93.8
97.5
76.9
69.4
92.6
81.6
83.1
76.0
a     The  operating  conditions  for the  automated  Soxhlet  were  as  follows;
      immersion time 60 min; reflux time 60 min.

b     Multiple results from two different extractors.

Data from Reference 15.
                                  8081 - 46
    Revision 0
September 1994

-------
            TABLE 16.   MULTI-LABORATORY PRECISION AND ACCURACY DATA
                  FOR THE EXTRACTION OF PCBS FROM SPIKED SOIL
                      BY METHOD 3541  (AUTOMATED  SOXHLET)
Laboratory
Lab 1 ! Num
! Average
] St Dev
Lab 2 | Num
* Average
• St Dev
Lab 3 ! Num
I Average
] St Dev
«**«***. «....™™.™.,»™,»..™.i,....™jj«»..1™.»..»™,»i™.™™,,
Lab 4 I Num
! Average
j St Dev
Lab 5 j Num
! Average
[St Dev
„...,..„.«.„ .„„....,„„....„.,,.., !„„„»..„..„.....„...,..,
Lab 6 i Num
! Average
! St Dev
1
Lab 7 | Num
! Average
j St Dev
Lab 8 i Num
! Average
j St Dev
Al 1 | Num
Laboratories ! Average
i st Dev
PCB Percent Recovery
Aroclor
1254
PCB Level
5
3.0
101.2
34.9

3.0
72.8
, 10.8
6.0
112.6
18.2

2.0
140.9
4.3
3.0
100.1
17.9
3.0
65.0
16.0
20.0
98.8
28.7
50 j 500
3.0
74.0
41.8
6.0
56.5
7.0
3.0
63.3
j. 8-3
6.0
144.3
30.4
3.0
97.1
8.7
3.0
127.7
15.5
3.0
123.4
14.6
3.0
38.3
21.9
30.0
92.5
42.9

6.0
66.9
15.4


3.0
80.1
5.1

„.,,.,.-...„,.,.

.„..,.,........„
9.0
71.3
14.1
1260
PCB Level
5
3.0
83.9
7.4

3.0
70.6
2.5
6.0
100.3
13.3

3.0
138.7
15.5
3.0
82.1
7.9
3.0
92.8
36.5
21.0
95.5
25.3
50
3.0
78.5
7.4
6.0
70.1
14.5
3.0
57.2
5.6
6.0
84.8
3.8
3.0
79.5
3.1
4.0
105.9
7.9
... , .
3.0
94.1
5.2
3.0
51.9
12.8
31.0
78.6
18.0
500

6.0
74.5
10.3

,„„„„.„„„„.
•"""•""""*"
	
3.0
77. 0
9.4


,. 	 „.„„
...,..„„.„.,„.
9.0
75.3
9.5
All
Level s
12.0
84.4
26.0
24.0
67.0
	 .13. 3 _
12.0
66.0
, l:.l 	
|,™*M>™.....™. ...«.,«..,
24.0
110.5
28.5
12.0
83.5
10.3
12.0
125.4
18.4
12.0
99.9
19.0
12.0
62.0
29.1
120.0
87.6
29.7
Data from Reference 13.
                                  8081  - 47
    Revision 0
September 1994

-------
                                        FIGURE 1.
          GAS CHROMATOGRAM  OF THE MIXED  ORGANOCHLORINE PESTICIDE STANDARD
Stan Tine : 0.00 Bin
Scale Factor:   0
                            End TiM  : 11.00 Bin
                            Plot Of fit!: 20 w
                     LM Point : 20.00 W
                     flat Scatt: 400 *v
                                                                 High Point : (20.00 «V
                                        Response [mV]
                           tin 11 i  11 i T i 111 111  111 111  11
                                               o      cr»     o     01     o
                                                      O     O     O     C3
       o
     13
     0)

     !D
     3
         .
     j O
                       =5-3.38
                       --4.68
                        -7.99
                                             -9.93
                                -10.78
                -11.05
            -11.81
                                          -13.65
                         •14.34
                                          -14.92
                                     -16.32

                                     	17.17
                                                   -17.63

                                                   '	18.56
                            -21.93
                                                •22.77
                                                           -23.18
                             -23.80
                              •26.23
                             ••-28.64
                                                                             -0.95
                                                                             -8.60
                                                                         -30.19
Column:
Temperature program:
30 m  x  0.25 mm  ID,  DB-5
100°C  (hold 2  minutes)  to  160°C at  15°C/min,  then  at
5°C/min to  270°C;  carrier  He at  16 psi.
                                      8081 - 48
                                                Revision  0
                                            September  1994

-------
                                       FIGURE  2.

     GAS  CHROMATOGRAM OF INDIVIDUAL ORGANOCHLORINE  PESTICIDE  STANDARD MIX A



          St«rt Tine : 0,00 «i(n      tnd Tint  : 33.00 »*n       ton »omt : 20.00 w      »i§n i>3i« : 270.60 «
          Scale Factor:   a         Plot Olfue: 30 mv         Plot Sou: 250 ay
         Ul—
      m
         ->.
      H

      3'
      CD
      3
         K3

         Uf
                               (Jl
                               o
 Response  [mV]

 —*          —i
 O          Ui

1
                                     to
                                     o
                                     o
CO
en
O
Column:

Temperature program:
                         '-7.93
                             1.60
                          I
                            •12.33
                            -14.27
  -17.08
      !0.22

      1,77
                                   22.68
                                 -23.73
                                    •28.52
                                                                               -8.54
                                                         •-9.86
                                                      -10.98
                                                     -13.58
                                         -17.54
                                           -18.47,
                                                             -19.24
                                                 -19.78
                                                        -21.13
                                                                               -23.03
                                                                         -30.05
30 m  x  0.25 mm  ID,  DB-5

100°C  (hold  I minutes) to  160°C  at 15°C/min,  then at

5°C/min  to 270°C; carrier  He at  16 psi.
                                      8081  -  49
                                                Revision 0

                                            September 1994

-------
                                      FIGURE 3
     GAS  CHROMATOGRAM OF  INDIVIDUAL ORGANOCHLORINE PESTICIDE STANDARD MIX 8

        Staft f»«* : O.DO sin     End fi^e  : 33.00 
O O O O
1 1 t 1 | 1 1 1 I ! 1 | 1 1 1 I 1 | j 1 !
















11

•6?.— . 71 01

.00

\

f^
Column:
Temperature program:
30 m x 0.25 ram ID, DB-5
100°C (hold 2  minutes)  to 160°C  at 15°C/min,  then  at
5°C/rain to  270°C;  carrier He at  16 psi.
                                     8081 - 50
                                               Revision 0
                                           September  1994

-------
                                       FIGURE 4.
                     GAS CHROMATOGRAM OF THE TOXAPHENE  STANDARD


      Stir; Tine : 0.00 Bin      En£ Ti*» : 13.00 Din      la* Mint : 20.80 W      Hif* Point ; SO.00 an
      Sc«U Metor:   a         Pict Offut: 20 «         Plot ««««: 6C M
                                     Response  [mV]
     o-
C        O

 I I I II I I I II I I I I I I I I II
                                       •

                                      Ti 1111 n i in 1111
   O        O
IIIJI! 1 t I111II I I I I I I II 11
     Ul—
   13
   ftl
   H
                            Y*f
                                                                           24.32
Coluran:
Temperature program:
      30 m  x 0.25 mm  ID,  DB-5
      100°C  (hold  2 minutes)  to  160"C at  15°C/min»  then  at
      5°C/min  to 270°C; carrier  He at  16 psi.
                                     8081  - 51
                                                      Revision  0
                                                  September  1994

-------
                                       FIGURE 5,
                    GAS CHROMATOGRAM OF  THE AROCLOR-1016 STANDARD

         Start ft« : 0.00 niin      End Time  ; 33.00 Bin      Lay Point ! 20.00 ail      High Point i 120.80 m»
         Scale Factor:   9         Plot Offset: 20 *tf         Hot Scilt: 109 W
                                        Response
                       IN)
                       O
        f™
        f 1111 i
Ol
o
00
o
o
o
      -I
      5'
        L-J
                                  -1,81
                                                         -12.95
                                                                             -1.03
Column:
Temperature program:
30 m x 0.25 mm ID DB-S fused silica capillary.
100°C  (hold 2  minutes)  to  160°C  at  15°C/nnn,  then at
5°C/min to  270°C;  carrier  He at 16 psi.
                                     8081  - 52
                                                Revision 0
                                           September 1994

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                                  FIGURE 6.

           GAS CHROMATOGRAM OF  THE TECHNICAL  CHLORDANE STANDARD



    Stirt tine  : 0.00 nin     End Tine  : 33.00 mm      lav foim : 20.00 DM      nigh Point : 220.00 IN
    Seat* Fictor:  0        Plot OHict: 20 nV         Hot Jciio: 200 «
                                   Response  [mV]
                         1
                                          o
                                          o
       y
       o

i   i  i   I   i
KJ
O
o
33   -
n

5


H

~*
_i

fit
    .
  o
                                i..59
                    —4.33




                    •5.83
                         -8.87
                                           13.60
                                    38
                                                              17.11

                                                             17.65
Column:

Temperature program:
                      30  m x 0,25 mm ID D8-5 fused  silica capillary.

                      100°C  (hold  2 minutes) to  160°C at  15°C/min,  then  at

                      5°C/min  to 270"C; carrier  He at  16 psi.
                                  8081 - 53
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                                                                     September 1994

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           DB-1701
   LJ
          Di-5
FIGURE 7,    GC/ECD chromatogram of Toxaphene analyzed, on a DB-5/DB-1701 fused-
            silica open-tubular column pair.  The GC operating conditions were
            as follows:   30 m x 0.53  ram ID DB-5 (1.5-M"i film thickness) and 30
            m x 0.53 mm ID OB-1701 (l.C-^ra  film thickness)  connected to a J&W
            Scientific press-fit Y-shaped  inlet  splitter.  Temperature program:
            150°C  (0.5 min  hold) to 190°C (2 min hold)  at 12°C/min then  to 275°C
            (10 min hold)  at 4°C/rnin.
                                  8081  - 54
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              08-1701
              DB-S
FIGURE 8.    GC/ECD chromatogram of  Strobane  analyzed on a DB-5/DB-1701  fused-
            silica open-tubular column pair.  The GC operating conditions were
            as follows:  30 m x 0.53 mm ID DB-5 (1.5-^m film thickness)  and 30
            m x 0.53 mm ID DB-17Q1  (1.0-/Ltm film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet  splitter.  Temperature program:
            150°C  (0.5  min  hold) to  190°C (2 rain hold) at 12°C/min then  to 27S°C
            (10 min hold)  at 4°C/">in.
                                   8081  -  55
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                                                       DB-1701
                                                       DB-5
     •JlJL
                                        a-
                                        u-
                                        0
FIGURE 9.    GC/ECD chromatogram  of Aroclor  1016  analyzed  on a  DB-5/DB-1701
            fused-silica open-tubular  column pair.  The EC operating conditions
            were as follows:  30 m x 0.53 ram ID DB-5 (LS-^m film thickness) and
            30 m x 0.53 mm ID DB-1701 (1.0-^m film thickness) connected to a J&W
            Scientific press-fit  Y-shaped inlet splitter.  Temperature program:
            150°C (0.5 min hold)  to  190°C (2 min hold) at 12°C/min then to 275°C
            (10 min  hold) at 4°C/rain.
                                  8081  -  56
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                   01
                                                       OB-1701
                            4.
                            0-
                            f*-0
      o
      p~
                                                      DB-5
FIGURE 10.  GC/ECD  chromatogram of  Aroclor  1221  analyzed on  a DB-5/DB-1701
            fused-silica open-tubular column pair.  The GC  operating  conditions
            were as follows:   30 m x 0.53 mm ID DB-5 (1.5-/am film thickness)  and
            30 m x 0.53 mm ID DB-1701 (1.0-Mm  film thickness) connected to a  J&W
            Scientific press-fit Y-shaped inlet splitter.   Temperature program;
            150°C (0.5 min hold) to  190°C  (2 min hold) at lZ°C/min then to 275°C
            (10 min hold) at 4°C/min.
                                   8081  - 57
    Revision 0
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                                                   DB-1701
                                                     -5
FIGURE 11.   GC/ECD chromatogram  of Aroclor  1232  analyzed  on  a  DB-5/DB-1701
            fused-silica open-tubular  column  pair.  The GC operating conditions
            were as follows:  30 m x 0.53 nwi ID  DB-5 (l,5-/*m film thickness) and
            30 m x 0.53 mm ID DB-1701 (1.0-^m film thickness)  connected to  a J&W
            Scientific press-fit  Y-shaped inlet splitter.  Temperature program:
            150°C (0.5 min hold)  to  190°C (2 min hold) at 120C/min  then to  275°C
            (10 min hold) at 4°C/min.
                                  8081  -  58
    Revision 0
September 1994

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          9-
          m



1
4
1
WD "1
•a
*


Sy
                                                          OB-1701
       siJy
                                                         DB-5
FIGURE 12.  GC/ECD  chromatogram of Aroclor  1242  analyzed  on a  DB-5/DB-1701
            fused-silica open-tubular column  pair.  The GC operating conditions
            were as follows:   30 m x 0,53 mm ID Di-i {1,5-Mm film thickness) and
            30 m x 0.53 mm ID DB-1701 (1.0-^m film thickness) connected to i JiW
            Scientific press-fit Y-shaped inlet splitter.  Temperature program;
            150°C to.5 min hold) to  190°C (2 min hold)  at IZt/mJn then to 275°C
            (10 min hold) at 40C/min.
                                   8081  -  59
    Revision 0
September 1994

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                                                              DB-1701
                                                        »  *
                                                        £  A
                                                             DB-5
                01  ft
                a  m
                o>  -
FIGURE 13.  GC/ECD chromatogram  of  Aroclor 1248  analyzed on  a DB-5/DB-17Q1
            fused-silici open-tubular column pair.   The GC  operating conditions
            were as follows:  30 m x 0.53 mm ID  DB-5 (1.5-^1) film thickness)  and
            30 m x 0.53 mm ID DB-1701 (l.Q-jim film thickness) connected to a  J&W
            Scientific press-fit  Y-shaped inlet splitter.   Temperature program:
            150°C (0.5 min hold) to  190°C (2 min hold) at 12°C/min then to 275°C
            (10 min hold) at 4'C/min.
                                  8081  -  60
    Revision 0
September 1994

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                                                             DB-1701
                                                             »
                                                             *
                                                             «
                                                            »
                                                            m
                                                                  r»
                                                                  n
                                                             DB-5
         0 Clt  U Ml !•»
           -«>  Ol*'! -
                               r«
FIGURE 14.  GC/ECD  chroraatogram of  Aroclor  1254  analyzed  on  a  DB-5/DB-1701
            fused-silica open-tubular column pair.   The GC operating  conditions
            were as follows:   30 m x 0,53 mm ID DB-5 (1.5-
-------
                         DB-1701
                        DB-5
                                                     Hn
FISURE 15.  GC/ECD  chromitogram  of Aroclor  1260  analyzed  on  a  DB-5/DB-1701
            fused-silica open-tubular column  pair.  The GC operating conditions
            were as follows;  30 m x 0,53 ram ID DB-5 (LS-^n film thickness) and
            30 m x 0.53 mm ID DB-1701 (1.0-/im film thickness) connected to a J&W
            Scientific press-fit Y-shiped inlet  splitter.  Temperature program:
            150°C (0.5 min hold)  to  190°C (2 min hold) at 12°C/min  then to 275°C
            (10 min hold) at 4°C/min.
                                   8081  -  62
    Revision 0
September 1994

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                                                        OB-1701
»
0>
                                                       DB-5
            9    o T o> fwBO
           -ni o  OIM a> ~  ~
                                               e 
-------
                                                Di-1701
FIGURE 17.  GC/ECD  chromatogram  of Halowax  1001  analyzed  on  a  DB-5/DB-1701
            fused-silica open-tubular  column  pair.  The GC operating conditions
            were as follows:  30 m x 0.53 mm ID  DB-5 (1.5-^m film thickness) and
            30 m x 0.53 mm ID DB-1701 (1.0-p film thickness) connected to a J&W
            Scientific press-fit  Y-shaped inlet splitter.  Temperature program:
            150eC (0.5 ruin hold)  to  190°C (2 min hold)  at 12°C/min  then to 275°C
            (10 min hold) at 4°C/nnn.
                                  8081  -  64
    Revision 0
September 1994

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                                                          01-1701
                                                          DB-5
                  3
FIGURE 18.   GC/ECD chromatogram  of  Halowax  1099  analyzed  on  a  DB-5/DB-17Q1
            fused-sillca open-tubular column  pair.  The GC operating conditions
            were as follows:  30 m x 0.53 ran ID DB-5 (1.5-jim film thickness) and
            30 m x 0.53 mm ID DB-1701 (1.0-Min film thickness)  connected to a JiW
            Scientific press-fit  Y-shaped inlet splitter.  Temperature program:
            150°C (0.5 min hold) to  190°C (2 min hold) at 12°C/min  then to 275°C
            (10 min hold) at 4°C/min.
                                  8081  - 65
    Revision 0
September 1994

-------
           H
           m
           
-------
                        DB-I70I
                 ^CLi^
FIGURE 20.   GC/ECD chromatogram  of Halowax  1014  analyzed on  a DB-5/DB-1701
            fused-silica open-tubular column pair.  The GC  operating conditions
            were as follows:  30 ra x 0.53 mm ID OB-5 (1.5-pm film thickness) and
            30 m x 0,53 mm ID DB-1701 (1.0-Mm film thickness) connected to a J&W
            Scientific press-fit  Y-shaped inlet splitter.   Temperature program:
            150°C  (O.S min hold) to 190°C  (2 min hold)  at 12°C/min then to 275"C
            (10 min hold)  at 4°C/min.
                                  8081 - 67
    Revision 0
September 1994

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                             OB-1701
                             DB-5
FIGURE 21.  GC/ECD  chromatogram  of Halowax  1051 analyzed  on a  DB-5/DB-1701
            fused-silica open-tubular column  pair.  The GC operating conditions
            were as follows:  30 m x 0.53 mm ID DB-5 (1.5-Mm film thickness) and
            30 m x 0.53 mm ID OB-1701 (l.O-'pm film thickness) connected to a J&W
            Scientific press-fit  Y-shaped inlet splitter.  Temperature program:
            150°C (0,5 min hold) to  190°C (2 min hold) at 12°C/nnn then to 27i°C
            (10 min hold) at 4"C/min.
                                  8081  - 68
    Revision 0
September 1194

-------
                                     DB-5
       2    <
                                    DB-1701
i 2


3


t


1 j

I
it


S 1

J, .
f
t
j
J

im*
I


0 I


I I


t 1


1 ,
'«


ij?
1
1
1 V
ti


» JJ
_i
4 3

                                                               M
                                                           y
FIGURE 22.   GC/ECD chromatogram of the organochlorine pesticides analyzed on a
            DB-5/DB-1701  fused-silica  open-tubular  column  pair.    The  GC
            operating conditions were  as follows:  30 m x 0.53 mm ID DB-5 (0.83-
            j*m  film  thickness) and 30  m x  0.53 mm  ID DB-1701  (1.0-^m film
            thickness)  connected  to  an  8  in  injection  tee  (Supelco  Inc.).
            Temperature program:  140°C (2 min hold)  to 270°C  (1 min hold) at
                                  8081  - 69
    Revision 0
September 1994
                                                                          \

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                                     METHOD 8081

              ORGANOCHLORINE PESTICIDES AND  PCBs AS AROCLORS  BY GAS
                    CHROMATOGRAPHY: CAPILLARY COLUMN TECHNIQUE
     7.1.11
  appropriate cxtncfon
        (M* Ctvptar 2)
        1
   7.1.2 Add tpectttod
  iraftta spto to mnpto.
        I
     fracfcnaflort
        I
 7.3 SM ctaamlagrapMe
      condUorw.
        I
7.4 Rotor to IMhoti 8000
  for prepflr oMbndion
 7.4.2 Prim or daocttvaie GC
7.5 Perform GCanaly*»(s
        7.SJ
      Anysampte
      poaklmr
                                                              DOT. and BHC done hen».
                                    8081  - 70
                                          Revision 0
                                      September 1994

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                                 LIST OF TABLES

Table  1     Gas chromatographic retention times and method detection  limits  for
            the Organochlorine Pesticides and PCBs  as Aroclors using wide-bore
            capillary columns, single column analysis

Table  2     Gas chromatographic retention times and method detection  limits  for
            the Organochlorine pesticides  and PCBs as Aroclors using narrow-bore
            capillary columns, single column analysis

Table  3     Estimated quantitation limits (EQLJ for various matrices

Table  4     GC Operating conditions for  Organochlorine compounds,  single column
            analysis

Table  5     Retention times of the Organochlorine pesticides, dual  column method
            of analysis

Table  6     GC operating conditions for Organochlorine pesticides, dual column
            method of analysis, low temperature, thin film

Table  7     GC operating conditions for Organochlorine pesticides, dual column
            method of analysis, high temperature, thick film

Table  8     Summary of  retention  times  (min)  of Aroclors  on  the  DB  5 column,
            dual system of analysis

Table  9     Summary of retention times  (min) of Aroclors on the DB 1701 column,
            dual system of analysis

Table  10    Peaks diagnostic of PCBs observed in  0.53  mm  ID  column,  single
            column system of analysis

Table  11    Specific Congeners in Aroclors

Table  12    Recovery from Sewage Sludge

Table  13    Recovery DCE still bottoms

Table  14    Single Laboratory Accuracy Data for the Extraction of Organochlorine
            Pesticides from Spiked Clay  Soil by  Method 3541  (Automated Soxhlet)

Table  15    Single Laboratory Recovery Data for Extraction of PCBs  from Clay and
            Soil by Method 3541 (Automated Soxhlet)

Table  16    Multi-laboratory Precision  and Accuracy Data for the Extraction of
            PCBs from Spiked Soil by Hethod 3541 (Automated Soxhlet)
                                   8081  -  71
    Revision 0
September 1994

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                                LIST OF FIGURES

Figure 1.   GC of the Mixed Organochlorine Pesticide Standard.  The GC operating
            conditions  were   as  follows:   30  m x  0.25  mm ID  DB-5  column.
            Temperature program:   100°C  (hold  2  minutes)  to 160°C  at  15°C/min}
            then at 5DC/min  to 270°C;  carrier  He  at  16 psi.

Figure 2.   GC of  Individual  Organochlorine Pesticide Standard Mix A.   The GC
            operating  conditions were as  follows:    30 m  x 0.25 mm  ID DB-5
            column.   Temperature program:   100°C (hold 2 minutes) to  160°C at
            15°C/min,  then at 5°C/min  to  270°C; carrier  He  at 16 psi.

Figure 3.   GC of  Individual  Organochlorine Pesticide Standard Mix B.   The GC
            operating  conditions were as  follows:    30 m  x 0.25 mm  ID DB-5
            column.   Temperature program:   100°C (hold 2 minutes) to  160°C at
            15°C/min,  then at 5°C/min  to  270°C; carrier  He  at 16 psi.

Figure 4.   GC of the Toxaphene  Standard.  The GC operating conditions were as
            follows:   30 m  x 0.25 mm ID  DB-5  column.   Temperature program:
            100°C (hold 2 minutes) to 160°C at 15°C/min, then at 5°C/min to  270°C;
            carrier He at 16  psi.

Figure 5.   GC of the Aroclor-1016 Standard.  The GC operating conditions were
            as follows:  30 m x  0.25 ram  ID DB-5  fused silica capillary column.
            Temperature program:   100°C  (hold  2  minutes)  to 160°C  at 15°C/min,
            then at 5°C/min  to 270°C;  carrier  He  at  16 psi.

Figure 6.   GC of the  Technical Chlordane Standard.  The GC operating conditions
            were as  follows:   30 m x  0.25  mm ID DB-5  fused silica capillary
            column.   Temperature program:   100°C (hold 2 minutes) to  160°C at
            15°C/min,  then at St/min  to  270°C; carrier  He  at 16 psi.

Figure 7.   GC/ECD chromatogram  of Toxaphene analyzed on a DB-5/DB-1701 fused-
            silica open-tubular  column pair.  The GC operating conditions were
            as follows:  30 m x 0.53 mm ID DB-5  (LS-^m film thickness) and 30
            m x 0.53 mm ID DB-1701  (LO-^m  film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.   Temperature program:
            150°C (0.5 min hold)  to  190°C (2 min hold) at 120C/"nrt  then  to 275°C
            (10 min hold) at 4°C/min.

Figure 8.   GC/ECD chromatogram  of  Strobane analyzed on a DB-5/DB-1701 fused-
            silica open-tubular column pair.  The GC operating conditions were
            as follows:  30 m x 0.53 im ID DB-5 (1.5-Mm film thickness) and 30
            m x 0.53 mm ID DB-1701  (LO-^m  film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.  Temperature program:
            150°C (0.5 min hold)  to  190°C (2 min hold) at 12°C/min  then  to 275°C
            (10 min hold) at 4°C/m1n.
                                   8081  -  72
    Revision 0
September 1994

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Figure 9.   GC/ECD  chromatogram of  Aroclor 1016  analyzed on  a DB-5/DB-1701
            fused-silica open-tubular column pair.   The GC  operating conditions
            were as follows:  30 m x 0.53 mm ID  DB-5 (l,5-/im film thickness) and
            30 m x 0,53 mm  10  DB-17Q1 (1.0-^m film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.   Temperature program:
            150°C (0.5 min  hold) to  190°C  (2 min hold) at 12°C/nnn then to 275°C
            (10 min hold) at  40C/nnn.

Figure 10.  GC/ECD  chromatogram of  Aroclor 1221  analyzed on  a DB-5/DB-17Q1
            fused-silica open-tubular column pair.   The GC  operating conditions
            were as follows:  30 m x 0.53 mm ID  DB-5 (1.5-^m film thickness) and
            30 m x 0.53 mm  ID  DB-1701 (LO-^m film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.   Temperature program:
            150°C {0.5 min  hold) to  190°C  (2 min hold) at 12°C/min then  to 275°C
            (10 min hold) at  4°C/min.

Figure 11.  GC/ECD  chromatogram of  Aroclor 1232  analyzed on  a DB-S/DB-17Q1
            fused-silica open-tubular column pair.   The GC  operating conditions
            were as follows:  30 m x 0.53 mm ID  DB-5 (LB-^m film thickness) and
            30 m x 0.53 mm  ID  DB-1701 (1,0-pm film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.   Temperature program:
            150°C (0.5 min  hold) to  190°C  (2 min hold) at 12°C/min then  to 275°C
            (10 min hold) at  4°C/min.

Figure 12.  GC/ECD  chromatogram of  Aroclor 1242  analyzed on  a DB-5/DB-1701
            fused-silica open-tybular column pair.   The GC  operating conditions
            were as follows:  30 m x 0.53 mm ID  DB-5 (1.5-^m film thickness) and
            30 m x 0.53 mm  ID  DB-1701 (1.0-pm film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.   Temperature program:
            150°C (0.5 min  hold) to  190°C  (2 min hold) at 12°C/nnn then to 275°C
            (10 min hold) at 4'C/nH.n.

Figure 13.  GC/ECD  chroraatogram of  Aroclor 1248  analyzed on  a DB-5/DB-1701
            fused-silica open-tubular column pair.   The GC  operating conditions
            were as follows:  30 m x 0.53 mm ID  DB-5 (1.5-fM film thickness) and
            30 m x 0.53 ram  ID DB-1701 (1.0-/im film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.   Temperature program:
            150°C (0.5 min  hold) to  190°C  (2 min hold} at 12°C/min then to 275°C
            (10 min hold) at 4°C/min.

Figure 14.  GC/ECD  chromatogram of  Aroclor 1254  analyzed on  a DB-5/DB-1701
            fused-silica open-tubular column pair.   The GC  operating conditions
            were as follows:  30 m x 0.53 mm ID  DB-5 (1.5-/im film thickness) and
            30 m x 0.53 mm ID DB-1701 (1.0-^m film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.   Temperature program:
            150°C (0.5 min  hold) to  190°C  (2 min hold) at 12°C/min then to 275°C
            (10 min hold) at 4°C/min.
                                  8081  - 73
    Revision 0
September 1994

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Figure  15.  GC/ECD  chromatogram of  Aroclor  1260  analyzed  on  a  DB-5/DB-1701
            fused-silica open-tubular column pair.  The GC operating conditions
            were as follows:  30 m x 0.53 mm ID DB-5 (1.5-pm film thickness) and
            30 m x 0.53 ram  ID  DB-1701 (1.0-/jm  film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.  Temperature program;
            150°C (0.5 rain  hold) to  190°C  (2 min  hold)  at  12°C/min then to 275°C
            (10 min hold)  at  4°C/min.

Figure  16.  GC/ECD  chromatogram of  Halowax  1000  analyzed  on  a  DB-5/DB-1701
            fused-silica open-tubular column pair.  The EC operating conditions
            were as follows:  30 m x 0.53 mm ID DB-5 (1.5-jim film thickness) and
            30 m x 0.53 mm  ID  DB-1701 (1.0-pi film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.  Temperature program:
            150°C (0.5 min  hold) to  190°C  (2 min  hold)  at  12°C/min then to 275°C
            (10 min hold)  at  4°C/m1n.

Figure  17.  GC/ECD  chromatogram of, Halowax  1001  analyzed  on  a  DB-5/DB-1701
            fused-silica open-tubular column pair.  The GC operating conditions
            were as follows:  30 m x 0.53 mm ID DB-5 (1.5-jum film thickness) and
            30 m x 0.53 mm  ID  DB-1701 (1.0-jjm film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.  Temperature program:
            150°C (0.5 min  hold) to  190°C  (2 min  hold)  at  12°C/nnn then to 275°C
            (10 min hold)  at  4°C/min.

Figure  18.  GC/ECD  chromatogram of  Halowax  1099  analyzed  on  a  DB-5/DB-1701
            fused-silica open-tubular column pair.  The GC operating conditions
            were as follows:  30 m x 0.53 mm ID DB-5 (l.S^pm film thickness) and
            30 m x 0.53 mm  ID  DB-1701 (1.0-^m film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.   Temperature program:
            150°C (0.5 min  hold) to  190°C  (2 min  hold) at  12°C/min then to 275°C
            (10 min hold)  at  4°C/rnin.

Figure 19.  GC/ECD  chromatogram of  Halowax 1013  analyzed  on  a  DB-5/DB-1701
            fused-silica open-tubular column pair.   The GC operating conditions
            were as follows:  30 m x 0.53 mm ID DB-5 (1.5-/im film thickness) and
            30 m x 0.53 mm  ID  DB-1701 (1.0-^m film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.   Temperature program:
            150DC (0.5 nln  hold) to  190°C  (2 min  hold) at  12°C/min then to 275°C
            (10 min hold)  at  4°C/nnn.

Figure 20.  GC/ECD  chromatogram of  Halowax 1014  analyzed  on  a  DB-5/DB-1701
            fused-silica open-tubular column pair.   The GC operating conditions
            were as follows:  30 m x 0.53 mm ID DB-5 (1.5-jum film thickness)  and
            30 m x 0.53 mm  ID  DB-1701 (1.0-pm film thickness) connected to a J&W
            Scientific press-fit Y-shaped inlet splitter.   Temperature program:
            150°C (0.5 min  hold) to  190°C  (2 min  hold) at  12°C/n>in then to 275°C
            (10 min hold)  at  4°C/min.
                                   8081  -  74
    Revision 0
September 1994

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Figure 21.  GC/ECD  chromatogram of  Halowax 1051  analyzed on  a DB-5/DB-1701
            fused-silica open-tubular column pair.   The GC  operating conditions
            were as follows:   30 m x 0.53 mm ID DB-5 (1.5-/im film thickness)  and
            30 m x 0.53 mm  ID Dfi-1701 (1.0-/im film thickness) connected to a  J&M
            Scientific press-fit Y-shaped inlet splitter.   Temperature  program:
            150°C (0.5 min  hold) to  190°C  (2 min hold) at 12°C/min then to 275°C
            {10 min hold) at 4°C/min.

Figure 22.  GC/ECD chromatogram of the organochlorine pesticides analyzed on  a
            DB-5/DB-1701  fused-silica  open-tubular  column  pair.    The  GC
            operating conditions were as  follows:  30 m x 0.53 mm ID DB-5  (0,83-
            ^m  film thickness) and  30 m  x 0.53 mm  ID DB-1701  (1,0-^in film
            thickness)  connected  to  an   8  in  injection  tee  (Supelco  Inc.).
            Temperature program:  140°C  (2  min hold)  to  270°C (1 min hold) at
            2.8°C/min.
                                  8081  -  75                         Revision 0
                                                                September  1994

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                                 METHOD 8090

                      NITROAROMATICS AND CYCLIC KETONES
1.0  SCOPE AND APPLICATION

     1.1  Method 8090  is  used  to  determine  the  concentration  of various
nitroaroiatlc and cyclic ketone compounds.    Table 1 indicates compounds that
may be determined by this method and lists the method detection limit for each
compound 1n reagent water.    Table  2  lists the practical  quantisation limit
(PQL) for other matrices.


2.0  SUMMARY OF METHOD

     2.1  Method  8090  provides   gas   chromatographic  conditions  for  the
detection of ppb levels of  nitroaromatic  and cyclic ketone compounds.  Prior
to use of this method, appropriate  sample extraction techniques must be used.
Both neat and diluted  organic  liquids  (Method  3580, Waste Dilution) may be
analyzed by direct injection.  A 2- to 5-uL aliquot of the extract is Injected
Into a gas chromatograph  (GC) using the solvent flush technique, and compounds
in the GC effluent are  detected  by  an  electron capture detector (ECD) or a
flame lonization detector  (FID).    The  dlnitrotoluenes are determined using
ECD, whereas the other compounds amenable  to this method are determined using
FID.

     2.2  If interferences  prevent  proper  detection  of  the  analytes, the
method may also be performed on extracts that have undergone cleanup.


3.0  INTERFERENCES

     3.1  Refer to Method 3500, 3600, and 8000.

     3.2  Solvents,  reagents, glassware,  and other sample-processing hardware
may   yield   discrete    artifacts    and/or   elevated   baselines   causing
misinterpretation of gas  chromatograms.    All  of   these  materials must be
demonstrated to  be   free  from   interferences,  under the  conditions  of the
analysis, by analyzing   method  blanks.    Specific  selection  of reagents and
purification of solvents by distillation  1n  all-glass  systems may be required.

     3.3  Interferences  coextracted  from  samples  will vary considerably from
source  to source, depending upon   the  waste being sampled.  Although general
cleanup techniques are  recommended as part   of this method, unique  samples may
require additional cleanup.
                                   8090  -  1
                                                          Revision      0
                                                          Date  September  1986

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TABLE 1.  GAS CHROMATOGRAPHY OF NITROAROMATICS AND ISOPHORONE

                                Retention time (m1n)      Method detection
                                                            limit (ug/L)
Compound                         Col. la    Col. 2b        ECD        FID
Isophorone
Nitrobenzene
2,4-D1n1trotoluene
2,6-D1n1trotoluene
D1 nitrobenzene
Naphthoqulnone
4.49
3.31
5.35
3.52


5.72
4.31
6.54
4.75


15.7
13.7
0.02
0.01


5.7
3.6
-
-


  aColumn 1:  Gas-Chrom  Q   (80/100  mesh)  coated  with 1.95% QF-1/1.5% OV-17
packed 1n a 1.2-m x 2-mm or  4-mm  I.D.  glass column.  A 2-mm I.D. column and
nitrogen gas at 44 mL/m1n flow  rate were used when determining Isophorone and
nitrobenzene by GC/FID.  The  column  temperature was held Isothermal at 85*C.
A 4-mm I.D. column and  10%  methane/90%  argon  carrier gas at 44 mL/m1n flow
rate were used when  determining  the  dlnltrotoluenes  by GC/ECD.  The column
temperature was held Isothermal at 145*C.

  bColumn 2:  Gas-Chrom Q (80/100 mesh) coated with 3% OV-101 packed In a 3.0-
m x 2-mm or 4-mm I.D. glass  column.   A 2-mm I.D. column and nitrogen carrier
gas  at  44  mL/m1n  flow  rate  were  used  when  determining  Isophorone and
nitrobenzene by GC/FID.  The column  temperature was held Isothermal at 100'C.
A 4-mm I.D. column and  10%  methane/90%  argon  carrier gas at 44 ml/mln flow
rate were  used  to  determine  the  dlnltrotoluenes  by  GC/ECD.   The column
temperature was held Isothermal at 150*C.
 TABLE  2.   DETERMINATION  OF PRACTICAL QUANTITATIQN  LIMITS  (PQL)  FOR VARIOUS
           MATRICES3


     Matrix                                                    Factorb


 Ground water                                                     10
 Low-level  soil  by sonlcatlon with GPC  cleanup                   670
 High-level soil and  sludges by sonlcatlon                    10,000
 Non-water mlsdble waste                                    100,000


      aSample PQLs are highly  matrix-dependent.     The  PQLs listed  herein  are
      provided for guidance and may not always be achievable.

      Multiply the  Method  Detection   Limits  In  Table  1  by  the Factor to
      determine the PQL for each analyte In the matrix to be analyzed.
                                   8090 - 2
                                                          Revision      0
                                                          Date  September 1986

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4.0  APPARATUS AND MATERIALS

     4.1  Gas chromatograph;

          4.1.1  Gas  chromatograph;    Analytical  system  complete  with gas
     chromatograph  suitable  for   on-column   Injections  and  all  required
     accessories, Including detectors,  column  supplies, recorder, gases, and
     syringes.  A data system for  measuring peak areas and/or peak heights Is
     recommended.

          4.1.2  Columns:

               4.1.2.1  Column 1:  1.2-m x 2- or 4-mm I.D. glass column packed
          with  1.951  QF-1/1.5%  OV-17  on   Gas-Chrom  Q  (80/100  mesh)  or
          equivalent.

               4.1.2.2  Column 2:  3.0-m x 2- or 4-mm I.D. glass column packed
          with 3% OV-101 on Gas-Chrom Q (80/100 mesh) or equivalent.

          4.1.3  Detectors:  Flame ionlzation (FID) or electron capture (ECD).

     4.2  Kuderna-Danlsh (K-D) apparatus;

          4,2.1  Concentrator tube:  10-mL, graduated (Kontes K-570050-1025 or
     equivalent).  Ground-glass  stopper  Is  used  to  prevent evaporation of
     extracts

          4.2.2  Evaporation   flask:      500-mL   (Kontes   K-570001-500  or
     equivalent).  Attach to concentrator tube with springs.

          4.2.3  Snyder column:    Three-ball  macro  (Kontes K-503000-0121 or
     equivalent),

          4.2.4  Snyder  column:    Two-ball  micro  (Kontes  K-569001-0219 or
     equivalent).

     4.3  Boiling chips;  Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).

     4-4  Water  bath;    Heated,  with  concentric  ring  cover,  capable  of
temperature control  (+5*C).  The bath should be used 1n a hood.

     4.5  Volumetric flasks:  10-, 50-, and 100-mL, ground-glass stopper.

     4-6  Mlcrosyrlnge;  10-uL.

     4.7  Syr1nge;   5-mL.

     4.8  Vials;  Glass, 2-, 10-,  and  20-mL capacity with Teflon-lined  screw
cap.
                                  8090  - 3
                                                         Revision
                                                         Date  September 1986

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5.0  REAGENTS

     5'1  Solvents;  hexane, acetone (pesticide quality or equivalent.)

     5,2  Stock standard solutions:

          5.2.1  Prepare stock standard solutions  at  a concentration of 1.00
     ug/uL by dissolving 0.0100 g of  assayed reference material 1n hexane and
     diluting to volume In a  10-mL  volumetric  flask.  Larger volumes can be
     used at the convenience of the  analyst.  When compound purity Is assayed
     to be 96%  or  greater,  the  weight  can  be  used without correction to
     calculate the concentration of the stock standard.  Commercially prepared
     stock standards can be used at any concentration If they are certified by
     the manufacturer or by an Independent source.

          5.2.2  Transfer  i',.z  stock  standard  solutions  Into Teflon-sealed
     screw-cap bottles.  Store at 4*C and protect from light.  Stock standards
     should  be checked  frequently  for  signs  of degradation or evaporation,
     especially just prior to preparing calibration standards from them.

          5.2.3  Stock  standard solutions must be  replaced after one year, or
     sooner  1f comparison with check standards Indicates a problem.

     5,3  Calibration standards;  Calibration  standards  at a minimum of five
 concentration levels are prepared through dilution of the stock standards with
 hexane.  One of the  concentration  levels   should be at a concentration near,
 but  above, the method   detection  limit.     The remaining concentration levels
 should  correspond  to   the  expected  range  of  concentrations  found 1n real
 samples or should  define the working  range  of the GC.  Calibration solutions
 must be replaced   after six  months,  or  sooner  If  comparison with a check
 standard Indicates a problem.

     5.4   Internal standards  (1f  Internal  standard  calibration 1s used);  To
 use  this approach, the  analyst must select one or more Internal standards that
 are  similar  In analytical behavior  to  the compounds of  Interest.  The analyst
 must further demonstrate that the measurement  of the  Internal  standard 1s  not
 affected by  method or matrix  Interferences.    Because of these  limitations, no
 Internal standard  can be suggested  that  Is applicable  to all samples.

           5.4.1  Prepare  calibration    standards   at   a   minimum  of  five
     concentration levels   for  each  parameter  of  Interest   as described 1n
     Paragraph 5.3.

           5.4.2  To  each calibration standard, add  a  known constant amount of
     one or  more Internal standards, and dilute  to volume with  hexane.

           5.4.3  Analyze each calibration  standard according to Section 7.0.

     5.5   Surrogate  standards;  The analyst   should monitor the performance of
 the  extractlon,  cleanup(when  used),   and   analytical   system and the effec-
 tiveness of  the  method   1n   dealing with  each   sample  matrix  by  spiking  each
                                   8090 - 4
                                                          Revision
                                                          Date  September 1986

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sample, standard, and reagent water blank with one or two surrogates (e.g.,  2-
f1uoroblpheny1) recommended to encompass the  range of the temperature program
used 1n this method.   Method  3500,  Section 5.3.1.1, details Instructions  on
the preparation of base/neutral  surrogates.    Deuterated analogs of analytes
should not be  used  as  surrogates  for  gas  chromatographlc analysis due  to
coelutlon problems.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  See the Introductory  material  to  this  chapter, Organic Analytes,
Section 4.1.  Extracts must be  stored under refrigeration and analyzed within
40 days of extraction.


7.0  PROCEDURE

     7.1  Extraction;

          7.1.1  Refer to Chapter Two for guidance on choosing the appropriate
     extraction  procedure.  In general,  water  samples  are extracted at a pH
     between  5 to 9 with methylene  chloride, using either Method 3510 or 3520.
     Solid samples are extracted using either Method  3540 or 3550.

          7.1.2  Prior to gas  chromatographlc analysis,  the extraction solvent
     must be  exchanged to hexane.    The  exchange 1s performed during the K-D
     procedures  listed 1n all  of the extraction methods.  The exchange may be
     performed 1n one of two ways,  depending on the data requirements.  If the
     detection limits cited 1n Table 1  must be achieved, the exchange should
     be performed as described starting  1n  Section 7.1.4.  If these detection
     limits are  not necessary,  solvent  exchange  1s performed as outlined 1n
     Section  7.1.3.

          7.1.3  Solvent exchange when  detection  limits  In  Table  1 are not
     required:

               7.1.3.1  Following K-D of the methylene chloride extract to
          1 ml using the macro-Snyder column,  allow  the apparatus to cool and
          drain  for at least  10 m1n.

               7.1.3.2  Momentarily remove  the  Snyder   column,  add  50 mL of
          hexane, a new boiling  chip,   and reattach the macro-Snyder column.
          Concentrate  the extract using  1   mL  of  hexane to prewet the Snyder
          column.   Place the   K-D   apparatus  on   the water  bath so that the
          concentrator tube 1s partially  Immersed  1n   the hot water.  Adjust
          the vertical position of  the  apparatus and  the water temperature, as
          required, to complete concentration 1n 5-10 mln.  At the proper rate
          of  distillation the  balls of   the column will  actively chatter, but
          the chambers will not  flood.     When  the  apparent volume of liquid
          reaches  1 mL, remove the   K-D  apparatus  and   allow It to drain and
          cool for  at  least 10 m1n.    The  extract will  be  handled differently
                                   8090  -  5
                                                          Revision       0
                                                          Date   September  1986

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    at this point, depending on  whether  or  not cleanup 1s needed.  If
    cleanup 1s riot required, proceed  to  Paragraph 7.1.3.3.  If cleanup
    1s needed, proceed to Paragraph 7.1.3.4,

         7.1.3.3  If cleanup of the extract  1s not required, remove the
    Snyder column and  rinse  the  flask  and  Its  lower joint Into the
    concentrator tube  with  1-2  ml  of  hexane.    A  5-mL  syringe 1s
    recommended for this operation.  Adjust the extract volume to
    10.0 ml.  Stopper  the  concentrator  tube and store refrigerated at
    4'C 1f further processing will not be performed Immediately.  If the
    extract  will  be  stored  longer   than  two  days,  1t  should  be
    transferred to a  Teflon-sealed  screw-cap  vial.   Proceed with gas
    chromatographlc analysis.

         7.1.3.4  If cleanup  of  the  extract  1s  required, remove the
    Snyder column and  rinse  the  flask  and  Its  lower joint Into the
    concentrator tube with a minimum  amount  of hexane.  A 5-mL syringe
    1s recommended for this operation.   Add a clean boiling chip to the
    concentrator tube and attach a two-ball mlcro-Snyder column.  Prewet
    the column by adding about 0.5 ml  of   hexane to the top.  Place the
    m1cro-K-D apparatus on the  water  bath  (80*C)  so that the concen-
    trator tube  1s partially  Immersed  1n  the  hot  water.  Adjust the
    vertical position of  the  apparatus  and  the water temperature, as
    required, to  complete concentration 1n  5-10 mln.  At the proper rate
    of distillation  the balls of   the  column will actively chatter, but
    the chambers  will not   flood.    When   the apparent volume of liquid
    reaches  0.5 mL,  remove the K-D apparatus  and allow 1t to drain and
    cool  for at  least 10 m1n.

          7.1.3.5   Remove  the mlcro-Snyder column and rinse  the  flask and
     Its  lower joint  Into  the  concentrator  tube  with  0.2  ml of hexane.
    Adjust  the  extract  volume to  2.0 ml and proceed with Method 3620.

     7.1.4  Solvent exchange when  detection  limits  listed  In Table  1 must
be achieved:

          7.1.4.1  Following K-D of the methylene chloride  extract  to
     1 ml using  the macro-Snyder column,  allow the  apparatus to cool and
     drain for at least  10 mln.

          7.1.4.2  Remove the  Snyder column   and   rinse  the flask and Its
     lower joint Into  the  concentrator tube  with   1-2  ml of  methylene
     chloride,   A 5-mL syringe  1s  recommended  for this  operation. Add
     1-2 mL of hexane,  a clean boiling  chip, and  attach  a  two-ball  mlcro-
     Snyder column.   Prewet  the  column  by   adding 0.5  mL of hexane  to the
     top.   Place the m1cro-K-D  apparatus   on  the water  bath (60-65*C)  so
     that the concentrator tube  1s  partially   Immersed  1n the hot  water.
     Adjust  the  vertical   position  of the   apparatus  and  the   water
     temperature,  as required,  to  complete  concentration 1n 5-10 mln.   At
     the proper  rate  of  distillation   the  balls   of   the  column will
     actively chatter,   but   the   chambers   will   not   flood.    When the
     apparent volume of liquid reaches   0.5   mL,  remove  the K-D  apparatus
     and allow 1t to drain and cool for at  least 10  mln.

                             8090  - 6
                                                    Revision     0
                                                    Date  September 1986

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               7.1.4.3  Remove the micro-Snyder column  and rinse the flask and
          Its lower joint Into the concentrator  tube with a minimum amount of
          hexane.   The volume of the  extract  should be adjusted to 1.0 ml 1f
          the extract will  be analyzed  without  cleanup.   If the extract will
          require  cleanup,  adjust the volume  to  2.0 ml with hexane.  Stopper
          the concentrator  tube  and  store  refrigerated  at  4*C 1f further
          processing will not be performed  Immediately.   If the extract will
          be stored longer  than  two  days,  1t  should  be  transferred to a
          Teflon-sealed screw-cap vial.    Proceed  with  either gas chromato-
          graphlc  analysis or with cleanup,  as necessary.
     7.2  Gas chromatography conditions
          	3graphy conditions  (Recommended);
dlnitrotoluenesshoutabe  performedusingGC/ECD.
amenable to this method are to be analyzed by GC/FID.
The determination of
All  other compounds
          7.2,1  Column 1:   Set  10%  methane/90%  argon  carrier gas flow at
     44 mL/m1n flow rate.   For a 2-mm I.D.  column, set  the temperature at 85* C
     isothermal.    For  a   4-mm  I.D.  column,   set  the  temperature at  145*C
     Isothermal.

          7.2.2  Column 2:   Set  10%  methane/90%  argon  carrier gas flow at
     44 ml_/m1n flow rate.    For  a  2-mm  I.D.   column, set the temperature at
     100*C Isothermal.  For a 4-mm  I.D.  column,  set the temperature at  150*C
     i sothermal .
     7,3  Calibration;
                          Refer   to   Method   8000  for  proper  calibration
                         and especially  Table 2 for guidance on selecting the
techniques"  Use Table 1
lowest point on the calibration curve.

          7,3.1  The procedure for  Internal  or external  standard calibration
     may be used.  Refer to  Method  8000  for  a description of each of these
     procedures .

          7.3.4  If cleanup is performed  on  the  samples, the analyst should
     process a series  of  standards  through  the  cleanup procedure and then
     analyze the samples by GC.    This  will confirm elution patterns and the
     absence of interferents from the reagents.

     7.4  Gas chromatographlc analysis;

          7.4.1  Refer to Method 8000.    If the internal  standard calibration
     technique 1s used, add 10 uL of  internal standard to the sample prior to
     Injection.

          7,4.2  Follow Section 7.6  1n  Method  8000  for Instructions on the
     analysis sequence,  appropriate  dilutions,  establishing dally retention
     time windows, and identification criteria.   Include a mid-level standard
     after each group of 10  samples  in  the analysis sequence when using FID
     and after each group of  5  samples  in  the analysis sequence when using
     ECD.
                                  8090 - 7
                                                         Revision      0
                                                         Date  September 1986

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          7.4.3   An  example   of  a  GC/FID  chromatogram  for nitrobenzene and
     Isophorone  1s shown  1n  Figure  1.    Figure  2   1s an example of a GC/ECD
     chromatogram of the  dlnltrotoluenes.

          7.4.4   Record the   sample   volume   Injected and   the  resulting peak
     sizes (1n area  units or peak heights).

          7.4.5   Using either the  Internal   or external  calibration procedure
     (Method 8000),  determine the Identity  and  quantity of each analyte peak
     In  the  sample  chromatogram.     See  Section   7.8  of Method  8000 for
     calculation equations.

          7.4.6   If  peak  detection  and  Identification   are prevented due  to
     Interferences,  the hexane extract may  undergo cleanup using Method 3620.

     7.5  Cleanup;

          7.5.1   Proceed  with  Method  3620,   using   the  2-mL  hexane extracts
     obtained from either Paragraph  7.1.3.5 or 7.1.4.3.

          7,5.2   Following cleanup,  the extracts  should   be  analyzed by GC,  as
     described 1n the previous paragraphs and 1n  Method 8000.


8.0  QUALITY CONTROL

     8.1  Refer  to  Chapter  One  for  specific   quality control  procedures.
Quality control  to validate sample  extraction Is  covered  1n  Method  3500 and  1n
the extraction method utilized.  If  extract  cleanup was  performed,  follow the
QC 1n Method 3600 and 1n  the specific cleanup method.

     8,2  Procedures to check  the  GC  system  operation  are  found 1n Method
8000, Section 8.6.

          8.2.1  The quality control   check  sample  concentrate (Method  8000,
     Section 8.6) should contain each  parameter  of  Interest 1n acetone at a
     concentration of 20  ug/mL  for  each  dlnltrotoluene  and  100 ug/mL for
     Isophorone  and nitrobenzene.

          8.2.2  Table 3 Indicates the  calibration and QC acceptance criteria
     for  this  method.    Table  4  gives  method  accuracy  and  precision as
     functions of concentration for the analytes of  Interest.  The contents of
     both Tables should  be  used to  evaluate a laboratory's ability to perform
     and  generate acceptable data by this method.

     8,3  Calculate  surrogate standard  recovery  on  all samples, blanks, and
 spikes.   Determine  1f the   recovery   1s  within limits  (limits established by
 performing  QC procedures outlined 1n Method  8000, Section 8.10).
                                  8090  - 8
                                                         Revision
                                                         Date  September 1986

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             COLUMN: 1.5% OV-17 +1.SS* QF-1
                      ON GAS CHROM Q
             TBVIPERATURE: 85°C.
             DETECTOR: FLAME IONIZAT10N
            24    t   I  10   12
            RETENTION TIME-MINUTES
Figure 1. Gas chromatogram of nitrobenzene and isophorone.
                     8090 - 9
                                           Revision      Q
                                           Date  September  1986

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          COLUMN: 1.5% OV-17 +1.95% QF-1
                   ON GAS CHROM Q
          TEMPERATURE: 145°C.
          DETECTOR: ELECTRON CAPTURE
                  w
                  tu
                  3
                  C
             o
o
cc
             o    -
             CE    Z
             I    !
             O    N*
             (0
               u
           2468
      RETENTION TIME-MINUTES
Figure 2. Gas chromatoiram of dinitrotoluenes.

                  8090  - 10
                                        Revision
                                    0
                                        Date  September  1986

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          8.3.1   If recovery is  not within  limits,  the  following  1s  required.

               •   Check to  be  sure  there  are  no  errors   1n  calculations,
                  surrogate solutions  and   Internal  standards.   Also,  check
                  Instrument performance.

               •   Recalculate the data and/or reanalyze  the  extract 1f any of
                  the above checks reveal a problem.

               *   Reextract and  reanalyze the sample  1f none of  the above are
                  a problem or flag the data as "estimated concentration."


9.0  METHOD PERFORMANCE

     9.1  The method  was  tested  by  18   laboratories  using  reagent water,
drinking water,  surface water, and  three  industrial  wastewaters  spiked at six
concentrations over the range  1.0  to  515  ug/L.   Single operator precision,
overall precision, and method accuracy  were  found  to be directly related to
the concentration of the parameter  and  essentially Independent  of the sample
matrix.    Linear  equations  to  describe  these  relationships   for  a flame
1onizat1on detector are presented in Table 4.

     9.2  The accuracy and precision obtained will  be determined by the sample
matrix, sample-preparation technique, and calibration procedures used.


10.0  REFERENCES

1.  "Development and Application of Test Procedures for Specific Organic Toxic
Substances in  Wastewaters.    Category  4  -  Nitroaromatics and Isophorone,'
Report for EPA Contract 68-03-2624  (in preparation).

2.  "Determination  of  Nitroaromatics   and   Isophorone  in  Industrial  and
Municipal  Wastewaters,"    EPA-600/4-82-024,   U.S.  Environmental  Protection
Agency, Environmental  Monitoring  and  Support  Laboratory,  Cincinnati, Ohio
45268, June 1982.

3.  Burke, J.A.  "Gas  Chromatography  for  Pesticide  Residue  Analysis,- Some
Practical  Aspects,"  Journal  of   the  Association  of  Official  Analytical
Chemists, 48, 1037, 1965.

4.  "EPA  Method  Validation   Study   19,    Method  609  (Nitroaromatics  and
Isophorone)," Report for  EPA  Contract 68-03-2624 (In preparation).

5.  U.S.  EPA 40 CFR Part  136, "Guidelines  Establishing Test Procedures for the
Analysis  of Pollutants Under  the Clean Water Act;  Final Rule and Interim Final
Rule and  Proposed Rule,"  October 26,  1984.

6.  Provost, L.P. and  R.S.   Elder,   "Interpretation of Percent Recovery Data,"
American  Laboratory, 15,  pp.  58-63,  1983.
                                  8090 - 11
                                                         Revision      0
                                                         Date  September  1986

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TABLE 3.  QC ACCEPTANCE CRITERIA4


Parameter
2,4-D1n1trotoluene
2,6-D1n1trotoluene
Isophorone
Nitrobenzene
Test
cone.
(ug/L)
20
20
100
100
Limit
for s
(ug/L)
5.1
4.8
32.3
33.3
Range
for X
(ug/L)
3.6-22.8
3.8-23.0
8.0-100.0
25.7-100.0
Range
P, PS
(«
6-125
8-126
D-117
6-118
     s = Standard deviation of four recovery measurements, In ug/L.

     J = Average recovery for four recovery measurements, 1n ug/L.

     P, Ps = Percent recovery measured.

     D = Detected,- result must be greater than zero.

     aCr1ter1a from 40 CFR Part 136 for  Hethod 609.  These criteria are based
directly upon the method performance  data  1n  Table 4.  Where necessary, the
limits for recovery have been broadened  to assure applicability of the limits
to concentrations below those used to develop Table 4.
                                  8090  -  12
                                                         Revision      0
                                                         Date  September 1986

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TABLE 4.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION
Parameter
2, 4-D1 nl trotol uene
2,4-D1n1troto1uene
Isophorene
Nitrobenzene
Accuracy, as
recovery, x1
(ug/L)
0.65C-I-0.22
0.66C+0.20
0.49C+2.93
0.60C+2.00
Single analyst
precision, sr'
(ug/L)
0.20X+0.08
0.19X+O.Q6
0.28X+2.77
0.25X+2.53
Overal 1
precision,
S1 (ug/L)
0.37X-0.07
0.36X-0.00
0.46X+0.31
0.37X-0.78
     x1  = Expected  recovery  for  one  or  more  measurements  of  a  sample
           containing a concentration of C, 1n ug/L.

     sr' * Expected single analyst  standard  deviation  of measurements at an
           average concentration of X, 1n ug/L.

     S1  » Expected Interlaboratory standard  deviation  of measurements at an
           average concentration found of X, 1n ug/L.

     C   » True value for the concentration, 1n ug/L.

     X   * Average recovery found for measurements of samples containing a
           concentration of C, 1n ug/L.
                                  8090 - 13
                                                         Revision
                                                         Date  September 1986

-------

-------
                                         METHOD BO9O

                              NITROAROMATICS AND CYCLIC KETONES
                         (      Start      J
7
. 1. 1 1
Choose
extract Ion
procedure from
Chapter 2
                               7. 1.2
7.1.3
       Rinse
   with hexone:
 re-concentrate
    to .5 mL:
 adjust to 2 mL
                     Yes
Are the MDL 6
 in table 2
  required?
                           Concentrate to
                           1 mL using K-O
                             apparatus
                                          Yes
 Is  cleanup
  required?
7.1.3
 Cleanup using
  Method 362O


7. 1.3
into cor
tor tut
hexane:
to t


Rinse
flesh
icentra-
e with
adjust
0 mL
                             0
                                                    7.1.4
                                                           Rinse
                                                     .  with hexane;
                                                      concetrate  to
                                                    .5 ml  using K-O
                                                       Is  cleanup
                                                       required?

7.1.4



Adjust volume
to
1 mL
                                                                             7.1.4
                                                   Adjust volume
                                                      to 2 mL
                                                                             7.1.4
                                                   Cleanup using
                                                    Method 3620
                                     8090  - 14
                                                                Revision       p
                                                                Date   September  1986

-------
           METHOD 8090

NITROAROMATXCS AND CYCLIC KETONES
           (Continued!
         _i^J
          Set GC column
           ccnflitlens
          7,3
          Calibrate («e*
          M*tnod eooo)
          7.4
               Perform
            GC •n*ly*i*
             (•*« Method
               •000)
       f     Stop      j
    8090  -  15
                              Revision       p
                              Date  September 1986

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                                 METHOD 8100

                      POLYNUCLEAR AROMATIC HYDROCARBONS
1.0  SCOPE AND APPLICATION

     1.1  Method 8100  Is  used  to  determine  the  concentration  of certain
polynuclear aromatic hydrocarbons (PAH),  Table 1 Indicates compounds that may
be determined by this method.

     1.2  The packed column gas  chromatographlc  method described here cannot
adequately resolve the  following  four  pairs  of  compounds:  anthracene and
phenanthrene;  chrysene   and   benzo(a)anthracene;  benzo(b)fluoranthene  and
benzo(k)fluoranthene; and  dlbenzo(a,h)anthracene  and 1ndeno(l,2,3-cd)pyrene.
The use of a capillary column Instead  of the packed column, also described In
this method, may adequately resolve  these  PAHs.  However, unless the purpose
of the  analysis  can  be  served  by  reporting  a  quantitative  sum  for an
unresolved PAH pair, either liquid chromatography (Method 8310) or gas chroma-
tography/mass spectroscopy (Method 8270) should be used for these compounds.


2.0  SUMMARY OF METHOD

     2.1  Method  8100  provides   gas   chromatographlc  conditions  for  the
detection of ppb levels of  certain  polynuclear aromatic hydrocarbons.  Prior
to use of this method, appropriate  sample extraction techniques must be used.
Both neat and diluted  organic  liquids  (Method  3580, Waste Dilution) may be
analyzed by direct  Injection.  A 2- to  5-uL aliquot of the extract 1s Injected
into a gas chromatograph  (GC) using the solvent flush technique, and compounds
1n the GC effluent  are detected by a flame 1onizat1on detector  (FID).

     2.2  If  interferences  prevent  proper  detection  of   the  analytes  of
Interest, the method may  also  be  performed  on extracts that have undergone
cleanup using silica gel  column cleanup (Method 3630).


3.0  INTERFERENCES

     3.1  Refer to  Methods 3500, 3600,  and 8000.

     3.2  Solvents,  reagents, glassware, and  other sample processing hardware
may   yield   discrete    artifacts     and/or   elevated   baselines   causing
misinterpretation of  gas chromatograms.    All  of  these   materials must be
demonstrated to  be free from  interferences,  under  the   conditions of the
analysis, by analyzing  method  blanks.    Specific  selection of reagents and
purification of solvents  by distillation 1n all-glass systems may be required.

     3.3  Interferences coextracted from  samples  will vary  considerably from
source to source, depending upon  the   waste  being sampled.  Although general
cleanup techniques  are recommended as part  of this method, unique samples may
require additional  cleanup,


                                  8100  - 1
                                                         Revision      0
                                                         Date September 1986

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TABLE 1.  GAS CHROMATOGRAPHY OF POLYNUCLEAR AROMATIC HYDROCARBONS3

Compound                                    Retention time (m1n)
Acenaphthene                                        10.8
Acenaphthylene                                      10.4
Anthracene                                          15.9
Benzo(a)anthracene                                  20.6
Benzo(a) pyrene                                      29.4
Benzo(b)fluoranthene                                28.0
Benzo(J)f1uoranthene
Benzo(k)fluoranthene                                28.0
Benzo(ghl)perylene                                  38.6
Chrysene                                            24.7
D1benz(a,h)acr1d1ne
D1benz(a,j)acr1d1ne
D1benzo(a,h)anthracene                              36.2
7H-D1benzo(c,g)carbazole
D1benzo(a,e
D1benzo(a,h
D1benzo(a,1
pyrene
pyrene
pyrene
Fluoranthene                                        19.8
Fluorene                                            12.6
Indeno(l,2,3-cd)pyrene                              36.2
3-Methylcholanthrene
Naphthalene                                          4.5
Phenanthrene                                        15.9
Pyrene                                              20.6
      aResults  obtained  using Column  1,
                                   8100 - 2
                                                          Revision      0
                                                          Date  September 1986

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4.0  APPARATUS AND MATERIALS

     4.1  Gas chromatograph;

          4.1.1  Gas  chromatograph:    Analytical  system  complete  with gas
     chromatograph  suitable  for   on-column   Injections  and  all  required
     accessories, Including detectors,  column  supplies, recorder, gases, and
     syringes.  A data system for  measuring peak areas and/or peak heights 1s
     recommended.

          4.1.2  Columns:

               4.1.2.1  Column 1:  1.8-m x  2-ntm I.D. glass column packed with
          3% OV-17 on Chromosorb W-AW-DCMS (100/120 mesh) or equivalent.

               4.1.2.2  Column 2:   30-m  x  0.25-mm  I.D.  SE-54 fused silica
          capillary column.

               4.1.2.3  Column 3:   30-m  x  0.32-mm  I.D.  SE-54 fused silica
          capillary column.

          4.1.3  Detector:  Flame 1on1zat1on (FID).

     4.2  Volumetric flask;  10-, 50-, and 100-mL, ground-glass stopper.

     4.3  M1crosyr1nge;  10-uL.


5.0  REAGENTS

     5.1  Solvents;    Hexane,  Isooctane  (2,2,4-trSmethylpentane) (pesticide
quality or equivalent).

     5.2  Stockstandard solut1ons;

          5,2.1  Prepare stock standard solutions  at  a concentration of 1.00
     ug/uL by dissolving 0.0100 g  of  assayed reference material  1n Isooctane
     and diluting to volume 1n a  10-mL  volumetric flask.  Larger volumes can
     be used at the  convenience  of  the  analyst.    When compound purity 1s
     assayed to be 96% or greater,  the  weight can be used without correction
     to calculate  the  concentration  of  the  stock  standard.   Commercially
     prepared stock standards can  be  used  at  any concentration 1f they are
     certified by the manufacturer or by an  Independent  source.

          5.2.2  Transfer  the   stock  standard  solutions  Into Teflon-sealed
     screw-cap bottles.  Store at 4*C and protect  from light.  Stock standards
     should be checked  frequently  for  signs  of degradation or  evaporation,
     especially just prior to preparing calibration standards from them.

          5.2.3  Stock standard  solutions must be  replaced after  one year, or
     sooner 1f comparison with check  standards Indicates a problem.
                                  8100 - 3
                                                         Revision
                                                         Date  September 1986

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     5.3  Calibration standards;  Calibration  standards  at a minimum of five
concentrationlevelsshouldbe  prepared  through  dilution  of  the  stock
standards with Isooctane.   One  of  the  concentration  levels should be at a
concentration near, but  above,  the  method  detection  limit.  The remaining
concentration levels should correspond to the expected range of concentrations
found in real samples or should  define  the  working  range of the GC.  Cali-
bration solutions must be replaced  after  six months, or sooner if comparison
with a check standard indicates a problem.

     5.4  Internal standards (if internal  standard  calibration is used);  To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to  the compounds of interest.  The analyst
must further demonstrate that the measurement  of the internal standard is not
affected by method or matrix interferences.   Because of these limitations, no
internal standard can be suggested that is applicable to all samples.

          5.4.1  Prepare  calibration   standards   at   a   minimum  of  five
     concentration  levels  for  each  analyte  of  interest  as  described in
     Paragraph 5.3.

          5.4.2  To each calibration standard, add  a known constant amount of
     one or more internal standards, and dilute to volume with Isooctane.

          5.4.3  Analyze each calibration standard according to Section 7.0.

     5.5  Surrogate standards;  The analyst  should monitor the performance of
the  extraction,cleanup(when   used),   and   analytical  system  and  the
effectiveness of the method in dealing with each sample matrix by spiking each
sample, standard, and reagent water blank with one or two surrogates (e.g., 2-
fluorobiphenyl and 1-fluoronaphthalene) recommended  to encompass the range of
the temperature program used in  this  method.   Method 3500, Section 5.3.1.1,
details  instructions   on   the   preparation   of  base/neutral  surrogates.
Deuterated analogs of  analytes  should  not  be  used  as  surrogates for gas
chromatographic analysis due to coelution problems.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  See the introductory  material  to  this  chapter, Organic Analytes,
Section 4.1.  Extracts must be  stored under refrigeration and must be analyzed
within 40 days of extraction.


7.0  PROCEDURE

     7.1  Extraction;

          7.1.1   Refer to Chapter  Two for guidance  on choosing the appropriate
     extraction procedure.   In general,  water  samples   are   extracted  at  a
     neutral  pH with methylene  chloride,  using  either  Method  3510 or 3520.
     Solid samples are extracted using either Method  3540 or  3550.   To achieve
     maximum  sensitivity with  this method, the extract must be concentrated to
     1 ml.

                                   8100 - 4
                                                         Revision      0
                                                         Date  September 1986

-------
     7.2  Gas  chromatography conditions  (Recommended);

          7.2.1  Column 1:   Set  nitrogen   carrier gas  flow  at  40-ml_/m1n  flow
     rate.  Set column temperature at 100*C for 4  mln; then program at  8*C/m1n
     to a final hold at 280*C.

          7.2.2  Column 2:   Set  helium  carrier  gas  at 20-cm/sec flow rate.
     Set column temperature at  35*C  for  2  mln;   then  program  at 10'C/mln  to
     265*C and hold for 12  m1n.

          7.2.3  Column 3:   Set  helium  carrier  gas  at 60  cm/sec flow rate.
     Set column temperature at  35*C  for  2  m1n;   then  program  at 10*C/m1n  to
     265*C and hold for 3 mln.

     7»3  Calibration;    Refer   to  Method   8000   for  proper  calibration
techniques.

          7.3.1  The procedure  for  Internal  or external standard calibration
     may be used.  Refer to  Method  8000   for  a description of each of these
     procedures.

          7.3.2  If cleanup 1s  performed  on  the  samples,  the  analyst should
     process a series  of  standards  through  the  cleanup procedure and then
     analyze the samples by GC.   This  will validate  elutlon patterns and the
     absence of Interferents from the reagents.

     7.4  Gas chromatographlc analysis;

          7.4.1  Refer to Method 8000.    If the Internal standard calibration
     technique Is used, add 10 uL of  Internal standard  to the sample prior to
     Injection.

          7.4.2  Follow Section 7.6  1n   Method  8000   for Instructions on the
     analysis sequence,  appropriate  dilutions,  establishing dally retention
     time windows, and Identification criteria.   Include a mid-level standard
     after each group of 10 samples 1n the analysis sequence.

          7.4.3  Record the  sample  volume  Injected   and  the  resulting peak
     sizes (1n area units or peak heights).

          7.4.4  Using either the  Internal  or external calibration procedure
     (Method 8000), determine the Identity and quantity  of each component peak
     1n the sample chromatogram  which  corresponds  to  the compounds used for
     calibration purposes.   See  Section  7.8  of  Method 8000 for calculation
     equations.

          7.4.5  If peak detection  and  identification   are  prevented due to
     Interferences, the extract may undergo cleanup using Method 3630.

     7.5  Cleanup;

          7.5.1  Proceed with Method  3630.    Instructions  are given In this
     method for exchanging the solvent of the extract to hexane.

                                  8100 - 5
                                                         Revision      0
                                                         Date  September 1986

-------
          7.5.2  Following cleanup,  the extracts should  be analyzed by GC,
     described 1n the previous paragraphs and 1n Method 8000.
                                            as
8.0  QUALITY CONTROL

     8.1  Refer  to  Chapter  One  for  specific  quality  control procedures.
Quality control to validate sample extraction 1s covered 1n Method 3500 and 1n
the extraction method utilized.  If  extract cleanup was performed, follow the
QC In Method 3600 and 1n the specific cleanup method.
     8.2  Procedures to check
8000, Section 8.6.
the  GC  system  operation  are found in Method
          8.2.1  The quality control  check  sample  concentrate (Method 8000,
     Section 8.6) should contain each  analyte at the following concentrations
     1n acetonltrlle:    naphthalene,  100  ug/mL;  acenaphthylene, 100 ug/mLj
     acenaphthene, 100 ug/mL;  fluorene,  100  ug/mLj phenanthrene, 100 ug/mL,'
     anthracene, 100 ug/mL; benzo(k)fluoranthene,  5  ug/mL; and any other PAH
     at 10 ug/mL.

          8.2.2  Table 2 Indicates  the  calibration and QC acceptance criteria
     for this  method.     Table  3   gives  method  accuracy  and  precision as
     functions of concentration for the analytes of interest.  The contents of
     both Tables should be used to   evaluate a laboratory's ability to perform
     and generate acceptable data by this method.

     8.3  Calculate  surrogate  standard  recovery  on  all samples, blanks, and
 spikes.  Determine if  the recovery is  within limits  (limits established by
 performing QC procedures outlined 1n Method 8000, Section 8.10).

          8.3.1  If  recovery 1s  not within  limits, the following procedures
     are required.

                -  Check to be sure there  are  no  errors   1n calculations,
                  surrogate solutions and  internal  standards.   Also, check
                  instrument performance.

                •  Recalculate  the data and/or reanalyze  the extract  if any of
                  the  above checks  reveal a problem.

                *  Reextract and reanalyze the sample  if none  of the  above are
                  a  problem or flag the data as  "estimated concentration."


 9.0 METHOD  PERFORMANCE

     9.1  The method  was   tested   by  16   laboratories  using reagent water,
 drinking water,  surface water, and   three  Industrial  wastewaters spiked at six
 concentrations  over  the  range  0.1   to  425  ug/L.  Single operator precision,
 overall precision, and method  accuracy  were  found   to  be directly  related to
                                   8100 - 6
                                                          Revision      0
                                                          Date  September 1986

-------
the concentration of the  analyte  and  essentially  independent of the sample
matrix.    Linear  equations  to  describe  these  relationships  for  a flame
ionization detector are presented in Table 3.

     9.2  This method has been  tested  for  linearity  of spike recovery from
reagent  water  and  has   been   demonstrated   to  be  applicable  over  the
concentration range from 8 x MDL  to  800  x MDL with the following exception:
benzo(ghi)perylene recovery at 80  x  and  800  x  MDL  were low (35% and 45%,
respectively).

     9.3  The accuracy and precision obtained will be determined by the sample
matrix, sample-preparation technique, and calibration procedures used.

10.0  REFERENCES

1.  "Development and Application of Test Procedures for Specific Organic Toxic
Substances 1n Wastewaters.  Category 9 - PAHs," Report for EPA Contract 68-03-
2624 (in preparation).

2.  Sauter, A.D., L.D. Betowski, T.R. Smith, V.A. Strickler, R.G. Belmer,
B.N. Colby, and J.E. Wilkinson,  "Fused  Silica Capillary Column GC/MS for the
Analysis of Priority Pollutants," Journal of HRC&CC 4, 366-384, 1981.

3.  "Determination of  Polynuclear  Aromatic  Hydrocarbons  in  Industrial and
Municipal  Wastewaters,"   EPA-600/4-82-025,   U.S.  Environmental  Protection
Agency, Environmental  Monitoring  and  Support   Laboratory,  Cincinnati, Ohio
45268, September 1982.

4.  Burke, J.A.  "Gas  Chromatography  for   Pesticide  Residue  Analysis; Some
Practical  Aspects,"  Journal  of   the  Association  of  Official  Analytical
Chemists,  48,  1037,  1965.

5.  "EPA   Method  Validation   Study   20,  Method 610   (Polynuclear  Aromatic
Hydrocarbons)," Report for EPA Contract 68-03-2624 (in preparation).

6.  U.S.  EPA  40 CFR  Part  136,  "Guidelines Establishing Test Procedures for the
Analysis  of Pollutants Under  the Clean Water Act; Final Rule and Interim  Final
Rule and  Proposed Rule,"  October 26, 1984.

7.  Provost,  L.P. and R.S.  Elder,   "Interpretation of Percent  Recovery Data,"
American  Laboratory, Iji,  pp.  58-63,  1983.
                                  8100 -  7
                                                          Revision       0
                                                          Date  September  1986

-------
TABLE 2.  QC ACCEPTANCE CRITERIA4
Parameter
Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo(a)pyrene
Benzo (b) f 1 uoranthene
Benzo(ghi)perylene
Benzo (k) f 1 uoranthene
Chrysene
Dlbenzo (a ,h) anthracene
Fl uoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
Test
cone.
(ug/L)
100
100
100
10
10
10
10
5
10
10
10
100
10
100
100
10
Limit
for s
(ug/L)
40.3
45.1
28.7
4.0
4.0
3.1
2.3
2.5
4.2
2.0
3.0
43.0
3.0
40.7
37.7
3.4
Range
for 7
(ug/L)
D-105.7
22.1-112.1
11.2-112.3
3.1-11.6
0.2-11.0
1.8-13.8
D-10.7
D-7.0
D-17.5
0.3-10.0
2.7-11.1
D-119
1.2-10.0
21.5-100.0
8.4-133.7
1.4-12.1
Range
P, Ps
(%)
D-124
D-139
D-126
12-135
D-128
6-150
D-116
D-159
D-199
D-110
14-123
D-142
D-116
D-122
D-155
D-140
     s = Standard deviation of four recovery measurements, 1n ug/L.

     7 = Average recovery for four recovery measurements, 1n ug/L.

     P, Ps =  Percent recovery measured.

     D = Detected;  result must be greater than zero.

     Criteria  from 40  CFR  Part  136 for  Method 610.  These criteria are based
 directly upon the method performance  data  1n  Table 3.  Where necessary, the
 limits for recovery have been broadened  to assure  applicability of the limits
 to  concentrations below those used to develop Table 3.
                                   8100 - 8
                                                          Revision
                                                          Date   September 1986

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TABLE 3.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION
Parameter
Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo(a}pyrene
Benzo (b) f 1 uoranthene
Benzo (ghl)perylene
Benzo (k) f 1 uoranthene
Chrysene
Dlbenzo (a, h) anthracene
FT uoranthene
Fl uorene
Ideno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
Accuracy, as
recovery, x1
(ug/L)
0.52C+0.54
0.69C-1.89
0.63C-1.26
0.73C+0.05
0.56C+0.01
0.78C+0.01
0.44G+0.30
0.59C+0.00
0.77C-0.18
0.41C-0.11
0.68C+0.07
0.56C-0.52
0.54C+0.06
0.57C-0.70
0.72C-0.95
0.69C-0.12
Single analyst
precision, sr'
(ug/L)
0.397+0.76
0.367+0.29
0.237+1.16
0.287+0.04
0.38X-0.01
0.217+0.01
0.257+0.04
0.447-0.00
0.321-0.18
0.247+0.02
0.227+0.06
0.441-1.12
0.297+0.02
0.397-0.18
0.29X+0.05
0.257+0.14
Overall
precision,
S1 (ug/L)
0.537+1.32
0.427+0.52
0.417+0.45
0.347+0.02
0.53X-0.01
0.387-0.00
0.587+0.10
0.697+0.10
0.66X-0.22
0.457+0.03
0.327+0.03
0.637-0.65
0.427+0.01
0.417+0.74
0.477-0.25
0.427-0.00
     x1  - Expected  recovery  for  one  or  more  measurements  of  a  sample
           containing a concentration of C, in ug/L.

     sr' = Expected single analyst  standard  deviation  of measurements at an
           average concentration of 7, in ug/L.

     S1  = Expected Inter!aboratory standard  deviation  of measurements at an
           average concentration found of 7, 1n ug/L.

     C   = True value for the concentration, in ug/L.

     7   = Average recovery found for measurements of samples containing a
           concentration of C, in ug/L.
                                  8100 - 9
                                                         Revision      0
                                                         Date  September 1986

-------

-------
                                         METHOD B1OO

                               POLYNUCLEAH  AROMATIC HVDROCAHBQNS
C
 7,1. i
        Choose
      ' appro-
 priate extraet
  lon procedure
     Irefer to
    Chapter z)
  7.8
     Set g«*
     om«toor
   conditions
                         through cleanup
                             procvoures
.Do GC analysis
   (refer to
 Method 8000)
  7.3
        Refer Co
     Method 800O
     for proper
     calibration
     techniques
     O
                                                                             7.S. t
                            Do cleanup
                           using Method
                              3630
                                      8100 - 10
                                                                Revision        0
                                                                Date  September  1986

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                                 METHOD 8110

                       HALOETHERS BY GAS CHROMATOGRAPHY


1.0   SCOPE AND APPLICATION

      1.1   This method covers  the  determination  of certain haloethers.   The
following compounds can be determined by this method:


                                                   Appropriate Technique    ~
Compound Name                  CAS  No.a    3510    3520    3540    3550    3580
Bi s (2-chl oroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropy1) ether
4-Bromophenyl phenyl ether
4-Chlorophenyl phenyl ether
111-91-1
111-44-4
108-60-1
101-55-3
7005-72-3
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
   a  Chemical  Abstract  Services  Registry  Number.
   X  Greater than 70 percent recovery by  this technique.

      1.2   This  is  a  gas  chromatographic  (GC)   method  applicable  to  the
determination  of  the  compounds  listed  above  in  municipal  and  industrial
discharges.  When this method is used to analyze unfamiliar samples for any or
all of the compounds above, compound identifications should be supported by at
least one additional  qualitative technique.   This method  describes analytical
conditions of a second GC column that can  be used to confirm measurements made
with  the  primary  column.    Method  8270  provides  gas  chromatograph/mass
spectrometer (GC/MS) conditions appropriate for the qualitative and quantitative
confirmation of results  for all of the parameters listed above, using the extract
from this method.

      1.3   The method detection limit  (MDL,  defined  in Section  9.1)  for each
parameter is listed  in  Table  1.  The  MDL  for  a specific wastewater may differ
from  that  listed, depending  upon  the nature  of  interferences  in  the sample
matrix.

      1.4   This  method  is  restricted to  use  by  or under the  supervision of
analysts experienced in  the use  of gas chromatography and in the interpretation
of gas  chromatograms.   Each analyst must demonstrate  the  ability to  generate
acceptable results with  this method  using the procedure described  in Section 8.2.

      1.5   The toxicity or carcinogenicity of each  reagent used in this method
has not  been precisely defined.   However, each  chemical  compound should be
treated as a potential  health hazard.   From this  viewpoint,  exposure  to these
chemicals  must  be  reduced to  the lowest  possible level  by whatever  means
available.  The  laboratory  is responsible for maintaining  a  current awareness
file of OSHA regulations regarding  the safe  handling of the chemicals specified
in this method.  A reference fi]e of material  data handling sheets should also

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be made available to all  personnel  involved in the chemical analysis.  Additional
references to laboratory safety are available and have been identified.


2.0   SUMMARY OF METHOD

      2.1   A measured  volume  of sample, approximately one-liter,  is  solvent
extracted with  methylene  chloride using a  separatory funnel.   The methylene
chloride extract  is  dried and exchanged to  hexane during concentration  to  a
volume of 10 ml or less.  GC conditions are described which permit the separation
and measurement  of the compounds in the extract using a  halide specific detector.

      2.2   Method 8110  provides gas chromatographic conditions for the detection
of ppb concentrations of haloethers.   Prior to use of this method,  appropriate
sample extraction  techniques must be used.  Both neat and diluted organic liquids
(Method 3580,  Waste  Dilution)  may be  analyzed by direct injection.  A 2 to 5 jiL
aliquot  of the  extract is  injected  into a  gas  chromatograph (GC)  using the
solvent  flush technique,  and  compounds  in  the GC effluent are detected  by an
electrolytic  conductivity detector (HECD).


3.0   INTERFERENCES

      3.1   Refer to Methods 3500, 3600, and 8000.

      3.2   Matrix  interferences  may   be  caused   by  contaminants  that  are
coextracted from  the sample.   The extent of matrix  interferences  will  vary
considerably from source to source, depending upon the nature and diversity of
the industrial complex or municipality being sampled.  The cleanup procedures in
Section  7.3 can  be  used to overcome many  of these interferences,  but  unique
samples may require additional cleanup  approaches to achieve the MDL listed in
Table 1.

      3.3   Dichlorobenzenes are known to coelute with haloethers  under some gas
chromatographic conditions.  If these materials  are  present in a sample, it may
be  necessary  to  analyze  the  extract  with   two  different  column  packings to
completely resolve all  of the compounds.

      3.4   Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms.   All these materials must  be demonstrated to  be free from
interferences under the  conditions  of the analysis, by  analyzing reagent blanks.
Specific selection of reagents and purification of solvents by distillation in
all-glass systems may be required.


4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph

            4.1.1 Gas  chromatograph  -   An   analytical  system  complete  with
      temperature  programmable   gas   chromatograph  suitable  for  on-column
      injection and  all  required  accessories including  syringes, analytical
      columns,  gases,  detector,  and strip-chart  recorder.   A data system is

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                                                                     July  1992

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      recommended for measuring peak areas.

            4.1.2 Columns

                  4.1,2.1     Column 1 -  1.8  m x 2 mm ID  pyrex  glass,  packed
            with  Supelcoport,  (100/120  mesh)  coated  with  3%  SP-1000  or
            equivalent,  this column was used  to develop the method performance
            statements in  Section  9.0.    Guidelines  for  the use  of alternate
            column packings are provided in Section 7.3.1.

                  4.1.2.2     Column 2-1.8mx2mmID  pyrex  glass,  packed
            with  2,6-diphenylene  oxide  polymer  (Tenax-GC  60/80  mesh)  or
            equivalent.

            4.1.3 Detector  - Electrolytic  conductivity  or  microcoulometric.
      These detectors have proven effective 1n the analysis of wastewaters for
      the parameters listed in the  scope of this method.  The Hall conductivity
      detector (HECD) was used to develop  the method performance statements in
      Section 9.0.  Guidelines for the use of alternate detectors are provided
      in Section 7.3.1.  Although less selective, an electron capture detector
      (ECD) is an acceptable alternative.

      4.2   Kuderna-Danish (K-D) apparatus

            4.2.1 Concentrator tube -  10 ml graduated (Kontes K-570050-1025 or
      equivalent).  A  ground glass stopper is used to prevent  evaporation of
      extracts.

            4.2.2 Evaporation  flask  -   500  ml   (Kontes   K-570001-0500  or
      equivalent).   Attach  to  concentrator tube  with  springs,  clamps,  or
      equivalent.

            4.2.3 Snyder column  -  Three  ball  macro (Kontes K-503000-0121  or
      equivalent).

            4.2.4 Springs -  1/2 inch  (Kontes K-662750 or equivalent).

      4.3   Vials - Amber glass,  10 to 15 ml capacity, with Teflon lined screw-
cap or crimp top.

      4.4   Boiling  chips  -  Approximately  10/40  mesh.    Heat  to  400°C  for
30 minutes or Soxhlet extract with methylene chloride.

      4.5   Water  bath  -  Heated,  with  concentric ring  cover,  capable  of
temperature control (± 2°C).   The bath should be  used  in  a  hood.

      4.6   Balance - Analytical, 0.0001 g.

      4.7   Volumetric flasks, Class A  -  Appropriate sizes  with  ground glass
stoppers.
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5.0   REAGENTS

      5.1   Reagent grade inorganic chemicals shall  be used in all  tests.  Unless
otherwise indicated, it  is intended that all inorganic reagents shall conform to
the specifications  of the  Committee  on Analytical  Reagents of  the  American
Chemical Society, where  such specifications are available.  Other grades may be
used,  provided it is first ascertained  that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.

      5.2   Organic-free reagent water  - All  references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Acetone, CH3CQCH3  -  Pesticide quality or equivalent.

      5.4   Hexane, C6H14 -  Pesticide quality or equivalent.

      5.5   Isooctane, (CH3)3CCH2CH(CH3)2 -  Pesticide quality  or equivalent.

      5.6   Stock standard solutions (1000  mg/L) -  Stock standard solutions can
be prepared from pure standard materials or purchased as certified solutions.

            5.6.1 Prepare  stock  standard   solutions  by  accurately  weighing
      0.1000 ± 0.0010 g  of  pure  material.   Dissolve  the  material  in pesticide
      quality acetone and dilute to volume  in a 100  ml volumetric flask.  Larger
      volumes can be used at the convenience of the  analyst.   If compound purity
      is certified at 96% or greater, the weight can be used without correction
      to  calculate the  concentration   of  the stock  standard.    Commercially
      prepared stock  standards  can be  used  at  any concentration  if  they are
      certified by the manufacturer or by  an independent source.

            5.6.2 Transfer the stock standard solutions into bottles with Teflon
      lined screw-caps  or crimp tops.    Store at  4°C and  protect  from light.
      Stock  standard solutions  should  be  checked  frequently  for  signs  of
      degradation or evaporation, especially just prior to preparing calibration
      standards from them.

            5.6.3 Stock standard solutions  must be replaced after  six months, or
      sooner if comparison with check standards indicates a problem.

      5.7   Calibration  standards - Calibration standards at a minimum of five
concentrations should be prepared through  dilution of the stock standards with
isooctane.  One  of the  concentrations  should be at a  concentration near, but
above,  the method  detection  limit.    The  remaining  concentrations  should
correspond to  the expected range of concentrations  found in real  samples or
should  define  the  working  range of the  GC.   Calibration  solutions  must be
replaced after six months, or sooner if comparison with check standards  indicates
a problem.

      5.8   Internal standards  (if internal standard calibration is used) - To
use this approach, the analyst must select one or more internal  standards that
are similar in analytical behavior  to  the  compounds  of interest.  The analyst
must further demonstrate that  the measurement of  the  internal  standard is not
affected by method  or matrix  interferences.   Because  of these limitations, no
internal standard can be suggested that is applicable to all samples.

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            5.8.1 Prepare  calibration   standards  at   a  minimum   of   five
      concentrations for each analyte of interest as described in Section 5.7.

            5.8.2 To each calibration standard, add a known constant amount of
      one or more internal standards, and dilute to volume with isooctane.

            5.8.3 Analyze each calibration standard according to Section 7.0.

      5.9   Surrogate standards -  The analyst should monitor the performance of
the extraction,  cleanup  (when used), and analytical  system and the effectiveness
of  the  method  in  dealing with  each  sample  matrix by  spiking each  sample,
standard, and reagent blank with one or two surrogates (e.g. haloethers that are
not expected  to  be  in  the sample)  recommended to encompass the range  of the
temperature program  used in this method.  Method 3500 details instructions on the
preparation of base/neutral  surrogates.  Deuterated analogs of analytes should
not be  used  as  surrogates for  gas  chromatographic analysis due to coelution
problems.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to  this chapter,  Organic Analytes,
Section 4.1.   Extracts  must be stored  at 4°C  and analyzed within  40  days of
extraction.
7.0   PROCEDURE

      7.1   Extraction

            7.1.1 Refer to Chapter Two  for guidance on choosing the appropriate
      extraction  procedure.    In  general,  water  samples  are  extracted  at  a
      neutral, or as is, pH with methylene chloride,  using either Method 3510 or
      3520.  Solid samples are extracted using either Method 3540 or 3550.

            NOTE: Some of the  haloethers  are very  volatile  and  significant
                  losses  will  occur  in concentration  steps  if  care  is  not
                  exercised.   It  is important to  maintain  a  constant  gentle
                  evaporation rate and  not to  allow  the  liquid volume to fall
                  below 1  to 2 mL before removing  the K-D  apparatus from the hot
                  water bath.

            7.1.2 Prior to gas  chromatographic  analysis,  the extraction solvent
      must be exchanged to  hexane.   The exchange is performed during the K-D
      procedures  listed  in all of  the extraction methods.    The exchange  is
      performed as follows.

                  7.1.2.1      Following K-D of the methylene chloride extract to
            1 mL using the macro-Snyder column, allow the apparatus to cool and
            drain for at least 10 minutes.

                  7.1.2.2     Momentarily remove the Snyder column, add 50 mL of
            hexane, a new boiling chip,  and  reattach  the macro-Snyder column.
            Concentrate the extract using 1  mL of  hexane to prewet  the  Snyder

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      column.    Place  the K-D  apparatus  on the water  bath so that  the
      concentrator tube is partially immersed in the hot water.   Adjust
      the vertical position of the apparatus and the water temperature, as
      required,  to complete concentration in 5-10 minutes.  At the proper
      rate of  distillation the  balls of the column will  actively chatter,
      but the  chambers will not flood.  When the apparent volume of liquid
      reaches  1 ml, remove the K-D apparatus  and allow it to  drain  and
      cool  for  at  least  10  minutes.    The  extract  will  be  handled
      differently  at this point, depending on whether  or not  cleanup is
      needed.   If cleanup  is not required, proceed to Section 7.1.2.3.   If
      cleanup  is needed, proceed to Section 7.1.2.4.

            7.1.2.3      If cleanup of the extract is not required, remove
      the Snyder column and rinse the  flask and  its lower joint into  the
      concentrator  tube with  1-2 ml of  hexane.   A  5 ml  syringe  is
      recommended  for  this  operation.   Adjust  the extract   volume  to
      10.0 ml.  Stopper the  concentrator tube and  store  refrigerated at
      4°C if further processing will not  be  performed immediately.  If the
      extract   will   be   stored  longer  than  two  days,  it  should   be
      transferred  to a  Teflon  lined screw-cap vial.   Proceed with  gas
      chromatographic analysis.

            7.1.2.4      If cleanup of the extract is required, remove  the
      Snyder  column  and rinse the  flask  and  its  lower joint into  the
      concentrator tube with  a minimum amount  of  hexane.   A 5 ml  syringe
      is recommended for this operation.  Add a clean boiling chip to  the
      concentrator tube  and attach a two  ball micro-Snyder column.  Prewet
      the column by  adding about 0.5 ml  of  hexane to  the top.   Place  the
      micro-K-D  apparatus   on   the  water bath   (80°C)   so   that   the
      concentrator tube is partially immersed in the hot water.   Adjust
      the vertical position of the apparatus and the water temperature, as
      required,  to complete concentration in 5-10 minutes.  At the proper
      rate of  distillation the  balls of the column will  actively chatter,
      but the  chambers will not flood.  When the apparent volume of liquid
      reaches  0.5  ml, remove  the K-D apparatus and allow it to drain  and
      cool for at  least 10 minutes.

            7.1.2.5     Remove the micro-Snyder column and rinse the flask
      and  its lower joint  into the  concentrator  tube with  0.2 ml  of
      hexane.  Adjust the  extract volume to  2.0 ml and proceed with either
      Method 3610  or 3620.

7.2   Cleanup

      7.2.1 Proceed with   Method 3620,  using the  2 ml  hexane extracts
obtained from Section 7.1.2.5.

      7.2.2 Following cleanup,  the extracts should be analyzed by GC, as
described in the previous paragraphs and in Method 8000.

7.3   Gas Chromatography Conditions

      7.3.1 Table 1 summarizes the recommended operating  conditions  for
the gas chromatograph.   This  table includes retention times and MDLs that

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      were  obtained  under  these  conditions.    Examples  of  the  parameter
      separations achieved by these columns are shown in Figures  1 and 2.  Other
      packed columns, chromatographic conditions, or detectors  may be  used if
      the requirements of  Section 8.2 are met.  Capillary (open-tubular)  columns
      may also  be  used  if the  relative standard deviations of  responses  for
      replicate  injections  are demonstrated  to  be  less  than   6%  and  the
      requirements of Section 8.2 are met.

      7.4   Calibration  -  Refer to Method 8000 for proper calibration techniques.
Use Table 1  and  especially Table 2 for guidance on selecting the lowest point on
the calibration curve.

            7.4.1 The procedure  for  internal  or external  calibration may be
      used.   Refer  to Method 8000 for a description of each of these procedures.

            7.4.2 If cleanup  is  performed  on  the samples, the  analyst  should
      process a  series  of  standards  through  the cleanup  procedure and  then
      analyze the  samples  by  GC.   This  will confirm elution patterns  and  the
      absence of interferents from the reagents.

      7.5   Gas chromatographic analysis

            7.5.1 Refer  to Method 8000.  If the internal  standard  calibration
      technique is used, add 10 pL of internal standard to the  sample prior to
      injection.

            7.5.2 Method 8000 provides  instructions on the  analysis sequence,
      appropriate  dilutions,  establishing  daily retention  time windows,  and
      identification criteria.   Include a mid-concentration check standard after
      each group of 10 samples in the analysis sequence.

            7.5.3 Examples of GC/HECD chromatograms for haloethers  are shown in
      Figures 1 and 2.

            7.5.4 Record the sample volume injected  and  the resulting peak sizes
      (in area units or  peak heights).

            7.5.5 Using  either  the internal or  external  calibration procedure
      (Method 8000),  determine the identity and quantity of each analyte peak in
      the sample chromatogram.  See Method  8000  for  calculation  equations.

            7.5.6 If peak detection  and identification  are  prevented due to
      interferences, the hexane  extract  may undergo cleanup using either Method
      3610 or 3620.
8.0   QUALITY CONTROL

      8.1   Refer  to  Chapter  One for  specific  quality  control  procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method  utilized.  If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.
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      8,2   Procedures to check the GC system operation are found in Method 8000,
Section 8.6.

            8.2.1 The quality control  (QC) reference sample concentrate (Method
      8000, Section 8.6) should contain each analyte of interest at 20 mg/L.

            8.2.2 Table  1   indicates   the   recommended  operating  conditions,
      retention  times,  and  MDLs  that were obtained  under  these  conditions.
      Table 2 gives method  accuracy and precision for the analytes of interest.
      The  contents  of both Tables  should be  used to evaluate  a laboratory's
      ability to perform and generate acceptable data by this method.

      8.3   Calculate surrogate standard recovery  on  all  samples,  blanks, and
spikes.   Determine if  the  recovery  is within  limits  (limits  established  by
performing QC procedures outlined in Method 8000,  Section 8.10),

            8.3.1 If recovery is not within limits, the following is required.

            •     Check  to  be  sure that  there are no  errors in calculations,
                  surrogate  solutions and  internal  standards.   Also,  check
                  instrument performance,

            »     Recalculate the data and/or reanalyze the  extract if any of
                  the above checks reveal  a problem.

            »     Reextract and reanalyze  the  sample  if  none  of  the above are a
                  problem or flag the data as "estimated concentration."


9.0   METHOD PERFORMANCE

      9.1   This method  has  been  tested for linearity of recovery from spiked
organic-free reagent water  and  has  been demonstrated  to be applicable for the
concentration range from 4 x MDL to 1000 x MDL.

      9.2   In  a single laboratory  (Monsanto  Research Center),  using spiked
wastewater samples, the  average recoveries presented in Table 2 were obtained.
Each spiked sample was analyzed in triplicate on three separate occasions. The
standard deviation of the percent recovery is also included  in Table 2.


10.0  REFERENCES

1.    Fed. Regist. 1984, 49, 43234; October 26,

2.    Mills, P.A. "Variation of Florisil  Activity: Simple Method for Measuring
      Absorbent Capacity and Its Use in Standardizing Florisil Columns"; Journal
      of the Association of Official Analytical  Chemists 1968, 51, 29.

3-    Handbook   of   Analytical   Quality   Control   in   Water  andWastewater
      Laboratories; U.S. Environmental Protection Agency. Office of Research and
      Development.  Environmental   Monitoring   and  Support   Laboratory.  ORD
      Publication  Offices  of Center  for  Environmental  Research Information:
      Cincinnati, OH, 1979;  EPA-600/4-79-019.

                                   8110 - 8                         Revision 0
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4.    Methods for  Chemical  Analysis of  Mater and Wastes;  U.S.  Environmental
      Protection Agency.  Office  of Research  and Development.  Environmental
      Monitoring and Support Laboratory. ORD Publication Offices of Center for
      Environmental Research Information:  Cincinnati, OH, 1983; EPA-600/4-79-
      020.

5.    Burke, J.A.  "Gas Chromatography  for  Pesticide Residue Analysis;  Some
      Practical  Aspects";  Journal if the  Association if  Official  Analytical
      Chemists 1965, 48, 1037.

6.    "EPA Method Validation Study 21 Methods 611  (Haloethers)," Report for EPA
      Contract 68-03-2633.

7.    "Determination of Haloethers in Industrial  and Municipal  Wastewaters";
      Report for EPA Contract 68-03-2633 (In preparation).
                                   8110 - 9                         Revision 0
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                                   TABLE 1.
            CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
Analyte
  Retention Time
     (minutes)	
Column I    Column 2
    Method
Detection Limit
    (MA)
B1s(2-chloroisopropyl) ether
Bis(2-chloroethyl) ether
Bi s (2 -chl oroethoxy) methane
4-Chlorophenyl phenyl ether
4-Bromophenyl phenyl ether
8.4
9.4
13.1
19.4
21.2
9.7
9.1
10.0
15.0
16.2
0.8
0.3
0.5
3.9
2.3
Column 1 conditions:
   Carrier gas (He) flow rate:
   Initial temperature:
   Temperature program:
   Final temperature:
  40 mL/min
  60°C, hold for 2 minutes
  eO°C to 230°C at 8°C/rnin
  230°C, hold for 4 minutes
   Under these conditions the retention time for aldrin is 22.6 minutes.
Column 2 conditions:
   Carrier gas (He) flow rate:
   Initial temperature:
   Temperature program:
   Final temperature:
  40 mL/min
  150°C, hold for 4 minutes
  150°C to 310°C at 16°C/min
  310°C
   Under these conditions the retention time for aldrin is 18.4 minutes.
                                   8110 - 10
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                                   TABLE 2.
                    SINGLE OPERATOR ACCURACY AND PRECISION
                             Average   Standard    Spike    Number
                             Percent   Deviation   Range      of     Matrix
Analyte                      Recovery      %       (Mg/L)  Analyses  Types

Bi s(2-chl oroethoxy)methane62§73        138        27       3  "
Bis(2-chloroethyl) ether         59       4.5         97        27       3
Bis(2-chloroisopropyl) ether     67       4.0         54        27       3
4-Bromophenyl phenyl ether       78       3.5         14        27       3
4-Chlorophenyl phenyl ether      73       4.5         30        27       3
                                   8110 -  11                        Revision 0
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               FIGURE  1.
   GAS CHROMATOGRAH OF HALOETHERS
Column: 3% SP-10QO on Supilcoport
Progrtm: $0*C. -2 mtnutoi i*/mtnuto to
Detector: H»H a/tctrofyttc conduetivtty
             !
                      I
       *    *
   2   4  6  8   10  12   14  tf  ft  20  22 24
                8110  - 12
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                FIGURE  2.
    GAS CHROMATOGRAM OF HALOETHERS
Column: Ttnax GC
Progrtm: 1SO°C.-4 mmutts 16°/minut» to 310°C.
Detector: Htll electrolytic conductivity
                   12      16     20

             Retention time, minuttt
24
                8110  - 13
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                         METHOD  8110
            HALOETHERS  BY  GAS CHROMATOGRAPHY
                               Start
                           711 Choose
                            appropriate
                            extrac tion
                             pr ocedure
                           7.1.2 Perform
                         solvent exchange
                           using hexane
  7.1.2.4  Perform
micro-K-D  procedure
   using hexane;
proceed with Method
   3610 or  3620
Yes
                          7.123 Adjust
                         extract volume and
                           pr oceed with
                         ana lysis or  store
                          in appropriate
                              manner
                          7 3 1 Refer  to
                            Table 1  for
                            recommended
                             operating
                         conditions for  the
                                GC
                              7  4  Refer to Method
                                8000 for proper
                                  ca 1 ibra tion
                                  techniques
                                7.5.1 Refer to
                                Method 8000 for
                                guidance on CC
                                  ana 1ysis
                              754 Record sample
                              vo1ume injected and
                              resulting peak size
                                 755 Perform
                                  appropria te
                              calculations (refe
                                to Method 8000)
                                    Stop
                            8110 -  14
                                                   Revision  0
                                                     July 1992

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                                 METHOD 8120A

                CHLORINATED HYDROCARBONS  BY  GAS CHROMATOGRAPHY
 1.0    SCOPE AND APPLICATION

       1.1   Method  8120  is  used  to  determine  the  concentration  of certain
 chlorinated hydrocarbons.   The following compounds can  be determined by this
 method:
                                            Appropriate PreparationTechniques

Compounds                         CAS No8     3510     3520  3540/   3550   3580
                                                            3541
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichloro benzene
Hexachl orobenzene
Hexachl orobutad i ene
Hexachl orocyclohexane
Hexachl orocycl o pentad i ene
Hexachl oroethane
Pentachlorohexane
Tetrachlorobenzenes
1 , 2 , 4-Tri chl orobenzene
91-58-7
95-50-1
541-73-1
106-46-7
118-74-1
87-68-3
608-73-1
77-47-4
67-72-1
_-
_-
120-82-1
X
X
X
X
X .
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
   a  Chemical Abstract Services Registry Number.
   x  Greater than 70 percent recovery by this technique
   ND Not determined.

      1.2   Table 1 indicates compounds that may be determined by this method and
lists the method detection limit for each compound in organic-free reagent water.
Table 2 lists the estimated quantisation limit (EQL) for other matrices.


2.0   SUMMARY OF METHOD

      2.1   Method 8120 provides gas chromatographic conditions for the detection
of ppb concentrations of certain chlorinated hydrocarbons.  Prior to use of this
method, appropriate sample extraction  techniques must  be used.   Both neat and
diluted organic liquids (Method 3580,  Waste Dilution) may be analyzed by direct
injection.    A  2 to  5 pi aliquot  of the extract  is injected  into a  gas
chromatograph (GC),  and compounds in the GC effluent are detected by an electron
capture detector  (ECD).
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      2,2   If Interferences are encountered  in  the  analysis,  Method 8120 may
also be performed on extracts that have undergone cleanup using Method 3620.

3.0   INTERFERENCES

      3,1   Refer to Hethods 3500,  3600,  and 8000.

      3.2   Solvents,  reagents,  glassware,  and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms.  All  of these  materials must  be  demonstrated to be free
from interferences, under the conditions  of the  analysis,  by analyzing method
blanks.    Specific  selection  of  reagents and  purification  of  solvents  by
distillation in all glass systems may be required.

      3.3   Interferences coextracted from samples will vary considerably from
source to  source,  depending upon  the  waste being  sampled.   Although general
cleanup techniques are recommended as  part of this  method,  unique samples may
require additional cleanup.


4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph

            4.1.1  Gas  chromatograph  - Analytical   system  complete with  gas
      chromatograph  suitable  for   on-column  injections   and  all  required
      accessories, including detectors, column supplies, recorder, gases,  and
      syringes.  A data system  for measuring peak areas and/or peak heights is
      recommended.

            4.1.2  Columns

                  4.1.2.1     Column 1 -  1.8  m x 2  mm  ID glass  column packed
            with  1%  SP-1000  on Supelcoport  (100/120 mesh) or equivalent.

                  4.1.2.2     Column 2 -  1.8  m x 2  mm  ID glass  column packed
            with   1.5% OV-1/2.4%  OV-225   on   Supelcoport   (80/100  mesh)   or
            equivalent.

            4.1.3  Detector  - Electron  capture  (ECD).

      4.2   Kuderna-Danish (K-D)  apparatus

            4.2.1  Concentrator tube - 10 ml_, graduated  (Kontes K-570050-1Q25 or
      equivalent).   A ground glass stopper is used  to  prevent evaporation of
      extracts

            4.2.2  Evaporation   flask  -    500  ml   (Kontes   K-570Q01-500   or
      equivalent).    Attach  to  concentrator  tube  with  springs,  clamps  or
      equivalent.

            4.2.3  Snyder  column - Three  ball  macro (Kontes  K-503000-0121  or
      equivalent).


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            4.2.4  Snyder column  - Two  ball  micro  (Kontes  K-569001-0219 or
      equivalent).

            4.2.5  Springs  -   1/2  inch  (Kontes  K-66275D or  equivalent).

      4.3   Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).

      4.4   Water  bath  -  Heated,  with  concentric  ring   cover,  capable of
temperature control (± 5°C).   The  bath  should be used in a  hood.

      4.5   Volumetric flasks -  10,  50,  and  100 ml, with ground glass stoppers.

      4.6   Microsyringe  -  10 ^L.

      4.7   Syringe -  5 ml.

      4.8   Vials - Glass,  2, 10,  and 20 ml capacity with  Teflon  lined screw-
caps or crimp tops.


5.0   REAGENTS

      5.1   Reagent grade inorganic chemicals shall be used  in  all tests. Unless
otherwise  indicated,  it  is  intended  that   all  reagents  shall conform  to the
specifications of the  Committee  on Analytical Reagents  of the American Chemical
Society, where  such specifications  are  available.   Other  grades may be used,
provided it is first ascertained that the reagent is of  sufficiently high purity
to permit its use without lessening the accuracy of the determination.

      5.2   Organic-free  reagent water.  All  references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Solvents

            5.3.1  Hexane, C6H14.   Pesticide  quality  or equivalent.

            5.3.2  Acetone, CH3COCH3.  Pesticide quality or equivalent.

            5.3.3  Isooctane,  C8H18.   Pesticide  quality or equivalent,

      5.4   Stock standard  solutions

            5.4.1  Prepare stock standard solutions  at  a concentration of  1000
      mg/L  by dissolving  0.0100 g of assayed reference material in isooctane or
      hexane and diluting to volume in a 10 ml volumetric flask.  Larger volumes
      can be used at the convenience of the analyst.   When compound  purity is
      assayed to be 96% or greater, the weight can  be  used without correction to
      calculate the concentration of the stock  standard.  Commercially prepared
      stock standards  can be  used at any concentration  if they are certified by
      the manufacturer or by  an  independent  source.
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            5.4.2  Transfer the  stock standard  solutions  into vials with Teflon
      lined screw  caps  or crimp tops.   Store at 4°C and  protect from light.
      Stock standards should be checked frequently for signs of degradation or
      evaporation, especially just prior to preparing calibration standards.

            5.4.3  Stock standard solutions must  be replaced after one year, or
      sooner if comparison with check standards indicates a problem.

      5.5   Calibration  standards  - Calibration standards at a minimum of five
concentrations should be prepared through dilution of the stock standards with
isooctane or hexane.  One of the concentrations  should  be at a  concentration
near, but above, the method detection limit.  The remaining concentrations should
correspond  to  the expected range of concentrations  found in  real  samples or
should  define  the working  range  of  the  SC.   Calibration solutions  must be
replaced after six months, or sooner if comparison with check standards indicates
a problem.

      5.6   Internal  standards (if  internal  standard  calibration  is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior  to the compounds  of  interest.   The analyst
must further demonstrate that the measurement  of the internal  standard is not
affected by method or matrix  interferences.   Because of these limitations, no
internal standard can be suggested that is applicable to all samples.

            5.6.1   Prepare   calibration   standards   at   a  minimum   of  five
      concentrations  for each analyte of interest as  described in Sec.  5.5.

            5.6.2   To each calibration standard, add  a known constant amount of
      one or more  internal  standards, and dilute to  volume with  isooctane or
      hexane.

            5.6.3   Analyze each  calibration standard  according  to  Sec.  7.0.

      5.7   Surrogate standards  - The  analyst should monitor the performance of
the extraction, cleanup  (when used), and analytical system and the effectiveness
of  the  method in dealing  with each sample  matrix   by  spiking  each  sample,
standard, and organic-free reagent  water blank  with one or two surrogates (e.g.
chlorinated hydrocarbons that are not expected  to  be  in the sample) recommended
to encompass the range of the temperature program used in this method.  Method
3500  details   instructions  on  the  preparation   of   base/neutral  surrogates.
Deuterated  analogs of  analytes should not  be   used as  surrogates  for  gas
chromatographic analysis due to coelutlon problems.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the introductory material to this chapter,  Organic Analytes, Sec.
4.1.

      6.2   Extracts must be stored under  refrigeration  and analyzed within 40
days of extraction.
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7.0   PROCEDURE

      7.1    Extraction

            7.1.1  Refer to Chapter Two for guidance on choosing the appropriate
      extraction procedure.   In  general,  water  samples  are  extracted  at  a
      neutral,  or as is, pH with methylene chloride, using either Method 3510 or
      3520.  Solid samples are extracted using either Methods 3540/3541 or  3550.

            7.1.2  Prior to gas chromatographic  analysis, the extraction solvent
      must  be exchanged to hexane.   The exchange is performed during  the  K-D
      procedures listed in  all  of  the extraction methods.   The exchange  is
      performed as  follows.

                  7.1.2.1     Following K-D of the methylene chloride  extract
            to  1 ml using  the  macro  Snyder column, allow the apparatus  to cool
            and  drain for  at least 10 minutes.

                  7.1.2.2     Momentarily  remove the Snyder column, add  50  ml
            of hexane, a new boiling  chip, and reattach the macro Snyder column.
            Concentrate the extract  using  1  ml  of hexane to prewet the Snyder
            column.   Place the  K-D  apparatus  on  the  water bath  so  that the
            concentrator tube  is partially  immersed  in the hot water.  Adjust
            the vertical position of the apparatus and the water temperature,  as
            required, to complete concentration  in 5-10 minutes.   At the proper
            rate of distillation the balls of the column will actively  chatter,
            but the chambers will not flood.  When the apparent  volume  of liquid
            reaches 1 ml,  remove the K-D apparatus and  allow  it to drain and
            cool  for at   least  10  minutes.    The  extract will  be   handled
            differently at this  point,  depending on  whether or not cleanup  is
            needed.   If cleanup  is  not required, proceed to Sec. 7.1.2.3.   If
            cleanup is needed, proceed to Sec.  7.1.2.4.

                  7.1.2.3     If cleanup of the extract is not  required, remove
            the Snyder column  and rinse  the flask and  its lower joint  into the
            concentrator  tube  with  1-2 mi  of  hexane.    A 5  ml  syringe   is
            recommended  for this  operation.   Adjust  the  extract volume   to
            10.0 ml.  Stopper the concentrator tube and  store refrigerated at  4°C
            if  further  processing  will not be  performed  immediately.   If the
            extract  will   be  stored,  longer than  two days,   it  should   be
            transferred to a vial with a Teflon lined  screw cap or crimp top.
            Proceed with gas chromatographic analysis.

                  7.1.2.4     If cleanup of the extract is required, remove the
            Snyder  column  and rinse  the flask  and  its lower  joint  into the
            concentrator tube  with a minimum amount of hexane.   A 5 ml  syringe
            is recommended for this operation.  Add a clean  boiling  chip to the
            concentrator tube and attach a two ball micro Snyder column.  Prewet
            the column by adding about 0.5 ml of hexane to the top.  Place the
           micro K-D apparatus on the water bath (80°CJ so that  the concentrator
            tube is partially  immersed  in  the hot water.   Adjust the  vertical
            position of  the apparatus and the water temperature,  as required,  to
           complete  concentration  in  5-10  minutes.    At  the   proper  rate   of


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            distillation the  balls  of the column will actively chatter, but the
            chambers will not flood.  When the apparent volume of liquid reaches
            0.5 ml,  remove  the K-D  apparatus  and allow it to drain and cool for
            at least 10 minutes.

                  7.1.2.5     Remove the micro Snyder column and rinse the flask
            and its  lower  joint  into the  concentrator  tube with  0.2 ml  of
            hexane.   Adjust the extract volume to  2.0 ml and proceed with Method
            3620.

      7.2   Gas chromatographic conditions  (Recommended)

            7.2.1  Column 1

            Carrier  gas (5% methane/95% argon) flow  rate =  25 mL/min
            Column temperature =     65°C isothermal, unless otherwise specified
                                    (see Table 1).

            7.2.2  Column 2

            Carrier  gas (5% methane/95% argon} flow  rate =  25 mL/min
            Column temperature =     75°C isothermal, unless otherwise specified
                                    (see Table 1).

      7.3   Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1  and especially Table 2 for guidance on selecting the lowest point on
the calibration curve.

            7.3.1  The  procedure  for  internal or  external  calibration may  be
      used.  Refer to Method 8000  for a description of each of these procedures.

            7.3.2  If cleanup  is  performed  on the samples, the analyst  should
      process  a series of standards  through the cleanup  procedure and  then
      analyze  the  samples by GC.   This will  validate elution patterns  and the
      absence  of interferents  from  the reagents.

      7.4   Gas  chromatographic analysis

            7.4.1  Refer to Method 8000.  If  the  internal  standard calibration
      technique is used,  add  10 pi  of internal standard to  the sample  prior to
      injecting.

            7.4.2  Method 8000 provides  instructions on the  analysis  sequence,
      appropriate  dilutions,  establishing  daily  retention  time  windows,  and
      identification criteria.  Include a mid-concentration standard after each
      group  of 10 samples in the analysis sequence.

            7.4.3  Examples  of GC/ECD chromatograms for  certain  chlorinated
      hydrocarbons are  shown  in Figures  1 and 2.

            7.4.4  Record the  sample volume injected and the resulting peak sizes
      (in area units or peak heights).
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            7.4.5  Using  either the internal  or external  calibration procedure
      (Method 8000), determine the identity and quantity of each component peak
      in the  sample  chromatogram which corresponds to the compounds  used for
      calibration purposes.  See Method 8000  for calculation  equations.

            7.4.6  If peak detection  and  identification  are prevented  due to
      interferences, the hexane extract may undergo cleanup using Method 3620.

      7.5   Cleanup:  If required, the samples  may be cleaned up using the Methods
presented in Chapter 4.

            7.5.1  Proceed  with  Method 3620   using  the 2  ml  hexane  extracts
      obtained from Sec.  7.1.2.5.

            7.5.2  Following  cleanup,  the extracts should be analyzed by GC, as
      described in the previous paragraphs and in Method 8000.


8.0   QUALITY CONTROL

      8.1   Refer to  Chapter  One for  specific  quality  control  procedures.
Quality control to validate sample extraction is covered  in Method 3500 and in
the extraction method utilized.   If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.

      8.2   Procedures to check the GC  system operation are  found in Method 8000.

            8.2.1 The  quality control check  sample concentrate  (Method 8000)
      should contain each parameter of interest  at the following concentrations
      in acetone: hexachloro-substituted  hydrocarbon,  10  mg/L; and any other
      chlorinated hydrocarbon, 100 mg/L.

            8.2.2 Table 3  indicates the calibration and QC acceptance  criteria
      for this method.  Table 4 gives method accuracy and precision as functions
      of concentration for the  analytes  of  interest.   The  contents  of  both
      Tables should be used to  evaluate a  laboratory's ability to perform and
      generate acceptable data by this method.

      8.3   Calculate surrogate standard recovery on all  samples,  blanks,  and
spikes.    Determine  if the recovery   is within  limits  (limits established by
performing QC procedures outlined in Method 8000).

            8.3.1 If recovery is not within limits, the following procedures are
      required.

                  •     Check to  be sure there  are no  errors in  calculations,
                        surrogate  solutions   and  internal standards.    Also,
                        check instrument performance.

                  •     Recalculate the data and/or  reanalyze the  extract if
                        any of  the above checks reveal  a problem.
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                         Reextract and reanalyze the sample if none  of the  above
                         are   a  problem  or  flag   the   data  as   "estimated
                         concentration".
9.0   METHOD PERFORMANCE

      9.1   The method was tested  by 20  laboratories using organic-free reagent
water, drinking water, surface water, and three Industrial wastewaters  spiked at
six concentrations over the range 1.0 to 356 M9/L-  Single operator precision,
overall precision, and method accuracy were found to be directly related to the
concentration of the  parameter and essentially independent of the sample matrix.
Linear equations to describe these relationships for a  flame  ionization detector
are presented in Table 4.

      9.2   The accuracy  and precision obtained will be determined by the sample
matrix, sample preparation technique,  and calibration procedures used.


10.0  REFERENCES

1.    "Development and Application of Test Procedures for Specific Organic Toxic
      Substances in  Wastewaters.   Category 3  -  Chlorinated Hydrocarbons,  and
      Category 8 - Phenols,"  Report for EPA Contract 68-03-2625.

2.    Burke, J.A.  "Gas  Chromatography  for Pesticide Residue Analysis;  Some
      Practical  Aspects,"  Journal  of the  Association of Official  Analytical
      Chemists,  48, 1037, 1965.

3.    "EPA Method Validation  Study 22, Method 612 (Chlorinated Hydrocarbons),"
      Report for EPA  Contract 68-03-2625.

4.    "Method  Performance  for  Hexachlorocyclopentadiene   by   Method  612,"
      Memorandum  from  R.  Slater,   U.S.   Environmental   Protection  Agency,
      Environmental Monitoring and Support Laboratory, Cincinnati,  Ohio 45268,
      December 7,  1983.

5.    U.S. EPA 40 CFR Part 136,  "Guidelines Establishing Test  Procedures for the
      Analysis  of Pollutants  Under the Clean Water Act;  Final Rule  and Interim
      Final  Rule and  Proposed Rule," October 26,  1984.

6.    "Determination  of  Chlorinated Hydrocarbons in  Industrial  and  Municipal
      Wastewaters," Report for  EPA Contract 68-03-2625.
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                                TABLE  1.
             GAS CHROHATOGRAPHY OF CHLORINATED  HYDROCARBONS


Compound
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Diehloro benzene
1 » 4-Di ehl orobenzene
Hexachl orobenzene
Hexachl oro butadiene
Hexachl orocycl ohexane
Hexachl orocycl opentadi ene
Hexachl oroethane
Pentachlorohexane
Tetrachl orobenzenes
1,2, 4-Tri chl orobenzene
Retention

Col. 1
2.7'
6.6
4.5
5.2
5.6'
7.7

ND
4.9
--
--
15.5
time (min)

Col . 2
3.6"
9.3
6.8
7.6
10. l"
20.0

16. 5C
8.3

..
22.3
Method
Detection
limit (tig/I)
0.94
1.14
1.19
1.34
0.05
0.34

0.40
0.03
--
--
0.05
ND - Not determined.
*150°C  column  temperature.
b165°C  column  temperature.
C100°C  column  temperature.
                                8120A -  9
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                                TABLE 2.
                 DETERMINATION OF  ESTIMATED QUANTITATION
                   LIMITS  (EQL) FOR VARIOUS MATRICES"
Matrix                                                             Factor
Ground water                                                            10
Low-concentration soil  by ultrasonic extraction with GPC cleanup       670
High-concentration soil and sludges by ultrasonic extraction        10,000
Non-water miscible waste                                           100,000
      EQL - [Method detection limit  (see  Table  1}]  X [Factor found in this
      table].   For non-aqueous samples,  the factor is on a wet weight basis.
      Sample EQLs  are highly matrix  dependent.   The EQLs  to be determined
      herein are provided for guidance and may not always be achievable.
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                        TABLE  3.
                 QC ACCEPTANCE CRITERIA"
Parameter
2-Chl oronaphthal ene
1 , 2-Di chl orobenzene
1 ,3-Di chl orobenzene
1 , 4-Di chl orobenzene
Hexachl orobenzene
Hexachl orobutadiene
Hexachl orocyclopentadi ene
Hexachl oroethane
1 , 2, 4-Tri chl orobenzene
Test
cone.
(M9/L)
100
100
100
100
10
10
10
10
100
Limit Range
for s for x
(MA) (MA)
37,3 29.5-126.9
28.3 23.5-145.1
26.4 7.2-138.6
20.8 22.7-126.9
2.4 2.6-14.8
2.2 D-12.7
2.5 D-10.4
3.3 2.4-12.3
31.6 20.2-133.7
Range
P> P.
(*)
9-148
9-160
D-150
13-137
15-159
D-139
D-lll
8-139
5-149
s = Standard deviation of four recovery measurements, in /*gA-
x = Average recovery
P,P8 = Percent recovery
D * Detected; result
a Criteria from 40
for four recovery
measured.
measurements, in pg/L.



must be greater than zero.
CFR Part 136 for
Method 612. These criteria are
based directly upon the method performance data in Table 4.  Where
necessary, the  limits  for recovery have  been  broadened to assure
applicability of the limits  to  concentrations  below those used to
develop Table 4.
                      8120A - 11
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                                   TABLE 4.
          METHOD  ACCURACY AND  PRECISION AS  FUNCTIONS  OF  CONCENTRATION'


Parameter
Chloronaphthalene
1 , 2-Di chl orobenzene
1 , 3-Di chl orobenzene
1 , 4-Di chl orobenzene
Hexachl orobenzene
Hexachl orobutadiene
Hexachl orocyclopentadiene8
Hexachl oroethane
1, 2, 4-Tri chl orobenzene
Accuracy, as
recovery, x'
(M9/L)
0.75C+3.21
0.85C-0.70
0.72C+0.87
0.72C+2.8Q
0.87C-0.02
0.61C+0.03
0.47C
0.74C-0.02
0.76C+0.98
Single analyst
precision, s/
(M9/L)
0.28X-1.17
0.22X-2.95
0.21X-1.03
0.16X-0.48
O.Hx+0.07
Q.18x+0.08
0.24x
0.23X+0.07
0.23x-0.44
Overal 1
precision,
S' (M9/L)
0.38X-1.39
0.41X-3.92
0.49X-3.98
0.35X-0.57
0.36X-0.19
0,53x-0,12
0,50x
0.36X-0.00
0.40x-1.37
X'


S/



S'


C

x
Expected  recovery  for  one  or  more  measurements   of   a   sample
containing a concentration of C, in iig/L.

Expected  single  analyst  standard deviation of  measurements at an
average concentration of x,  in /^g/L.

Expected  inter! aboratory standajd deviation  of  measurements at an
average concentration found of x, in
True value for the concentration, in /iig/L,

Average recovery  found for  measurements  of  samples  containing a
concentration of C, in
            Estimates based upon the  performance in a single laboratory.
                                  8120A - 12
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                                  FIGURE 1
             Column;      1.5% OV-1 + 1.5% OV-225 on Ga» Chrom. Q
             Teuipe rature: 75 * C
             Detector:    Electron Capture
                 4         I       12       II
                   ftenimoN TIME IMINUTISI
20
Gas chrcamatagram of chlorinated hydrocarbons (high molecular weight confounds) .
                                 8120A  -  13
                Revision  1
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                                     FIGURE 2
                           Column:      1.5% OV-1 + 1.5% OV-225 on Gas Chrom.  Q
                           Temperature: 160 • C
                           Detector:    Electron Capture
                        |
                   04        I       12      U
                          MTINT1ON HMf QltNUTfS}
Gag chromatagram of chlorinated hydrocarbons (low molecular weight compounds) .
                                     8120A -  14
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                                   METHOD  8120A
              CHLORINATED  HYDROCARBONS BY  GAS  CHRQMATQGRAPHY
 j    Stan    J
  7.1.1  Choose
   appropriate
    extraction
  procedure {sea
   Chapter 2|.
 7.1.2 Exchange
extraction solvent
 to hsxane during
 K-D procedures.
   7.2 Set gas
  chromatography
   conditions.
7,3 Refer to Method
  8000 for proper
    calibration
    technique*.
   7.3.2 Is
   cleanup
  necessary?
 7.3.2 Process a
series of standards
 through cleanup
procedure; analyze
     by GC.
7.4 Perform GC
 anal/sit (see
Method 8000).
                                        7.4.5
                                   Is identification
                                     & detection
                                     prevented by
                                    interferences?
                            7.5.1 Cleanup using
                               Method 3620.
                                        Stop

                                    812QA  -  15
                                            Revision 1
                                       September  1994

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                                  METHOD 8121

  CHLORINATED HYDROCARBONS BY GAS CHROHATOGRAPHY: CAPILLARY COLUMN TECHNIQUE


1.0   SCOPE AND APPLICATION

      1.1   Method 8121 describes the determination  of chlorinated hydrocarbons
in extracts prepared from environmental samples and RCRA wastes.  It describes
wide-bore open-tubular, capillary column gas chromatography procedures using both
single  column/single  detector and dual-column/dual-detector  approaches.   The
following compounds can be determined by this method:


      Compound Name                           CAS Registry No."

      Benzal chloride98-87-3
      Benzotrichloride                           98-07-7
      Benzyl chloride                           100-44-7
      2-Chloronaphthalene                        91-58-7
      1,2-Dichlorobenzene                        95-50-1
      1,3-Dichlorobenzene                       541-73-1
      1,4-Dichlorobenzene                       106-46-1
      Hexachlorobenzene                         118-74-1
      Hexachlorobutadiene                        87-68-3
      a~Hexachlorocyclohexane (a-BHC)           319-84-6
      0-Hexachlorocyclohexane (j8-BHC)           319-85-7
      7-Hexachlorocyclohexane (7-BHC)            58-89-9
      5-Hexachlorocyclohexane (tf-BHC)           319-86-8
      Hexachlorocyclopentadiene                  77-47-4
      Hexachloroethane                           67-72-1
      Pentachlorobenzene                        608-93-5
      1,2,3,4-Tetrachlorobenzene                634-66-2
      1,2,4,5-Tetrachlorobenzene                 95-94-2
      1,2,3,5-Tetrachlorobenzene                634-90-2
      1,2,4-Trichlorobenzene                    120-82-1
      1,2,3-Trichlorobenzene                     87-61-6
      1,3,5-Trichlorobenzene                    108-70-3

      a   Chemical  Abstract  Services  Registry  Number.

      1.2   The  dual-column/dual-detector  approach  involves  the  use  of  two
30 m x 0.53 mm ID fused-silica open-tubular columns of different polarities, thus
different selectivities towards the target compounds. The columns are connected
to an injection tee and two  identical  detectors.   When  compared to the packed
columns,  the  megabore  fused-silica   open-tubular columns   offer  improved
resolution, better selectivity,  increased sensitivity,  and faster analysis.

      1.3   Table 1 lists method  detection limits (MDL)  for each compound in an
organic-free reagent water matrix.   The MDLs for the compounds  of a specific
sample may differ from those listed in Table 1 because they are dependent upon
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the nature of interferences 1n the sample matrix.  Table 2 lists the estimated
quantitation limits  (EQL) for other matrices.

      1.4   Table 3 lists the  compounds that have been determined by this method
and their retention times using the single column technique.  Table 4 lists dual
column/dual detector retention  time  data.   Figures  1  and  2  are chromatograms
showing the single column technique.  Figure 3 shows a chromatogratn of the target
analytes eluted from a pair of DB-5/DB-1701 columns and detected with electron
capture detectors  (ECD)  under the prescribed GC conditions listed in Table 2.

      1.5   This  method  is  restricted to use  by or under the  supervision of
analysts experienced in the  use of a gas chromatograph and in the interpretation
of gas chromatograms.


2.0   SUMMARY OF METHOD

      2.1   Method 8121 provides gas chromatographic conditions for the detection
of ppb  concentrations of chlorinated hydrocarbons  in water and  soil  or  ppm
concentrations in waste samples.  Prior to use of this method, appropriate sample
extraction techniques must be used for environmental samples (refer to Chapt. 2).
Both neat and diluted  organic liquids (Method  3580)  may  be analyzed  by direct
injection.  Spiked  samples  are used  to  verify  the applicability  of  the chosen
extraction technique to  each new sample type.  Analysis is accomplished by gas
chromatography utilizing an  instrument equipped with wide bore capillary columns
and single or dual electron capture detectors.


3.0   INTERFERENCES

      3.1   Refer to Methods 3500, 3600, and 8000.

      3.2   The  electron capture  detector  responds  to  all  electronegative
compounds. Therefore, interferences are possible by other halogenated compounds,
as well  as phthalates  and  other  oxygenated  compounds,  and,  organonitrogen,
organosulfur and organophosphorus compounds.  Second column confirmation or GC/MS
confirmation  are   necessary  to   ensure  proper  analyte identification  unless
previous characterization of the  sample source will ensure proper identification.

      3.3   Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially  analyzed.  To  reduce carryover,  the
syringe used  for  injection  must be  rinsed  out between samples with  solvent.
Whenever  an  extract  concentration  exceeds  that of  the highest calibration
standard, it should be followed by the analysis  of a solvent blank to check for
cross-contaiination.   Additional  solvent blanks interspersed with the  sample
extracts should  be considered whenever the analysis of a solvent blank indicates
cross-contamination problems.

      3.4   Phthalate esters,  if present in  a sample, will  interfere only with
the BHC  isomers because they elute  in Fraction  2  of the Florisil  procedure
described in  Method 3620.  The  presence of phthalate esters can usually be
minimized by  avoiding contact  with   any plastic materials  and  by  following
standard decontamination procedures of reagents and  glassware.

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      3,5   The presence of elemental sulfur will result in large peaks, and can
often mask the region of compounds eluting after 1,2,4,5-tetrachlorobenzene,  The
tetrabutylammonium  (TBA)-sulfite  procedure (Method  3660)  works well  for  the
removal of elemental sulfur,

      3.6   In  certain  cases  some  compounds  coelute  on  either  one  or both
columns.   In  these cases  the  compounds must  be  reported as coeluting.   The
mixture can be reanalyzed by GC/MS techniques, see Sec. 8,7 and Hethod 8270.

            3.6,1 Using  the dual  column  system  of  analysis  the  following
      compounds coeluted:

            DB-5        1,4-dichlorobenzene/benzyl chloride
                        1,2,3.5-tetrachloroberizene/1,2,4,5-tetrachl orobenzene
                        1,2,3,4-tetrachlorobenzene/2-chloronaphthal ene

            DB-17Q1     benzyl  chloride/1,2-dichlorobenzene/hexachloroethane
                        benzal  chloride/1,2,4-trich!orobenzene/
                        hexachlorobutadiene

            Some of the  injections showed a separation of 1,2,4-trichlorobenzene
      from the other two compounds, however, this is not always the case, so the
      compounds are listed as coeluting,

      3,7   Solvents,  reagents,  glassware,  and  other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms.  All  these materials  must be demonstrated to be free from
interferences under the  conditions of the analysis,  by analyzing reagent blanks,


4,0   APPARATUS AND MATERIALS

      4,1   Gas  chromatograph:  An   analytical  system  complete  with  a  gas
chromatograph suitable  for on-column  and  split-splitless injection,  and  all
required accessories, including syringes,  analytical  columns, gases,  and  two
electron capture detectors. A data  system for measuring peak areas,  and dual
display of chromatograras is recommended.  A GC  equipped with a single GC column
and detector are acceptable, however,  second  column confirmation  is obviously
more time consuming.  Following are  the  single and  dual  column  configurations
used for developing  the retention time data  presented in the method.  The columns
listed  in  the  dual  column  configuration  may  also  be  used for single column
analysis.

            4.1.1 Single Column Analysis:

                  4.1.1,1     Column  1 -  30  m  x  0.53  mm  ID  fused-silica
            capillary column  chemically  bonded  with  trifluoropropyl  methyl
            silicone {DB-210 or equivalent).

                  4.1.1.2     Column  2 -  30  m  x  0.53  mm  ID  fused-silica
            capillary column chemically bonded  with polyethylene glycol (DB-WAX
            or equivalent).


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            4.1.2 Dual Column Analysis:

                  4.1.2.1     Column  1  -  30 m x  0.53  mm  ID  fused-silica
            open-tubular  column,  cross!inked and  chemically  bonded  with 95
            percent dimethyl and 5 percent  diphenyl-polysiloxane  (DB-5,  RTx-5,
            SPB-5, or equivalent),  0.83 pm  or 1.5 jim film  thickness.

                  4.1.2.2     Column  2  -  30 m x  0.53  mm  ID  fused-silica
            open-tubular  column  cross!inked  and chemically  bonded   with 14
            percent  cyanopropylphenyl  and   86  percent  dimethyl-polysiloxane
            (DB-17Q1, RTX-1701,  or equivalent), 1.0 ^tm film thickness.

            4.1.3 Splitter:  If  the splitter approach to dual column injection
      is  chosen,  following  are  three  suggested splitters.   An  equivalent
      splitter  is  acceptable.    See Sec. 7.5.1  for a  caution on the use of
      splitters.

                  4.1.3.1     Splitter  1  -  JliW  Scientific press-fit   Y-shaped
            glass 3-way union splitter  (J&W Scientific, Catalog no. 705-0733).

                  4.1.3.2     Splitter  2  -  Supelco  8 in.  glass injection  tee,
            deactivated (Supelco,  Catalog no.  2-3665M),

                  4.1.3.3     Splitter   3  -  Restek   Y-shaped   fused-silica
            connector (Restek, Catalog no. 20405).

            4.1.4 Column rinsing  kit (optional):  Bonded-phase column rinse kit
      (J&W Scientific, Catalog no. 430-3000 or equivalent).

            4.1.5 Microsyringes  - 100 /it,  50 nL>  10 y.1  (Hamilton 701  N or
      equivalent), and 50 /iL (Blunted, Hamilton  705SNR or  equivalent).

            4.1.6 Balances - Analytical, 0.0001 g.

            4.1.7 Volumetric flasks, Class A  - 10 ml to 1000 ml.


5.0   REAGENTS

      5.1   Reagent grade inorganic chemicals shall be used  in all tests. Unless
otherwise indicated,  it  is  intended  that all  reagents  shall  conform to the
specifications of the Committee  on Analytical  Reagents of the American  Chemical
Society, where  such  specifications are available.   Other  grades  may  be used,
provided it is  first  ascertained that the chemicals are of sufficiently  high
purity to permit their use without affecting  the accuracy of the determinations.

      NOTE:  Store  the  standard  solutions    (stock,  composite,   calibration,
            internal, and surrogate) at 4'C  in Teflon-sealed containers in the
            dark.   All  standard solutions must be replaced after six months or
            sooner if routine QC  (Sec. 8) indicates a problem.
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       5.2    Solvents

             5.2.1  Hexane,  C6H14 - Pesticide quality or equivalent.

             5.2.2  Acetone,  CH3COCH3 - Pesticide quality or equivalent.

             5.2.3  Isooctane, (CH3)3CCH2CH(CH3)2 - Pesticide qua! ity or equivalent.

       5.3    Stock  standard solutions  (1000  mg/L): Can  be  prepared  from pure
standard materials or can  be purchased as  certified solutions.

             5.3.1  Prepare  stock  standard solutions by  accurately weighing about
       0.0100 g of  pure compound.  Dissolve the compound  in  isooctane or hexane
       and dilute to volume in  a  10 ml volumetric  flask.  If compound purity  is
       96 percent  or greater,  the weight  can be used  without  correction   to
       calculate the concentration of the stock standard  solution. Commercially
       prepared stock standard solutions can be used at any concentration  if they
       are certified by the manufacturer or by an  independent  source.

             5.3.2  For those compounds which are not adequately soluble in hexane
       or isooctane, mixtures of  acetone and  hexane are recommended.

       5.4    Composite  stock standard:  Can be prepared  from  individual  stock
solutions.   For  composite  stock standards containing  less than 25 components,
take exactly 1 ml  of each  individual stock solution at 1000 mg/L, add solvent,
and mix the solutions in  a  25 ml  volumetric flask.  For example, for a composite
containing 20 individual  standards, the  resulting concentration of each component
in the mixture,  after the  volume is  adjusted to  25 ml, will be 40 mg/L.  This
composite solution can be further diluted  to  obtain the desired concentrations.

       5.5    Calibration  standards should  be  prepared  at  a  minimum of  five
concentrations by  dilution of the composite  stock standard with isooctane  or
hexane.    The concentrations   should  correspond  to  the  expected  range   of
concentrations found in real samples and  should bracket the  linear range of the
detector.  A suggested list of calibration  solution standards  is found in Table
7.

       5.6    Recommended  internal standard:  Make  a solution  of 1000 mg/L   of
1,3,5-tribromobenzene.   (Two  other  internal  standards,  2,5-dibromotoluene and
alpha,alpha'-dibromo-m-xylene,  are  suggested if  matrix interferences are  a
problem.)  For spiking, dilute  this solution to  50 ng/j*L. Use a spiking volume
of 10  jiL/mL  of extract.    The  spiking  concentration of the  internal  standards
should be kept constant  for all samples and  calibration standards.  Store the
internal standard  spiking  solutions  at 4*C in Teflon-sealed containers  in the
dark.

      5.7    Recommended  surrogate standards:   Monitor the  performance  of the
method using surrogate compounds. Surrogate standards are added to all samples,
method blanks, matrix  spikes,  and calibration standards.   Hake  a  solution   of
1000 mg/L of 1,4-dichloronaphthalene and  dilute it to  100 ng/jiL.  Use a spiking
volume of  100 pi  for  a 1  L  aqueous sample.   If matrix interferences  are  a
                                   8121 - 5   •                      Revision 0
                                                                September 1994

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problem,  two  alternative  surrogates  are:  alpha,  2,6-trichlorotoluene  or
2,3,4,5,6-pentachlorotoluene.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the Introductory material  to this Chapter, Organic Analytes, Sec,
4.1.

      6.2   Extracts must  be stored  at  4  "C and  analyzed  within 40  days  of
extraction.


7.0   PROCEDURE

      7.1   Extraction and Cleanup;

            7.1.1 Refer to Chapter Two and Method 3500 for guidance on choosing
      the  appropriate  extraction procedure.   In  general,  water  samples  are
      extracted at a neutral, or as is, pH with methylene chloride, using either
      Method 3510 or 3520,   Solid samples  are extracted us-ing  either  Methods
      3540,  3541,  or   3550  with  methyline  chloride/acetone  (1:1)  as  the
      extraction solvent.

            7.1.2 If required,  the samples may be cleaned up using Method 3620
      (Florisil)  and/or Method  3640 (Gel  Permeation  Chromatography).    See
      Chapter Two, Sec, 2.3,2 and Method 3600 for  general guidance on  cleanup
      and method selection.  Method 3660  is  used  for sulfur  removal.

            7.1.3 Prior to gas chromatographic analysis, the extraction solvent
      must exchanged into  hexane using  the  Kuderna-Danish  concentration step
      found in any of the  extraction methods.  Any methylene  chloride remaining
      in the extract will  cause  a very broad solvent peak.

      7.2   Gas Chromatographic  Conditions:

            7.2.1 Retention  time  information  for  each of the  analytes  is
      presented in Tables  3 and 4.  The recommended GC operating conditions are
      provided  in  Tables  5  and  6.   Figures 1,  2 and  3   illustrate  typical
      Chromatography of the method  analytes for both the single column approach
      and the dual column  approach when operated at the conditions specified in
      Tables 5 and 6.

      7.3   Calibration:

            7.3.1 Prepare  calibration standards  using  the procedures  in Sec.
      5.0.    Refer  to  Method  8000  for  proper  calibration  procedures.  The
      procedure for internal  or  external  calibration may be  used.

            7,3.2 Refer to Method 8000 for the establishment of retention time
      windows.
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7.4   Gas chromatographic analysis:

      7,4.1 Method 8000 provides  instructions  on  the analysis sequence,
appropriate  dilutions,  establishing daily  retention time  windows,  and
identification criteria.

      7.4.2 Automatic injections of 1 pL are recommended.  Hand injections
of no more than 2 /iL may be  used if the analyst demonstrates quantitation
precision of < 10 percent  relative standard  deviation.  The solvent flush
technique may be used if the amount of solvent is kept at a minimum.  If
the  internal  standard  calibration technique is used,  add 10 pi  of the
internal standard to each ml of sample extract prior to injection,

      7.4.3 Tentative identification of an analyte occurs  when a peak from
a sample extract falls within the daily retention time window.

      7.4.4 Validation  of   gas   chromatographic   system   qualitative
performance: Use the midconcentration  standards  interspersed  throughout
the analysis sequence (Sec, 7.3)  to evaluate this  criterion.   If  any of
the standards fall  outside their daily retention time windows,  the system
is out of control.  Determine the cause of the problem and correct it (see
Sec. 7.5).

      7.4.5 Record the  volume  injected  to  the nearest  0.05 ^l and the
resulting peak  size in peak height or  area  units.   Using either  the
internal or the  external  calibration procedure  (Method  8000),  determine
the  identity  and  the  quantity of  each  component peak  in the  sample
chromatogram which  corresponds to the compounds  used  for  calibration
purposes.  See Method 8000 for calculation equations.

      7.4.6 If the responses exceed the linear  range of the system,  dilute
the extract and reanalyze. Peak height measurements are recommended over
peak  area  integration  when  overlapping  peaks   cause   errors  in  area
integration.

      7.4.7 If partially overlapping or coeluting peaks are found,  change
columns  or  try  a  GC/MS  technique (see  Sec. 8.7 and  Method  8270).
Interferences that prevent analyte identification and/or quantitation may
be removed by the cleanup  techniques mentioned above.

      7.4.8 If the peak  response is less than 2.5 times the baseline noise
level, the validity of the quantitative result may be questionable.  The
analyst should consult with  the source of the sample to determine whether
further concentration of the sample is warranted.

7.5   Instrument Maintenance:

      7.5.1  Injection of sample extracts from  waste sites often leaves a
high boiling residue  in: the injection port area, splitters when used, and
the  injection  port  end  of the  chromatographic   column.   This  residue
effects chromatography in many ways  (i.e.,  peak tailing,  retention time
shifts, analyte degradation, etc.)  and, therefore, instrument maintenance


                             8121  - 7                         Revision 0
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      is very  important.  Residue  buildup  in a splitter may limit flow through
      one leg  and therefore change the split ratios.   If this occurs during an
      analytical run,  the quantitative data may be incorrect.  Proper cleanup
      techniques will minimize the problem and  instrument QC will indicate when
      instrument maintenance is required.

            7.5.2 Suggested chromatograph  maintenance: Corrective measures may
      require  any one or more of the  following  remedial actions.  Also see Sec.
      7  in Method   8000  for  additional   guidance  on  corrective   action  for
      capillary columns and the injection  port.

                  7.5.2.1     Splitter connections: For dual columns which are
            connected  using a press-fit  Y-shaped glass splitter or a Y-shaped
            fused-silica connector, clean and deactivate the splitter or replace
            with a cleaned and  deactivated splitter.   Break off the first few
            inches (up to one foot)  of the injection  port  side of the column.
            Remove   the  columns   and solvent  backflush   according  to  the
            manufacturer's instructions.   If these procedures fail to eliminate
            the degradation  problem,  it may be necessary to  deactivate the metal
            injector body and/or replace the columns.


8.0   QUALITY  CONTROL

      8.1   Refer to Chapter One  and Method 8000 for  specific quality control
procedures.  Quality control  to  validate  sample extraction  is covered in Method
3500 and in the extraction method  utilized.  If extract cleanup was performed,
follow the QC  in Method 3600 and in the specific cleanup method.

      8.2   Quality control required to evaluate the GC system operation is found
in Method 8000, Sec. 8.3.

      8.3   Calculate surrogate  standard  recoveries for all  samples,  blanks, and
spikes.    Determine   if the  recovery   is  within limits (limits  established  by
performing QC  procedures outlined  in  Method 8000, Sec. 8).   If the recovery is
not within Limits, the following are  required:

            8.3.1 Check  to   be  sure  there  are  no   errors  in  calculations,
      surrogate  solutions  and  internal   standards.    Also,  check  instrument
      performance.

            8.3.2 Recalculate the  data and/or  reanalyze the  extract if  any of
      the above checks reveal a problem.

            8.3.3 Reextract  and reanalyze  the  sample  if none  of the above are
      a  problem, or flag the data as  "estimated concentrations".

      8.4   Data from systems that  automatically identify target  analytes on the
basis of  retention  time or  retention time indices should be  reviewed  by  an
experienced analyst  before they are reported.

      8.5   When using  the internal standard calibration technique, an internal
standard peak area check must be  performed on all samples.  The internal standard

                                   8121  - 8                         Revision 0
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must be evaluated for acceptance by determining whether the measured area for the
internal standard deviates by more than 50 percent from the average area for the
internal standard in the calibration standards.  When the internal  standard  peak
area is outside  that  limit,  all samples that  fall outside the QC  criteria  must
be reanalyzed.

      8.6    Include a mid-concentration calibration standard after each group of
£0  samples   in   the  analysis  sequence.     The  response  factors  for   the
mid-concentration calibration must be within ± 15 percent of the average values
for the multiconcentration calibration.  When the response factors fall outside
that  limit,  all samples  analyzed  after  that  mid-concentration calibration
standard must be reanalyzed  after performing  instrument maintenance to correct
the usual  source of  the problem.   If this  fails to correct the problem, a  new
calibration  curve must  be established.

      8.7    GC/MS confirmation;

             8.7.1 GC/MS techniques  should  be  judiciously employed  to support
      qualitative  identifications made with  this method.   Follow  the GC/MS
      operating  requirements specified in  Method 8270.   Ensure  that there is
      sufficient concentration of the analyte(s) to be confirmed,  in the extract
      for  GC/MS  analysis.

             8.7.2 When  available,  chemical   ipnization  mass  spectra may be
      employed to aid in the qualitative identification process.

             8.7.3 To  confirm an  identification of a  compound,  the background
      corrected  mass  spectrum of the  compound must be obtained from the sample
      extract  and must be  compared with  a  mass  spectrum from a  stock or
      calibration standard analyzed  under the same chromatographic conditions.
      At  least   25 ng  of material  should be injected  into  the GC/MS.    The
      identification  criteria  specified  in  Method   8270  must  be  met   for
      qualitative confirmation.

                  8.7.3.1     Should   the   MS   procedure   fail  to  provide
             satisfactory  results,   additional   steps  may   be  taken  before
             reanalysis.  These steps may include the use  of alternate packed or
             capillary GC columns or  additional sample cleanup.


9.0   METHOD PERFORMANCE

      9.1   The HDL is defined in Chapter One.  The MDLs  listed in Table 1 were
obtained by using organic-free reagent water.   Details on how to determine MDLs
are given  in Chapter One.  The MDLs  actually achieved in a given analysis will
vary since they  depend  on instrument  sensitivity and matrix effects.

      9.2   This  method has been  tested   in a  single  laboratory   by  using
organic-free reagent  water,  sandy  loam samples and  extracts which were spiked
with the test  compounds at one concentration.   Single-operator precision  and
method accuracy were  found to be related to the concentration of compound and  the
type of matrix.


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      9.3   Single  laboratory  accuracy  data  were obtained  for  chlorinated
hydrocarbons in a clay  soil.  The spiking concentrations ranged from 500 to iOOO
ng/kg,  depending on the  sensitivity of the  analyte  to  the  electron capture
detector.  The spiking  solution was mixed into the soil during addition and then
immediatly transferred to the extraction device and immersed in the extraction
solvent.   The  spiked  sample  was then  extracted by  Method  3541  (Automated
Soxhletj.  The data represents a single determination.  Analysis was by capillary
column gas chromatography/electron capture detector following Method 8121 for the
chlorinated hydrocarbons.  These data are listed  in Table 9 and were taken from
Reference 4.
10.0  REFERENCES

1.    Lopez-Avila,  V.,  N.S.  Dodhiwala,   and  J.  Milanes,  "Single  Laboratory
      Evaluation of Method 8120, Chlorinated Hydrocarbons",  1988, EPA Contract
      Numbers 68-03-3226 and 68-03-3511.

2.    Glazer, J.A.,  G.D.  Foerst,  G.D. McKee, S.A.  Quave, and W.L. Budde, "Trace
      Analyses for Wastewaters,"  Environ.  Sci. and Techno!.  15:1426-1431, 1981.

3.    Lopez-Avila, V.; Baldin,  E.;  Benedicto,  J; Milanes,  J.;  Beckert,  W.  F.
      "Application of Open-Tubular Columns to  SW 846 GC Methods"; final report
      to  the U.S.  Environmental Protection  Agency  on  Contract  68-03-3511;
      Mid-Pacific Environmental  Laboratory, Mountain View,  CA,  1990.

4.    Lopez-Avila, V. (Beckert,  W.,  Project Officer), "Development of a Soxtec
      Extraction  Procedure  for  Extracting  Organic  Compounds  from  Soils  and
      Sediments", EPA 600/X-91/140,  US EPA, Environmental  Monitoring Systems
      Laboratory-Las Vegas,  October 1991.
                                  8121  - 10                         Revision 0
                                                                September 1994

-------
                             TABLE 1
      METHOD DETECTION  LIMITS FOR CHLORINATED HYDROCARBONS
                SINGLE  COLUHN METHOD OF ANALYSIS
Compound name
Benzal chloride
Benzotri chloride
Benzyl chloride
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachl orobenzene
Hexachl orobutadiene
a-Hexachlorocyclohexane (o-BHC)
/3-Hexachlorocyclohexane (0-BHC)
7-Hexachlorocyclohexane (^-BHC)
5-Hexachlorocyclohexane (5-BHC)
Hexachl orocyclopentadiene
Hexachl oroethane
Pentachl orobenzene
1,2,3, 4 -Tetrachl orobenzene
1,2,4 , 5-Tetrachl orobenzene
1,2,3 , 5-Tetrachl orobenzene
1,2, 4-Trichl orobenzene
1 , 2 , 3-Tr i chl orobenzene
1,3, 5-Trichl orobenzene
CAS Reg. No.
98-87-3
98-07-7
100-44-7
91-58-7
95-50-1
541-73-1
106-46-1
118-74-1
87-68-3
319-84-6
319-85-7
58-89-9
319-86-8
77-47-4
67-72-1
608-93-5
634-66-2
95-94-2
634-90-2
120-82-1
87-61-6
108-70-3
HDL"
(ng/L)
2-5"
6.0
180
1,300
270
250
890
5.6
1.4
11
31
23
20
240
1.6
38
11
9.5
8.1
130
39
12
MDL is the method detection limit for organic-free reagent water.  HDL
was determined from the analysis of eight replicate aliquots processed
through the entire  analytical method  (extraction,  Florisil  cartridge
cleanup, and GC/ECD analysis).

      MDL = T/DC(n.1>a . ,99!js)

where V1039, is  the  student's  t  value appropriate for a  99  percent
confidence  interval  and a  standard  deviation  with  n-1  degrees  of
freedom,  and  SD  is  the standard  deviation of  the eight  replicate
measurements.

Estimated from the instrument detection limit.
                              8121 - 11                         Revision 0
                                                            September 1994

-------
                                 TABLE 2
     ESTIMATED  QUANTITATION  LIMIT  (EQL)  FACTORS FOR VARIOUS  MATRICES*
      Matrix                                                Factor
Ground water                                                     10
Low-concentration soil  by ultrasonic extraction                 670
  with GPC cleanup
High-concentration soil  and sludges by ultrasonic            10,000
  extraction
Waste not miscible with  water                               100,000
B   EQL  = [Method detection limit (see Table 1}] x [Factor  found  in this
    table].   For  nonaqueous  samples,  the factor is on  a  wet-weight basis.
    Sample  EQLs are highly matrix-dependent.  The EQLs  listed herein  are
    provided  for  guidance  and may  not  always be achievable.
                                  8121 - 12                         Revision 0
                                                                September 1994

-------
                                 TABLE 3
 GAS CHRQMATQGRAPHIC RETENTION TIMES FOR CHLORINATED HYDROCARBONS:  SINGLE
                        COLUMN METHOD OF ANALYSIS
 Compound name
Retention time 1mln)
DB-210"DB-WAX"
Benzal chloride
Benzotrlchloride
Benzyl chloride
2-Chloronaphthal ene
1 , 2 -Di chl orobenzene
1,3-Dlchlorobenzene
1,4-Dichlorobenzene
Hexachl orobenzene
Hexachl orobutadi ene
0-BHC
K-BHC

-------
                                TABLE 4
             RETENTION TIMES OF  THE  CHLORINATED  HYDROCARBONS8
                      DUAL  COLUMN METHOD OF ANALYSIS
Compound
1,3-Dichlorobenzene
1 ,4-Di chl orobenzene
Benzyl chloride
1,2-Dichlorobenzene
Hexachloroethane
1, 3, 5-Tri chl orobenzene
Benzal chloride
1, 2, 4-Tri chl orobenzene
1,2,3-Trichl orobenzene
Hexachlorobutadiene
Benzotri chloride
1,2,3, 5-Tetrachl orobenzene
1,2,4, 5-Tetrachl orobenzene
Hexachlorocyclopentadiene
1,2,3, 4-Tetrachl orobenzene
2-Chl oronaphthal ene
Pentachl orobenzene
a-BHC
Hexachl orobenzene
£-BHC
7-BHC
5-BHC
DB-5
RT(min)
5,82
6.00
6.00
6.64
7.91
10.07
10,27
11.97
13.58
13.88
14.09
19.35
19.35
19.85
21.97
21.77
29.02
34.64
34.98
35.99
36.25
37.39
DB-1701
RT(min)
7.22
7.53
8.47
8.58
8.58
11.55
14.41
14.54
16.93
14.41
17.12
21.85
22.07
21.17
25.71
26.60
31.05
38.79
36.52
43.77
40.59
44.62
Internal Standard
1,3,5-Tribromobenzene                         11.83          13.34

Surrogate
1,4-Dichloronaphthalene                       15.42          17.71

"The  GC operating conditions were  as follows: 30  m x 0.53  mm ID  DB-5
(0.83-/im   film  thickness) and 30  m x 0.53  mm ID DB-1701  (1.0 pun  film
thickness)  connected to an 8-in injection tee (Supelco Inc.).  Temperature
program: 80°C (1.5 rain hold) to 125*C (1 win hold) at 2'C/min then to 240'C
(2 min hold) at  56C/min;  injector temperature 250"C;  detector  temperature
320°C; helium  carrier gas 6 mL/min; nitrogen makeup gas 20 mL/min.
                                  8121  -  14                         Revision 0
                                                                September 1994

-------
                              TABLE 5
             GC OPERATING CONDITIONS  FOR CHLOROHYDROCARBONS
                    SINGLE COLUMN METHOD OF ANALYSIS
Column  1:  DB-210   30  m  x 0.53  mm  ID fused-silica  capillary  colum
chemically bonded with trifluoropropyl methyl silicone

    Carrier gas  (He)     10 mL/min
    Column temperature:
                  Initial  temperature        65°C
                  Temperature program        65°C  to 175"C at 4°C/min
                  Final  temperature          175'C, hold 20 minutes.
    Injector  temperature       220*C
    Detector  temperature       250*C
    Injection volume           1-2 pi


    Column 2:  DB-WAX    30  m x  0.53 mm ID fused-silica capillary  column
    chemically bonded with  polyethylene glycol

    Carrier gas  (He)     10 mL/min
    Column temperature:
                  Initial  temperature        60°C
                  Temperature program        60°C  to 170°C at 4'C/min
                  Final  temperature          170°C, hold 30 minutes.
    Injector  temperature       200°C
    Detector  temperature       230°C
    Injection volume           1-2 jiL
                                  8121 - 15                         Revision  0
                                                                September  1994

-------
Column 1:
                              TABLE 6
           EC OPERATING CONDITIONS FOR CHLORINATED HYDROCARBONS
                      DUAL COLUMN METHOD  OF  ANALYSIS
                  Type:  DB-1701 (J&W Scientific) or equivalent
                  Dimensions;  30 in x 0.53 mm ID
                  Film Thickness: 1.0 (pm)
Column 2:
                  Type:  DB-5 (J&W Scientific) or equivalent
                  Dimensions:  30 m x 0.53 ran ID
                  Film Thickness: 0.83 (urn)
Carrier gas flowrate (mL/win):  i (Helium)
Makeup gas flowrate (mL/min):  20 (Nitrogen)
Temperature program:  80*C (1.5  min hold)  to 125*C (1 min hold) at  2"C/min
then to 24Q°C (2 min hold) at S'C/win.
Injector temperature:  250*C
Detector temperature:  320*C
Injection volume:  2 pi
Solvent:  Hexane
Type of injector:  Flash vaporization
Detector type:  Dual ECD
Range:  10
Attenuation:  32 (DB-1701)/32 (DB-5)
Type of splitter:  Supelco 8-in injection tee
                                   8121  -  16                         Revision 0
                                                                September i994

-------
                                 TABLE 7

         SUGGESTED CONCENTRATIONS FOR THE CALIBRATION SOLUTIONS'


                              Concentration (ng/jjL)
Benzal chloride
Benzotri chloride
Benzyl chloride
2-Chloronaphthalene
1 , 2 -Di chl orobenzene
1 » 3-Di chl orobenzene
1 > 4-Di chl orobenzene
Hexachl orobenzene
Hexachl orobutadiene
a-BHC
/S-BHC
7-BHC
5-BHC
Hexachl orocyclopentadiene
Hexachl oroethane
Pentachl orobenzene
1,2,3, 4-Tetrachl orobenzene
1,2,4, 5-Tetrachl orobenzene
1,2,3, 5-Tetrachl orobenzene
1,2, 4-Tri chl orobenzene
1, 2, 3-Trichl orobenzene
1 , 3 , 5-Tri chl orobenzene
0.1
0.1
0.1
2.0
1.0
1.0
1.0
0.01
0.01
0.1
0.1
0.1
0.1
0.01
0.01
0.01
0.
0.
0.
0.
0.
0.
0.2
0.2
0.2
4.0
2.0
2.0
2.0
0.02
0.02
0.2
0.2
0.2
0.2
0.02
0.02
0.02
0.2
0.2
0.2
0.2
0.2
0.2
0.5
0.5
0.5
10
5.0
5.0
5.0
0.05
0.05
0.5
0.5
0.5
0.5
0.05
0.05
0.05
0.5
0.5
0.5
0.5
0.5
0.5
0.8
0.8
0.8
16
8.0
8.0
8.0
0.08
0.08
0.8
0.8
0,8
0.8
0.08
0.08
0.08
0.8
0.8
0.8
0.8
0.8
0.8
1.0
1.0
1.0
20
10
10
10
0.1
0.1
1.0
1.0
1.0
1.0
0.1
0.1
0.1
1.0
1.0
1.0
1.0
1.0
1.0
Surrogates

a,2,6-Trichlorotoluene        0.02   0.05    0.1      0.15    0.2
1,4-Dichloronaphthalene       0.2    0.5     1.0      1.5     2.0
2,3,4,5>6-Pentachlorotoluene  0.02   0.05    0.1      0.15    0.2
   One  or  more  internal  standards  should be  spiked prior  to  6C/ECD
   analysis into all  calibration solutions.  The spike concentration  of
   the  internal  standards  should  be kept  constant  for all  calibration
   solutions.
                                   8121  -  17
    Revision 0
September 1994

-------
                                 TABLE 8

               ELUTION  PATTERNS  OF  CHLORINATED  HYDROCARBONS
  FROM THE FLORISIL COLUMN BY ELUTION WITH PETROLEUM ETHER (FRACTION 1)
           AND 1:1  PETROLEUM  ETHER/DIETHYL  ETHER (FRACTION 2)
Compound
Benzal chloride51
Benzoin chloride
Benzyl chloride
2-Chl oronaphthal ene
1 , 2-Dichl orobenzene
1 , 3-Di chl orobenzene
1 , 4-Di chl orobenzene
Hexachl orobenzene
Hexachl orobutad i ene
a-BHC
jS-BHC
7-BHC
5-BHC
Hexachl orocycl opentadi ene
Hexachl oroethane
Pentachl orobenzene
1,2, 3, 4-Tetrachl orobenzene
1,2,4,5-Tetrachlorobenzene"
1,2, 3, 5-Tetrachl orobenzene"
1, 2, 4-Tri chl orobenzene
1, 2, 3-Tri chl orobenzene
1, 3, 5-Tri chl orobenzene
Amount
(M9)
10
10
100
200
100
100
100
1.0
1.0
10
10
10
10
1.0
1.0
1.0
10
10
10
10
10
10
Recovery
Fraction 1"
0
0
82
115
102
103
104
116
101




93
100
129
104
102
102
59
96
102
(percent)"
Fraction 2°
0
0
16






95
108
105
71









*   Values  given represent  average values of duplicate experiments.

b   Fraction  1  was  eluted with  200 mL petroleum ether.

c   Fraction  2  was  eluted with 200 mL petroleum ether/diethyl ether (1:1).

d   This    compound  coelutes   with   1,2,4-trichlorobenzene;   separate
    experiments were performed with  benzil  chloride to verify that  this
    compound  is not recovered from the Florisil  cleanup in either fraction.

e   This  pair  cannot  be resolved  on the  DB-210 fused-silica capillary
    columns.
                                  8121  -  18
    Revision 0
September 1994

-------
                                    TABLE 9
             SINGLE LABORATORY ACCURACY DATA FOR THE  EXTRACTION OF
         CHLORINATED HYDROCARBONS FROM SPIKED CLAY SOIL BY METHOD 3541
                              (AUTOMATED  SOXHLET}*
Compound Name
Spike Level
Recovery
                                                      DB-5
                                    DB-1701
1,3-Dichl orobenzene
1,2-Dichl orobenzene
Benzal chloride
Benzotrichloride
Hexachl orocycl opentadi ene
Pentachl orobenzene
alpha-BHC
delta-BHC
Hexachl orobenzene
5000
5000
500
500
500
500
500
500
500
b
94
61
48
30
76
89
86
84
39
77
66
53
32
73
94
b
88
a     The  operating  conditions  for the  automated Soxhlet  were  as  follows:
      immersion time 45 min; extraction time  45  min;  the  sample size  was 10 g
      clay soil, extraction solvent, 1:1 acetone/hexane.  No equilibration time
      following spiking.

b     Not able to determine because of interference.

Data taken from Reference 4.
                                   8121  -  19
                                      Revision 0
                                  September 1994

-------
                         20 121
                                  IT
                                                        11 11 n
                                                     U
                             10
    it
TIMIdnUi)
ao
ai
ao
Figure 1.    GC/ECD chromatogram of Method 8121 composite standard analyzed on a
            30 n  x 0.53  mn  ID  DB-210  fused-slUca  capillary  column,    GC
            operating  conditions  are given  1n  Section  7.4.   See Table  3  for
            compound Identification.
                                  8121 - 20
                   Revision 0
               September 1994

-------
           »s
                                4

                                If
                                              11
                                              IS

                                             JL
             10     IS     20    26     30     38

                                TIME (mln)
40
so     ss
Figyre 2.   GC/ECD ehromatograa of Method 8121 composite standard analyzed on a
  9         30 B x  0.53 m  ID DB-tiAX fused-siUca  capillary column.    GC
            operating conditions are  given 1n Section 7.4.   See Table  3  for
            compound identification.
                                  8121  -  21
               Revision 0
            September  1994

-------
                                     If
DB-S
i


_*
1 *
11





II


,
fl 1
tl

1
.



                                      DB-1701
              i          i*
              t          i
                        T    -Jl     It It     II  it     If
           i
                  II   II  tl    IB
 If
uu
LJU
Figure 3.   GC/ECD chromatogram  of chlorinated hydrocarbons  analyzed on  a  DB
            5/DB 1701 fused-slllca, open-tubular column pair.   The GC operating
            conditions were as follows:  30  m x O.S3 mi ID DB 5  (0.83 pm film
            thickness) and 30 m  x 0.53 m ID  DB  1701 (1.0 Mm film thickness)
            connected to  an  8 In  Injection  tee  (Supelco  Inc.).   Temperature
            program:  80°C  (1.5 nin hold) to 125°C  (1 m1n hold) at 2"C/m1n,  then
            to 240°C  (2 Bin hold) at 5aC/m1n.
                                   8121  -  22
                         Revision 0
                     September 1994
                                                                                \

-------
                                METHOD 8121

CHLORINATED HYDROCARBONS BY GAS CHROMATOGRAPHY: CAPILLARY  COLUMN TECHNIQUE
                               7.2 Eatfwng* fOf
                               •riwa » iwxvw dtdng
                                 8121  - 23
    Revision 0
September 1994

-------
   METHOD  8121
   (continued)
  7.2.3 Stopper ojmantMtur
      and refrigerate
7.4.1 Set column 1 conditions
 7.4.2 Sat column 2 conditions
 7.5.1 Refer to Method 8000 tor
 caabradon techniques: Mtect
 lowest point an cubntton an*
  7.5.2 Choose Md partarm
internal or external calibration
   (refer to Method 8000)
  7.6.1 Add internal standard
        if necessary
7.6.2 Establish daSy retention tens
cflutions, and Wontilicftlion orisons
!
(
        o
       8121  -  24
     Revision 0
September 1994

-------
                       METHOD 8121
                       (concluded)
          0
  7.6.3 Record sample volume
  Injected and resulting peak
          stew
  7.6.4 Determine Identity and
quantity of each component peak
 ttwt oofTB&pondfi ID compound
     used tor calibration
           7.6.5
        Does pea*
       exceed working
         range of
         syttwn?
7.6.5 Dilute extract raanriyzs
 7.6.6 Compam standard and
   sampteretertwfi times;
                          8121  -  25
                          Revision  0
                    September  1994


-------

-------
                                 METHOD 8140

                         ORGANOPHOSPHORUS PESTICIDES
1.0  SCOPE AND APPLICATION

     1.1  Method 8140 Is a gas  chromatographic  (GC)  method used to determine
the concentration of various organosphosphorus  pesticides.   Table 1 Indicates
compounds that may be determined by this method and lists the method detection
Hm1t for each  compound  1n  reagent  water.     Table  2  lists the practical
quantltatlon limit (PQL) for other matrices.

     1.2  When Method 8140  1s  used  to  analyze unfamiliar samples, compound
identifications should be  supported  by  at  least two additional qualitative
techniques if mass spectroscopy  1s  not  employed.   Section 8.4 provides gas
chromatograph/mass  spectrometer   (GC/MS)   criteria   appropriate   for  the
qualitative confirmation of compound identifications.


2.0  SUMMARY OF METHOD

     2.1  Method  8140  provides   gas   chromatographic  conditions  for  the
detection of ppb levels  of  organophosphorus  pesticides.  Prior to analysis,
appropriate sample extraction techniques must be  used.  Both neat and diluted
organic liquids  (Method  3580,  Waste  Dilution)  may  be  analyzed by direct
Injection.  A 2-  to  5-uL  aliquot  of  the  extract  is  injected into a gas
chromatograph, and compounds in  the  GC  effluent  are  detected with a flame
photometric or thermionic detector.

     2.2  If Interferences are encountered  1n  the  analysis, Method 8140 may
also be performed on extracts  that  have  undergone cleanup using Method 3620
and/or Method 3660.


3.0  INTERFERENCES

     3.1  Refer to Methods 3500  (Section 3.5, In particular), 3600, and 8000.

     3.2  The use of Flor1s1l cleanup materials  (Method 3620) for some of the
compounds 1n this method has  been  demonstrated to yield recoveries less than
85% and 1s therefore not recommended for  all  compounds.  Refer to Table 2 of
Method 3620 for recoveries  of  organophosphorous  pesticides as a function of
FloHsil  fractions.    Use  of  phosphorus-  or  halogen-specific  detectors,
however, often obviates the necessity  for cleanup for relatively clean sample
matrices.   If  particular  circumstances  demand  the  use  of an alternative
cleanup  procedure,  the  analyst  must  determine  the  elution  profile  and
demonstrate that the recovery of each analyte is no less than 85%.
                                  8140 - 1
                                                         Revision      0
                                                         Date  September 1986

-------
TABLE 1.  GAS CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION  LIMITS  FOR
          OR6ANOPHOSPHOROUS PESTICIDES3
Compound
Azinphos methyl
Bolstar
Chlorpyrlfos
Coumaphos
Demeton-0
Demeton-S
Diazlnon
Dichlorvos
Disulfoton
Ethoprop
Fensulfothlon
Fenthion
Merphos
Mevlnphos
Naled
Parathlon methyl
Phorate
Ronnel
Stlrophos (Tetrachlorvlnphos)
Tokuthlon (Prothlofos)
Trlchloronate
GC
column0
la
la
2
la
la
la
2
lb, 3
la
2
la
la
2
lb
3
2
la
2
lb, 3
la
la
Retention
time
(m1n)
6.80
4.23
6.16
11.6
2.53
1.16
7.73
0.8, 1.50
2.10
3.02
6.41
3.12
7.45
2.41
3.28
3.37
1.43
5.57
8.52, 5.51
3.40
2.94
Method
detection
Hm1t (ug/L)
1.5
0.15
0,3
1.5
0.25
0.25
0.6
0.1
0.20
0.25
1.5
0.10
0.25
0.3
0.1
0.03
0.15
0.3
5.0
0.5
0.15
      Development of   Analytical  Test   Procedures  for  Organic Pollutants in
      Wastewater; Report  for  EPA Contract 68-03-2711 (in preparation).

           Sections  4.2.1 and 7.2  for  column descriptions and conditions.
                                   8140 - 2
                                                         Revision
                                                         Date  September  1986

-------
TABLE 2.  DETERMINATION OF PRACTICAL QUANTITATIQN LIMITS (PQL)  FOR VARIOUS
          MATRICES3


    Matrix                                                   Factor0
Ground water                                                     10
Low-level soil by sonlcation with 6PC cleanup                   670
High-level soil and sludges by sonlcatlon                    10,000
Non-water mlsdble waste                                    100,000


     aSample PQLs are highly  matrix-dependent.    The  PQLs listed herein are
     provided for guidance and may not always be achievable.

     bPQL « [Method detection Hm1t (Table 1)] X [Factor (Table 2)].  For non-
     aqueous samples, the factor 1s on a wet-weight basis.
                                  8140 - 3
                                                         Revision
                                                         Date  September 1986

-------
     3.3  Use of a  flame  photometric  detector  1n  the phosphorus mode will
minimize  Interferences  from  materials   that  do  not  contain  phosphorus.
Elemental sulfur, however,  may  Interfere  with  the determination of certain
organophosphorus pesticides by flame  photometric  gas chromatography.  Sulfur
cleanup using Method 3660 may alleviate this Interference.

     3.4  A  halogen-specific  detector  (I.e.,  electrolytic  conductivity or
m1crocoulometr1c) 1s very selective  for the halogen-containing pesticides and
1s recommended for use with dlchlorvos, naled, and stlrophos.


4.0  APPARATUS AND MATERIALS

     4.1  Gas   chrpmatograph:      Analytical   system   complete   with  gas
chromatograph suitable for cm-column  Injections and all required accessories,
Including detectors, column supplies, recorder,  gases,  and syringes.  A data
system for measuring peak areas and/or peak heights 1s recommended.

          4.1.1  Columns:

               4.1.1.1  Column la and Ib:    1.8-m  x  2-mm I.D. glass, packed
          with 5% SP-2401 on Supelcoport, 100/120 mesh  (or equivalent).

               4.1.1.2  Column 2:  1,8-m x 2-mm I.D. glass, packed with 3% SP-
          2401 on Supelcoport, 100/120 mesh (or equivalent).

               4.1.1.3  Column 3:  50-cm x l/8-1n O.D. Teflon, packed with 15%
          SE-54 on Gas Chrom Q, 100/120 mesh  (or equivalent).

          4.1.2  Detectors:  The following  detectors have proven effective 1n
     analysis for the analytes listed  1n Table  1 and were used to develop the
     accuracy and precision statements  1n Section 9.0.

               4.1.2.1  Phosphorus-specific:      Nitrogen/Phosphorus    (N/P),
          operated  1n phosphorus-sensitive mode.

               4.1.2.2  Flame  Photometric  (FPD):     FPD  1s more  selective for
          phosphorus than the  N/P.

               4.1.2.3  Halogen-specific:       Electrolytic    conductivity  or
          m1crocoulometr1c.   These   are very  selective  for those  pesticides
          containing halogen  substltuents.

     4-2 Balance;  analytical,  capable of  accurately  weighing  to  the nearest
 0.0001 g.

     4,3 Vials;  Amber glass,  10-   to 15-mt  capacity with  Teflon-Hned screw-
 cap.

     4.4 Kuderna-Dan1sh  (K-D)  apparatus;

          4.4.1   Concentrator tube:   10-mL, graduated  (Kontes K-570050-1025 or
     equivalent).   Ground-glass   stopper  Is   used   to   prevent  evaporation of
     extracts

                                  8140 - 4
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          4.4,2  Evaporation   flask:       500-mL   (Kontes   K-570Q01-SOO   or
     equivalent).  Attach to concentrator tube with springs,

          4.4.3  Snyder column:    Three-ball   macro  (Kontes K-503000-0121  or
     equivalent).

          4.4.4  Snyder  column:    Two-ball   micro  (Kontes   K-569001-0219  or
     equivalent).

     4.5  Boiling chips;  Solvent extracted,  approximately 10/40 mesh (silicon
carbide or equivalent).

     4«6  Water  bath;    Heated,  with  concentric  ring  cover,  capable   of
temperaturecontrol (+5*C).  The bath  should be used In a hood.

     4*7  Microsyringe;  10-uL.

     4.8  Syringe:  5-mL.

     4.9  Volumetric flasks;  10-, 50-, and 100-mL, ground-glass stopper.
                       Hexane,   acetone,  Isooctane  (2,2,4-trlmethylpentane)
5.0  REAGENTS

     5.1  Solvents;
(pest1d de qua!1 ty or equivalent).

     5.2  Stock standard solutlgns;

          5.2.1  Prepare stock standard solutions by accurately weighing about
     0.0100 g of pure  material.    Dissolve  the  material  1n hexane or other
     suitable solvent  and  dilute   to  volume  In  a  10-mL volumetric flask.
     Larger volumes can  be  used  at  the  convenience  of  the  analyst.   If
     compound purity 1s certified at  96%  or  greater, the weight can be used
     without correction to calculate the  concentration of the stock standard.
     Commercially prepared stock standards can be used at any concentration 1f
     they are certified by the manufacturer or by an Independent source.

          5.2.2  Transfer  the  stock  standard  solutions  Into Teflon-sealed
     screw-cap bottles.  Store at 4*C  and protect from light.  Stock standard
     solutions should  be  checked  frequently  for  signs  of  degradation or
     evaporation, especially  just  prior  to  preparing calibration standards
     from them.

          5.2.3  Stock standard solutions must be  replaced after one year, or
     sooner 1f comparison with check standards Indicates a problem.

     5.3  Calibration standards:  Calibration  standards  at a minimum of five
concentration levels for each parameter of Interest should be prepared through
dilution of the stock  standards  with  Isooctane.    One of the concentration
levels should be at  a  concentration  near,  but  above, the method detection
                                  8140 - 5
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limit.  The remaining concentration  levels  should correspond to the expected
range of concentrations found  1n  real   samples  or should define the working
range of the GC.  Calibration standards   must be replaced after six months,  or
sooner 1f comparison with check standards Indicates a problem.

     5.4  Internal standards (If Internal  standard  calibration 1s used);  To
use this approach, the analyst must select one or more Internal standards that
are similar 1n analytical behavior to  the compounds of Interest.  The analyst
must further demonstrate that the measurement  of the Internal standard 1s not
affected by method or matrix Interferences.   Because of these limitations,  no
Internal standard can be suggested that 1s applicable to all samples.

          5.4.1  Prepare  calibration   standards   at   a   minimum  of  five
     concentration levels  for  each  parameter  of  Interest  as described 1n
     Paragraph 5.3.

          5.4.2  To each calibration standard, add  a known constant amount of
     one or more Internal standards, and dilute to volume with hexane or other
     suitable solvent.

          5.4.3  Analyze each calibration  standard according to Section 7.0.

     5.5  Surrogate standards;  The analyst  should monitor the performance of
the  extraction,cleanup(when   used),   and   analytical  system  and  the
effectiveness of the method  1n dealing with each sample matrix by spiking each
sample, standard, and  reagent water  blank with  one or two surrogates (e.g.,
organophosphorous  pesticides  not  expected  to  be  present  1n  the sample)
recommended to  encompass the  range  of  the  temperature program used 1n this
method.  Deuterated analogs  of analytes  should  not be used as surrogates for
gas chromatographlc analysis due to coelutlon problems.


6.0  SAMPLE COLLECTION,  PRESERVATION, AND  HANDLING

      6.1  See the Introductory  material   to  this  chapter, Organic Analytes,
Section 4.1.  Extracts must  be  stored under refrigeration and analyzed within
40 days of extraction.


7.0   PROCEDURE

      7.1   Extraction;

           7.1.1  Refer to  Chapter  Two for  guidance on  choosing the  appropriate
      extraction procedure.    In  general,   water  samples   are  extracted at a
      neutral, or as  1s,  pH  with   methylene chloride,  using  either  Method 3510
      or 3520.   Solid samples are extracted using either Method 3540 or 3550.

           7.1.2  Prior to  gas chromatographlc  analysis,  the extraction solvent
      may be exchanged to hexane.   This   1s recommended 1f the detector used 1s
      halogen-specific.  The exchange  1s  performed  during the K-D procedures
      listed 1n  all  of the   extraction   methods.   The exchange 1s performed as
      follows.

                                   8140  - 6
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                                                          Date  September 1986

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              7.1.2.1  Following K-D of the methylene chloride extract to
         1 ml using the macro-Snyder column,  allow the apparatus to cool and
         drain for at least 10 tnin.

              7.1.2.2  Momentarily remove the  Snyder  column,  add  50 ml of
         hexane, a new boiling  chip,  and  reattaeh the macro-Snyder column.
         Concentrate the extract using 1  ml  of  hexane to prewet the Snyder
         column.  Place the  K-D  apparatus  on  the  water  bath so that the
         concentrator tube 1s partially  immersed  in  the hot water.  Adjust
         the vertical position of the apparatus and the water temperature, as
         required, to complete concentration 1n 5-10 m1n.  At the proper rate
         of distillation the balls of  the  column will actively chatter, but
         the chambers will not  flood.    When  the apparent volume of liquid
         reaches 1 ml, remove the  K-D  apparatus  and  allow it to drain and
         cool for at least 10 min.

              7.1.2.3  Remove the Snyder column   and  rinse the flask and Its
         lower joint into the concentrator  tube with 1-2 ml of hexane.  A
         5-mL syringe is recommended for  this operation.  Adjust the extract
         volume  to  10.0  ml.    Stopper   the  concentrator  tube  and  store
         refrigerated at 4*C  1f  further   processing  will  not be performed
         Immediately.  If the extract will  be stored longer than two days, it
         should be transferred to  a  Teflon-sealed  screw-cap vial.  Proceed
         with  gas  chromatographic  analysis   if  further  cleanup  1s  not
         required.

     7.2 Gas chromatography conditions(Recommended):

         7.2.1  Column la:  Set   helium  carrier  gas  flow at 30 ml_/m1n flow
     rate.   Column temperature 1s  set  at  150*C for 1 m1n  and then programmed
     at 25*C/min to 220*C and held.

         7.2.2  Column Ib:  Set nitrogen  carrier gas flow at 30 mL/m1n flow
     rate.   Column temperature 1s  set  at  170*C for 2 min  and then programmed
     at 20*C/min to 220*C and held.

         7.2.3  Column 2:  Set  helium  carrier   gas  at 25 mL/min flow  rate.
     Column temperature 1s set  at 170*C  for  7  m1n  and then programmed at
     10*C/min to 250*C and held.

         7.2.4  Column 3:  Set nitrogen  carrier  gas at 30 ml_/m1n flow  rate.
     Column temperature 1s set  at 100*C  and  then  immediately programmed at
     25*C/m1n to 200*C and held.

     7«3 Calibration;     Refer    to   Method   8000   for   proper   calibration
techniques'Use  Table  1 and  especially  Table  2 for guidance  on  selecting the
lowest point on  the  calibration curve.

          7.3.1   The  procedure  for  Internal or   external  calibration may be
     used.     Refer  to   Method   8000  for   a   description  of  each   of  these
     procedures.
                                  8140 - 7
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                                                         Date  September 1986

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         7.3.2  If cleanup 1s performed  on  the  samples, the analyst should
    process a series  of  standards  through  the  cleanup procedure and then
    analyze the samples by GC.    This  will confirm elutlon patterns and the
    absence of Interferents from the reagents.

    7.4  Gas chromatographlcanalysis;

         7.4.1  Refer to Method 8000.    If the Internal standard calibration
    technique 1s used, add 10 uL of  Internal standard to the sample prior to
    Injection.

         7.4.2  Follow Section 7.6  1n  Method  8000  for Instructions on the
    analysis sequence,  appropriate  dilutions,  establishing dally retention
    time windows,  and Identification criteria.   Include a mid-level standard
    after  each group of 10 samples in the  analysis sequence.

         7.4.3  Examples  of  chromatograms   for  various  organophosphorous
    pesticides are shown  1n Figures 1 through 4.

         7.4.4  Record the  sample  volume  Injected  and  the  resulting peak
     sizes  (1n area units  or peak  heights).

         7.4.5  Using either  the   Internal  or  external  calibration procedure
     (Method 8000), determine  the  Identity  and quantity  of each  component peak
     in the sample chromatogram  which   corresponds  to  the compounds  used  for
     calibration purposes.   See  Section  7.8 of  Method 8000 for calculation
     equations.

          7.4.6   If peak  detection  and   Identification   are  prevented due to
     Interferences, the  hexane extract may   undergo  cleanup using Method 3620.
     The resultant extract(s)  may  be   analyzed   by   GC directly  or may undergo
     further cleanup to  remove sulfur  using Method  3660.

     7.5  Cleanup;

          7.5.1   Proceed  with  Method  3620,   followed  by,  1f  necessary, Method
     3660,  using  the 10-mL hexane  extracts  obtained  from Paragraph 7.1.2.3.

          7.5.2   Following cleanup,  the  extracts should   be analyzed  by GC,  as
     described 1n  the previous paragraphs and 1n Method  8000.


8.0  QUALITY CONTROL

     8,1  Refer  to  Chapter  One   for  specific  quality  control procedures.
Quality control  to validate sample extraction 1s covered In Method 3500 and In
the extraction method utilized.   If  extract cleanup was performed,  follow  the
QC in Method 3600  and 1n  the specific cleanup method.

     8.2  Procedures to  check  the  GC  system  operation  are  found  1n Method
8000,  Section 8.6.
                                  8140 - 8
                                                         Revision
                                                         Date  September 1986

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                         Column: 6% SP-2401 on Supelcoport
                         Temperature: 170°C 7 Minutes, then
                                    10°C/MmuM to 2500C
                         Detector: Phosphorus-Specific Flame Photometric
                    45678
                     RETENTION TIME (MINUTES)
10
11
12
Figure 1. Gas chromatogram of organophosphorus pesticides (Example 1).
                      8140 - 9
                                                Revision       p
                                                Date   September 1986

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    Column: 3% SP-2401
    Program: 170°C 7 MinuMi, 10°C/Minute
           tt>250°C
    Ofttctor: Phosphorut/Nitrogen
                                         i

                                        1
                                          tu
             §
              I

                       66432
                        RETENTION TIME (MINUTES)
Figurt 2. Gas chromstogram of organophosphorus pesticides (Example 2).
                    8140 - 10
                                              Revision      _g	
                                              Date  September 1986

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Column: 15% SE-54 on Gas Chrom Q
T«mptraturt: 100°C Initial, then
           2§oC/Minutt to 200°C
Detector: Hall Electrolytic Conduct!vity-Oxidative Mode
                     7    6    E    4    3    2    1
                        RETENTION TIME (MINUTES)
  Figure 3. Gas chromatogram of organophosphorus pesticides (Example 3).
                          8140  -  11
                                                    Revision       0	
                                                    Date  September  1986

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               Column: 5% SP-2401 on Supelcoport

               Temperature: 170°C 2 Minutes, then 20°C/Minute to 220°C

                Detector: Phosphorus-Specific Flame Photometric
                                                                      I
                                                                      o
                 3        4         S


                  RETENTION TIME (MINUTES)
Figure 4. Gas chromatogram of orgtnophosphorus pesticides (Example 4).
                           8140  - 12
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                                                     Date  September  1986

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          8.2.1  Select a representative spike  concentration  for each  analyte
     to be measured.    The  quality  control   check sample  concentrate  (Method
     8000,  Section  8.6)  should  contain   each  analyte   1n  acetone  at   a
     concentration 1,000  times  more  concentrated  than  the  selected spike
     concentration.

          8.2.2  Table 3 indicates Single  Operator Accuracy and Precision for
     this method.  Compare  the  results  obtained  with  the  results given  in
     Table 3 to determine if the data quality is acceptable.

     8.3  Calculate surrogate standard  recovery  on  all samples, blanks, and
spikes.  Determine if  the  recovery  1s  within limits (limits established by
performing QC procedures outlined in Method 8000, Section 8.10).

          8.3.1  If recovery is  not  within  limits, the following procedures
     are required.

               •  Check to  be  sure  there  are  no  errors  in calculations,
                  surrogate solutions  and  Internal  standards.   Also, check
                  instrument performance.

               •  Recalculate the data and/or reanalyze  the extract if any of
                  the above checks reveal a problem.

               «  Reextract and reanalyze the sample  1f none of the above are
                  a problem or flag the data as "estimated concentration."

     8.4  GC/MS confirmation;

          8.4.1  GC/MS techniques should  be  judiciously  employed to support
     qualitative Identifications made with  this  method.  The GC/MS operating
     conditions and procedures  for  analysis  are  those  specified in Method
     8270.

          8.4.2  When  available,  chemical  1on1zation  mass  spectra  may be
     employed to aid 1n the qualitative Identification process.

          8.4.3  Should  these  MS  procedures  fail  to  provide satisfactory
     results, additional steps may  be  taken  before reanalysls.  These steps
     may  include the  use  of  alternate  packed  or  capillary GC columns and
     additional cleanup.


9.0  METHOD PERFORMANCE

     9.1  Single-operator accuracy and  precision  studies have been conducted
using spiked wastewater  samples.   The  results of these studies are presented
In Table  3.
                                  8140 - 13
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                                                         Date  September 1986

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10.0  REFERENCES

1.  Pressley, T.A. and J.E. Longbottom, "The Determination of Organophosphorus
Pesticides 1n Industrial and Municipal Wastewater: Method 614," U.S. EPA/EMSL,
Cincinnati, OH, EPA-600/4-82-004, 1982.

2.  Burke, J.A.,  "Gas  Chromatography  for  Pesticide  Residue Analysis,- Some
Practical  Aspects,"    Journal  of  the  Association  of  Official Analytical
Chemists 48, 1037, 1965.

3.  U.S. EPA, "Analysis of  Volatile  Hazardous Substances by GC/MS: Pesticide
Methods Evaluation," Letter Reports 6,  12A,  and 14, EPA Contract 68-03-2697,
1982.

4.  U.S.   EPA,  "Method   622,  Organophosphorous  Pesticides,"  Environmental
Monitoring and Support  Laboratory, Cincinnati, OH 45268.
                                   8140 - 14
                                                          Revision      0
                                                          Date  September 1986

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TABLE 3.  SINGLE-OPERATOR ACCURACY AND PRECISION3
Parameter
Azinphos methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Dlazlnon
Dlchlorvos
Dlsulfoton
Ethoprop
Fensulfothlon
Fenthlon
Merphos
Mevlnphos
Naled
Parathlon methyl
Phorate
Ronnel
Stlrophos
Tokuthton
THchloronate
Average
recovery
f V \
X J
72.7
64.6
98.3
109.0
67.4
67.0
72.1
81.9
100.5
94.1
68.7
120.7
56.5
78.0
96.0
62.7
99.2
66.1
64.6
105.0
Standard
deviation
w
18.8
6.3
5.5
12.7
10.5
6.0
7.7
9.0
4.1
17.1
19.9
7.9
7.8
8.1
5.3
8.9
5.6
5.9
6.8
18.6
Spike
range
(ug/L)
21-250
4.9-46
1.0-50.5
25-225
11.9-314
5.6
15.6-517
5.2-92
1.0-51.5
23.9-110
5.3-64
1.0-50
15.5-520
25.8-294
0.5-500
4.9-47
1.0-50
30.3-505
5.3-64
20
Number
of
analyses
17
17
18
17
17
7
16
17
18
17
17
18
16
16
21
17
18
16
17
3
alnformat1on taken from Reference 4.
                                  8140 - 15
                                                          Revision      0
                                                          Date  September  1986

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                                         METHOD  B140

                                 ORGANOPHOSPHOBUS PESTICIDES
7. J. i
                                                       0
       Choose
    •pproprlate
    extraction
     procedure
 (see Chapter 2)
7.1.2
                                                    7.4
                             Perform GC
                           analysis  (sea
                            Metnod BOOO)
       Exchange
       SMtraet-
 lon aolvent to
       nexane
    during K-D
    procedures
 7.2
    Set BBS
 chromatogrephy
  conditions
                                                   7.5.11

                                                         Cleanup
                                                      using Method
                                                     362O and 3360
                                                      if necessary
7

.3
Ml
fe
CI
tt
Refer to
itnod 8OOO
ir proper
ilibration
>chniguas
       I*
    Cleanup
   nccaaaary?
                         7.3.8
       Process
       a series
   of standards
through cleanup
    procedure:
  analyze By GC
                                   8140 -  16
                                                              Revision       0
                                                              Date   September 1986

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                                 METHOD 8141A

               ORGANOPHQSPHORUS  COMPOUNDS  BY  GAS  CHROHATOGRAPHY:
                          CAPILLARY COLUMN TECHNIQUE
1.0   SCOPE AND APPLICATION

      1.1   Method 8141 is a capillary gas chroraatographic (GC) method used to
determine  the  concentration of organophosphorus  (OP)  compounds.    The fused-
silica, open-tubular columns specified in this method offer improved resolution,
better  selectivity,  increased  sensitivity,  and  faster  analysis  than packed
columns.  The compounds listed in the table below  can be determined by 6C using
capillary  columns  with  a  flame  photometric detector  (FPD)  or  a  nitrogen-
phosphorus detector (NPD).  Triazine herbicides can also be determined with this
method when the NPD is used.  Although performance data are presented for each
of the listed chemicals,  1t  is unlikely that all of them could be determined in
a  single  analysis.    This  limitation  results  because  the chemical   and
chromatographic behavior of many of these chemicals can  result in co-elution.
The analyst must select columns, detectors and  calibration  procedures for the
specific analytes of interest  in a study.  Any  listed  chemical  is a potential
method interference when it is not  a  target  analyte.
      Compound Name
                                  8141A - 1
CAS Registry No.
OP Pesticides
Aspon,b
Azinphos-methyl
Azinphos- ethyl*
Bo! star (Sulprofos)
Carbophenothion*
Chlorfenvinphos8
Chlorpyrifos
Chlorpyrifos methyl*
Coumaphos
Crotoxyphos*
Demeton-00
Demeton-S°
Diaz in on
Dichlorofenthion*
Dichlorvos (DDVP)
Dicrotophos*
Dimethoate
Dioxathion"'11
Disulfoton
EPN
Ethion1
Ethoprop
Famphur"
Fen i troth ion8
Fensulfothion

3244-90-4
86-50-0
2642-71-9
35400-43-2
786-19-6
470-90-6
2921-88-2
5598-13-0
56-72-4
7700-17-6
8065-48-3
8065-48-3
333-41-5
97-17-6
62-73-7
141-66-2
60-51-5
78-34-2
298-04-4
2104-64-5
563-12-2
13194-48-4
52-85-7
122-14-5
115-90-2
              Revision 1
          September 1994

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       Compound  Name
CAS Registry No.
Fonophos"
Fenthion
LeptophosM
Malathion
Merphos0
Mevinphos"
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Phosmet*
Phosphamldon"
Ronnel
Stirophos (Tetrachlorovinphos)
Sulfotepp
TEPP"
Terbufos"
Thionazina-b (Zinophos)
Tokuthion6 (Protothiofos)
Trichlorfon*
Trichloronateb
944-22-9
55-38-9
21609-90-5
121-75-5
150-50-5
7786-34-7
6923-22-4
300-76-5
56-38-2
298-00-0
298-02-2
732-11-6
13171-21-6
299-84-3
22248-79-9
3689-24-5
21646-99-1
13071-79-9
297-97-2
34643-46-4
52-68-6
327-98-0
Industrial Chemicals
      Hexamethylphosphoramide8 (HMPA)
      Tri-o-cresylphosphatea-d (TOCP)

Triazine Herbicides (NPD only)
      Atrazine"
      Simazine3
   680-31-9
    78-30-8
  1912-24-9
   122-34-9
      a     This analyte has been evaluated using a 30-m column only.
      b     Production discontinued in the U.S., standard not readily available.
      c     Standards may have multiple components because of oxidation.
      d     Compound is extremely toxic or neurotoxic.
      e     Adjacent major/minor peaks can be observed due to c is/trans isomers.
      1.2   A duc.]-column/dual-detector approach may be used for the analysis of
relatively clean extracts.   Two 15- or 30-m  x  0.53-mm ID fused-silica, open-
tubular columns of  different  polarities  are connected to an injection tee and
each is connected to a detector.  Analysts are cautioned  regarding the use of a
dual column configuration when their instrument is subject to mechanical stress,
                                   8141A -  2
              Revision  1
          September 1994

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when  many  samples  are analyzed  over  a  short  time,  or  when  extracts  of
contaminated  samples  are analyzed.

       1.3   Two detectors can be used for the listed OP chemicals.  The FPD works
by measuring the emission of phosphorus- or sulfur-containing species. Detector
performance is optimized by  selecting the proper optical filter and adjusting the
hydrogen and air flows to the flame.  The NPD is a flame ionization detector with
a  rubidium ceramic flame tip  which  enhances,the response  of phosphorus- and
nitrogen-containing analytes.  The FPD  is more sensitive and  more  selective, but
is a less  common detector in environmental  laboratories.

       1.4   Table 1 lists method detection limits (MDLs) for the target analytes,
using  15-m columns and FPD, for  water and soil  matrices.   Table 2  lists the
estimated quantitation limits (EQLs) for other matrices.  MDLs and EQLs using 30-
m columns will be very  similar to those obtained from li-m columns,

       1.5   The use of a 15-m column system has not been  fully validated for the
determination  of  the  following compounds.    The   analyst must  demonstrate
chromatographic  resolution   of  all   analytes,  recoveries of greater than  70
percent, with precision of no more than 15 percent  RSD,  before data generated on
the 15-m column system  can  be reported for  these,  or any additional,  analytes:

      Azinphos-ethyl    Ethion      Phosmet
      Carbophenothion   Famphur     Phosphamidon
      Chlorfenvinphos   HMPA       Terbufos
      Dioxathion        Leptophos   TOCP

       1.6   When Method 8141 is used  to  analyze  unfamiliar samples, compound
identifications should be supported by confirmatory analysis.  Sec. 8.0 provides
gas  chromatograph/mass  spectrometer  (6C/HS)  criteria  appropriate  for  the
qualitative confirmation of  compound identifications.

      1.7   This method is  restricted  to  use by,  or  under the supervision of,
analysts experienced  in the use of capillary gas  chromatography and  in  the
interpretation of chromatograms.


2.0   SUMHARY OF METHOD

      2.1   Method 8141 provides gas chromatographic conditions for the detection
of ppb concentrations of organophosphorus compounds.   Prior  to the use of this
method, appropriate sample preparation techniques  must be used.   Water samples
are extracted at a  neutral  pH with methylene chloride   by  using a separatory
funnel   (Method  3510)  or a  continuous  liquid-liquid extractor  (Method  3520).
Soxhlet extraction (Method 3540) or automated Soxhlet extraction (Method 3541)
using methylene chloride/acetone (1:1) are used for solid samples.   Both neat and
diluted organic liquids (Method 3580, Waste  Dilution) may be analyzed by direct
injection.   Spiked samples  are  used  to verify  the  applicability  of the chosen
extraction technique to each new sample type.  A gas chromatograph with a flame
photometric  or  nitrogen-phosphorus  detector  is  used  for   this  multiresidue
procedure.
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       2.2    Organophosphorus esters and thioesters  can hydrolyze under both acid
 and  base   conditions.   Samples  prepared using  acid  and  base partitioning
 procedures  are  not  suitable for  analysis  by Method 8141.

       2.3    Ultrasonic  Extraction  (Method 3550) is  not  an appropriate sample
 preparation  method for  Method  8141  and  should  not be  used because  of the
 potential for  destruction  of  target analytes  during the ultrasonic extraction
 process.


 3.0    INTERFERENCES

       3.1    Refer to Methods 3500, 3600,  and 8000, as well as to Sec. 1.1.

       3.2    The use of Florisil Cleanup  (Method 3620) for some of the compounds
 in this method  has been demonstrated to yield recoveries less than  85 percent and
 is therefore not recommended for  all compounds.  Refer to Table 2  of Method 3620
 for recoveries of organophosphorus compounds.  Use of an FPD often  eliminates the
 need  for sample cleanup.   If particular circumstances  demand  the use  of an
 alternative cleanup procedure, the analyst must determine the elution profile and
 demonstrate  that the recovery of each  analyte is not  less than 85 percent.

       3.3    The  use of Gel  Permeation Cleanup  (6PC)  (Method  3640)  for sample
 cleanup  has  been demonstrated  to yield recoveries  of less than  85 percent for
 many  method  analytes  because  they elute  before bis-(2-ethylhexyl)  phthalate.
 Method  3640 is  therefore  not recommended for use  with this method,  unless
 analytes of interest  are listed in Method 3640  or are demonstrated  to  give
 greater than 85 percent recovery.

      3.4    Use  of  a  flame photometric  detector  in  the  phosphorus  mode  will
 minimize interferences from materials  that do  not contain phosphorus or sulfur.
 Elemental   sulfur   will   interfere   with  the   determination   of   certain
 organophosphorus compounds by flame photometric gas chromatography.   If Method
 3660 is used  for sulfur cleanup, only the tetrabutylammonium (TBA)-sulfite option
 should be employed, since  copper and  mercury may destroy  OP  pesticides.   The
 stability of each analyte must be  tested to ensure that the recovery from the
 TBA-sulfite sulfur cleanup step  is not less than 85 percent.

      3.5   A  halogen-specific   detector  (i.e.,  electrolytic conductivity  or
 microcoulometry) is very selective  for the halogen-containing  compounds and may
 be used  for the determination of  Chlorpyrifos, Ronnel,  Coumaphos,  Tokuthion,
 Trichloronate,   Dichlorvos,  EPN,  Naled,  and  Stirophos only.   Many  of  the  OP
 pesticides may  also be detected by the  electron capture detector (ECD); however,
 the ECD is not  as specific  as  the NPD  or  FPD.  The ECD should  only be used when
 previous analyses have demonstrated that interferences will  not adversely effect
quantitation, and that the detector sensitivity is  sufficient to meet regulatory
 1 imits,

      3.6   Certain analytes  will coelute, particularly on 15-m columns (Table
3).   If  coelution  is  observed,  analysts  should (1)  select  a  second  column of
different polarity  for confirmation, (2)  use 30-m x 0,53-mm columns,  or (3) use
0.25-  or  0.32-mm ID columns.    See Figures  1  through  4 for combinations  of
compounds that do not coelute  on 15-m  columns.


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 3.7   The following pairs coeluted on the DB-5/DB-210 30-m column pair:

 DB-5  Terbufos/tri-o-cresyl phosphate
       Naled/Simazine/Atrazine
       Dichlorofenthion/Demeton-0
       Trichloronate/Aspon
       Bolstar/Stirophos/Carbophenothion
       Phosphamidon/Crotoxyphos
       Fensulfothion/EPN

DB-210 Terbufos/tri-o-cresyl phosphate
       Dichlorofenthion/Phosphamidon
       Chlorpyrifos, lethyl/Parathion, methyl
       Chlorpyrifos/Parathion,  ethyl
       Aspon/Fenthion
       Demeton-Q/Di methoate
       Leptophos/Az i nphos-methyl
       EPN/Phosmet
       Famphur/Carbophenothion

 See Table 4 for retention times  of these compounds  on 30-m columns.

 3.8   Analytical  difficulties  encountered for  target  analytes include:

       3.8.1 Tetraethyl  pyrophosphate  (TEPP) is  an unstable  diphosphate
 which is  readily  hydrolyzed  in  water  and  is  thermally  labile  (TEPP
 decomposes at  170°C).   Care must  be taken to minimize  loss during  GC
 analysis and during sample preparation.   Identification of  bad  standard
 lots is  difficult since the electron  impact (El)  mass spectrum of TEPP is
 nearly identical  to its  major  breakdown product, triethyl  phosphate.

       3.8.2 The water  solubility of Dichlorvos (DDVP)  is  10  g/L  at  20"C?
 and recovery is poor from aqueous solution.

       3,8.3 Naled  is   converted  to  Dichlorvos   (DDVP)   on  column   by
 debromination.   This reaction may also occur during  sample  workup.   The
 extent of debromination  will  depend on  the nature  of the matrix  being
 analyzed.   The  analyst must consider the potential  for debromination when
 Naled is to be  determined.

       3.8.4 Trichlorfon  rearranges and is dehydrochlorinated  in  acidic,
 neutral, or basic media  to form  Dichlorvos (DDVP)  and hydrochloric  acid.
 If this  method  is to be used for the determination  of organophosphates in
 the  presence  of  Trichlorfon,  the  analyst  should  be   aware   of  the
 possibility of  rearrangement to  Dichlorvos to  prevent misidentification.

       3.8.5 Demeton (Systox)  is  a mixture of two compounds;  0,0-diethyl
 0-[2-(ethy1thio)ethyl]phosphorothioate  (Demeton-0)  and 0,0-diethyl  S-[2-
 (ethylthio)ethyl]phosphorothioate (Demeton-S),  Two peaks  are observed in
 all   the chromatograms  corresponding  to  these  two   isomers.    It   is
 recommended that  the  early  eluting compound  (Demeton-S)  be used  for
 quantitation.
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            3.8.6 Dioxathion is a single-component pesticide.  However, several
      extra peaks are observed in the chromatograms of standards.  These peaks
      appear  to  be  the  result  of  spontaneous  oxygen-sulfur  isomerization.
      Because  of  this,   Dioxathion  is  not  included  in  composite  standard
      mixtures.

            3.8.7 Merphos (tributyl phosphorotrithioite) is a single-component
      pesticide  that  is  readily  oxidized to  its  phosphorotrithioate (Merphos
      oxone).   Chromatographic analysis  of Merphos almost always  results two
      peaks  (unoxidized  Merphos  elutes  first).    As  the relative  amounts  of
      oxidation  of  the  sample   and  the  standard   are  probably  different,
      quantitation based on the sum of both peaks may be most appropriate.

            3.8.8 Retention times of some analytes, particularly Monocrotophos,
      may increase with  increasing concentrations in the  injector.   Analysts
      should check for retention  time shifts in highly contaminated samples.

            3.8.9 Many  analytes  will  degrade   on   reactive   sites  in  the
      chromatographic system.   Analysts must ensure that  injectors and splitters
      are  free  from  contamination  and  are  si 1 anized.   Columns  should  be
      installed and maintained properly.

            3.8.10      Performance of chromatographic systems will degrade with
      time.  Column resolution, analyte breakdown  and  baselines may be improved
      by column washing.(Sec.  7).  Oxidation of columns  is  not  reversible.

      3.9   Method interferences  may  be caused  by contaminants in  solvents,
reagents, glassware,  and  other sample processing hardware that lead to discrete
artifacts or elevated  baselines in  gas chromatograms.  All these materials must
be routinely demonstrated to be free from interferences under the conditions of
the analysis by analyzing reagent blanks  (Sec. 8.0).

      3.10  NP Detector interferences:    Triazine herbicides, such  as Atrazine
and Simazine,  and other nitrogen-containing compounds may interfere.


4.0   APPARATUS AND MATERIALS

      4.1   Gas  chromatograph:  An analytical  system  complete  with  a  gas
chromatograph  suitable  for on-column  or split/splitless  injection, and  all
required accessories,  including  syringes, analytical  columns, gases,  suitable
detector(s), and a recording device.  The  analyst should select the detector for
the specific measurement application,  either the flame photometric  detector or
the nitrogen-phosphorus detector.  A data system  for  measuring  peak  areas and
dual  display of chromatograms  is  highly recommended.

            4.1.1 Capillary Columns (0.53-mm,  0.32-jnm, or 0.25-mm ID x 15-m or
      30-m length, depending on the resolution required).  Columns of 0.53-mm ID
      are recommended for most environmental  and  waste  analysis applications.
      Dual-column, single-injector  analysis requires columns of equal length and
      bore.   See Sec.  3.0 and  Figures 1 through 4 for guidance on selecting the
      proper length and diameter  for  the  column(s).
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            4.1.1.1     Column  1  -  15-  or  30-m  x  0.53-mm  wide-bore
      capillary column,  l.G-^m film thickness,  chemically bonded with 50%
      trifluoropropyl polysiloxane, 50% methyl polysiloxane (DB-210), or
      equivalent.

            4.1.1.2     Column  2  -  15-  or  30-m  x  0.53-mm  wide-bore
      capillary column,  Q.83-/im  film thickness,   chemically  bonded with
      35%  phenyl  methyl   polysiloxane  (DB-608,  SPB-608,  RTx-35),  or
      equivalent.

            4.1.1.3     Column  3  -  15-  or  30-m  x  0.53-mm  wide-bore
      capillary column,  1.0 ^m film thickness,  chemically bonded with 5%
      phenyl   polysiloxane, 95% methyl   polysiloxane  (DB-5, SPB-5, RTx-5),
      or equivalent.

            4.1.1.4     Column 4 - 15-  or 30-m x  0,53-mm ID fused-silica
      open-tubular column,  chemically bonded  with  methyl   polysiloxane
      (DB-1,  SPB-1, or equivalent), 1.0-^m or 1.5-/um film thickness.

            4.1.1.5     (optional) Column rinsing  kit: Bonded-phase column
      rinse kit (J&W Scientific,  Catalog no,  430-3000  or equivalent).

      4.1.2 Splitter: If a dual-column, single-injector  configuration  is
used, the open tubular columns should  be connected to one of the following
splitters, or equivalent:

            4.1.2.1     Splitter  1 -  J&W Scientific press-fit  Y-shaped
      glass 3-way union  splitter (J&W Scientific, Catalog no.  705-0733).

            4.1.2.2     Splitter 2 - Supelco 8-in glass  injection  tee,
      deactivated (Supelco, Catalog no. 2-3665H).

            4.1.2.3     Splitter  3  -   Restek   Y-shaped   fused-silica
      connector (Restek,  Catalog no.  20405).

      4.1.3 Injectors:

            4.1.3.1     Packed column, 1/4-in injector port with hourglass
      liner are recommended for 0.53-mm column.  These injector ports can
      be fitted with splitters (Sec.  4.0)  for dual-column analysis.

            4.1.3.2     Split/split!ess capillary injectors operated  in
      the split mode are  required for 0.25-mm and 0.32-mm columns.

      4.1.4 Detectors:

            4.1.4.1     Flame  Photometric Detector (FPD)  operated  in the
      phosphorus-specific  mode is recommended.

            4.1.4.2     Nitrogen-Phosphorus Detector (NPD) operated in the
      phosphorus-specific  mode is less  selective  but can  detect  triazine
      herbicides.
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                  4.1.4.3     Halogen-Specific     Detectors     (electrolytic
            conductivity or  microcoulometry)  may  be  used  only  for  a  limited
            number of halogenated or sulfur-containing analytes (Sec, 3.0).

                  4.1.4.4     Electron-capture  detectors  may  be  used  for  a
            limited number of analytes {Sec. 3.0).

            4.1.5 Data system:

                  4.1.5.1     Data system capable of presenting chromatograms,
            retention time, and peak integration data is strongly recommended.

                  4.1.5.2     Use of a data system that allows  storage  of raw
            chromatographic data is strongly recommended.


5.0   REAGENTS

      5.1   Solvents

            5.1.1 Isooctane,  {CH3}3CCH2CH(CH3)2 -  Pesticide quality or equivalent.

            5.1.2 Hexane, CeH14 - Pesticide quality or equivalent.

            5.1.3 Acetone,  CH3COCH3  - Pesticide  quality or equivalent.

            5.1.4 Tetrahydrofuran (THF), C4H80 -  Pesticide quality or equivalent
      (for triazine standards only).

            5.1.5 Methyl  tert-butyl-ether  (MTBE), CH3Ot-C4H9 - Pesticide quality
      or equivalent (for triazine standards only).

      5.2   Stock standard solutions  (1000 mg/L):  Can  be  prepared  from  pure
standard materials or can be  purchased  as  certified solutions.

            5.2.1 Prepare stock standard solutions  by accurately weighing about
      0.0100 g of pure compounds.  Dissolve the  compounds  in  suitable mixtures
      of acetone and hexane and  dilute to  volume  in  a  10-mL  volumetric  flask.
      If compound  purity  is  96  percent  or greater,  the  weight  can be  used
      without correction to calculate the  concentration of the  stock standard
      solution.  Commercially prepared  stock standard solutions  can be used at
      any concentration  if they are certified  by the  manufacturer or by  an
      independent source.

            5.2.2 Both Simazine and Atrazine have  low  solubilities  in  hexane.
      If Siraazine  and Atrazine  standards  are  required,  Atrazine  should  be
      dissolved in MTBE,  and  Simazine should be dissolved in acetone/MTBE/THF
      (1:3:1).

            5.2.3 Composite stock standard:  This standard can be prepared from
      individual  stock   solutions.   The  analyst  must demonstrate  that  the
      individual analytes  and common  oxidation  products  are resolved  by  the
      chromatographic system.  For  composite  stock standards containing  less


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      than 25 components, take exactly  1 ml of each individual  stock solution at
      1000 ig/L, add solvent,  and mix the solutions in a 25-mL  volumetric flask.
      For  example,  for  a composite containing  20  individual  standards,  the
      resulting concentration of each component in the mixture, after the volume
      is adjusted to  25 ml,  will be 40 mg/L.  This  composite solution can be
      further diluted  to obtain the desired  concentrations.   Composite stock
      standards containing more  than 25 components are not recommended.

            5.2.4 Store the standard solutions (stock, composite, calibration,
      internal, and surrogate) at 4'C  in Teflon-sealed containers in the dark.
      All standard solutions  should be replaced after two months, or sooner if
      routine  QC  (Sec,  8.0} indicates  a  problem.    Standards  for  easily
      hydrolyzed chemicals including TEPP, Methyl  Parathion, and Merphos should
      be checked every 30 days.

            5.2.5 It is  recommended that  lots of  standards be subdivided  and
      stored  in small  vials.   Individual  vials  should be  used as  working
      standards to minimize the potential for contamination or  hydrolysis of the
      entire lot.

      5.3   Calibration  standards   should be  prepared  at a  minimum of  five
concentrations by dilution of the  composite stock standard with  isooctane or
hexane.     The  concentrations should  correspond  to  the expected  range  of.
concentrations found in real  samples and should bracket the linear range of the
detector.  Organophosphorus calibration standards should be  replaced  after one
or two months,  or sooner if   comparison with check samples or historical  data
indicates that there is a problem.  Laboratories  may wish to  prepare separate
calibration solutions for the easily hydrolyzed standards identified  above.

      5.4   Internal  standard: Internal standards should only  be used on well-
characterized samples  by analysts experienced in the technique.  Use of internal
standards  is  complicated  by  co-elution  of  some OP  pesticides and  by  the
differences in detector response to dissimilar chemicals.

            5.4.1 FPD response for organophosphorus compounds is enhanced by the
      presence of sulfur atoms bonded  to the phosphorus atom.   It has not been
      established that a thiophosphate can  be  used as an internal  standard  for
      an OP with a different  numbers of sulfur atoms (e.g.,  phosphorothioates
      [P=S] as an internal standard for phosphates  [P04]) or phosphorodithioates
      [P-S2]).

            5.4.2 If internal  standards are  to be used, the analyst must select
      one or more internal standards that are similar in analytical behavior to
      the compounds  of interest.  The analyst must further demonstrate that  the
      measurement of the internal standard  is  not affected by  method  or matrix
      interferences.

            5.4.3 When  15-m  columns are used,  it may  be difficult to  fully
      resolve internal  standards  from target analytes, method interferences and
      matrix interferences.   The  analyst must  demonstrate that the measurement
      of  the  internal   standard   is   not   affected  by  method  or   matrix
      interferences.
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            5.4.4 The following NPD internal standard has been used for a 3Q-m
      column pair.  Make a solution of 1000 mg/L of l-bromo-2-nitrobenzene.  For
      spiking, dilute this  solution to 5 mg/L.  Use a spiking  volume of 10 fil/ml
      of extract. The spiking concentration of  the internal standards should be
      kept constant  for  all  samples and  calibration standards.   Since its FPD
      response is small, l-bromo-2-nitrobenzene is not an appropriate internal
      standard for that detector.  No FPD internal standard  is suggested.

      5.5   Surrogate standard spiking solutions -  The analyst should monitor the
performance of the extraction, cleanup (when used), and analytical system, and
the effectiveness of the method in dealing with each sample matrix,  by spiking
each  sample,  standard,   and  blank   with  one   or   two  surrogates  (e.g.,
organophosphorus  compounds  not expected  to be  present   in  the  sample).   If
multiple analytes are to be measured, two  surrogates (an early and  a late eluter)
are recommended.   Deuterated analogs of analytes are not appropriate surrogates
for gas chromatographic/FPD/NPD analysis.

            5.5.1 If surrogates are to be used, the analyst must select one or
      more compounds that are  similar in analytical behavior to the compounds of
      interest.  The analyst must  further demonstrate that the measurement of a
      surrogate  is  not  affected by method  or  matrix  interferences.   General
      guidance on the selection and use of surrogates is provided  in Sec. 5.0 of
      Method 3500.

            5.5.2 Tributyl  phosphate and triphenyl  phosphate are used as FPD and
      NPD surrogates. A volume of 1.0 ml  of a  1-jig/L spiking solution (1 ng of
      surrogate)  is added to  each water  sample and each  soil/sediment sample.
      If there is a  co-elution problem,  4-chloro-3-nitrobenzo-trifluoride has
      also been used as  an  NPD-only surrogate.


6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1   See the introductory material to Chapter Four, "Organic  Analytes,"
Sec. 4.0.

      6.2   Extracts are to be refrigerated at  4°C and  analyzed  within 40 days
of extraction.  See Sec. 5.2.4 for storage of standards.

      6.3   Organophosphorus  esters  will  hydrolyze   under  acidic  or  basic
conditions. Adjust  samples  to a pH of 5 to 8 using sodium hydroxide or sulfuric
acid solution  as soon as possible after  sample collection.   Record  the volume
used.

      6.4   Even   with   storage at  4°C   and  use  of mercuric  chloride  as  a
preservative,   most  OPs  in  groundwater   samples  collected  for  the  national
pesticide survey  degraded within a  14-day period.  Begin  sample extraction within
7 days of collection.
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7.0   PROCEDURE

      7,1   Extraction and cleanup:

            7.1.1  Refer to Chapter Two and Method 8140 for guidance on choosing
      the appropriate  extraction  procedure.   In general,  water samples  are
      extracted at a  neutral  pH  with methylene chloride, using  either  Method
      3510 or 3520.   Solid  samples  are  extracted using either Method 3540  or
      3541 with methylene chloride/acetone (1:1  v/v) or hexane/acetone (1:1 v/v)
      as the extraction solvent.   Method 3550  is an  inappropriate  extraction
      technique for the target analytes  of this method (See  Sec.  2,3).

            7.1.2  Extraction and cleanup  procedures that use solutions below pH
      4 or above pH 8 are  not appropriate for this method.

            7.1.3  If required,  the  samples  may  be cleaned  up using  the Methods
      presented in  Chapter Four, Sec. 2.  Florisil Column Cleanup  (Method 3620)
      and Sulfur Cleanup (Method 3660, TBA-sulfite option) may have  particular
      application  for OPs.   Gel  Permeation  Cleanup  (Method .3640)   should not
      generally be  used for OP pesticides.

                  7.1.3.1      If sulfur  cleanup by Method  3660 is required,  do
            not  use mercury or copper.

                  7.1.3.2      GPC  may  only  be  employed  if all   target   OP
            pesticides  are  listed   as  analytes  of  Method   3640,  or  if the
            laboratory has demonstrated  a recovery  of greater than  85 percent
            for  target  OPs  at a concentration not  greater  than  5 times the
            regulatory  action   level.      Laboratories  must   retain   data
            demonstrating  acceptable recovery.

            7.1.4  Prior to gas chromatographic analysis,  the  extraction solvent
      may be exchanged to hexane.  The analyst must ensure quantitative transfer
      of the extract concentrate.  Single-laboratory  data indicate that samples
      should not be transferred with  100-percent hexane during sample workup,  as
      the more  polar  organophosphorus compounds  may be  lost.    Transfer  of
      organophosphorus esters  is best accomplished using methylene chloride  or
      a hexane/acetone solvent  mixture.

            7.1.5 Methylene chloride may  be used  as  an injection solvent with
      both the  FPD  and the  NPD.

            NOTE: Follow manufacturer's instructions  as to suitability of using
                 methylene chloride with any specific detector.

      7.2   Gas  chromatographic conditions:

            7.2.1 Four 0.53-mm  ID   capillary  columns are   suggested  for the
      determination of organophosphates   by this method.   Column  1   (DB-210  or
      equivalent)  and  Column  2 (SPB-608 or equivalent)  of 30-m  length are
      recommended  if  a  large number of  organophosphorus analytes  are  to  be
      determined.   If superior chromatographic resolution is  not required, 15-m
      lengths columns may be appropriate.  Operating conditions for 15-m columns


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      are listed in Table 5.   Operating conditions for 30-m columns are listed
      in Table 6,

            7.2.2 Retention  times for  analytes  on  each  set  of  columns are
      presented in Tables 3 and 4.

      7.3   Calibration: Refer to Method 8000 for proper calibration techniques.
Use Table 5 and Table  6  for establishing the proper operating parameters for the
set of columns being  employed  in  the analyses.

      7.4   Gas chromatographic analysis:   Method 8000  provides instructions on
the analysis sequence, appropriate dilutions,  establishing  daily retention time
windows and identification criteria.

            7.4.1 Automatic injections of  I fj,l are recommended.  Hand injections
      of no more  than 2  /LtL may be used if  the  analyst demonstrates quantitation
      precision of ^ 10  percent relative standard deviation.  The solvent flush
      technique may be  used if the amount of solvent is kept at a minimum.  If
      the internal  standard calibration technique is used,  add 10 /siL of internal
      standard to each  mL of  sample  prior to  injection.   Chromatograms of the
      target organophosphorus compounds are shown in Figures ]  through 4,

            7.4.2 Figures 5 and 6 show chromatograms with and without Simazine,
      Atrazine, and Carbophenothion on 30-m columns.

      7.5   Record the  sample  volume  injected to the nearest 0.05 /*L and the
resulting peak sizes  (in area units or peak heights).  Using either the internal
or external  calibration procedure (Method  8000),  determine the  identity and
quantity of each  component peak in the sample  chromatogram which corresponds to
the compounds used for  calibration purposes.   See Method  8000  for calculation
equations.

            7.5.1 If  peak detection  and  identification  is  prevented by the
      presence of interferences,  the  use of an FPD or further sample cleanup is
      required.  Before  using  any cleanup  procedure, the analyst must process a
      series of calibration standards through the procedure to establish elution
      patterns and to determine  recovery  of target compounds.  The absence of
      interference from reagents must be demonstrated by routine  processing of
      reagent blanks through the  chosen cleanup  procedure.  Refer to  Sec. 3.0
      for interferences.

            7.5.2 If the responses exceed the linear range  of the system, dilute
      the extract and  reanalyze.   It  is recommended that extracts be diluted so
      that all peaks  are on  scale.  Overlapping peaks are not always evident
      when  peaks  are  off-scale.    Computer  reproduction  of  chromatograms,
      manipulated to ensure all peaks are  on  scale over  a 100-fold range, are
      acceptable  if linearity  is demonstrated.   Peak  height measurements are
      recommended over peak area integration when overlapping peaks cause errors
      in area integration.

            7.5.3 If the peak response is less than 2.5  times the baseline noise
      level,  the  validity of the quantitative result  may be questionable.   The
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      analyst should consult with the source of the sample to determine whether
      further concentration of the sample extract is warranted.

            7.5.4 If partially overlapping or coeluting peaks are found, change
      columns or try a GC/MS technique.  Refer to Sec. 8.0 and Method 8270.

      7.6   Suggested chromatograph maintenance: Corrective measures may require
any one or more of the following remedial actions.

            7.6.L Refer  to  Method   8000  for   general   information  on  the
      maintenance of capillary columns and injectors.

            7.6.2 Splitter connections:  For dual  columns which are  connected
      using a  press-fit Y-shaped  glass  splitter or  a  Y-shaped  fused-silica
      connector (J&W Scientific,  Restek,  or equivalent),  clean  and  deactivate
      the splitter.  Reattach the columns after  cleanly cutting off at least one
      foot from the  injection  port side of the column using a capillary cutting
      tool or  scribe.   The accumulation  of high boiling residues can  change
      split ratios between  dual  columns and thereby change calibration factors.

            7.6.3 Columns  will  be  damaged permanently   and  irreversibly  by
      contact with oxygen at elevated temperature.  Oxygen can enter the column
      during a septum  change, when oxygen traps are exhausted, through neoprene
      diaphragms of regulators, and  through leaks in  the gas manifold.   Polar
      columns  including  the  DB-210  and  DB-608 are more prone to  oxidation.
      Oxidized  columns  will   exhibit  baselines  that   rise  rapidly  during
      temperature programming.

            7.6.4 Peak tailing for all components will be exacerbated by dirty
      injectors, pre-columns,  and glass  "Y"s.   Additionally, cleaning  of this
      equipment (or replacement/clipping, as appropriate) will  greatly  reduce
      the peak  tailing.   Components  such  as  Fensulfothion, Naled,  Azinphos-
      methyl,  and Dimethoate  are very good indicators  of  system  performance.

      7.7   Detector maintenance:

            7.7.1 Older  FPDs   may  be  susceptible   to   stray   light  in  the
      photomultiplier  tube compartment.   This stray  light  will decrease  the
      sensitivity and the  linearity  of the detector.   Analysts can  check  for
      leaks by initiating an analysis in  a dark room and turning on the lights.
      A shift  in  the  baseline  indicates  that  light  may be leaking  into  the
      photomultiplier  tube  compartment.  Additional  shielding should be applied
      to eliminate light leaks and minimize stray light interference.

            7.7.2 The  bead of the  NPD will "become  exhausted with time,  which
      will  decrease  the sensitivity  and the selectivity  of  the  detector.   The
      collector may  become  contaminated which decreased detector sensitivity.

            7.7.3 Both types of detectors use  a flame to generate  a  response.
      Flow rates  of air and  hydrogen should  be  optimized to  give the most
      sensitive, linear detector response for target  analytes.
                                  8141A -  13                         Revision  1
                                                                September 1994

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8.0   QUALITY CONTROL

      8.1   Refer  to Chapter  One for  specific  quality  control  procedures.
Include a mid-level check standard after each group of 10 samples in the analysis
sequence.  Quality control to validate sample  extraction  is  covered  in Method
3500 and in the extraction method utilized.   If extract cleanup  was performed,
follow the QC in Method 3600 and in the  specific cleanup method.

      8.2   Procedures to check the GC  system operation are  found in Method 8000.

      8.3   GC/MS confirmation

            8.3.1 GC/MS techniques should be  judiciously  employed to  support
      qualitative  identifications  made  with this  method.   Follow the  GC/MS
      operating requirements specified in Method 8270,

            8.3.2 When  available,  chemical   ionizatlon mass  spectra  may  be
      employed to aid in the qualitative  identification process.

            8.3.3 To  confirm an identification of a compound, the  background-
      corrected mass  spectrum of the compound must  be  obtained from the sample
      extract and  must be  compared  with  a mass  spectrum  from  a  stock  or
      calibration standard  analyzed under the same  chromatographic  conditions.
      At least  25 ng  of  material should be   injected  into  the GC/MS.    The
      following criteria must be met for  qualitative confirmation:

                  8.3.3.1      The   qualitative   identification  of  compounds
            determined  by  this method  is based  on  retention  time,  and  on
            comparison of the sample mass  spectrum, after background  correction,
            with  characteristic   ions  in a  reference  mass  spectrum.    The
            reference mass  spectrum must  be  generated by  the laboratory  using
            the conditions of this method.  The characteristic  ions from  the
            reference mass spectrum are defined  to be the three ions  of greatest
            relative  intensity,  or any ions over 30% relative  intensity  if less
            than three  such  ions  occur in the  reference  spectrum.   Compounds
            should be identified as present when the criteria below are met.

                        8.3.3.].!   The intensities of  the characteristic ions
                  of  a compound maximize in the same scan or within  one  scan of
                  each  other.   Selection of a  peak  by a data  system target
                  compound  search  routine where the  search  is  based  on  the
                  presence  of  a  target  chromatographic peak containing  ions
                  specific  for  the target  compound  at  a   compound-specific
                  retention  time will  be  accepted as meeting  this criterion.

                        8.3.3.1,2   The RRT  of  the sample  component is within
                  ±0.06 RRT  units of  the  RRT of the standard component.

                        8.3.3.1.3   The    relative    intensities   of    the
                  characteristic   ions  agree   within  30%  of  the  relative
                  intensities  of  these   ions   in  the   reference  spectrum.
                  (Example:    For  an  ion with an  abundance of  50%  in  the
                  reference  spectrum,  the corresponding abundance in a sample
                  spectrum can  range between 20% and 80%.)

                                  8141A -  14                        Revision 1
                                                               September 1994

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            8,3.3.1.4   Structural isomers that produce very similar
      mass  spectra  should be identified  as  individual isomers if
      they  have   sufficiently  different   GC   retention  times.
      Sufficient  GC  resolution 1s  achieved  if the  height of the
      valley between two isomer peaks  is less than 25% of the sum of
      the  two  peak  heights.    Otherwise, structural  isomers are
      identified  as isomeric pairs.

            8.3.3.1.5   Identification  is  hampered  when  sample
      components  are  not  resolved  chromatographically and produce
      mass  spectra  containing  ions contributed  by  more  than one
      analyte.   When gas chromatographic  peaks obviously represent
      more  than one sample  component  (i.e.,  a broadened peak with
      shoulder(s)  or  a  valley  between  two  or  more  maxima),
      appropriate  selection  of  analyte  spectra  and  background
      spectra is  important.   Examination  of  extracted ion current
      profiles of appropriate  ions  can  aid  in  the  selection  of
      spectra,  and in  qualitative identification of compounds.  When
      analytes coelute (i.e.,  only  one  chromatographic  peak  is
      apparent),  the  identification criteria  can  be  met,  but each
      analyte spectrum will contain extraneous ions contributed by
      the coeluting compound.

      8.3.3.2     For samples containing components not associated
with the calibration standards,  a library search may be made for the
purpose of tentative  identification.   The  necessity to perform this
type of  identification will be determined by the purpose of the
analyses  being  conducted.    Computer  generated  library  search
routines  should  not  use  normalization   routines  that  would
misrepresent the library or unknown spectra  when  compared to each
other.  For  example, the RCRA permit or waste delisting requirements
may require the reporting  of nontarget analytes.  Only after visual
comparison of  sample spectra with the  nearest library searches will
the  mass spectral  interpretation  specialist  assign  a  tentative
identification. Guidelines for making  tentative identification are:

      (1)   Relative  intensities  of  major ions  in  the  reference
spectrum (ions  >  10% of the  most abundant  ion) should be present in
the sample spectrum.

      (2)   The relative intensities of  the major ions should agree
within + 20%.   (Example:  For an ion with an abundance of 50% in the
standard spectrum, the corresponding  sample  ion  abundance must  be
between 30 and  70%.)

      (3)   Molecular ions present  in  the  reference spectrum should
be present in  the sample spectrum.

      (4)   Ions   present  in the  sample  spectrum  but not in  the
reference  spectrum  should  be  reviewed  for  possible  background
contamination  or  presence of coeluting compounds.

      (5)   Ions  present in the reference spectrum but not in the
sample spectrum should be reviewed for  possible subtraction from the

                      8141A -  15                        Revision 1
                                                    September 1994

-------
            sample  spectrum because of  background  contamination  or coeluting
            peaks.  Data system library reduction programs  can  sometimes create
            these discrepancies.

            8.3.4 Where  available,  chemical  ionization mass  spectra  may be
      employed to aid  in the qualitative  identification process because of the
      extensive  fragmentation  of  organophosphorus  pesticides  during electron
      impact MS processes.

            8.3.5 Should the MS procedure fail  to provide satisfactory results,
      additional steps may be taken before reanalysis.  These steps may include
      the use of alternate  packed  or capillary GC columns  or additional sample
      cleanup.


9.0   METHOD PERFORMANCE

      9.1   Estimated MDLs  and associated chromatographic  conditions for water
and clean soil (uncontaminated with synthetic organics) are listed in Table 1.
As detection limits will vary with the particular matrix to be analyzed, guidance
for determining EQLs  is given in Table 2.  Recoveries for several method analytes
are provided in Tables 5, 6, and 7.


10,0  REFERENCES

1.    Taylor, V.; Hickey, D.M.; Marsden, P.J. "Single Laboratory Validation of
      EPA Method  8140"; U.S,  Environmental  Protection  Agency,  Environmental
      Monitoring Systems  Laboratory,  Office of  Research and  Development,  Las
      Vegas, NV, 1987; EPA-600/4-87-009.

2.    Pressley, T.A;  Longbottom,  J.E.   "The  Determination  of Organophosphorys
      Pesticides  in  Industrial  and Municipal Wastewater: Method 614";  U.S.
      Environmental   Protection Agency,  Environmental  Monitoring  and  Support
      Laboratory, Cincinnati, OH,  1982; EPA-600/4-82-004,

3.    "Analysis of Volatile Hazardous  Substances by GC/MS:  Pesticide  Methods
      Evaluation"; Letter  Reports  6,  12A,  and  14  to the U.S.  Environmental
      Protection Agency on Contract 68-03-2697, 1982.

4.    "Method 622, Organophosphorus Pesticides";  U.S. Environmental Protection
      Agency, Environmental Monitoring  and  Support  Laboratory, Cincinnati, OH
      45268.

5.    Lopez-Avila, V.;  Baldin,  E.; Benedicto,  J; Milanes,  J.;  Beckert,  W. F,
      "Application of Open-Tubular Columns to SW-846 GC Methods";  final report
      to the U.S. Environmental Protection Agency on Contract 68-03-3511; Mid-
      Pacific Environmental Laboratory, Mountain View, CA,  1990,

6.    Hatcher,  M.D.;    Hickey, D.M.;   Marsden,  P.J.;  and    Betowski,  L.D.;
      "Development of a GC/MS Module for RCRA Method 8141"; final report to the
      U.S. EPA Environmental Protection Agency  on  Contract  68-03-1958; S-Cubed,
      San Diego, CA, 1988.


                                  8141A - 16                        Revision 1
                                                                September 1994

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7.    Chau, A.S.Y.; Afghan, B.K. Analysis of Pesticides  in Water;  "Chlorine and
      Phosphorus-Containing Pesticides"; CRC: Boca Raton, FL, 1982, Vol. 2, pp
      91-113, 238,

8.    Hild,  0.;  Schulte,  E;  Thier,   H.P.   "Separation  of  Organophosphorus
      Pesticides   and   Their   Metabolites  on   Glass-Capillary   Columns";
      Chromatographia, 1978,  11-17.

9.    Luke,  M.A.;  Froberg,  J.E.;  Doose,  G.M.;  Masumoto,  H.T.  "Improved
      Hultiresidue  Gas  Chromatographic  Determination  of  Organophosphorus,
      Organonitrogen,  and Organohalogen  Pesticides   in  Produce,  Using Flame
      Photometric and Electrolytic Conductivity Detectors"; J. Assoc. Off, Anal.
      Chem, 1981, 1187, 64.

10.   Sherma, J.;  Berzoa,  H,  "Analysis  of Pesticide  Residues  in Human  and
      Environmental Samples";  U.S. Environmental  Protection Agency,  Research
      Triangle Park, NC; EPA-600/8-80-038.

11.   Desmarchelier,  J.M.;  Wustner,   D.A.;   Fukuto,  T.R.  "Mass  Spectra  of
      Organophosphorus Esters and Their Alteration Products"; Residue Reviews,
      1974, pp 63, 77.

12.   Munch, D.J.  and  Frebis, C.P., "Analyte Stability Studies Conducted during
      the National Pesticide Survey",  fS I F, 1992,  vol  26,  921-925.

13.   T.L. Jones,  "Organophosphorus Pesticide Standards:  Stability Study", EMSL-
      LV Research Report, EPA 600/X-92/040, April, 1992

14.   Kotronarou,  A.,  et  al.,  "Decomposition of Paratnion in Aqueous Solution by
      Ultrasonic Irradiation," ES&T,  1992, Vol.  26,  1460-1462.
                                  8141A - 17                        Revision 1
                                                                September 1994

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                              TABLE 1
           METHOD DETECTION LIMITS IN A WATER AND A SOIL
    MATRIX USING  15-m COLUMNS AND A  FLAME PHOTOMETRIC DETECTOR
Compound
Azinphos-methyl
Bolstar (Sulprofos)
Chlorpyrifos
Coumaphos
Demeton, -0, -S
Diazinon
Dlchlorvos (DDVP)
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfothion
Fenthion
Malathion
Merphos
Mevinphos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotepp
TEppc
Tetraehlorovinphos
Tokuthion (Protothiofos)c
Trichloronate6
Reagent
Water (3510)8
(M9/L)
0.10
0.07
0.07
0.20
0.12
0.20
0.80
0.26
0.07
0.04
0.20
0.08
0.08
0.11
0.20
0.50
0.50
0.06
0.12
0.04
0.07
0.07
0.80
0.80
0.07
0.80
Soil (3540)b
(M9/kg}
5.0
3.5
5.0
10.0
6.0
10.0
40.0
13.0
3.5
2.0
10.0
4.0
5.0
5.5
10.0
25.0
25.0
3.0
6.0
2.0
3.5
3.5
40.0
40.0
5.5
40.0
Sample  extracted using  Method  3510,   Separatory  Funnel  Liquid-Liquid
Extraction.

Sample extracted using Method 3540, Soxhlet Extraction,

Purity  of  these  standards  not  established  by the  EPA Pesticides  and
Industrial  Chemicals Repository,  Research Triangle Park, NC.
                            8141A - 18
    Revision 1
September 1994

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                                    TABLE  2
                DETERMINATION  OF  ESTIMATED QUANTITATION  LIMITS
                         (EQLs) FOR VARIOUS MATRICES'
   Matrix                                                            Factor
   Ground water (Methods 3510 or 3520)                                 10b
   Low-concentration soil by Soxhlet and no cleanup                    10C
   Non-water miscible waste (Method 3580)                            1000
c
a  EQL = [Method detection  limit  (see Table 1)] X [Factor found in this table].
For non-aqueous samples,  the factor is  on a wet-weight basis.   Sample EQLs are
highly matrix dependent.  The  EQLs to be determined herein are for guidance and
may not always be achievable,

b  Multiply this factor times  the reagent water MDL in Table 1.

c  Multiply this factor times  the soil  MDL in Table 1.
                                  8141A -  19                        Revision 1
                                                                September 1994

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                TABLE 3.
RETENTION TIMES FOR METHOD 8141A ANALYTES
          EMPLOYING  15-m COLUMNS


TEPP
Dichlorvos (DDVP)
Mevinphos
Deraeton, -0 and -S
Ethoprop
Naled
Phorate
Monochrotophos
Sulfotepp
Dimethoate
Disulfoton
Diazinon
Merphos
Ronnel
Chlorpyrifos
Malathion
Parathion, methyl
Parathion, ethyl
Trichloronate
Tetrachl orovi nphos
Tokuthion (Protothiofos)
Fensulfothion
8olstari (Sulprofos)
Famphur"
EPN
Azi nphos -methyl
Fenthion
Coumaphos
Method 8141A has not been fully
Initial temperature
Initial time
Program 1 rate
Program 1 final temp.
Program 1 hold
Program 2 rate
Program 2 final temp.
Program 2 hold
Capi
Compound

9.63
14.18
18.31
18.62

19.94
20.04
20.11
20.64
23.71
24.27
26.82
29.23
31.17
31.72
31.84
31.85
32.19
34.65
34.67
35.85
36.34
36.40

38.34
38.83
39.83
llary Column
DB-5
6.44
7.91
12.88
15.90
16.48
19.01
17.52
20.11
18.02
20.18
19.96
20.02
21.73
22,98
26.88
28.78
23.71
27,62
28.41
32.99
24.58
35.20
35.08
36.93
37.80
38.04
29.45
38.87

SPB-608
5.12
12.79
18.44
17.24
18.67
17.40
18.19
31.42
19,58
27.96
20.66
19.68
32.44
23.19
25.18
32.58
32.17
33.39
29.95
33.68
39.91
36.80
37.55
37.86
36.71
37.24
28.86
39.47

D8-210
10.66




19.35


















36.74



validated for Famphur.
130°C
3 minutes
5°C/min
180'C
10 minutes
2eC/min
250*C
15 minutes
50°C
1 minute
5"C/min
140°C
10 minutes
10'C/min
240'C
10 minutes
50'C
1 minute
5°C/min
140'C
10 minutes
10"C/min
240*C
10 minutes








            8141A - 20
    Revision 1
September 1994

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                                  TABLE 4.
                  RETENTION TIMES FOR METHOD 8141A ANALYTES
                            EMPLOYING 30-m COLUMNS8
Compound
DB-5
      RT (min)

DB-210      DB-608
DB-1
Trimethyl phosphate
Dichlorvos (DDVP)
Hexamethyl phosphorami de
Trichlorfon
TEPP
Thionazin
Hevinphos
Ethoprop
Diazinon
Sul fotepp
Terbufos
Tri-o-cresyl phosphate
Naled
Phorate
Fonophos
Disulfoton
Merphos
Oxidized Merphos
Dichlorofenthion
Chlorpyrifos, methyl
Ronnel
Chlorpyrifos
Trichloronate
Aspon
Fenthion
Demeton-S
Demeton-0
Monocrotophosc
Dimethoate
Tokuthion
Malathion
Parathion, methyl
Fenithrothion
Chlorfenvinphos
Parathion, ethyl
Bo! star
Stirophos
Ethion
b
7.45
b
11.22
b
12,32
12.20
12.57
13.23
13.39
13.69
13.69
14.18
12.27
14.44
14.74
14.89
20.25
15.55
15.94
16.30
17.06
17.29
17.29
17.87
11.10
15.57
19.08
18.11
19.29
19.83
20.15
20.63
21.07
21.38
22.09
22.06
22.55
2.36
6.99
7.97
11.63
13.82
24.71
10.82
15.29
18.60
16.32
18.23
18.23
15.85
16.57
18.38
18.84
23.22
24.87
20.09
20.45
21.01
22.22
22.73
21.98
22.11
14.86
17.21
15.98
17.21
24,77
21.75
20.45
21.42
23.66
22.22
27.57
24.63
27.12

6.56

12.69


11.85
18.69
24.03
20.04
22.97

18.92
20.12

23.89

35.16
26.11
26.29
27.33
29.48
30.44

29.14
21.40
17.70
19.62
20.59
33.30
28.87
25.98

32.05
29.29
38.10
33.40
37.61

10.43




14.45
18.52
21.87
19.60


18,78
19.65

21.73
26.23



23.67
24.85


24.63
20.18

19.3
19.87
27.63
24.57
22.97


24.82
29.53
26.90

                                                                   (continued)
                                  8141A -  21
                            Revision 1
                        September 1994

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                             TABLE 4.  (Continued)
 Compound
 DB-5
             RT  (ffiin)

       DB-210     DB-608
                         DB-1
 Phosphamidon
 Crotoxyphos
 Leptophos
 Fensulfothion
 EPN
 Phosmet
 Azinphos-methyl
 Azinphos-ethyl
 Famphur
 Coumaphos
 Atrazine
 Simazine
 Carbophenothion
 Dioxathion
 Trithion methyl
 Dicrotophos
 Internal Standard
 l-Bromo-2-nitrobenzene
 Surrogates
 Tributyl phosphate
 Triphenyl phosphate
 4-Cl-3-nitrobenzotrifluoride
22.77
22.77
24.62
27.54
27.58
27.89
28.70
29.27
29.41
33.22
13.98
13.85
22,
 d
14
 8.11
5.73
20.09
23.85
31.32
26.76
29.99
29.89
31.25
32.36
27.79
33.64
17.63
17.41
27.92
   d
      9.07
       5.40
                   25.88
                   32.65
                   44.32
                   36.58
                   41.94
                   41.24
                   43.33
                   45.55
                   38.24
                   48.02
                   22.24
                   36.62
                   19.33
                       11.1
                       33.4
28.58
31.60

32.33
34.82
a The 6C operating conditions were as follows:

DB-5 and DJL-210  - 30-ra  x  0.53-mm ID  column,  DB-5 (1.50-  m film thickness)  and
DB-210 (1.0- m film thickness).  Both connected to a  press-fit Y-shaped inlet
splitter.   Temperature  program:  120°C  (3-min hold) to 2709C  (10-min  hold)  at
5°C/min; injector temperature 2508C; detector temperature 30Q°C; bead temperature
400'C; bias  voltage  4.0;  hydrogen gas pressure  20 psi;  helium carrier  gas  6
mL/min; helium makeup gas 20 mL/min.

DB-608 - 30-m x 0.53-mm ID column,  DB-608  {1.50- m  film thickness) installed in
an 0.25-in packed-column  inlet.   Temperature program:  110°C  (0.5-min  hold)  to
250*C (4-min hold) at 3"C/min;  injector temperature 250*C; helium carrier gas 5
mL/min; flame photometric detector.

DB-1 30-m x 0.32-mm ID column, DB-1  (0.25- m film thickness) split/split!ess with
head pressure of  10 psi,  split valve closure at  45 sec,  injector  temp.  25Q*C,
50°C (1-min hold) to 28Q°C (2-min hold) at 6°C/min, mass spectrometer full scan
35-550 amu,

b Not detected at 20 ng per injection.
c Retention times may  shift to longer times with larger amounts injected (shifts
of over 30 seconds have been observed,  Hatcher et.  al.)
d Shows multiple peaks; therefore, not  included in the composite.
                                  8H1A - 22
                             Revision  1
                         September 1994

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                               TABLE 5.
PERCENT RECOVERY OF 27 QRGANOPHOSPHATES BY SEPARATORY FUNNEL  EXTRACTION
Compound
Azinphos methyl
Bol star
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dlchlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfonthion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathlon, ethyl
Parathion, methyl
Phorate
Ronnel
Sul fotep
TEPP
Tetracblorvinphos
Tokuthion
Trichloroate

Low
126
134
7
103
33
136
80
NR
48
113
82
84
NR
127
NR
NR
NR
NR
101
NR
94
67
87
96
79
NR
NR
Percent Recovery
Medium
143 + 8
141 + 8
89 + 6
90 + 6
67 + 11
121 + 9.5
79+11
47 + 3
92 + 7
125 + 9
90 + 6
82 + 12
48 + 10
92 + 6
79
NR
18 + 4
NR
94 + 5
46 + 4
77 + 6
97 + 5
85 + 4
55 + 72
90 + 7
45 + 3
35

High
101
101
86
96
74
82
72
101
84
97
80
96
89
86
81
55
NR
NR
86
44
73
87
83
63
80
90
94
NR = Not recovered.
                            8141A - 23
    Revision 1
September 1994
                                                                   \

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                                   TABLE 6.
PERCENT RECOVERY OF 27 ORGANOPHOSPHATES BY CONTINUOUS LIQUID-LIQUID EXTRACTION
Percent Recovery
Compound
Azinphos methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Famphur
Fensulfonthion
Fenthion
Halathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sul f otep
TEPP
Tetrachlorvinphos
Tokuthion
Trichloroate
Low
NR
NR
13
94
38
NR
81
NR
94
NR
39
--
90
8
105
NR
NR
NR
NR
106
NR
84
82
40
39
56
132
NR
Medium
129
126
82 + 4
79 + 1
23 + 3
128 + 37
32 + 1
10 + 8
69 + 5
104 + 18
76 + 2
63 + 15
67 + 26
32 + 2
87 + 4
80
87
30
NR
81 + 1
50 + 30
63 + 3
83 + 7
77 + 1
18 + 7
70 + 14
32 + 14
NR
High
122
128
88
89
41
118
74
102
81
119
83
--
90
86
86
79
49
1
74
87
43
74
89
85
70
83
90
21
   NR =  Not  recovered.
                               8141A - 24
    Revision 1
September 1994

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                               TABLE 7.
     PERCENT RECOVERY  OF 27  OR6ANOPHOSPHATES BY SOXHLET EXTRACTION
Percent Recovery
Compound
Azinphos methyl
Bo! star
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfonthion
Fenthion
Malathlon
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotep
TEPP
Tetrachlorvinphos
Tokuthion
Trichloroate
Low
156
102
NR
93
169
87
84
NR
78
114
65
72
NR
100
62
NR
NR
NR
75
NR
75
NR
67
36
50
NR
56
Medium
110 + 6
103 + 15
66 + 17
89 + 11
64 4- 6
96 4- 3
39 4- 21
48 4- 7
78 4- 6
93 + 8
70 + 7
81 + 18
43 + 7
81 + 8
53
71
NR
48
80 + 8
41 + 3
77 + 6
83 + 12
72 + 8
34 + 33
81 + 7
40 + 6
53
High
87
79
79
90
75
75
71
98
76
82
75
111
89
81
60
63
NR
NR
80
28
78
79
78
63
83
89
53
NR =*Not recovered.
                            8141A -  25
    Revision 1
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                                TABLE 8.

            SUGGESTED OPERATING CONDITIONS FOR 15-m COLUMNS
Columns 1 and 2 (DB-210 and SPB-608 or their equivalent)
Carrier gas (He) flow rate =
Initial temperature =
Temperature program =
Column 3  (DB-5 or equivalent)

Carrier gas (He) flow rate -
Initial temperature -
Temperature program =
5 mL/min
50'C, hold for 1 minute
50'C to 140°C at S*C/min, hold for
10 minutes,  followed by  140*C to
240°G  at  10eC/min,  hold  for  10
minutes (or a sufficient amount of
time for last compound to elute).
5 mL/min
13CTC, hold for 3 minutes
130'C to 180'C at 5'C/min, hold for
10 minutes,  followed by  180"C  to
250°C  at  2°C/min,  hold  for  15
minutes (or a sufficient amount of
time for last compound to elute).
                            8141A - 26
                    Revision 1
                September 1994

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                                      TABLE 9
                  SUGGESTED OPERATING CONDITIONS FOR 30-m COLUMNS
Column  1:
      Type:   DB-210
      Dimensions:  30-m x 0.53-mm ID
      Film Thickness (nm):  1.0
Column 2:
      Type:   DB-5
      Dimensions:  30-m x 0.53-mm ID
      Film Thickness (pm):  1.5

Carrier gas flowrate (mL/min):  6 (Helium)
Makeup gas flowrate (mL/min):  20 (Helium)
Temperature program:  120°C (3-min hold) to H70°C (10-min hold) at 5°C/min
Injector temperature:  250°C
Detector temperature:  300 °C
Injection volume:  2 #L
Solvent:  Hexane
Type of injector:  Flash vaporization
Detector type:  Dual NPD
Range:  1
Attenuation:   64
Type of splitter:   Y-shaped  or Tee
Data system:    Integrator
Hydrogen gas  pressure:   20 psi
Bead temperature:  400°C
Bias voltage:   4
                                  8141A - 27                        Revision 1
                                                                September 1994

-------
                               TABLE  10
        QUANTITATION AND CHARACTERISTIC IONS FOR OP PESTICIDES
Compound Name
Quantitation ions
Characteristic ions
Azinphos-methyl
Bolstar  (Sulprofos)
Chlorpyrifos
Coumaphos
Demeton-S
Diazinon
Dichlorvos  (DDVP)
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfothion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion,  ethyl
Parathion,  methyl
Phorate
Ronnel
Stirophos
Sulfotepp
TEPP
Tokuthion
       160
       156
       197
       109
        88
       137
       109
        87
        88
       157
       158
       293
       278
       173
       209
       127
       127
       109
       291
       109
        75
       285
       109
       322
        99
       113
  77,132
  140,143,113,33
  97,199,125.314
  97,226,362,21
  60,114,170
  179,152,93,199,304
  79,185,145
  93,125,58,143
  89,60,61,97,142
  169,141,63,185
  43,97,41,126
  97,125,141,109,308
  125,109,93,169
  125,127,93,158
  57,153,41,298
  109,67,192
  67,97,192,109
  145,147,79
  97,109,139,155
  125,263,79
  121,97,47,260
  125,287,79,109
  329,331,79
  97,65,93,121,202
  155,127,81,109
  43,162,267,309
                            8141A - 28
                                          Revision 1
                                      September 1994

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300.00
250.00
200.00
150.00
100.00
 50.00
 0.00
                 ..
                           va
                                                            i

                                                            I
                                                            
-------
300.00
250.00
200.00
150.00
100.00
 50.00
                                a
                                i
                                o
                                   V
a.
ui
                                                                 M
                                                                        M
                                                                        o
                                                                        a.
                                                                        c
  0.00   • i •«• i " ' t •' • i •" • i • • * i •i * i *' • i''' i'' • i • • • i • • • i»• • i • • • i • • •! • • • t •  ' t • * • i' • • i' • • i " • i • • • i
         1  3  5   7   9 11  13  15 17  19  21 23  25  27 29  31  33 35 37  39 41  43  45
 Figure  2.   Chromatogram of  target organophosphorus compounds  from a  15-m DB-E10
 column  with  FPD detector.  More  compounds are shown in Figure 1.   See  Table 3 for
 retention  times.
                                    8141A  -  30
    Revision  1
September  1994

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300.00
250.00
200.00-<
150.00-
100,00-
 50.00-
  0.00 ^
        (A
        a
                                                                             ^b
                                                                             i
  r»t-r*i-n
        1   3  5   7  9  11 13  15 17  19 21  23 25  27  29 31  33 35 37  39 41  43  45
 Figure  3.   Chromatogram  of target  organophosphorus  compounds  from a  15-m DB-210
 column  with NPO  detector.  More  compounds are  shown In  Figure 4. See  Table 3 for
 retention times.
                                     8141A  -  31
    Revision  1
September  1994

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300.00-
250.00 —
200.00 -
150.00
100430-
 50.00-
        1  3   5  7  9  11 13  15 17 19  21  23 25  27  29 31 33  35 37 39 4t  43 45
  Figure  4.   Chromatogram  of  target organophosphorus compounds  from a  15-m DB-210
  column  with NPD detector.  More compounds are  shown in Figure 3,   See  Table 3 for
  retention times.
                                     8141A - 32
    Revision  1
September  1994

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                                                            08-210
                                                           DB-5
Figure 5.  Chromatogram of target organophosphorus compounds  on  a 30-m DB-5/DB-210
column pair with NPD detector, without Simazine, Atrazine and  Carbophenothion.  See
Table 4 for retention times and for GC operating conditions.
                                  8141A - 33
    Revision 1
September 1994

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                   If
                                                  DB-210
                                       It
                                   If
                                   11
                        J
                                          n
                                          u
        u—UJ
                                   n
                                   a    m
                                                            D6-5
Figure 6,   Chromatogram of target  organophosphorus  compounds on a 30-m DB-5/DB-210
column pair with NPD detector, with  Simazine,  Atrazine and Carbophenothion.  See
Table 4 for retention  times and for GC  operating  conditions.
                                  8141A  - 34
    Revision 1
September 1994

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                                      METHOD 8141A
               ORGANOPHOSPHORUS  COMPOUNDS BY GAS CHROMATOGRAPHY:
                              CAPILLARY COLUMN TECHNIQUE
   (   Start     j

            ~^
7.1.1 Refer to Chapter
  Two for guidance on
choosing the appropriate
  extraction procedure.
    7.1.2 Perform
   solvent exchange
      during K-D
   procedures in all
  extraction methods.
     7.2 Select GC
      condition!.
  7.3 Refer to Method
       8000 for
 calibration techniques.
   7.3.1 Internal or
      external
   calibration may
      be used.
  7.4.1 Add internal
  standard to sample
    if necessary.
     7,4,2 Refer to
   Method 8000, Sac,
   7.6 for instructions
  on analysis sequence,
dilutions, retention times,
    and  identification
        criteria.
  7.4.3 Inject sample.
                                        I
  7.4.5 Record sample
  volume injected and
  resulting peak cizas.
    7.4.6 Determine
      identity and
    quantity of aach
    component peak;
    refer to Method
   8O00, See. 7.8 for
  calculation aquations.
        7.4.7
       Is poak
    detection and
    identification
    prevented by
       interfer-
       ences?
   7.5,1 Perform
appropriate cleanup.
                                 7.5,2 Reanalyze by
                                        GC.
  c
                                                                       Stop
                                    8141A -  35
                                                Revision  1
                                           September  1994
                                                                            \

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                                 METHOD 8150B

                 CHLORINATED HERBICIDES BY GAS CHROMATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   Method 8150  is  a gas chromatographic  (GC)  method  for determining
certain chlorinated acid herbicides.   The following compounds can be determined
by this method:
      Compound Name                         CAS No.*


      2,4-D                                  94-75-7
      2,4-DB                                 94-82-6
      2,4,5-TP (Silvex)                      93-72-1
      2,4,5-T                                93-76-5
      Dalapon                                75-99-0
      Dicamba                              1918-00-9
      Dichloroprop                          120-36-5
      Dinoseb                                88-85-7
      MCPA                                   94-74-6
      MCPP                                   93-65-2


      "   Chemical  Abstract Services Registry  Number.

      1.2   Table  1  lists  the  method  detection  limit  for  each compound  in
organic-free reagent  water.  Table 2 lists the estimated quantitation limit (EQL)
for other matrices.

      1.3   When  Method  8150  is used to analyze  unfamiliar  samples,  compound
identifications should  be  supported  by at  least one  additional  qualitative
technique.   This  method  describes analytical conditions  for  a  second  gas
chromatographic column that can be used to confirm measurements  made  with the
primary column.  Sec. 8.4 provides gas chromatograph/mass spectrometer (GC/MS)
criteria   appropriate   for  the  qualitative   confirmation   of   compound
identifications.

      1.4   Only   experienced   analysts  should  be   allowed  to  work   with
diazomethane due to the potential  hazards associated with its use (the compound
is explosive and carcinogenic).


2.0   SUMMARY OF METHOD

      2.1   Method   8150   provides  extraction,    esterification,    and   gas
chromatographic conditions  for  the analysis  of  chlorinated  acid  herbicides.
Spiked samples are used  to verify the  applicability  of the  chosen  extraction
technique to each  new  sample  type.  The esters are  hydrolyzed with  potassium


                                   8150B -  1                         Revision 2
                                                                September 1994

-------
 hydroxide,  and extraneous  organic material is removed by a solvent wash.   After
 acidification, the acids are extracted with solvent and converted to their methyl
 esters  using diazomethane as the derivatizing agent.  After excess  reagent  is
 removed,  the esters  are determined  by  gas  chromatography  employing an  electron
 capture detector,   microcoulometric  detector,   or  electrolytic  conductivity
 detector  (Goerlitz and  Lamar,  1967).    The  results  are  reported as the  acid
 equivalents.

       2,2    The sensitivity  of  Method 8150  usually depends on  the level  of
 interferences rather than  on instrumental  limitations.
3.0    INTERFERENCES

       3.1    Refer  to Method 8000.

       3.2    Method interferences may  be  caused by  contaminants  in solvents,
reagents,  glassware,  and other sample processing hardware that  lead  to discrete
artifacts  or elevated baselines in gas chromatograms.  All  these materials must
be routinely demonstrated to be free from interferences under the conditions of
the  analysis, by analyzing  reagent  blanks.

             3.2.1  Glassware must  be scrupulously cleaned.  Clean each piece of
       glassware  as  soon  as possible  after  use by  rinsing  it with  the last
       solvent used in it. This should  be followed by detergent  washing with hot
       water  and  rinses with tap water, then  with  organic-free reagent water.
       Glassware  should be  solvent-rinsed  with acetone  and  pesticide-quality
       hexane.  After rinsing and drying, glassware should be sealed and stored
       in  a  clean  environment  to  prevent  any  accumulation  of dust  or other
       contaminants.   Store glassware  inverted or capped  with aluminum foil.
       Immediately prior to use, glassware should be rinsed with  the next solvent
       to be  used.

             3.2.2  The use of high purity reagents and solvents helps  to minimize
       interference problems.  Purification of  solvents by distillation in all-
       glass  systems  may be  required.

       3.3    Matrix   interferences  may  be  caused   by  contaminants that  are
coextracted  from  the sample.   The  extent  of matrix  interferences will  vary
considerably from waste to waste, depending upon the nature and  diversity of the
waste  being  sampled.

       3.4    Organic  acids,  especially  chlorinated acids, cause the most direct
interference with the determination.  Phenols, including chlorophenols, may also
interfere with this  procedure.

       3.5    Alk line  hydrolysis and subsequent extraction of the basic solution
remove many  chl: *inated hydrocarbons and phthalate esters that might otherwise
interfere with the electron capture analysis.

       3.6    The  herbicides, being  strong  organic  acids,  react readily  with
alkaline substances and may be lost during analysis.  Therefore, glassware and
glass  wool  must be  acid rinsed,  and  sodium  sulfate  must be  acidified  with
sulfuric acid prior to use to avoid this possibility.

                                   8150B -  2                         Revision 2
                                                                September 1994

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      3.7   Sample  extracts  should be  dry  prior to methylation  or  else poor
recoveries will be  obtained.
4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph

            4.1.1  Gas  chromatograph,  analytical  system  complete  with  gas
      chromatograph  suitable   for   on-column   injections   and  all   required
      accessories, including detectors, analytical columns,  recorder, gases, and
      syringes.  A data system for measuring peak heights and/or peak areas is
      recommended.

            4.1.2  Columns

                   4.1.2.1     Column  la and Ib  - 1.8 m x 4 mm ID glass, packed
            with  1.5%  SP-2250/1.95% SP-2401 on Supelcoport  (100/120  mesh) or
            equivalent.

                   4.1.2.2     Column  2 - 1.8 m  x 4 mm ID glass, packed with 5%
            OV-210 on Gas Chrom Q (100/120 mesh) or equivalent.

                   4.1.2.3     Column  3  -  1.98  m x 2 mm  ID  glass,  packed with
            0.1% SP-1000 on 80/100 mesh Carbopack C or equivalent.

            4.1.3  Detector  - Electron capture (ECD).

      4.2   Erlenmeyer flasks - 250  and 500 ml  Pyrex,  with  24/40 ground glass
joint.

      4.3   Beaker - 500 ml,

      4.4   Diazomethane generator - Refer to Sec. 7.4 to determine which method
of diazomethane generation should be used  for a particular application.

            4.4.1  Diazald kit - recommended for the generation of diazomethane
      using the procedure given in  Sec. 7.4.2  (Aldrich Chemical  Co.,  Cat.  No.
      210,025-2 or equivalent).

            4.4.2 Assemble from two 20 x 150 mm  test tubes, two Neoprene rubber
      stoppers, and a  source of nitrogen.   Use Neoprene rubber  stoppers with
      holes drilled in  them  to accommodate glass delivery tubes.  The exit tube
      must  be  drawn to  a  point  to  bubble diazomethane  through the  sample
      extract.   The generator assembly is shown  in Figure 1.  The procedure for
      use of this type  of generator is given in Sec.  7.4.3.

      4.5   Vials  - 10 to 15 ml,  amber glass,  with Teflon  lined  screw cap or
crimp top.

      4.6   Separatory funnel - 2000 ml,  125 ml, and 60 ml.

      4.7   Drying column -  400  mm x 20 mm ID Pyrex chromatographic column with
Pyrex glass wool at bottom and  a Teflon stopcock.

                                  8150B - 3                         Revision 2
                                                                September 1994

-------
      NOTE: Fritted  glass discs are  difficult to decontaminate  after highly
            contaminated  extracts  have been passed through.   Columns without
            frits may  be purchased.   Use  a small  pad of  Pyrex  glass wool to
            retain the adsorbent,   Prewash  the  glass wool pad with  50  ml of
            acetone  followed  by  50  ml of elution solvent prior to packing the
            column with adsorbent,

      4.8   Kuderna-Danish  (K-D) apparatus

            4.8.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or
      equivalent).   A  ground  glass stopper  is used to prevent evaporation of
      extracts

            4.8.2 Evaporation   flask  -   500   ml  (Kontes   K-570001-500   or
      equivalent).   Attach  to  concentrator  tube with  springs,  clamps  or
      equivalent.

            4.8.3 Snyder  column  -   Three  ball  macro  (Kontes  K-503000-0121 or
      equivalent).

            4,8.4 Snyder  column -  Two  ball micro  (Kontes  K-5690Q1-Q219  or
      equivalent).

            4,8.5 Springs -   1/2 inch  (Kontes K-662750 or equivalent).

      4.9   Boiling chips -  Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).

      4.10  Water  bath  -  Heated,  with  concentric  ring  cover,  capable  of
temperature control  (± 5°C).  The bath should be  used  in  a  hood-

      4.11  Microsyringe  -  10 pL.

      4.12  Wrist shaker  - Burrell  Model 75 or equivalent.

      4.13  Glass wool  -  Pyrex,  acid washed.

      4.14  Balance - Analytical, capable of accurately weighing to 0.0001  g.

      4.15  Syringe - 5 ml.

      4.16  Glass rod.


5,0   REAGENTS

      5.1   Reagent  grade  inorganic  chemicals  shall   be used  in all  tests.
Unless otherwise indicated,  it is intended that all reagents  shall conform to the
specifications of the Committee on Analytical Reagents  of the American Chemical
Society, where  such  specifications  are available.   Other grades  may  be  used,
provided it  is  first ascertained that the reagent  is of sufficiently high purity
to permit its  use without lessening the accuracy  of the determination.
                                  8150B  - 4                         Revision 2
                                                                September 1994

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      5,2   Organic-free reagent water.  All references to water in this method
refer to organic-free reagent  water,  as  defined  in Chapter One.

      5.3   Sulfuric acid  solution

            5,3.1  ((1:1) (v/v)) -  Slowly add 50 ml H2S04 (sp. gr. 1.84} to 50 ml
      of organic-free reagent  water.

            5.3.2  {(1:3) (v/v)) -  Slowly add 25 ml H2S04 (sp. gr. 1.84) to 75 ml
      of organic-free reagent  water.

      5.4   Hydrochloric  acid  ((1:9)  (v/v)),   HC1.    Add  one   volume  of
concentrated HC1 to  9 volumes  of organic-free  reagent water.

      5.5   Potassium hydroxide solution  (KOH)  - 37% aqueous solution  (w/v).
Dissolve 37 g  potassium hydroxide pellets in  organic-free reagent  water,  and
dilute to 100 ml.

      5.6   Carbitol  (Diethylene glycol  monoethyl ether), C2H5OCH2CH2OCH2CH2OH.
 Available from Aldrich  Chemical Co.

      5,7   Solvents

            5.7.1  Acetone,  CH3COCH3 - Pesticide quality or equivalent.

            5.7.2  Methanol,  CH3OH  - Pesticide  quality or  equivalent.

            5.7.3  Isooctane,    (CH3)3CCH2CH(CH3)2   -   Pesticide   quality   or
      equivalent.

            5.7.4  Hexane,  C6H14 -  Pesticide quality or equivalent.

            5.7.5  Diethyl  Ether,  C2H5OC2H5,   Pesticide quality or  equivalent.
      Must be  free  of peroxides   as  Indicated by  test   strips  (EM Quant,  or
      equivalent).   Procedures for removal of peroxides  are provided with  the
      test strips.  After cleanup, 20 ml of ethyl  alcohol preservative must be
      added to each  liter of ether.

      5.8   Sodium sulfate  (granular,  acidified,  anhydrous),  Na2S04.  Purify by
heating at 400°C for 4 hours in a shallow tray,  or by precleaning  the  sodium
sulfate with methylene  chloride.   If the sodium sulfate  is  precleaned  with
methylene chloride, a method blank  must be  analyzed, demonstrating that there is
no interference  from the sodium sulfate.   Acidify  by slurrying 100 g  sodium
sulfate with enough  diethyl  ether  to  just  cover the  solid; then add  0.1 ml of
concentrated sulfuric acid  and  mix  thoroughly.  Remove the ether under a vacuum.
Mix 1 g  of the  resulting  solid with  5  ml of organic-free  reagent water  and
measure the pH of  the mixture.  It must be below  a pH of  4,  Store  at 130°C.

      5.9   N-Methyl-N-nitroso-p-toluenesulfonamide (Diazald), CH3C6H4S02N(CH3}NO.
 Available from Aldrich  Chemical Co.

      5.10  Silicic  acid.   Chromatographic grade, nominal 100 mesh.  Store at
130°C.

                                   8150B  -  5                         Revision  2
                                                                 September  1994

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      5.11   Stock standard solutions - Stock standard solutions  can be prepared
from pure standard materials or purchased as certified solutions.

             5.11.1       Prepare stock standard solutions  by accurately weighing
      about  0,0100 g  of pure acids.  Dissolve the  acids in  pesticide quality
      acetone and dissolve the esters in 10% acetone/isooctane (v/v) and dilute
      to volume in a 10 mi volumetric flask.  Larger volumes can be used at the
      convenience of  the analyst.   If compound purity is certified  at  96% or
      greater,  the  weight  can be  used without  correction  to  calculate the
      concentration  of  the  stock  standard.     Commercially  prepared  stock
      standards can be  used  at  any concentration  if they are  certified  by the
      manufacturer or by an  independent source.

             5.11.2       Transfer the  stock  standard solutions  into  vials with
      Teflon  lined  screw caps or  crimp  tops.   Store at 4°C and  protect from
      light.  Stock standard  solutions should be checked frequently for signs of
      degradation or evaporation, especially just prior to preparing calibration
      standards from them.

             5.11.3       Stock standard solutions of the derivatized acids must
      be replaced after  1 year, or sooner,  if comparison with  check standards
      indicates a problem.  Stock standard  solutions of the free acids degrade
      more  quickly  and  should be  replaced after  two   months,  or sooner  if
      comparison with check standards indicates a problem.

      5.12   Calibration standards - A minimum of five calibration standards  for
each parameter  of  interest  should  be  prepared  through  dilution of  the  stock
standards with  diethyl  ether.    One of  the  concentrations  should  be   at  a
concentration near,  but  above,  the  method detection limit.   The  remaining
concentrations should correspond to the expected range of concentrations  found
in real  samples or should define  the working range  of  the  GC.   Calibration
solutions must be replaced after six months, or sooner if comparison with  check
standards indicates a problem.

      5.13   Internal  standards (if  internal  standard calibration is  used) - To
use this approach,  the analyst must select  one or more internal  standards that
are similar  in  analytical behavior  to the compounds of  interest.   The analyst
must further demonstrate that the  measurement of  the internal  standard  is not
affected by me^od or matrix  interferences.  Because of  these  limitations,  no
internal standard can  be suggested that is  applicable to  all  samples.

            5,13.1      Prepare  calibration standards  at a minimum of  five
      concentrations for each parameter of  interest  as described in  Sec.  5.12.

            5.13.2      To  each calibration  standard,   add  a  known  constant
      amount  of one  or  more internal  standards,  and dilute  to volume  with
      hexam

            5.13.3      Analyze each calibration standard per Sec. 7.0.

      5.14  Surrogate standards - The analyst should monitor the performance of
the extraction,  cleanup (when used), and analytical system, and the effectiveness
of the  method  in  dealing with  each sample  matrix by  spiking each  sample,


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standard,  and organic-free  reagent water  blank  with one  or two  herbicide
surrogates (e.g.  herbicides that are not expected  to  be present in the sample).
The surrogates selected should elute over the range of the temperature program
used in this method.  2,4-Dichlorophenylacetic acid (DCAA) is recommended as a
surrogate  compound.   Deuterated  analogs of  analytes should  not  be  used  as
surrogates for gas chromatographic analysis due to coelution problems.


6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1   See the  introductory  material  to this Chapter,  Organic  Analytes,
Sec. 4.1.  Extracts must be  stored  under refrigeration and  analyzed  within  40
days of extraction.


7.0  PROCEDURE

      7.1   Preparation of waste samples

            7.1.1 Extraction

                  7.1.1.1     Foilow Method 3580 except use diethyl ether as the
            dilution solvent, acidified anhydrous  sodium sulfate,  and  acidified
            glass wool.

                  7.1.1.2     Transfer 1.0 mL  (a lesser volume or a dilution may
            be required  if  herbicide concentrations are high)  to a 250 mL ground
            glass-stoppered Erlenmeyer  flask.  Proceed to Sec. 7.2,2 hydrolysis.

      7.2   Preparation of soil, sediment, and other solid samples

            7.2.1 Extraction

                  7.2.1.1     To a 500 ml,  wide mouth Erlenmeyer  flask add  50
            g (dry weight as  determined in Method 3540, Sec.  7.2.1) of the well
            mixed, moist solid  sample.   Adjust  the pH to 2  (See Method  9045)
            with   concentrated  HC1  and monitor  the   pH  for  15  minutes  with
            occasional stirring.  If necessary, add additional HC1  until the  pH
            remains at 2.

                  7.2.1.2     Add  20   mL  acetone  to the  flask   and  mix the
            contents with the wrist shaker  for 20 minutes.   Add 80 ml diethyl
            ether to the same flask and shake again for 20 minutes.  Decant the
            extract and  measure  the volume of solvent recovered.

                  7.2.1.3     Extract  the  sample twice  more using  20 mL  of
            acetone followed  by  80 ml of diethyl ether. After addition of each
            solvent, the mixture  should be shaken with  the wrist shaker for
            10 minutes and  the  acetone-ether extract  decanted.

                  7.2.1.4     After the third extraction,  the volume of extract
            recovered should be at  least  75%  of the volume of added  solvent.
            If this is not the case, additional extractions  may be necessary.
            Combine the  extracts  in a 2 liter  separatory  funnel containing

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250 mL of reagent water.   If  an  emulsion forms,  slowly add 5 g of
acidified sodium sulfate (anhydrous) until the solvent-water mixture
separates.   A quantity of  acidified  sodium sulfate  equal  to the
weight of the sample may be added, if necessary.

      7,2,1.5     Check the pH of the extract.  If it is not at or
below  pH  2,  add more concentrated  HC1  until  stabilized  at the
desired pH.   Gently mix the contents  of the separatory funnel for
1 minute and  allow  the layers to  separate.  Collect  the aqueous
phase  in  a clean beaker  and  the extract  phase  (top layer)  in  a
500 mL ground glass-stoppered Erlenmeyer flask.   Place the aqueous
phase back into the  separatory funnel  and re-extract using 25 ml of
diethyl ether.  Allow the layers to separate and discard the aqueous
layer»  Combine the ether extracts in the 500 ml Erlenmeyer flask.

      7.2.1.6     An   alternative  extraction   procedure   using
ultrasonic extraction can be found in Sec. 7.2 of Method 8151.

7.2.2 Hydrolysis

      7.2.2.1     Add 30 ml of organic-free reagent water, 5 mL of
37% KOH,  and one or two clean  boiling chips to the flask.  Place a
three ball  Snyder column  on the flask, evaporate the diethyl ether
on a water bath, and continue  to heat until the  hydrolysis step is
completed (usually 1 to 2 hours).

      7.2.2.2     Remove the flask from the water bath and allow to
cool.  Transfer the water solution to a 125 ml separatory funnel and
extract the  basic  solutions once with  40 ml and then  twice with
20 ml of diethyl ether.   Allow sufficient time for the  layers to
separate and discard the ether layer  each  time.   The  phenoxy-acid
herbicides remain soluble in the aqueous phase as potassium salts.

7.2.3 Solvent cleanup

      7.2.3.1     Adjust  the  pH to  2 by  adding  5 mL  cold  (4°C)
sulfuric acid (1:3)  to  the  separatory  funnel.  Be sure to check the
pH at this  point. Extract the herbicides once with 40 ml and twice
with 20 mL of diethyl  ether.  Discard the aqueous phase.

      7.2.3.2     Combine  ether  extracts  in  a  125 mL  Erlenmeyer
flask  containing 5-7  g  of  acidified  anhydrous  sodium  sulfate.
Stopper  and  allow  the  extract  to  remain  in   contact  with  the
acidified sodium sulfate.   If  concentration and  esterification are
not to be performed immediately,  store the sample overnight in the
refrigerator.

      NOTE: The drying step is very critical  to  ensuring complete
            esterification.   Any moisture remaining  in  the ether
            will result in low herbicide recoveries.  The amount of
            sodium  sulfate   is  adequate   if   some   free=flowing
            crystals are visible when swirling the flask.   If all
            the  sodium sulfate  solidifies  in  a  cake,  add  a few
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                   additional grams  of  acidified  sodium sulfate and again
                   test by swirling.  The 2 hour drying time is a minimum,
                   however,  the extracts may  be held overnight in contact
                   with the  sodium sulfate.

            7.2.3.3      Transfer  the  ether  extract,  through  a  funnel
      plugged  with  acid washed  glass wool,  into  a  500 ml  K-D  flask
      equipped with  a 10 ml concentrator tube.   Use a glass rod to crush
      caked sodium sulfate during  the transfer.   Rinse  the Erlenmeyer
      flask and  column   with 20-30  ml  of diethyl ether to complete the
      quantitative transfer.

            7.2.3.4      Add one or  two clean boiling chips to the flask
      and attach a three ball Snyder column.   Prewet the Snyder column by
      adding about 1 ml of diethyl ether to the top.   Place the apparatus
      on  a  hot water bath  (60°-65°C)  so  that the concentrator  tube is
      partially  immersed in the  hot water and the  entire lower rounded
      surface  of the flask is bathed in vapor.   Adjust  the  vertical
      position of  the apparatus and the water temperature, as required,
      to complete the concentration  in  15-20 minutes.  At  the proper rate
      of distillation the balls of the column will actively chatter, but
      the chambers will  not flood.   When  the apparent  volume  of liquid
      reaches 1 ml, remove the K-D apparatus from the water bath and allow
      it to drain and cool for at least 10 minutes.

            7.2.3.5      Remove the Snyder column and rinse the flask and
      its lower joints into the concentrator  tube with 1-2 ml of diethyl
      ether.  A  5  rat syringe  is  recommended  for this  operation.   Add a
      fresh boiling chip, attach a micro Snyder column  to the concentrator
      tube, and prewet the column by adding 0.5 ml of ethyl ether to the
      top.  Place  the micro K-D apparatus  on the water bath so that the
      concentrator tube  is partially immersed in the  hot  water.   Adjust
      the vertical  position of  the apparatus  and  the water temperature as
      required  to  complete concentration in 5-10 minutes.   When  the
      apparent volume of the liquid reaches 0.5 ml, remove the micro K-D
      from the bath  and  allow  it  to drain and cool.   Remove the Snyder
      column  and  add  0.1  ml  of  methanol.   Rinse  the  walls  of  the
      concentrator tube while adjusting the extract volume to 1.0 ml with
      diethyl  ether.  Proceed  to Sec. 7.4 for esterification.

7.3   Preparation of aqueous samples

      7.3.1 Extraction

            7.3.1.1      Using   a  1  liter  graduated cylinder, measure  1
      liter (nominal) of sample,  record the sample volume to the nearest
      5 mL, and quantitatively transfer  it  to the separatory funnel. If
      high concentrations are  anticipated, a smaller  volume may be used
      and then diluted with organic-free reagent water to 1 liter.  Adjust
      the pH to less than 2 with  sulfuric acid (1:1).

            7.3.1.2      Add 150 ml of diethyl ether to the sample bottle,
      seal, and shake for  30 seconds to rinse the walls.  Transfer the
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solvent  wash  to the  separatory funnel  and extract  the  sample by
shaking  the funnel  for 2  minutes with periodic venting to release
excess pressure.  Allow the organic layer to separate from the water
layer  for a  minimum of  10  minutes.   If the  emulsion  interface
between  layers is more than one  third the size of the  solvent layer,
the analyst must employ mechanical  techniques  to complete the phase
separation.  The optimum technique depends upon the  sample and may
include  stirring,  filtration of the  emulsion  through  glass wool,
centrifugation, or other physical methods. Drain the aqueous phase
into a 1  liter Erlenmeyer flask.  Collect the solvent extract in a
250 ml ground  glass Erlenmeyer flask containing 2 ml  of  37% KOH.
Approximately 80 ml  of the diethyl  ether will  remain dissolved in
the aqueous phase.

      7.3.1.3     Repeat the extraction two more times using 50 ml
of diethyl ether each time.   Combine  the extracts in  the Erlenmeyer
flask.   (Rinse  the  1 liter flask with each  additional  aliquot of
extracting solvent.)

7.3.2 Hydrolysis

      7.3.2.1     Add  one or two clean  boiling  chips and  15 ml of
organic-free reagent water to the  250 ml  flask  and  attach  a three
ball Snyder column.  Prewet the Snyder column by adding about 1 ml
of diethyl ether to the top of the column.  Place the apparatus on
a hot water bath  (60°-65°C) so that the bottom of  the flask is bathed
with hot water vapor.  Although  the diethyl ether will evaporate in
about 15 minutes,  continue heating  until the  hydrolysis  step  is
completed  (usually  1  to 2  hours).     Remove the apparatus  and let
stand at  room temperature for at least 10 minutes.

      7.3.2.2     Transfer the solution to a 60 ml separatory funnel
using  5-10 ml  of  organic-free reagent  water.   Wash the  basic
solution  twice  by  shaking  for  1  minute  with  20  ml  portions  of
diethyl  ether.  Discard the organic  phase.   The herbicides remain
in the aqueous phase.

7.3.3 Solvent cleanup

      7.3.3.1     Acidify the contents of the separatory funnel  to
pH 2 by adding 2 ml  of  cold (4°C) sulfuric acid  (1:3).  Test with pH
indicator paper.   Add 20 ml  diethyl ether and shake  vigorously for
2 minutes.  Drain the aqueous layer into a 250 ml Erlenmeyer flask,
and pour  the organic  layer into a 125  ml Erlenmeyer flask containing
about 5-7 g  of acidified sodium sulfate.  Repeat  the extraction
twice more with 10  mL aliquots of  diethyl  ether,   combining  all
solvent in the 125 ml flask.   Allow the extract to remain in contact
with the sodium sulfate for approximately 2 hours.

      NOTE: The drying  step is  very  critical  to ensuring  complete
            esterification.   Any moisture remaining in the ether
            will result in low  herbicide recoveries.  The amount of
            sodium  sulfate  is  adequate  if  some   free   flowing


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                   crystals are visible when swirling the flask.   If  all
                   the sodium  sulfate  solidifies  in  a cake,  add a  few
                   additional  grams of  acidified  sodium sulfate  and again
                   test by swirling.  The 2 hour drying time  is a minimum,
                   however, the extracts  may be  held overnight in  contact
                   with the sodium sulfate.

             7.3.3.2     Transfer  the  ether  extract,  through  a   funnel
       plugged  with  acid  washed  glass wool,  into a  500 ml K-D  flask
       equipped with a 10 ml concentrator tube.   Use a  glass  rod to crush
       caked  sodium  sulfate during the transfer.   Rinse  the Erlenmeyer
       flask  and  column  with  20-30 mL  of diethyl  ether to  complete  the
       quantitative transfer.

             7.3.3.3     Add one or two clean boiling chips to  the  flask
       and attach a three  ball  Snyder column.  Prewet the Snyder  column by
       adding about 1  ml of diethyl ether to  the  top.   Place the  apparatus
       on  a  hot water bath (6Q0-65°C)  so that the  concentrator tube is
       partially  immersed  in the hot water  and  the entire lower  rounded
       surface  of  the flask  is  bathed in  vapor.   Adjust  the vertical
       position of  the apparatus and the water temperature,  as  required,
       to complete  the concentration in  15-20 minutes.   At  the  proper rate
       of distillation the balls  of the column will actively chatter, but
       the chambers will  not flood.  When the apparent volume of  liquid
       reaches 1 ml, remove the K-D apparatus  from the water bath  and allow
       it to drain  and cool for  at  least  10 minutes.

             7.3.3.4     Remove  the Snyder column and rinse the  flask and
       its lower joints into the  concentrator tube with  1-2 ml of diethyl
       ether.  A  5 ml syringe is recommended for  this  operation.   Add  a
       fresh boiling chip, attach a  micro Snyder column  to the concentrator
       tube, and prewet the column  by adding  0.5 ml of ethyl  ether to the
       top.   Place  the micro K-D apparatus on the water bath  so that the
       concentrator tube  is partially immersed in the  hot water.  Adjust
       the vertical  position of the apparatus and  the water temperature as
       required  to  complete  concentration   in  5-10 minutes.    When the
       apparent volume of  the  liquid reaches  0.5 ml, remove the micro K-D
       from the bath and  allow it  to drain  and  cool.   Remove the Snyder
       column  and  add 0.1 mL  of  methanol.    Rinse  the walls  of the
       concentrator tube while adjusting the  extract volume to  1.0 ml with
       diethyl ether.

7.4    Esterification

       7.4.1 Two methods  may be used for  the generation of diazomethane:
the bubbler method (set up shown in Figure 1) and the Diazald  kit method.
The  bubbler  method  is suggested  when  small batches  (10-15)  of samples
require esterification.   The bubbler method works well with samples that
have low concentrations of herbicides (e.g.  aqueous samples)  and is safer
to use than the Diazald kit procedure.  The Diazald  kit  method  is good for
large  quantities   of  samples  needing   esterification.   The  Diazald kit
method is more effective  than  the bubbler method for soils  or samples that
may contain high concentrations of  herbicides (e.g., samples such as soils


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that result in yellow extracts following  hydrolysis  may be difficult to
handle by the bubbler method).  The diazomethane derivatization (U.S. EPA,
1971} procedures, described below,  will  react efficiently with all of the
chlorinated herbicides described  in this method and should be used only by
experienced analysts, due  to the potential hazards  associated  with its
use.  The following precautions should be taken:

      CAUTION:    Diazomethane  is  a  carcinogen  and  can  explode  under
                  certain  conditions.

                  Use a safety- screen.
                  Use mechanical  pipetting aides.
                  Do not heat above 90°C -- EXPLOSION may result.
                  Avoid grinding  surfaces, ground glass joints,  sleeve
                  bearings, glass stirrers --    EXPLOSION may result.
                  Store away from alkali metals -- EXPLOSION may result.
                  Solutions  of diazomethane  decompose  rapidly in  the
                  presence  of solid  materials such  as copper  powder,
                  calcium chloride, and boiling chips.

      7.4.2 Diazald kit method -  Instructions for preparing diazomethane
are provided with the generator kit.

            7.4.2.1     Add 2 mL of diazomethane  solution and let sample
      stand for 10 minutes with occasional swirling.

            7.4.2.2     Rinse  inside  wall  of  the  ampule  with  several
      hundred  pi  of  diethyl  ether.     Allow   solvent   to   evaporate
      spontaneously at room temperature to about  2 mL.

            7.4.2.3     Dissolve the residue in 5 ml of hexane.   Analyze
      by gas chromatography.

      7.4.3 Bubbler  method  -  Assemble  the diazomethane  bubbler  (see
Figure 1).

            7.4.3.1     Add 5 mL  of diethyl ether to the first test tube.
      Add 1 ml of diethyl ether,  1 ml of carbitol, 1.5 mL of 37% KOH, and
      0.1-0.2  g Diazald to the second test tube.   Immediately  place the
      exit tube into the concentrator tube containing  the sample extract.

            Apply nitrogen  flow (10 mL/min) to bubble diazomethane through
      the extract for 10 minutes or until the yellow color of diazomethane
      persists.    The  amount   of  Diazald  used   is   sufficient   for
      esterification   of  approximately   three  sample  extracts.     An
      additional  0.1-0.2 g  of Diazald may be  added  (after the  initial
      Diazald  is consumed)  to extend  the generation of the  diazomethane.
      There is sufficient KOH present in the original  solution to perform
      a maximum of approximately  20 minutes of  total  esterification.

            7.4.3.2     Remove the concentrator tube  and seal  it  with a
      Neoprene or Teflon stopper.  Store at room temperature in a hood for
      20 minutes.
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                  7.4.3.3     Destroy  any  unreacted  diazomethane  by  adding
            0.1-0.2 g  silicic acid  to the concentrator tube.   Allow to stand
            until the evolution  of nitrogen gas has stopped.  Adjust the sample
            volume to  10.0 ml with  hexane.   Stoppe^  the concentrator tube and
            store  refrigerated  if  further processing  will  not  be  performed
            immediately.   It is  recommended  that the  methylated extracts be
            analyzed immediately to minimize the trans-esterification and other
            potential reactions  that may occur.  Analyze by gas chromatography.

      7.5   Gas chromatographic conditions (Recommended)

            7.5.1 Column la

            Carrier gas (5% methane/95% argon) flow rate:     70  mL/min
            Temperature program:     185°C, isothermal.

            7.5.2 Column Ib

            Carrier gas (5% methane/95% argon) flow rate:     70  mL/min
            Initial temperature:     140°C, hold for 6 minutes
            Temperature program:     140°C to 200°C at  !0°C/m1n, hold  until  last
                                     compound  has  eluted.

            7.5.3 Column 2

            Carrier gas (5% methane/95% argon) flow rate:     70  mL/min
            Temperature program:     185°C, isothermal.

            7.5.4 Column 3

            Carrier gas (ultra-high purity N2) flow rate:     25  mL/min
            Initial temperature:     100°C, no hold
            Temperature program:     100°C to 150°C at  10°C/min, hold  until  last
                                     compound  has  eluted.

      7.6   Calibration  -  Refer  to  Hethod  8000   for   proper calibration
techniques.   Use Table 1 and especially Table 2 for  guidance on selecting the
lowest point on the calibration  curve.

            7.6.1 The  procedure  for internal   or  external  calibration  may be
      used.  Refer to Method 8000 for a  description of each of these procedures.

            7.6.2 The following  gas  chromatographic columns are recommended for
      the compounds indicated:


            Analyte           Column            Analyte           Column

            Dicantba            la, 2             Dalapon              3
            2,4-D              la,2             MCPP                 Ib
            2,4,5-TP           la,2             MCPA                 Ib
            2,4,5-T            la,2             Dichloroprop         Ib
            2,4-DB             la               Dinoseb              Ib


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      7.7    Gas  chromatographic  analysis

             7.7.1 Refer  to Method 8000.   If the internal standard calibration
      technique  is used, add 10 ^L of  internal  standard  to the sample prior to
      injection.

             7.7.2 Method 8000  provides instructions on the analysis sequence,
      appropriate dilutions,  establishing  daily  retention time  windows,  and
      identification criteria.   Include a mid-concentration check  standard after
      each group of 10 samples in the  analysis  sequence.

             7.7.3 Examples of  chromatograms for  various  chlorophenoxy  acid
      herbicides are shown  in Figures  2 through 4.

             7.7.4 Record the sample volume injected and the resulting peak sizes
      (in area units or  peak heights).

             7.7.5 Using  either  the internal  or external  calibration procedure
      (Method 8000), determine the identity and  quantity  of each component peak
      in the sample  chromatogram which corresponds to the  compounds  used  for
      calibration purposes.

             7.7.6 If calibration standards have  been analyzed in the same manner
      as the samples (e.g.   have undergone hydrolysis and esterification),  then
      the calculation  of concentration given  in  Method  8000  should  be used.
      However, if calibration  is done using standards made  from methyl ester
      compounds  (compounds  not esterified by application of this method),  then
      the  calculation  of   concentration  must   include  a  correction  for  the
      molecular weight of  the methyl  ester versus the acid herbicide.

             7.7.7 If peak  detection  and  identification  are prevented  due  to
      interferences, further  cleanup  is  required.   Before using  any  cleanup
      procedure,  the analyst  must process  a series of  standards  through  the
      procedure to validate elution  patterns and  the  absence of interferences
      from reagents.


8.0   QUALITY CONTROL

      8.1    Refer to  Chapter  One for specific  quality control  procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized.   If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.

      8.2    Procedures to  check the  GC  system  operation are  found  in  Method
8000.

            8.2.1 Select a representative spike  concentration for each compound
      (acid or ester) to  be measured.   Using  stock standards, prepare a quality
      control cr  :k  sample  concentrate in  acetone  1,000 times more concentrated
      than the    ected concentrations.
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            8.2.2  Table 3  indicates  single operator accuracy and precision for
      this  method.  Compare  the results obtained  with the results  given in
      Table 3 to determine  if the data quality is acceptable.

      8.3   Calculate  surrogate  standard  recovery  on  all  samples,  blanks, and
spikes.   Determine if the recovery  is  within limits  (limits  established by
performing QC procedures outlined in Method 8000).

            8.3.1  If recovery is not  within limits, the following procedures are
      required.

                   »     Check to be  sure  there are no errors in calculations,
                        surrogate  solutions  and  internal  standards.   Also,
                        check instrument  performance.

                   •     Recalculate  the  data and/or  reanalyze the  extract if
                        none of  the  above checks reveal a problem.

                   •     Re-extract  and re-analyze the  sample  if none  of the
                        above  are a  problem  or flag  the data as  "estimated
                        concentration".

      8.4   GC/MS  confirmation

            8.4.1  GC/MS techniques  should be judiciously employed  to support
      qualitative  identifications made with this method.  Refer to Method 8270
      for the appropriate GC/MS operating conditions and analysis  procedures.

            8.4.2  When  available,  chemical   ionization  mass  spectra may  be
      employed to  aid the qualitative identification process.

            8.4.3  Should  these  MS   procedures  fail  to provide  satisfactory
      results, additional  steps may be taken before reanalysis.  These  steps may
      include the use of alternate packed  or capillary GC columns or additional
      cleanup.


9.0   METHOD PERFORMANCE

      9.1   In  a  single   laboratory,  using  organic-free reagent  water  and
effluents from  publicly owned  treatment works (POTW),  the  average  recoveries
presented in  Table 3  were  obtained.   The standard deviations of the percent
recoveries of these measurements are also included in  Table  3.
10.0  REFERENCES

1.    U.S. EPA, National  Pollutant Discharge Elimination System,  Appendix A,
      Fed. Reg.,  38,  No.  75,  Pt. II,  Method  for  Chlorinated Phenoxy  Acid
      Herbicides in Industrial Effluents, Cincinnati, Ohio,  1971.

2.    Goerlitz, D.G., and W.L. Lamar,  "Determination of Phenoxy Acid Herbicides
      in Water  by  Electron Capture and  Microcoulometric  Gas  Chromatography,"
      U.S. Geol. Survey Water Supply Paper, 1817-C, 19671

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3.    Burke, J.A.,  "Gas  Chromatography for Pesticide Residue  Analysis;   Some
      Practical Aspects,"   Journal  of the Association  of Official  Analytical
      Chemists, 48, 1037, 1965.

4.    U.S.  EPA,  "Extraction and  Cleanup Procedure  for the Determination of
      Phenoxy Acid Herbicides  in  Sediment,"  EPA Toxicant and Analysis Center,
      Bay St. Louis, Mississippi, 1972,

5.    "Pesticide Methods Evaluation,"  Letter Report 133 for EPA  Contract No. 68-
      03-2697.   Available   from   U.S.   Environmental   Protection   Agency,
      Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268.

6.    Eichelberger, J.W., L.E. Harris, and W.L,  Budde,  "Reference Compound to
      Calibrate   Ion   Abundance   Measurement   in   Gas   Chromatography-Mass
      Spectrometry," Analytical Chemistry, 47, 995,  1975.

7.    Glaser,  J.A.  et.al.,  "Trace  Analysis  for Wastewaters,"  Environmental
      Science I Technology, 15, 1426,  1981.

8,    Gurka, D.F, Shore, F.L., Pan, S-T,  "Single Laboratory Validation  of EPA
      Method 8150  for Determination  of  Chlorinated  Herbicides  in  Hazardous
      Waste", JAOAC, 69,  970, 1986.

9.    U.S.  EPA,  "Method  615. The Determination  of Chlorinated  Herbicides  in
      Industrial and Municipal Wastewater," Environmental  Monitoring and Support
      Laboratory,  Cincinnati, Ohio,  45268, June 1982.
                                  8150B -  16                        Revision 2
                                                                September 1994

-------
                                    TABLE  1.
                CHROMATOGRAPHIC CONDITIONS AND DETECTION LIMITS
                           FOR CHLORINATED HERBICIDES
Retention time (min)a

Compound
2,4-0
2,4-DB
2,4,5-T
2,4,5-TP (Silvex)
Oalapon
Dicamba
Dichloroprop
Dinoseb
HCPA
HCPP

Col. la
2.0
4.1
3.4
2.7
-
1.2
-
-
-
-

Col.lb

-
-
-
-
-
4.8
11.2
4.1
3.4

Col. 2 Col. 3
1.6
-
2.4
2.0
5.0
1.0
.
_
.
-
Method
detection
limit (M9/L)
1.2
0.91
0.20
0.17
5.8
0.27
0.65
0.07
249
192
"Column conditions are given in Sees.  4.1 and 7.5.
                                   TABLE 2.
                    DETERMINATION OF  ESTIMATED QUANTITATION
                       LIMITS  (EQL) FOR VARIOUS MATRICES3
    Matrix
  Factor
Ground water (based on one liter sample size)
Soil/sediment and other solids
Waste samples
     10
    200
100,000
aEQL = [Method detection limit (see Table  1}]  X  [Factor  found in this table].
For non-aqueous samples, the factor is on a wet weight basis.  Sample EQLs are
highly matrix  dependent.   The EQLs to  be determined herein  are  provided for
guidance and may not always be achievable.
                                  8150B - 17
        Revision 2
    September 1994

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                                   TABLE 3.
                    SINGLE OPERATOR ACCURACY AND PRECISION8
Compound
2,4-D


Dalapon


2,4-DB


Dicamba


Dichlorprop


Dinoseb

MCPA


MCPP


2,4,5-T


2,4,5-TP


Sample
Type
DW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
Spike
10.9
10.1
200
23.4
23.4
468
10.3
10.4
208
1.2
1.1
22.2
10.7
10.7
213
0.5
102
2020
2020
21400
2080
2100
20440
1.1
1.3
25.5
1.0
1.3
25.0
Mean
Recovery
75
77
65
66
§6
81
93
93
77
79
86
82
97
72
100
86
81
98
73
97
94
97
95
85
83
78
88
88
72
Standard
deviation
4
4
5
8
13
9
3
3
6
7
9
6
2
3
2
4
3
4
3
2
4
3
2
6
4
5
5
4
5
aAT1  results based upon seven replicate analyses. Esterification performed using
the bubbler method. Data obtained from reference 8.

DW - ASTM Type II
MW = Municipal water
                                  8150B - 18
    Revision 2
September 1994

-------
                                  FIGURE 1.
                            DIAZOMETHANE GENERATOR
    nitrogen
rubber  ilopp*r
                                                                 glass tubing
                                                       -I	f
                     lub« 1
lube 2
                                   81BOB  -  19
                         Revision  2
                     September 1994

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                       FIGURE 2.
     GAS  CHROMATOGRAH OF CHLORINATED HERBICIDES
Column: 1 J% $P«22SO/1JS% 8*240!
Twnpfrtturt: tottwmul it 185°C
Draeior: ElMtren C*ptur*
I100/120M**)
         012341
           RETENTION TIME {MINUTES)
                      8150B - 20
                Revision 2
            September  1994

-------
                  FIGURE 3.
GAS CHROMATOGRAM OF CHLORINATED HERBICIDES
  Column: 1J% S?-22SO/1.»S% SP-2401 on Suwteoport (100/120 MMh)
  ftefrvn: 140°C for 6 Min, 10°C/Mimm to 200°C
  DttKtor: Ettctron Ctpturt
                               I
                   I          •
                        {MINUTES)
  12
                 81BOB  -  21
    Revision 2
September 1994

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               FIGURE 4.
GAS CHRQMATOGRAM OF DALAPON, COLUMN 3
      Column: 0.1% 9*1000 on 10/100 M**hCwrtoomk C
             100°C, 10°&Minto 1gO«C
            : lltevwi C«ptuft

               8150B  -  22
    Rtvision  2
September  1994

-------
                                  METHOD 81SOB
            CHLORINATED  HERBICIDES BY  GAS  CHROMAT06RAPHY
    7.2.1.1
Adjust iample
 pH with MCI.
                                                   7.3.1.1 Miami
                                                     •ample pH
                                                    with H2S04.
7.2.1.2 Extract
 •ample with
 •c«tone and
 diethyl mttimt.
     I
7.2.1.3 Extract
  twica mor».
    7.2.1.4
   Combine
   •Mraeta.
 7.2.1.5 Ch.ck
 pH of extract,
   adju*t if
   n*c*»iry.
Saparat* layar*.
  7.2.1-i
 Re-extract
•nd di«e«rd
  •oucout
   7.1.1 Follow
 Method 3510 (or
 extraction, u»ing
   di»thyi fth*r,
•oidili»d •nhydroui
•odium culfat* *nd
  acidified plat*
      wool.
7.2.2 Proceed
    with
                           I
  7.3.1.2 Extract
   with diathyl
    7.1.1.2 Ute
     1.0 mi of
    *«npla for
    hvdroly»i».
     7.3,1,3
Extract twice more
   •nd connbinB
    •Xtracn.
7.2.3 Proceed
 With »otv»nt
  ctaanyp.
                                7.3.2 Proc««d
                                    with
                                  hydrely*!*.
                                                    7.3.3 ProcoBd
                                                     with «olv*nt
                                                      cl»inup.
                                               \
                                      V
                                   81BOB  -  23
                                                         Revision  2
                                                   September  1994
                                                                     \

-------
                                       METHOD 81SOB
                                        (Continued)
7,4.3 Astemble
 ditzomethane
   bubbler;
   generate
 diazomethana,
    7,4
   Chooae
 method for
eeterification
7,4.2 Prepare
diazomethane
 according to
     kit
 instruction*.
                             7.5 Set
                          eh romato graphic
                            condition!.
                           7.6 ClaibratB
                           according to
                           Method 8000.
                            7.6.2 Choo«e
                             appropriata
                             GC column.
                              7.7 Analyza
                              by GC (rafer
                              to Method
                                800O).
                                                          7.7.7 Do
                                                        interferences
                                                        prevent peak
                                                         detection?
                                                       7.7.7 Proc««e
                                                         •arie* of
                                                         •tsndardi
                                                      through «ystom
                                                         cleanup.
                                        8150B  - 24
                                                         Revision  2
                                                    September 1994

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                                  METHOD  8151

   CHLORINATED HERBICIDES BY GC USING METHYLATION OR PENTAFLUOROBENZYLATION
                  DERIVATIZATION: CAPILLARY COLUMN TECHNIQUE


1.0   SCOPE AND APPLICATION

      1.1   Method  8151  is  a  capillary  gas  chromatographic  (GC)  method  for
determining certain  chlorinated acid herbicides and related compounds  in aqueous,
soil and waste matrices.  Specifically, Method 8151 may  be  used to determine the
following compounds:
      Compound Name                                   CAS No."


      2,4-D                                           94-75-7
      2,4-DB                                          94-82-6
      2,4,5-TP (Silvex)                               93-72-1
      2,4,5-T                                         93-76-5
      Dalapon                                         75-99-0
      Dicamba                                       1918-00-9
      Dichloroprop                                   120-36-5
      Dinoseb                                         88-85-7
      MCPA                                            94-74-6
      MCPP                                            93-65-2
      4-Nitrophenol                                  100-02-1
      Pentachlorophenol                               87-86-5


      a     Chemical Abstract Services Registry Number.

      Because these compounds are produced and used in various  forms (i.e., acid,
salt, ester,  etc.),  Method 8151  describes a hydrolysis step that can be used to
convert  herbicide esters into the acid form prior to analysis.  Herbicide esters
generally have a half-life of less than one week in soil.

      1.2   When Method 8151  is  used to analyze unfamiliar  samples,  compound
identifications  should  be supported  by at least  one additional  qualitative
technique.   Sec.  8.4 provides  gas  chromatograph/mass  spectrometer  (GC/MS)
criteria   appropriate  for   the    qualitative   confirmation   of   compound
identifications.

      1.3   The estimated  detection limits  for  each of the compounds in aqueous
and soil matrices are listed in  Table 1.   The  detection limits  for  a  specific
waste sample may differ  from those  listed, depending  upon  the nature  of the
interferences and the sample matrix.
                                   8151 - 1                         Revision 0
                                                                September 1994

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      1.4   The following compounds may also be determined using this method:
      Compound Name                               CAS No.8


      Acifluorfen                          -    50594-66-6
      Bentazon                                  25057-89-0
      Chloramben                                  133-90-4
      DCPA diacidb                               2136-79-0
      3,5-Dichlorobenzoic acid                     51-36-5
      5-Hydroxydicamba                           7600-50-2
      Picloram                                   1918-02-1


      *      Chemical Abstract Services Registry Number.

      b      DCPA monoacid and diacid metabolites  included  in method scope; DCPA
            diacid metabolite used for validation studies.  DCPA is a dimethyl
            ester.


      1.5   This method  is  restricted to use  by or under the  supervision of
analysts  experienced  in  the use  of  gas  chromatography and  skilled  in  the
interpretation of gas  chromatograms.   Each analyst must demonstrate the ability
to generate acceptable results with this method.

      1.6   Only experienced analysts should be  allowed to work with diazomethane
due to the potential hazards associated with its use (explosive, carcinogenic).


2.0   SUMMARY OF METHOD

      2.1   Method  8151    provides   extraction,   derivatization,    and   gas
chromatographic conditions  for the analysis of chlorinated  acid herbicides in
water, soil, and waste samples.   An option for  the hydrolysis of esters is also
described.

            2.1.1 Water  samples  are  extracted  with  diethyl   ether  and  then
      esterified with  either diazomethane  or  pentafluorobenzyl  bromide.   The
      derivatives are  determined  by gas chromatography with an electron capture
      detector (GC/ECD).  The results  are reported as acid equivalents.

            2.1.2 Soil  and  waste  samples  are extracted  and   esterified  with
      either diazomethane or pentafluorobenzyl bromide.  The  derivatives  are
      determined  by  gas  chromatography  with  an  electron  capture  detector
      (GC/ECD).  The results are reported as acid equivalents.

            2.1.3 If herbicide esters are to  be  determined  using this method,
      hydrolysis  conditions for the  esters  in  water  and  soil extracts  are
      described.
                                   8151 - 2                         Revision 0
                                                                September 1994

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      2.2   The sensitivity of Method 8151 depends on the level of interferences
in  addition to  instrumental  limitations.   Table  1  lists  the GC/ECD and GC/MS
detection limits that can be obtained in aqueous and soil matrices in  the absence
of  interferences.  Detection  limits  for  a typical  waste sample should be higher.


3.0   INTERFERENCES

      3.1   Refer to Method 8000.

      3.2   Method  interferences  may be  caused  by contaminants  in solvents,
reagents, glassware, and other sample processing  hardware  that lead  to discrete
artifacts or elevated baselines in gas  chromatograms.  All these materials must
be routinely demonstrated to  be free from  interferences  under the conditions of
the analysis,  by analyzing reagent blanks.

            3.2.1 Glassware must be scrupulously cleaned.  Clean each piece of
      glassware  as  soon as  possible  after  use  by rinsing  it  with  the  last
      solvent used in it.  This should be followed by detergent washing with hot
      water and  rinses  with  tap water, then with  organic-free  reagent water.
      Glassware  should  be solvent-rinsed  with  acetone  and  pesticide-quality
      hexane.   After rinsing and drying, glassware should be sealed and stored
      in  a  clean environment  to prevent  any  accumulation  of  dust  or  other
      contaminants.   Store  glassware  inverted or capped with  aluminum  foil.
      Immediately prior to use, glassware should be rinsed with the next solvent
      to be used.

            3.2.2 The use of  high purity reagents  and solvents helps  to minimize
      interference problems.   Purification of solvents by distillation in all-
      glass systems may be required.

      3.3   Matrix  interferences may   be  caused   by   contaminants  that  are
coextracted from  the sample.   The  extent of  matrix  interferences  will  vary
considerably from waste  to waste, depending upon the nature and diversity of the
waste being sampled.

      3.4   Organic acids,  especially chlorinated acids, cause the most direct
interference  with  the   determination   by  methylation.    Phenols,  including
chlorophenols, may also  interfere with  this procedure.   The determination using
pentafluorobenzylation is more sensitive,  and more prone to interferences from
the presence of organic acids or phenols than by methylation.

      3.5   Alkaline hydrolysis and  subsequent extraction  of the basic solution
removes many chlorinated hydrocarbons and phthalate  esters that might otherwise
interfere with the electron capture analysis.   However,  hydrolysis may result in
the loss  of dinoseb and the  formation  of  aldol  condensation products  if any
residual acetone remains from the extraction  of solids.

      3.6   The  herbicides,  being  strong  organic  acids,  react  readily  with
alkaline substances and  may be lost  during analysis.  Therefore,  glassware must
be acid-rinsed and then rinsed to constant pH with organic-free  reagent water.
Sodium sulfate must be acidified.
                                   8151 - 3                         Revision 0
                                                                September 1994

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      3,7   Sample extracts  should  be dry  prior  to methylation or  else  poor
recoveries will be obtained.
4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph

            4.1.1 Gas  chromatograph  -  Analytical   system  complete  with  gas
      chromatograph suitable for Grob-type  injection  using capillary columns,
      and all  required accessories  including  detector, capillary  analytical
      columns,  recorder, gases,  and syringes.  A data system for measuring peak
      heights and/or peak areas  is  recommended.

            4.1.2 Columns

                  4.1.2.1     Narrow Bore Columns

                        4.1.2.1.1   Primary Column  1  -  30 Hi  x  0.25 mm,  5%
                  phenyl/95%  methyl   silicone  {DB-5,  J&W   Scientific,   or
                  equivalent),  0.25 jim film thickness.

                        4.1.2.1.2   Primary Column  la (GC/MS) - 30 m x 0.32 mm,
                  5% phenyl/95%  methyl  silicone,  (DB-5,  J&W  Scientific,  or
                  equivalent),  1  /urn film thickness,

                        4.1.2.1.3   Column  2  -  30  m  x  0.25  mm DB-608  (J&W
                  Scientific or  equivalent) with a  25 /urn film thickness.

                        4.1.2.1.4   Confirmation Column - 30  m x  0.25 mm,  14%
                  cyanopropyl  phenyl  silicone,  (DB-1701,  J&W  Scientific,  or
                  equivalent),  0.25 /im film thickness.

                  4.1.2.2     Wide-bore Columns

                        4.1.2.2.1   Primary Column  -  30 m x 0.53 mm DB-608 (J&W
                  Scientific or  equivalent) with 0.83 jum film thickness.

                        4.1.2.2.2   Confirmation Column - 30  m x  0.53 mm,  14%
                  cyanopropyl  phenyl  silicone,  (DB-I70I,  J&W  Scientific,  or
                  equivalent),  1.0  pm film thickness.

            4.1.3 Detector - Electron Capture  Detector (ECD)

      4.2   Kuderna-Danish (K-D)  apparatus

            4.2.1 Concentrator tube - 10 ml graduated (Kontes K-570050-1025 or
      equivalent).   A  ground glass  stopper is used to prevent evaporation of
      extracts.

            4.2.2 Evaporation   flask   -   500   ml   (Kontes  K-570001-500   or
      equivalent).    Attach  to   concentrator  tube  with  springs,  clamps,  or
      equivalent.


                                   8151 - 4                         Revision 0
                                                                September 1994

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            4,2.3 Snyder  column  - Three  ball  macro  (Kontes  K-503000-0121 or
      equivalent).

            4.2.4 Snyder  column   -  Two  ball  micro  (Kontes  K-569Q01-Q219 or
      equivalent).

            4.2.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).

      4.3   Diazomethane Generator:   Refer to Sec. 7.5 to determine which method
of diazomethane generation should be used for a particular generation.

            4.3.1 Diazald Kit - Recommended for the generation of diazomethane
      (Aldrich Chemical Co., Cat No. 210,025-0, or equivalent).

            4.3.2 As  an  alternative, assemble  from  two 20 mm x 150  mm test
      tubes,  two  Neoprene  rubber  stoppers, and  a source  of nitrogen.   Use
      Neoprene rubber stoppers with holes drilled in them to accommodate glass
      delivery  tubes.    The exit  tube must  be drawn  to  a  point  to bubble
      diazomethane through the sample extract.   The generator  assembly  is shown
      in Figure 1.  The procedure  for use  of this type of generator is given in
      Sec. 7.5.

      4.4   Other Glas.sware

            4.4.1 Beaker - 400 ml, thick walled.

            4.4.2 Funnel - 75 mm diameter.

            4.4.3 Separatory funnel  - 500 ml,  with Teflon stopcock.

            4.4.4 Centrifuge bottle - 500 ml (Pyrex 1260 or equivalent).

            4.4.5 Centrifuge bottle - 24/40 500 mL

            4.4.6 Continuous Extractor (Bershberg-Wolfe  type,  Lab Glass No. LG-
      6915, or equivalent)

            4.4.7 Pipet - Pasteur, glass,  disposable (140 mm x 5 mm ID).

            4.4.8 Vials -  10 ml,  glass, with  Teflon lined screw-caps.

            4.4.9 Volumetric flasks, Class A - 10 ml to  1000 ml.

      4.5   Filter paper - 15 cm diameter (Whatman No. 1 or equivalent).  .

      4.6   Glass Wool - Pyrex, acid washed.

      4.7   Boiling    chips    -     Solvent    extracted    with    methylene
chloride,approximately 10/40 mesh  (silicon carbide or equivalent).

      4.8   Water  bath  -   Heated,  with  concentric  ring   cover,  capable  of
temperature control  (+ 2°C).   The  bath  should  be used  in a  hood.
                                   8151 - 5                         Revision 0
                                                                September 1994

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      4.9   Balance - Analytical, capable of accurately weighing to 0.0001 g.

      4.10  Centrifuge.

      4.11  Ultrasonic preparation - A horn-type device equipped with a titanium
tip, or a device that will give equivalent performance, shall be used.

            4.11.1      Ultrasonic Disrupter - The disrupter must have  a minimum
      power wattage of 300 watts, with pulsing capability.   A device designed to
      reduce  the  cavitation  sound is  recommended.    Follow the manufacturers
      instructions for preparing the disrupter for extraction of samples.  Use
      a 3/4" horn for most samples.

      4.12  Sonabox -  Recommended with above disrupters for decreasing cavitation
sound (Heat Systems - Ultrasonics, Inc., Model 432B or equivalent).

      4.13  pH paper.

      4.14  Silica gel cleanup column (Bond Elut™ - Analytichem,  Harbor City, CA
            or equivalent).

5.0   REAGENTS

      5.1   Reagent grade  inorganic chemicals shall be  used  in all tests.  Unless
otherwise  indicated,  it   is  intended that all  reagents  shall  conform  to the
specifications of the Committee  on Analytical Reagents of the American Chemical
Society, where such  specifications  are available.   Other  grades  may  be used,
provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.

      5.2   Organic-free reagent water.   All  references to  water in this method
refer to organic-free water,  as defined in Chapter One.

      5.3   Sodium hydroxide  solution  (0.1  N),  NaOH.  Dissolve  4 g  NaOH in
organic-free reagent water and dilute to 1.0 L.

      5.4   Potassium  hydroxide  solution (37%  aqueous  solution  (w/v)),  KOH.
Dissolve 37  g potassium  hydroxide pellets  in organic-free  reagent water and
dilute to 100 ml.

      5.5   Phosphate buffer pH = 2.5 (0.1 M),  Dissolve 12 g sodium phosphate
(NaH2P04) in organic-free reagent water  and dilute to 1,0 L.   Add  phosphoric acid
to adjust the pH to 2.5.

      5.6   N-methyl-N-nitroso-p-toluenesulfonamide  (Diazald).    High  purity,
available from Aldrich Chemical  Co.  or  equivalent.

      5.7   Silicic acid,  H2Si05.  100 mesh  powder, store at 130°C.

      5.8   Potassium carbonate, K2C03.

      5.9   2,3,4,5,6-Pentafluorobenzyl bromide  (PFBBr), C6F5CH26r.   Pesticide
quality or equivalent.


                                   8151 - 6                         Revision 0
                                                                September 1994

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      5.10  Sodium sulfate (granular, acidified, anhydrous), Na2S04.   Purify by
heating at 400°C for 4  hours  in a shallow  tray,  or by precleaning the  sodium
sulfate with  methylene chloride.   If  the  sodium  sulfate  is  precleaned  with
methylene chloride,  a method blank must be analyzed, demonstrating that there is
no interference  from the sodium sulfate.   Acidify by  slurrying 100 g  sodium
sulfate with enough  diethyl ether  to  just cover the solid; then add  0.1 ml of
concentrated sulfuric acid and mix thoroughly.  Remove  the  ether under  vacuum.
Mix 1 g  of the  resulting  solid with  5 ml of  organic-free reagent water  and
measure the pH of the mixture.   It must be below a pH of 4.   Store the  remaining
solid at 130°C.
                        Methylene  chloride,
                                              CH2C12.
Pesticide  quality  or
5.11  Solvents

      5.11.1
equivalent.

      5.11.2

      5.11.3

      5.11.4

      5.11.5      Diethyl   Ether,   C2H5OC2H5.     Pesticide  quality   or
equivalent.  Must  be  free of peroxides  as  indicated by test strips  (EM
Quant, or equivalent).  Procedures for removal of peroxides  are  provided
with the test strips.   After cleanup,  20  ml  of ethyl  alcohol  preservative
must be added to each liter of ether.
                        Acetone, CH3COCH3.   Pesticide quality or equivalent.

                        Methanol,  CH3OH.   Pesticide quality or equivalent.

                        Toluene, C6H5CH3.   Pesticide  quality  or equivalent.
            5.11.6
      equivalent.

            5.11.7

            5.11.8
                        Isooctane,  (CH3)3CH2CH(CH3)2.    Pesticide  quality  or


                        Hexane, C6H14.   Pesticide  quality or equivalent.

                        Ethanol, absolute. C2H5OH
            5.11.9      Carbitol   (diethylene    glycol    monoethyl   ether),
      C2H5OCH2CH2OCH2CH20  - optional for  producing  alcohol-free diazomethane.
      5 "" /  ^irk stanria1'"1  -<:  ' 'l"^ ^,r-/' >  _
      O.-£l  Oi-UwK boanuG.vj  iw/vj^.u.^  ^«www -li^j/—y
standard materials or can be purchased as certified solutions.
                                                         be  prepared fro~
            5.12.1       Prepare stock standard solutions  by accurately weighing
      about 0.010 g of pure acid.   Dissolve the material in pesticide quality
      acetone and dilute to volume in a 10 ml volumetric flask.   Stocks prepared
      from pure  methyl  esters are  dissolved in  10%  acetone/isooctane  (v/v).
      Larger volumes may be used at the convenience of the analyst.   If compound
      purity is  certified  at  96% or greater,  the weight may  be used without
      correction to calculate  the concentration of the stock standard.

            5.12.2       Transfer the  stock  standard  solutions  to  vials with
      Teflon lined screw-caps.   Store  at  4°C,  protected from  light.    Stock
      standard solutions  should be  checked frequently for signs  of  degradation
                                   8151 - 7
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      or  evaporation,  especially  immediately  prior to  preparing calibration
      standards from them.

            5.12.3      Stock standard solutions of the derivatized acids must
      be replaced  after  I  year,  or sooner,  if comparison with check standards
      indicates a problem.  Stock  standard solutions of the free acids degrade
      more  quickly and  should  be replaced  after  two  months,  or sooner  if
      comparison with check standards indicates a problem.

      5.13  Internal Standard Spiking Solution (if internal standard calibration
is used) - To  use  this  approach, the  analyst must  select one or more internal
standards that are similar in analytical  behavior to the compounds of interest.
The  analyst  must  further demonstrate  that  the measurement  of  the  internal
standard is not affected by method or matrix  interferences.  The compound 4,4'-
dibromooctafluorobiphenyl  (DBOB) has  been shown  to  be  an  effective  internal
standard, but other compounds, such as 1,4-dichlorobenzene, may be  used if there
is a DBOB interference.

            5.13.1      Prepare  an  internal  standard  spiking  solution  by
      accurately weighing  approximately  0.0025  g of pure DBOB.   Dissolve the
      DBOB  in acetone  and  dilute to  volume  in  a  10  ml  volumetric  flask.
      Transfer the  internal  standard spiking solution  to a  vial  with  a Teflon
      lined screw-cap,  and store at room  temperature.  Addition of 10 pi of the
      internal standard spiking  solution to  10 ml of sample  extract results in
      a final  internal  standard concentration of 0.25  jug/l.  The solution should
      be replaced  if there is a change  in internal  standard  response greater
      than 20 percent of the original  response recorded.

      5.14  Calibration standards - Calibration  standards, at  a minimum of five
concentrations for each  parameter of  interest,  should  be  prepared  through
dilution of  the  stock  standards with diethyl  ether or  hexane.   One  of the
concentrations should be at a concentration near, but above, the method detection
limit.  The remaining concentrations should correspond to the expected range of
concentrations found in real samples or should define the working range of the
GC.   Calibration  solutions must be  replaced after  six  months,  or sooner  if
comparison with check standards  indicates a  problem.

            5.14.1      Derivatize each calibration standard prepared from free
      acids in  a  10 ml K-D  concentrator  tube,  according  to the  procedures
      beginning at Sec. 7.5.

            5.14.2      Add a known,  constant  amount of one  or  more  internal
      standards to each derivatized calibration standard, and dilute to volume
      with the solvent  indicated in the derivative option used.

      5.15  Surrogate standards - The analyst should monitor the performance of
the  extraction,   cleanup   (when  used),  and   determinative   step,   and  the
effectiveness of  the method in dealing with each sample matrix, by spiking sach
sample,   standard,   and  blank  with one  or  two  herbicide  surrogates  (e.g.,
herbicides that are not  expected to be present in the sample)  recommended  to
encompass the  range of  the temperature program used in this method.  Deuterated
analogs  of analytes  should not  be used  as   surrogates in gas chromatographic
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analysis due to coelution problems.  The  surrogate standard recommended for use
is 2,4-Dichlorophenylacetic acid (DCM),

            5.15.1      Prepare  a  surrogate  standard  spiking  solution  by
      accurately weighing approximately 0.001 g of pure DCAA.  Dissolve the DCAA
      in acetone, and dilute to volume in a 10 ml volumetric flask.   Transfer
      the surrogate  standard  spiking  solution to  a  vial  with  a  Teflon  lined
      screw-cap,  and  store at  room  temperature.   Addition of  50 juL of the
      surrogate standard spiking solution to 1 L of sample, prior to extraction,
      results in a final concentration in the extract of 0.5 mg/L.

      5.16  pH Adjustment Solutions

            5.16.1      Sodium hydroxide, NaOH, 6 N.

            5.16.2      Sulfuric acid, H2S04,  12  N.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to this chapter,  Organic Analytes,
Sec.  4.1.  1 L samples should be collected.

      6.2   Extracts must be stored under refrigeration (4°C).


7.0   PROCEDURE

      7.1   Preparation of High Concentration Waste Samples

            7.1.1 Extraction

                  7.1.1.1     Follow  Method  3580,  Waste Dilution,  with  the
            following exceptions:

                  •     use diethyl  ether as the dilution solvent,
                  •     use acidified anhydrous  sodium  sulfate,  and acidified
                        glass wool,
                  *     spike the sample with surrogate compound(s) according to
                        Sec. 5,16.1.

                  7.1.1.2     If the sample is to be analyzed  for both herbicide
            esters and acids, then the sample extract must  be  hydrolyzed.  In
            this case, transfer 1.0 mL (a  smaller volume or  a  dilution may be
            required if herbicide concentrations are large)  to  a 250 mL ground
            glass Erlenmeyer flask.   Proceed to Sec.  7.2.1.8.  If the analysis
            is  for   acid   herbicides  only,  proceed   to   Sec.   7.4.5   for
            derivatization by diazomethane (if PFB derivatization is selected,
            reduce the volume  of diethyl ether to 0.1  - 0.5 mL as per Sec.  7.4.2
            and then dilute to 4 mL with  acetone).
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7.2   Preparation of Soil, Sediment, and Other Solid Samples

      7.2.1 Extraction

            7.2.1.1     To a  400 ml,  thick-wall  beaker add  30 g  {dry
      weight as determined in Method 3540, Sec.  7.2.1)  of the well-mixed
      solid sample.   Adjust  the pH to  2  with concentrated  hydrochloric
      acid or acidify solids  in  each beaker with 85 ml of 0.1 M phosphate
      buffer  {pH  = 2.5)  and  thoroughly mix the  contents  with a  glass
      stirring rod.  Spike the sample with  surrogate compound(s) according
      to Sec. 5.16.1.

            7.2.1.2     The  ultrasonic extraction  of  solids  must  be
      optimized for  each  type of sample.   In  order for the  ultrasonic
      extractor to efficiently extract solid samples,  the sample must be
      free flowing when  the solvent  is  added.  Acidified anhydrous  sodium
      sulfate should be added to clay  type  soils  {normally  1:1),  or any
      other solid that is not a free flowing sandy mixture,  until  a free
      flowing mixture is obtained.

            7.2.1.3     Add 100 ml  of  methylene chloride/acetone  (1:1
      v/v)  to the  beaker.  Perform  ultrasonic extraction for  3  minutes,
      with output  control  knob set at 10 {full power) and with mode  switch
      on Pulse {pulsing energy rather than  continuous energy) and percent-
      duty cycle knob set at  50%  {energy  on 50% of time and  off  50% of
      time).   Allow the solids to settle.  Transfer the organic layer into
      a 500 ml centrifuge bottle.

            7.2.1.4     Ultrasonically extract the sample twice more using
      100 ml  of methylene chloride  and the same  ultrasonic  conditions.

            7.2.1.5     Combine the  three organic extracts from the  sample
      in the centrifuge bottle  and  centrifuge  10  minutes to  settle the
      fine particles.  Filter the combined  extract  through  filter  paper
      {Whatman #1,  or equivalent) containing 7-10 g of  acidified  sodium
      sulfate into a 500 ml 24/40 Erlenmeyer flask.  Add 10 g of acidified
      anhydrous  sodium  sulfate.    Periodically,  vigorously  shake  the
      extract and drying  agent  and  allow  the drying agent  to  remain  in
      contact with the extract for a minimum of 2 hours.  See NOTE in Sec.
      7.3.1.6  thai  emphasizes  the  need  for  a  dry  extract  prior  to
      esterification.

            7.2.1.6     Quantitatively transfer  the contents of the flask
      to a 500-mL  Kuderna-Danish flask with  a  10-mL concentrator  tube
      attached.   Add  boiling  chips  and attach the macro Snyder column.
      Evaporate the extract on the water bath to a volume of approximately
      5 ml.  Remove the flasks from the water bath and allow them to cool.

            7.2.1.7     If  hydrolysis  or  additional   cleanup is  not
      required and the sample  is dry,  proceed to  Sec. 7.4.4  -  Nitrogen
      Slowdown,
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      7.2.1.8     Usethis step only if herbicide esters in addition
to herbicide acids are to be determined:

            7.2.1.8.1   Add 5 ml  of 37%  aqueous potassium hydroxide
      and 30 ml  of  water to the extract.  Add  additional  boiling
      chips to the  flask.   Reflux the mixture  on  a  water  bath at
      60-65°C  until  the hydrolysis step is completed (usually 1 to
      2 hours).  Remove the flasks from the water bath and cool to
      room temperature. CAUTION - the presence of residual  acetone
      will result in the  formation of  aldol  condensation products
      which will  cause GC interference.

            7.2.1.8.2   Transfer the  hydrolyzed  aqueous solution to
      a 500 ml separatory funnel and  extract the  solution  three
      times with  100 ml portions of methylene  chloride.  Discard the
      methylene chloride phase.   At  this point the basic  (aqueous)
      solution contains the herbicide salts.

            7.2.1.8.3   Adjust the pH  of the solution to  <2 with
      cold (4°C)  sulfuric  acid (1:3) and extract once with 40 ml of
      diethyl  ether  and twice with 20 tnL portions of ether.  Combine
      the extracts and  pour them  through a pre-rinsed drying column
      containing  7 to 10 cm of acidified anhydrous sodium sulfate.
      Collect  the dried extracts  in a 500 ml Erlenmeyer flask (with
      a 24/40  joint) containing  10 g  of acidified  anhydrous sodium
      sulfate.    Periodically, vigorously shake  the extract  and
      drying agent and allow the  drying agent to remain  in  contact
      with the extract for a minimum of 2 hours.  See NOTE  in Sec.
      7.3.1.6  that emphasizes the need  for a  dry  extract prior to
      esterification.   Quantitatively transfer the contents of the
      flask  to  a  500-mL  Kuderna-Danish   flask   with   a  10-mL
      concentrator tube attached  when  the extract is known  to be
      dry.

            7.2.1.8.4   Proceed to Sec.  7.4, Extract Concentration.
      If additional  cleanup is required, proceed to Sec.  7.2.1.9.

      7.2,1.9      Use this step if additional cleanuELof the non-
hvdrolyzed herbicides is  required:

            7.2.1.9.1   Partition the herbicides by extracting the
      methylene  chloride  from   7.2.1.7   (or  diethyl  ether  from
      7.2.1.8.4)   with 3  x 15 ml  portions of  aqueous base prepared
      by carefully mixing 30 ml  of reagent water into 15  ml of 37%
      aqueous  potassium hydroxide.   Discard the  methylene chloride
      or ether phase.  At this point the  basic  (aqueous) solution
      contains  the herbicide salts.

            7.2.1.9.2   Adjust the pH  of  the solution to  <2 with
      cold (4°C)  sulfuric  acid (1:3)  and extract once with 40 ml of
      diethyl ether  and twice with 20  ml  portions of ether.  Combine
      the extracts and  pour them through a pre-rinsed drying column
      containing  7 to 10 cm of acidified anhydrous sodium sulfate.
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            Collect the dried extracts  in a 500 ml Erlenmeyer flask (with
            a 24/40 joint)  containing 10 g  of acidified anhydrous sodium
            sulfate.   Periodically, vigorously  shake  the extract  and
            drying agent and allow the  drying agent to remain  in contact
            with the extract for a minimum  of 2 hours.   See NOTE in Sec.
            7.3.1.6 that emphasizes the need for a  dry  extract  prior to
            esterification.   Quantitatively transfer the contents of the
            flask  to  a  500-mL  Kuderna-Danish   flask  with   a  10-rnL
            concentrator tube attached  when  the  extract is known  to be
            dry.

                  7.2.1.9.3    Proceed   to   section   7.4   for   extract
            concentration.

            7.2.1.10    An  alternative  wrist-shaker extraction  procedure
      can be found in Sec.  7.2  of Method 8150.

7.3   Preparation of Aqueous Samples

      7.3.1 Separatory Funnel

            7.3.1.1     Using  a  graduated  cylinder, measure  out  a  1-L
      sample and  transfer  it  into a 2-L separatory funnel.  Spike  the
      sample with surrogate  compound(s) according to Sec.  5.15.1.

            7.3,1.2     Add  250  g of NaCl to the  sample,  seal,  and shake
      to dissolve the salt.

            7.3.1.3     Use  this  step only if herbicide esters in addition
      to herbicide acids, are  to be determined:

                  7.3.1.3.1   Add 17 ml of  6 N  NaOH to  the  sample,  seal,
            and shake.   Check  the pH of the sample  with  pH  paper; if the
            sample does not  have  a pH greater than or equal  to  12, adjust
            the pH by adding more 6 N NaOH.  Let the  sample sit at room
            temperature until the hydrolysis step is completed  (usually 1
            to   2  hours),   shaking  the  separatory  funnel  and  contents
            periodically.

                  7.3.1.3.2   Add 60 ml of  methylene  chloride to  the
            sample bottle and  rinse both  the  bottle and  the graduated
            cylinder. Transfer the methylene chloride to the  separatory
            funnel and  extract the sample by vigorously shaking the funnel
            for  2 minutes,  with  periodic  venting  to  release  excess
            pressure.  Allow the  organic layer to separate from the water
            phase for a minimum of 10 minutes.  If the emulsion  interface
            between the layers  is more than one-third the  volume of the
            solvent layer,  the  analyst  must employ  mechanical  techniques
            to   complete  the phase  separation.    The optimum technique
            depends upon the sample, but may include stirring,  filtration
            through glass wool,  centrifugation,  or other physical  methods.
            Discard the methylene chloride  phase.
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            7.3.1.3.3   Add  a  second  60  ml  volume  of methylene
      chloride  to  the  separatory funnel  and repeat the extraction
      procedure  a  second time,  discarding  the  methylene chloride
      layer.  Perform a third extraction in the same manner,

      7.3.1.4     Add 17 ml of cold (4°C) 12 N sulfuric  acid to the
sample (or hydrolyzed sample),  seal, and shake to mix.   Check the pH
of the sample with pH paper:   if the sample does not have a pH less
than or equal to 2, adjust the pH by adding more acid.

      7.3.1.5     Add 120 ml diethyl ether  to the sample, seal, and
extract the sample by vigorously shaking the funnel for 2 min with
periodic  venting to release  excess  pressure.   Allow the  organic
layer to separate from the water phase  for  a minimum of  10 min.  If
the emulsion  interface  between layers is more than one third the
volume of the solvent  layer,  the analyst must  employ mechanical
techniques to complete the phase separation. The optimum techniques
to complete the  phase separation depends upon  the  sample,  but may
include stirring, filtration  through glass wool, centrifugation, or
other  physical   methods.    Remove the aqueous  phase  to   a  2  L
Erlenmeyer flask and collect  the ether  phase in a 500 ml Erlenmeyer
flask containing approximately  10  g of acidified  anhydrous sodium
sulfate.    Periodically,  vigorously shake  the  extract  and  drying
agent.

      7.3.1.6     Return the  aqueous phase to the separatory funnel,
add 60 ml of diethyl  ether  to the  sample, and repeat the extraction
procedure  a second  time,  combining   the  extracts   in the  500  ml
Erlenmeyer  flask.   Perform a third extraction with 60  ml  diethyl
ether in the same manner.  Allow the  extract to  remain in  contact
with the sodium sulfate for approximately 2 hours.

      NOTE:       The drying step is  very  critical  to  ensuring
                  complete esterification.   Any moisture remaining
                  in  the  ether  will   result   in   low  herbicide
                  recoveries.   The amount of  sodium  sulfate  is
                  adequate  if  some   free   flowing  crystals  are
                  visible when swirling the flask.   If all  of the
                  sodium sulfate  solidifies  in  a cake,  add  a few
                  additions1  grams c* ac'd'^isd sodium sulfate and
                  again test by  swirling.   The 2 hour drying  time
                  is a minimum,  however, the extracts may  be  held
                  in contact with the  sodium sulfate overnight.

      7.3.1.7     Pour the dried  extract through a funnel  plugged
with acid  washed glass  wool,  and  collect  the  extract  in  the K-D
concentrator.   Use  a  glass rod to crush any caked  sodium  sulfate
during the transfer.   Rinse the Erlenmeyer flask and funnel  with 20
to 30 ml  of diethyl  ether to  complete  the  quantitative transfer.
Proceed to Sec.  7.4 for extract concentration.
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 7.4   Extract Concentration

       7,4.1 Add one or two clean boiling chips to the flask and attach a
 three ball  Snyder column.  Prewet the Snyder column by adding about 1 ml
 of diethyl  ether to the top of the column.   Place the K-D apparatus on a
 hot water bath  (15-2Q°C above the boiling point of the solvent) so that the
 concentrator tube is partially  immersed in  the  hot  water and the entire
 lower rounded surface of the flask is bathed with hot vapor.   Adjust the
.vertical  position of the apparatus and the water temperature, as required,
 to complete the  concentration  in 10-20  minutes.   At the  proper  rate of
 distillation the  balls  of  the  column  will  actively  chatter,   but  the
 chambers  will not flood.  When the apparent  volume of liquid reaches 1 ml,
 remove the K-D apparatus  from  the water bath and allow  it to  drain  and
 cool for  at least 10 minutes.

       7.4.2 Remove  the Snyder  column  and  rinse  the flask and  its  lower
 joints into the  concentrator tube with  1-2 ml  of  diethyl  ether.   The
 extract may  be further  concentrated  by using  either  the micro  Snyder
 column technique  (Sec. 7.4.3) or nitrogen blowdown technique (Sec.  7.4.4),


       7.4.3 Micro Snyder Column Technique

             7.4,3.1 •    Add another one or two clean boiling chips to the
       concentrator tube  and attach a two  ball  micro Snyder column.   Prewet
       the column  by adding about 0.5 ml of diethyl ether to the top of the
       column.   Place the  K-D  apparatus  in  a hot water bath  so that  the
       concentrator  tube is partially  immersed in the hot  water.   Adjust
       the vertical position of the apparatus and the water temperature, as
       required,  to  complete  the  concentration in 5-10 minutes.  At  the
       proper rate of distillation the balls  of the  column will actively
       chatter,  but the chambers  will not flood.  When the apparent volume
       of  liquid reaches 0.5 ml,  remove the  K-D  apparatus  from  the  water
       bath  and  allow it to drain and cool for at least 10 minutes.   Remove
       the Snyder column  and  rinse the flask and its lower  joints  with
       about 0.2 ml of  diethyl  ether  and add to the concentrator  tube.
       Proceed to  Sec.  7.4.5.

       7.4.4 Nitrogen  Blowdown Technique

             7.4.4.1      Place the concentrator tube  in  a  warm water bath
       (approximately  35°C)  and  evaporate   the   solvent  volume  to  the
       required  level  using  a  gentle  stream of  clean,  dry nitrogen
       (filtered through  a column of activated carbon).

             CAUJJON:     Do not use plasticized tubing between the carbon
                         trap and the  sample.

             7.4.4.2      The internal wall of the tube must be rinsed down
       several  times  with diethyl  ether  during   the  operation.    During
       evaporation,  the solvent  level  in the tube must be positioned to
       prevent  water from  condensing  into  the sample (i.e.,  the  solvent
       level  should  be below the  level of the  water  bath).  Under normal


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            operating conditions, the extract  should  not  be  allowed to become
            dry.  Proceed to Sec. 7.4.5.

            7.4.5 Dilute  the  extract with  1 ml  of   isooctane  and  0.5  ml  of
      methanol.    Dilute  to a  final  volume  of 4  ml  with  diethyl ether.   The
      sample is  now ready for  methylation with diazomethane.  If PFB derivation
      is being performed, dilute to 4 ml with acetone.

      7.5   Esterification - For diazomethane derivatization  proceed with Sec.
7.5.1.  For PFB  derivatization proceed with Sec.  7.5.2.

            7.5.1 Diazomethane Derivatization - Two methods may  be used for the
      generation  of  diazomethane:    the bubbler  method  {see Figure  1),  Sec.
      7.5.1.1, and the Diazald kit method,  Sec. 7.5.1.2.

            CAUTION:     Diazomethane  is a  carcinogen and can  explode  under
                        certain conditions.

            The   bubbler  method  is  suggested  when  small   batches   of  samples
      .(10-15)  require  esterification.   The  bubbler  method  works  well  with
      samples  that have low concentrations of herbicides (e.g., aqueous samples)
      and is  safer to use  than  the Diazald kit  procedure.   The Diazald  kit
      method is   good  for large quantities of  samples needing  esterification.
      The Diazald kit method is more effective than the bubbler method for soils
      or  samples  that may  contain  high concentrations  of  herbicides  (e.g.,
      samples  such  as  soils   that  may result  in yellow extracts  following
      hydrolysis  may  be  difficult  to  handle  by the bubbler  method).    The
      diazomethane derivatization (U.S.EPA,  1971}  procedures, described below,
      will react efficiently with all of the  chlorinated herbicides described in
      this method and should be  used  only by experienced  analysts,  due to  the
      potential  hazards  associated  with its use.   The following  precautions
      should be  taken:

            •      Use a safety screen.
            •      Use mechanical  pipetting  aides.
            •      Do  not heat  above  90°C -  EXPLOSION may result.
            «      Avoid grinding  surfaces, ground-glass joints, sleeve bearings,
                  and glass stirrers - EXPLOSION  may  result.
            •      Store away from alkali metals -  EXPLOSION may  result.
            *      Solutions of diazomethane decompose  rapidly  Irs  the presence of
                  solid materials such as  copper  powder,  calcium chloride,  and
                  boil ing chips.

                  7.5.1.1     Bubbler method  - Assemble the diazomethane bubbler
            (see Figure 1).

                        7.5.1.1.1   Add  5 ml  of diethyl ether to the first test
                  tube.   Add 1  mL of diethyl  ether, 1  ml of carbitol, 1,5 mL of
                  37% KOH, and 0.1-0.2  g  of Diazald  to the  second  test  tube.
                  Immediately  place  the exit tube into the  concentrator tube
                  containing  the   sample   extract.     Apply   nitrogen   flow
                  (10 mL/min)  to bubble diazomethane  through the extract  for
                  10  minutes or until the yellow color  of diazomethane persists.


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      The amount of Diazald used is sufficient  for esterification of
      approximately three sample extracts.  An additional 0.1-0.2 g
      of  Diazald  may be  added  (after  the  initial  Diazald  is
      consumed) to extend the generation of the diazomethane.  There
      is sufficient KOH present in the original solution to perform
      a maximum of approximately 20 minutes of total esterification.

            7.5.1.1.2   Remove the  concentrator  tube and  seal  it
      with a Neoprene or  Teflon stopper.  Store at room temperature
      in a hood for 20 minutes.

            7.5.1.1.3   Destroy any unreacted diazomethane by adding
      0.1-0.2 g of silicic  acid to the concentrator tube.  Allow to
      stand until  the evolution of nitrogen gas has stopped.  Adjust
      the  sample  volume  to  10.0  ml with hexane.   Stopper  the
      concentrator tube or  transfer 1 ml of sample  to  a EC vial, and
      store refrigerated  if further processing  will not be performed
      immediately.  Analyze by gas chromatography.

            7.5.1.1.4   Extracts should be stored  at 4°C away from
      light.  Preservation study results indicate that most analytes
      are stable for  28  days;  however,  it  is  recommended that the
      methylated extracts be analyzed  immediately  to minimize the
      trans-esterification and other potential reactions that may
      occur.

      7.5.1.2     Diazald kit method -  Instructions  for preparing
diazomethane are provided with the generator kit.

            7.5.1.2.1   Add 2 ml  of diazomethane  solution  and let
      the sample stand for 10 minutes with  occasional  swirling.  The
      yellow  color  of diazomethane should  be evident  and  should
      persist for this period.

            7.5.1.2.2   Rinse the inside wall of the ampule with 700
      fj.1  of   diethyl   ether.     Reduce   the  sample   volume  to
      approximately 2 ml to remove excess  diazomethane by allowing
      the solvent to  evaporate  spontaneously  at room temperature.
      Alternatively, 10 mg  of silicic acid can be  added to destroy
      the excess diazomethane.

            7.5.1.2.3   Dilute the sample  to  10.0 ml with  hexane.
      Analyze by gas  chromatography.   It   is  recommended  that the
      methylated extracts be analyzed  immediately  to minimize the
      trans-esterification  and other potential reactions that may
      occur,

7.5.2 PFB Method

      7.5.2.1     Add 30 pL of 10% K2C03 and 200 ^L of 3% PFBBr in
acetone.  Close the tube with  a  glass  stopper and  mix  on a vortex
mixer.  Heat the tube at 60°C  for 3  hours.
                      8151  -  16                         Revision 0
                                                    September 1994

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            7.5.2.2     Evaporate the solution  to  0.5 ml with  a gentle
      stream of nitrogen.   Add  2  ml of hexane and repeat evaporation just
      to dryness at ambient temperature.

            7.5.2.3     Redissolve the residue in 2 ml of toluene:hexane
      (1:6) for column cleanup.

            7.5.2.4     Top a  silica  column  (Bond Elut™  or equivalent)
      with 0.5 cm of anhydrous  sodium sulfate.   Prewet the column with 5
      ml hexane and let the  solvent  drain to the  top  of  the adsorbent.
      Quantitatively transfer  the reaction residue  to the  column  with
      several  rinsings of  the toluenerhexane  solution (total 2-3 ml).

            7.5.2.5     Elute the column with sufficient toluene:hexane to
      collect  8  ml of eluent.   Discard  this  fraction,  which  contains
      excess reagent.

            7.5.2.6     Elute  the  column with  toluene:hexane  (9:1)  to
      collect  8  ml of  eluent  containing  PFB  derivatives   in  a 10  ml
      volumetric flask.  Dilute to  10 ml with hexane.  Analyze by GC/ECD.

7.6   Gas chromatographic  conditions  (recommended):

      7.6,1 Narrow Bore

            7.6.1.1     Primary Column 1:

            Temperature program:     60"C to 300°C,  at 4°C/min
            Helium carrier flow:     30 cm/sec
            Injection  volume:        2 nl, splitless,  45 sec delay
            Injector temperature:   250°C
            Detector temperature:   320°C

            7.6.1.2     Primary Column la:

            Temperature program:     60°C to 300°C,  at 4°C/min
            Helium carrier flow:     30 cm/sec
            Injection  volume:        2 nl,  splitless,  45 sec delay
            Injector temperature:   250°C
            Detector temperature:   320QC

            7.6.1.3     Column  2:

            Temperature program:     60°C to 300°C,  at 4°C/min
            Helium carrier flow:     30 cm/sec
            Injection  volume:        2 /uL,  splitless,  45 sec delay
            Injector temperature:   250°C
            Detector temperature:   320°C
                            8151 - 17                         Revision 0
                                                          September 1994

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            7.6.1.4     Confirmation Column:

            Temperature program:    60°C to 3000C,  at  4°C/min
            Helium carrier flow:    30  cm/sec
            Injection volume:       2 ^L,  splitless,  45  sec delay
            Injector temperature:   250°C
            Detector temperature:   320°C

      7.6.2 Wide-bore

            7.6.2.1     Primary Column:

            Temperature program:    0.5 minute at 1500C,  150°C to 270°C at
                                    5°C/min
            Helium carrier flow:    7 mL/min
            Injection volume:       1 ^l

            7.6.2.2     Confirmatory Column:

            Temperature program:    0.5 minute at 150°C,  150°C to 270°C at
                                    5°C/mi n
            Helium carrier flow:    7 mL/min
            Injection volume:       1 nl

7.7   Calibration

      7.7.1 The  procedure  for  internal  or external  calibration  may be
used.  Refer to Method 8000 for a description of each of these procedures.
Use Table 1 for guidance on  selecting the lowest  point on the calibration
curve.

7.8   Gas chromatographic analysis

      7.8.1 Refer to Method  8000.   If  the  internal standard calibration
technique is used, add 10 fj,l of internal standard to the sample prior to
injection.

      7.8.2 Follow Method 8000 for instructions on  the analysis sequence,
appropriate dilutions,  establishing daily retention  time  windows,  and
identification criteria.  Include  a mid-concentration  standard after each
group of 10 samples in the analysis sequence.

      7.8.3 An example  of a  chromatogram for a methylated chlorophenoxy
herbicide is shown in Figure 2.   Tables 2  and 3 present retention times
for  the  target  analytes  after esterification,  using  the  diazomethane
derivatization   procedure    and   the   PFB   derivatization   procedure,
respectively.

      7,8.4 Record the sample volume injected and the resulting peak sizes
(in area units or peak heights).

      7.8.5 Using either the internal  or external  calibration procedure
(Method 8000),  determine the identity and quantity  of each component peak


                             8151  -  18                         Revision 0
                                                          September 1994

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       in  the  sample chromatogram which corresponds to  the  compounds used for
       calibration purposes.

            7,8.6 If calibration standards have been analyzed in the  same manner
       as  the samples  (e.g. have  undergone  hydrolysis and esterification), then
       the  calculation of concentration given  in Method 8000  should be used.
       However,  if  calibration is  performed  using standards made  from methyl
       ester compounds (compounds not esterified by application  of this method),
       then the  calculation of concentration  must include a  correction for the
       molecular weight of the methyl ester versus the acid herbicide.

            7.8.7 If  peak  detection and  identification are prevented  due  to
       interferences,  further  cleanup is  required.   Before using  any cleanup
       procedure, the  analyst  must  process  a series of  standards  through the
       procedure to  validate elation patterns and the  absence  of interferences
       from reagents.


8.0    QUALITY CONTROL

       8.1   Refer  to  Chapter One  for  specific  quality control  procedures.
Quality control to validate sample  extraction is covered in Method 3500 and in
the extraction method  utilized.   If  extract cleanup was  performed, follow the QC
in Method 3600 and in the specific  cleanup method.

       8,2   Procedures to check the GC system operation are found in Method 8000.

            8.2.1 Select a representative  spike concentration for each compound
       (acid or ester)  to be measured.  Using  stock standards, prepare a quality
       control  check  sample concentrate,  in  acetone,  that is  1000  times  more
       concentrated than the selected concentrations.  Use this quality control
       check sample concentrate to prepare quality control check samples.

            8.2.2 Tables 4 and 5 present bias and precision data for water and
       clay matrices, using the diazomethane derivatization procedure.  Table 6
       presents  relative  recovery data  generated using  the  PFB derivatization
       procedure and  water samples. Compare the results obtained  with the results
      given in these Tables to determine if the data quality is acceptable.

       8.3   Calculate surrogate  standard  recovery or e1!  standards, samples,
blanks,  and  spikes.    Determine if  the   recovery  is  within   limits  (limits
established by performing QC procedures outlined in Method 8000),

            8.3.1 If recovery  is  not within limits, the following procedures are
       required:

                  8.3.1.1     Check  to   be  sure   there are   no   errors  in
            calculations,  surrogate solutions  and internal  standards.   Also,
            check instrument performance.

                  8.3.1.2     Recalculate the data and/or reanalyze the extract
            if any of the above checks reveal a problem.
                                   8151  -  19                        Revision 0
                                                                September 1994

-------
                  8.3.1.3     Reextract and reanalyze  the  sample if none of the
            above are a problem or flag the data as "estimated concentration."

      8.4   GC/MS confirmation

            8.4.1 GC/MS techniques  should  be judiciously employed  to support
      qualitative identifications made with this method.  Refer to Method 8270
      for the appropriate GC/MS operating conditions and analysis procedures.

            8.4.2 When  available,   chemical  ionization  mass  spectra may  be
      employed to aid the qualitative identification process.

            8.4.3 Should  these MS  procedures  fail   to provide  satisfactory
      results, additional  steps may  be taken before reanalysis.  These  steps may
      include the use of alternate packed or capillary GC columns or additional
      cleanup.


9.0   METHOD PERFORMANCE

      9.1   In single laboratory studies using  organic-free  reagent  water and
clay/still bottom samples, the mean  recoveries presented in Tables 4 and 5 were
obtained for diazomethane derivatization. The standard deviations of the percent
recoveries of these measurements  are also in Tables 4  and 5.

      9.2   Table 6  presents relative recoveries of the target analytes obtained
using the PFB derivatization procedure with spiked water samples.


10.0  REFERENCES

1.    Fed. Reg.  1971, 38,  No.  75,  Pt. II.

2.    Goerlitz,  D. G.; Lamar, W.L.,  "Determination of Phenoxy Acid Herbicides in
      Water by Electron Capture and Microcoulometric Gas  Chromatography,".  U.S.
      Geol. Survey Water Supply Paper 1967, 1817-C.

3.    Burke, J.  A.  "Gas  Chromatography  for  Pesticide  Residue Analysis;  Some
      Practical  Aspects, J. Assoc.  Off Anal.  Chem. 1965, 48,  1037.

4.    "Extraction and Cleanup  Procedures for the Determination of Phenoxy Acid
      Herbicides  in Sediment";  U.S.   Environmental  Protection Agency.    EPA
      Toxicant and Analysis Center:  Bay St. Louis, MS. 1972.

5.    Shore, F.L.;  Amick,  E.N.; Pan,  S.  T.  "Single  Laboratory Validation of EPA
      Method  8151  for  the Analysis  of Chlorinated  Herbicides  in  Hazardous
      Waste";  U.S.  Environmental  Protection Agency.   Environmental  Monitoring
      Systems Laboratory.  Office of Research  and  Development, Las  Vegas, NV,
      1985; EPA-60014-85-060.

6.    Method  515.1,  "Determination of  Chlorinated  Acids   in  Water by  Gas
      Chromatography with  an  Electron  Capture Detector",  Revision  4.0,  USEPA,
      Office  of  Research  and Development,  Environmental  Monitoring Systems
      Laboratory, Cincinnati,  Ohio.

                                  8151  - 20                         Revision 0
                                                                September 1994

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7.    Method 1618,  "Organo-halide and Organo-phosphorus Pesticides and Phenoxy-
      acid  Herbicides  by Wide Bore  Capillary Column Gas  Chromatography with
      Selective  Detectors",  Revision  A,  July  1989,  USEPA,  Office  of Water
      Regulations and Standards,  Washington, DC.

8.    Gurka, D.F, Shore, F.L., Pan, S-T,  "Single  Laboratory Validation of EPA
      Method 8150  for  Determination  of  Chlorinated  Herbicides  in  Hazardous
      Waste", JAOAC, 69, 970, 1986.
                                  8151 - 21                         Revision 0
                                                                September 1994

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                                 Figure  1
                         DIAZOMETHANE GENERATOR
    nitrogen
rubber  ttoppvr
                        o
                                                                  glass tubing
                                                                                  \
                     tub* 1
tube 2
                                   8151  - 22
                        Revision 0
                    September 1994

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                                   Figure 2
              CHROHATOGRAM OF METHYL  ESTERS OF CHLOROPHENOXYACIDS
too o-i
        A

       271
     ^J
               393
317
       443
ulr
   200
   3;20
    400
    6:40
J
1O4B
C
813 E

B













S43
|^ 633 893 Al

81
*













s

Ifi

G
864











,
1










,

1











I







A - Daiapon. mwthyl *M*r
B = Dicamba. methyl attar
C = MCPP. methyl attir
D - MCPA. methyl mt*r
E - Oichlorprop. rrvethyl a«taf
F : 2.4. -D methyl ••Mr
G - Silve». niaiiiyl estar
H - 2.4.6 T. nMthy)e»ter
1 - 2.4-Db. malhyl a»ter
J - Dino»«b. meMiyl «th«r


80*0 ' 800 1OOO 12OO
10:00 13:20 16:40 2P:OO
                                 Scan Tim*
                                   8151 - 23
                                                        Revision 0
                                                    September 1994

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                                    TABLE 1
               ESTIMATED METHOD DETECTION LIMITS FOR METHOD 8151,
                          DIAZOMETHANE DERIVATIZAT10N
Aqueous Samples




Analyte
Acifluorfen
Bentazon
Chloramben
2,4-D
Dalapon
2,4-DB
DCPA diacid"
Dicamba
3,5-Dichlorobenzoic acid
Dichloroprop
Dinoseb
5-Hydroxydicamba
MCPP
MCPA
4-Nitrophenol
Pentachl orophenol
Picloram
2,4S5-T
2,4,5-TP
GC/ECD
Estimated
Detection
Limit8
(MgA)
0.096
0.2
0.093
0.2
1.3
0.8
0.02
0.081
0.061
0.26
0.19
0.04
0.09d
0.056d
0.13
0.076
0.14
0.08
0.075
Soil Samples
SC/ECD
Estimated
Detection
Limit"
(Mg/kg)


4.0
0.11
0.12



0.38



66
43
0.34
0.16


0.28
GC/MS
Estimated
Identification
Limitc
(ng}


1.7
1.25
0.5



0.65



0.43
0.3
0.44
1.3


4.5
   EDL = estimated detection limit;  defined  as  either the MDL  (40 CFR Part 136,
   Appendix B,  Revision 1.11  ),  or  a  concentration of  analyte  in  a  sample
   yielding  a  peak  in the   final   extract   with  signal-to-noise  ratio  of
   approximately 5, whichever value is higher.
Detection
sampleSj
             limits determined from  standard  solutions  corrected  back to 50 g
             extracted  and  concentrated  to  1C  ml,   with  5  y.L  injected.
Chromatography  using   narrow
5% phenyl/95% methyl  si li cone.
                                bore  capillary   column,   0.25
                                                                         film,
   The minimum amount of analyte to give  a  Finnigan  INCOS  FIT value of 800 as
   the methyl derivative vs.  the spectrum  obtained from 50 ng of the respective
   free acid herbicide.
   40 CFR Part 136, Appendix  B  (49  FR 43234).
   capillary column.
                                             Chromatography using wide-bore
e  DCPA monoacid and diacid metabolites  included  in  method  scope;  DCPA diacid
   metabolite used for validation studies.  DCPA is a dimethyl  ester.
                                  8151  -  24
                                                                 Revision 0
                                                             September 1994

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                                  TABLE  2
RETENTION TIMES (MINUTES) OF METHYL DERIVATIVES OF CHLORINATED HERBICIDES
 Megabore Columns

Narrow
Primary'
Analyte Column
Dalapon
3,5-Dichlorobenzoic acid
4-Nitrophenol
DCAA (surrogate)
Dicamba
Dichloroprop
2,4-D
DBOB (internal std.)
Pentachl orophenol
Chloramben
2,4,5-TP
5-Hydroxydicamba
2,4,5-T
2,4-DB
Dinoseb
Bentazon
Picloram
DCPA diacidc
Acifluorfen
MCPP
MCPA
3.4
18.6
18.6
22.0
22.1
25.0
25.5
27.5
28.3
29.7
29.7
30.0
30.5
32.2
32.4
33.3
34.4
35.8
41.5


Bore Columns
Wide-bore Columns
Confirmation8 Primary"
Column Column
4.7
17.7
20.5
14.9
22.6
25.6
27.0
27.6
27.0
32.8
29.5
30.7
30.9
32.2
34.1
34.6
37.5
37.8
42.8






4.39
5.15
5.85



6.97

7.92
8.74





4.24
4.74
Confirmation13
Column




4.39
5.46
6.05



7.37

8.20
9.02





4.55
4.94
 Primary Column:
 Confirmation  Column;
          Temperature  program:
          Helium  carrier flow:
          Injection  volume:
          Injector temperature:
          Detector temperature:
 Primary Column:
 Confirmatory  Column:
          Temperature  program:

          Helium  carrier flow:
          Injection  volume:
5% phenyl/95% methyl  silicone
14% cyanopropyl phenyl  silicone
60°C  to  300°C,  at 4°C/min
30 cm/sec
2 juL, splitless, 45 sec delay
250°C
320°C
DB-608
14% cyanopropyl phenyl  silicone
0.5 minute at 150°C,
150°C to 270°C,  at 5°C/min
7 mL/min
1 uL
 DCPA monoacid and diacid metabolites included in method scope;  DCPA diacid
 metabolite used for validation studies.   DCPA is a dimethyl  ester.
                                8151  - 25
                                Revision 0
                            September  1994

-------
                                    TABLE  3
    RETENTION TIMES (MINUTES) OF PFB DERIVATIVES OF CHLORINATED HERBICIDES
Herbicide
                           Gas Chromatographic Column
Thin-film DB-5a
SP-225Qe
Thick-film DB-5C
Dalapon
MCPP
Dicamba
MCPA
Dichloroprop
2,4-D
Si 1 vex
2,4,5-T
Dinoseb
2,4-DB
10.41
18.22
18.73
18.88
19.10
19.84
21.00
22.03
22.11
23.85
12.94
22.30
23.57
23.95
24.10
26.33
27.90
31.45
28.93
35.61
13.54
22.98
23.94
24.18
24.70
26.20
29.02
31.36
31.57
35.97
   DB-5 capillary column,  0.25 pm film thickness, 0.25 mm ID x 30 m long.
   Column temperature,  programmed:  70°C  for  1 minute,  program  10°C/min. to
   240°C,  hold for  17 minutes.

   SP-2550 capillary column,  0.25 urn film thickness,  0.25 mm ID x 30 m long.
   Column temperature,  programmed:  70°C  for  1 minute,  program  10°C/min. to
   240°C,  hold for  10 minutes.

   DB-5 capillary column,  1.0 /zm film thickness, 0.32 mm ID x 30 m long.
   Column temperature,  programmed:  70°C  for  1 minute,  program  10°C/min. to
   240°C,  hold for  10 minutes.
                                  8151 - 26
                                                    Revision 0
                                                September 1994

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                                 TABLE 4
                 ACCURACY AND  PRECISION FOR METHOD 8151
      DIAZOMETHANE DERIVATIZATION,  ORGANIC-FREE REAGENT WATER MATRIX
Analyte
Acifluorfen
Bentazon
Chloramben
2,4-D
Dalapon
2,4-DB
DCPA diacidb
Dicamba
3,5-Dichlorobenzoic acid
Diehloroprop
Dinoseb
5-Hydroxydicamba
4-Nitrophenol
Pentachl orophenol
Picloram
2,4,5-TP
2,4,5~T
Spike
Concentration
(Mi/L)
0.2
1
0.4
1
10
4
0.2
0.4
0.6
2
0.4
0.2
1
0.04
0.6
0.4
0.2
Mean3 Standard
Percent Deviation of
Recovery Percent Recovery
121
120
111
131
100
87
74
135
102
107
42
103
131
130
91
117
134
15.7
16.8
14.4
27.5
20.0
13.1
9.7
32.4
16.3
20.3
14.3
16.5
23.6
31.2
15.5
16.4
30.8
a  Mean percent recovery calculated from 7-8 determinations of spiked
   organic-free reagent water.

b  DCPA monoacid and diacid metabolites included in method scope; DCPA
   diacid metabolite used for validation studies.   DCPA is a dimethyl ester.
                                8151  - 27
    Revision 0
September 1994

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                                  TABLE 5
                  ACCURACY AND PRECISION FOR METHOD 8151
                 DIAZOHETHANE DERIVATIZATION, CLAY MATRIX
Analyte
     Mean
Percent Recovery8
   Linear
Concentration
   Rangefa
   (ng/g)
      Percent
     Relative
Standard Deviation0
      (n=ZO)
Dicamba
MCPP
MCPA
Dichloroprop
2,4-D
2,4,5-TP
2,4,5-T
2,4-DB
Dinoseb
95.7
98,3
96.9
97.3
84.3
94.5
83.1
90.7
93.7
0.52
620
620
1.5
1.2
0.42
0.42
4.0
0.82
104
- 61,800
- 61,200
- 3,000
- 2,440
- 828
- 828
- 8,060
- 1,620
7.5
3.4
5.3
5.0
5.3
5.7
7.3
7.6
8.7
   Mean percent recovery calculated from 10 determinations of spiked clay
   and clay/still  bottom-samples over the linear concentration range.

   Linear concentration range was determined using standard solutions and
   corrected to 50 g solid samples.

   Percent relative standard deviation was calculated using standard
   solutions,  10 samples high in the linear concentration range,  and 10
   samples low in  the range.
                                8151  - 28
                                               Revision 0
                                           September 1994

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                                            TABLE 6
                     RELATIVF. RECOVERIES OF PFB DERIVATIVES OF HERBICIDES3
           Standard
         Concentration
Relative recoveries,  %
Analyte
MCPP
Dicamba
MCPA
Dichloroprop
2,4-D
Silvex
2,4,5-T
2,4-DB
Mean
mg/L
5.
3.
10.
6.
9.
10.
12.
20.

1
9
1
0
8
4
8
1

1
95.6
91.4
89.6
88.4
55.6
95.3
78.6
99.8
86.8
2
88.8
99.2
79.7
80.3
90.3
85.8
65.6
96.3
85.7
3
97.1
100
87.0
89.5
100
91.5
69.2
100
91.8
4
100
92.7
100
100
65.9
100
100
88.4
93.4
5
95.5
84.0
89.5
85.2
58.3
91.3
81.6
97.1
85.3
6
97.2
93.0
84.9
87.9
61.6
95.0
90.1
92.4
89.0
7
98.1
91.1
92.3
84.5
60.8
91.1
84.3
91.6
87.1
8
98.2
90.1
98.6
90.5
67.6
96.0
98.5
91.6
91.4
Mean
96.3
92.7
90.2
88.3
70.0
93.3
83.5
95.0

Percent recovery determinations made using eight spiked water samples.
                                           8151  -  29
                                               Revision 0
                                           September 1994

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                                          METHOD 8151
CHLORINATED  HERBICIDES  BY GC USING  METHYLATION OR  PENTAFLUOROBENZYLATION
                     DERIVATIZATION:  CAPILLARY  COLUMN  TECHNIQUE

                 Extraction/Hydrolysis  of Waste  and Soil  Samples
              NO
1

Concentrate and/or
dilute taaad on
whether nanvswaton
is by diazomalhane
or PFB
                                                  700008
                                                sarnpiacon
                                                 tain a high
                                                  ooneof
                                                  waste?
                        7.2-1.8.1 AddKQHand
                        water. Reflux for 2 hrs.
                        AJtawtDCOd
                        7,2.1.8.2 Transfer**
                        hydnMyzed soution n a
                        sap funnel and extract 3
                        Smes wrtti MeCI.
                        Discard BxtracB
                       7.2.1,8.3 Acidity and
                       attract 3 times with
                       dialhyl after. Combine
                       and dry ma extracts 2 hn
                                        7,2.1.9.1  Extract 3 times
                                        twthKOH. Discard tw
                                        MeCt.
                                        7.2.1.9.2 Aodifyand
                                        extract 3 Smes with
                                        dtetJiyi 6*»(.  Combine
                                        and dry the attracts 2 hrs.
            7,2.1.1 Wetghsampte
            ami add ID boaKar:
            add acid and spike;
            7,2.1.2 Optimize
           ultrasonic solid extrac-
           tion tar each matrix
           7.2.1.3 Add MeCI/
           acetone ID sample 4
           extracts min.:M
           same & dacant extract
           7.2.1.445 UWa.
           soncalty flxtract samptoi
           2 mots times with MeCI
                                                                   7.2.1.5 Combine organic
                                                                   extracts, centntuge, and
                                                                   fll»f9«raet Dry to
                                                                    2 hrs.
           7.2.1.S  Concentrate
           exoact to about 5 ml
           with Snyder column.
                                                                YES
                   If hydrolysis is not
                   required, proceed to Sactkm
                   7.4.4, Nitrogen Slowdown.
    7.2.1.7
 Does analysis
include hertmada
    estafs?
                                            8151  -  30
                                   Revision  0
                             September  1994

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                                         METHOD 8151
                                         (continued)

Extraction/Hydrolysis  of  Aqueous  Samples  and  Extract  Concentration
            7.3.1.1  MsasurelLof
            sample and transfer to
                    tunnel
             7,3.1.2 Add 2503 NaC:
             to sample and snake
             to dissolve
    7.3.1.4 Add 12Nsulfune
    acid and snake. Add
    until pH < 2
    7.3.1 5 Adddte»y<
    Mhar ta sampto and
    extract Sam both
    phases
                                                                                Employ mechanical techniques
                                                                                to compNMB phase separation
                                                                                («.g, stirring, filtration trough
                                                                                glass wool, eentrtugatlon, or
                                                                                otfier physical methods).
                                                                                Save both phases.
           7.3.t.3.1 AddSNNaOHto
           sample and shate. Add
           until pH> 12.  Lai stand
           1 hr.
            7.3.1.3.2 AddMeQand
            extract by shaking tor
            Zrrin, Discard MeCl.
7.3.1.6 Return aqueous phase
to separaUry lunnti arid repeat
exlractKxi 2 mats fimes. contxne
axoacts, and altow octract tc
remain in contact with sodium
suKate tor 2 hrs.
                                                                                   7.3.1.7 Pouraxtract
                                                                                   through glass wool and
                                                                                   proceed to Section 7 4 1
                                        Employ mechanical tBctiraques
                                        to comptota phase separation
                                        (e.g. stinlng, filtration throo^i
                                        glass wool, »ntnfugatlon. or
                                        otfwr physical methods).
                                        Discard MaCI.
                                   7.4.1  Ptecn K-
                                   in water bath, concentrate
                                   and cool
                                   7.4.2 • 7.4.4 Complete
                                   concentration writft fftcro-
                                   Snydef column or rwoger,
                                   blow down.
              7.3.1.3.3 Repeat
              extraction twice more.
              Discard MaCI.
                                   7.4,5 Dilute extract
                                   wrth t mL isooctane and
                                   0.5 mi. meffanra
                                           8151  -  31
                                              Revision  0
                                        September   1994

-------
                                    METHOD 8151
                                    (continued)

                            Extract  Derivatization
 7.4.5 Dituw extract
 to 4 tnLMiti acetone
7.5.2.1  Add potassium
carbonate and PFBBr
Ctoss ube, mix ft heat
                                  7.5.1.1  AssamMettw
                                 diazometiane buboter
                                      (figur» 1)
                                               OiazaU
 75.22 Evaporate With
 nitrogen to O.S ml. Add
 2 ml twxane and repeat
 752.3 ftedaaahe mt
 residue in 2 mL totuena:
 nexane (1 ; 6)
7 5.1 1 1 AddSmLto Isttsst
tube. Add 1 mL dieoiyi ether,
1 mL carftitol, 1 .B mL of 37% KOH
and 01  02 g DiazakJ to the
did lube. Bubble wMt nitrogen
tor 10 min or until yellow persists
7.S.Z4 Load sodium
MMat*/ silica dMflup
column wrtfi residua.
    7.S.1.1.2 Remove con-
    centrator tube and seal
    It Store at rocrn wnp,

7.5.25 Buneofymn
wrth enougn tduena :
hexane ID catect 8 ml
aluant
                                                                        7.5.1.2.t  Add2mL
                                                                        diaromethanfi soHilicfi.
                                                                        Let stand for 1D mm
                                                                        andswin
75.1 1 3 Addsifacaodto
concentrator tube and let stand
until nitrogen evolution has
stopped.  Adjust sample volume
ID 10 mL win nexane. Stopper.
immediate analysis is recommended
                                       7 5.1 2.2 Rinse ampule with
                                       diettiyl aAier and evaporate
                                       ID 2 rnL ID remove diazometfiana
                                       Altamsttveiy, silicic acid
                                       may fie added.
1
7.5,2.6 Discard
and continue ttul
enough tgtuene :
to colMct 8 mL m
Transfer to a 10
(task and dilute IE
with nexane
i
1st fraction
ion with
haxane (t : 9)
omeiuant
TIL voJunmric
i the mark



1
7,5.1.1.5 itnaoessary
store at 4 C in tha dark
tor a max of 28 days.
i
7.6.1 & ?.6.2 Set GC
GOn

f
7.5.1.2.3 Dilute sample
to 10 ml with hexane



                                      8151  -  32
                                                           Revision  0
                                                     September   1994

-------
                           METHOD  8151
                           (continued)

             Analysis  by  Gas  Chromatography
    7.7 Internal of extsmaJ
    calibration may ba used
    (See method 8000).
                                7.8.1 Add 10 uL internal
                                standard to tie sample
                                prior to tnjecflon.
7.8.2 See method 8000 tar
analysis sequence, appropriate
dilutions, establishing daily
retention ttme windows, and
identification criteria. Chock
  734 Racordvolume
  injected and (he resulting
  peak sizes.
CsjculatB me comecoor,
tef motecuiar waoTit of
metiyl »jtBf vs hertuctd*
                                     ! 7.8.S Calculate con-
                                      cen
-------

-------
4.3  DETERMINATION OF  ORGANIC  ANALYTES

     4.3.2 GAS CHROMATOGRAPHIC/MASS  SPECTROMETRIC METHODS

         The following methods are included in this section:
         Method 8240B:

         Method 8250A:

         Method 8260A:


         Method 8270B:


         Method 8280:

               Appendix A:
               Appendix B:

         Method 8290;
Volatile    Organic    Compounds    by     Gas
Chromatography/Mass Spectrometry (GC/MS)
Semi volatile    Organic    Compounds    by    Gas
Chromatography/Hass Spectrometry (GC/MS)
Volatile    Organic    Compounds    by     Gas
Chronratography/Mass    Spectrometry   (GC/MS):
Capillary Column Technique
Semi volatile    Organic    Compounds    by    Gas
Chromatography/Mass    Spectrometry   (GC/MS):
Capillary Column Technique
The Analysis of Polychlorinated Dibenzo-p-Dioxins
and Polychlorinated Dibenzofurans
      Signal-to-Noise  Determination  Methods
      Recommended Safety  and Handling  Procedures
      for PCDDs/PCDFs
Polychlorinated    Dibenzodioxins   (PCDDs)    and
Polychlorinated   Dibenzofurans  (PCDFs)  by High-
Resolution   Gas   Chromatography/High-Resolution
Mass Spectrometry (HRGC/HRMS)
                                 FOUR  - 11
                                      Revision 2
                                  September 1994

-------

-------
                                 METHOD 8240B

  VOLATILE ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROHETRY (GC/MS1
1.0   SCOPE AND APPLICATION

      1.1   Method 8240  is  used  to determine volatile organic  compounds in a
variety of solid waste matrices.   This method  is applicable to nearly all types
of samples, regardless of water content, including ground water,
caustic  liquors,  acid liquors,  waste solvents,  oily  wastes
fibrous  wastes,  polymeric   emulsions,   filter  cakes,  spent
catalysts, soils, and sediments.   The following compounds can
this method:
                         aqueous sludges,
                           mousses,  tars,
                          carbons,  spent
                         be determined by
Analyte
                                                  Appropriate Technique
CAS No.b   Purge-and-Trap
Direct
Injection
Acetone
Acetonitrile
Acrolein (Propenal)
Acrylonitrile
Ally! alcohol
Ally! chloride
Benzene
Benzyl chloride
Bromoacetone
Bromochloromethane (I.S.)
Bromodi chl oromethane
4-Bromof 1 uorobenzene ( surr . )
Bromoform
Bromomethane
2-Butanone (MEK)
Carbon disulfide
Carbon tetrachloride
Chloral hydrate
Chlorobenzene
Chlorobenzene-d5 (I.S.)
Chlorodibromomethane
Chloroethane
2-Chloroethanol
bis-(2-Chloroethyl) sulfide
2-Chloroethyl vinyl ether
Chloroform
Chl oromethane
Chloroprene
3-Chloropropionitrile
l,2-Dibromo-3-chloropropane
1,2-Dibromoethane
67-64-1
75-05-8
107-02-8
107-13-1
107-18-6
107-05-1
71-43-2
100-44-7
598-31-2
74-97-5
75-27-4
460-00-4
75-25-2
74-83-9
78-93-3
75-15-0
56-23-5
302-17-0
108-90-7
3114-55-4
, 124-48-1
75-00-3
107-07-3
505-60-2
110-75-8
67-66-3
74-87-3
126-99-8
542-76-7
96-12-8
106-93-4
PP
PP
PP
PP
pp
a
a
PP
PP
a
a
a
a
a
PP
PP
a
PP
a
a
a
a
PP
PP
a
a
a
a
ND
PP
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
pc
pc
a
a
                                  8240B  -  1
                               Revision 2
                           September 1994

-------
                Appropriate  Technique
Analyte
Dibromomethane
l,4-Dichloro-2-butene
Di chl orodi f 1 uoromethane
1 , 1 -Di chl oroethane
1,2-Dichloroethane
l,2-Dichloroethane-d4(surr.)
1 , 1 -Di chl oroethene
trans- 1 ,2-Di chl oroethene
1 , 2-Di chl oropropane
1,3-Di chl oro-2- propane!
cis-1 ,3-Dichloropropene
trans-1 ,3-Dichl oropropene
1,2,3,4-Diepoxybutane
1,4-Difluorobenzene (I.S.)
1,4-Dioxane
Epichlorohydrin
Ethanol
Ethyl benzene
Ethyl ene oxide
Ethyl methacrylate
2-Hexanone
2-Hydroxypropionitrile
lodomethane
Isobutyl alcohol
Malononitrile
Methacrylonitrile
Methyl ene chloride
Methyl iodide
Methyl methacrylate
4-Methyl -2-pentanone
Pentachl oroethane
2-Picoline
Propargyl alcohol
B-Propiol actone
Propionitrile
n-Propylamine
Pyridine
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1, 2, 2-Tetrachl oroethane
Tetrachloroethene
Toluene
Toluene-d8 (surr.)
1,1,1-Tri chl oroethane
1,1, 2-Tri chl oroethane
Tri chl oroethene
Tri chl orof 1 uoromethane
CAS No.b
74-95-3
764-41-0
75-71-8
75-34-3
107-06-2
107-06-2
75-35-4
156-60-5
78-87-5
96-23-1
10061-01-5
10061-02-6
1464-53-5
540-36-3
123-91-1
106-89-8
64-17-5
100-41-4
75-21-8
97-63-2
591-78-6
78-97-7
74-88-4
78-83-1
109-77-3
126-98-7
75-09-2
74-88-4
80-62-6
108-10-1
76-01-7
109-06-8
107-19-7
57-57-8
107-12-0
107-10-8
110-86-1
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
2037-26-5
71-55-6
79-00-5
79-01-6
75-69-4
Purge-and-Trap
a
PP
a
a
a
a
a
a
a
PP
a
a
a
a
PP
i
i
a
PP
a
PP
ND
a
PP
PP
PP
a
a
a
PP
i
PP
PP
PP
PP
a
i
a
a
a
a
a
a
a
a
a
a
Direct
Injection
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
pc
a
a
a
a
a
a
a
a
pc
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
8240B - 2
    Revision 2
September 1994

-------
                                                  Appropriate Technique
                                                                  Direct
Analyte                              CAS No.b   Purge-and-Trap    Injection
1,2,3-Trichloropropane
Vinyl acetate
Vinyl chloride
Xylene (Total)
96-18-4
108-05-4
75-01-4
1330-20-7
a
a
a
a
a
a
a
a
a     Adequate response by this technique.
b     Chemical Abstract Services Registry Number.
pp    Poor purging efficiency resulting in high EQLs.
i     Inappropriate technique for this analyte.
pc    Poor chromatographic behavior.
surr  Surrogate
I.S.  Internal Standard
ND    Not determined

      1.2   Method  8240  can be  used  to  quantitate  most  volatile  organic
compounds that have boiling points below 200°C and that are insoluble or slightly
soluble  in water.   Volatile water-soluble  compounds can  be included  in  this
analytical technique.   However,  for the more  soluble  compounds,  quantisation
limits are approximately ten times  higher  because  of poor  purging efficiency.
The method is  also  limited to compounds that  elute  as sharp peaks  from  a GC
column packed  with  graphitized  carbon lightly  coated  with  a carbowax.   Such
compounds  include  low molecular  weight  halogenated hydrocarbons,  aromatics,
ketones,  nitriles,  acetates,  acrylates, ethers, and sulfides.   See Table 1 for
a list of compounds,  retention times,  and  their characteristic  ions  that  have
been evaluated on a purge-and-trap GC/MS system.

      1.3   The  estimated quantitation  limit  (EQL)  of  Method  8240  for  an
individual compound  is  approximately 5 M9/kg   (wet  weight)  for soil/sediment
samples,  0.5 mg/kg  (wet weight)  for wastes,  and 5 M9/L for  ground water  (see
Table 2).  EQLs will  be proportionately higher for sample  extracts and  samples
that require dilution  or reduced sample size to avoid saturation of the detector.

      1.4   This method is restricted  to use by,  or  under  the  supervision of,
analysts   experienced  in  the   use  of   purge-and-trap   systems  and   gas
chromatograph/mass  spectrometers,  and skilled  in  the  interpretation  of  mass
spectra and their use as a quantitative tool.

      1.5.  To  increase purging efficiencies  of acrylonitrile and  acrolein,
refer to  Methods 5030 and 8030 for proper purge-and-trap conditions.


2.0  SUMMARY OF METHOD

      2.1   The volatile compounds are introduced  into  the gas chromatograph by
the purge-and-trap method or by direct injection (in limited applications}.   The


                                  82408 - 3                         Revision 2
                                                                September  1994

-------
components  are  separated  via  the gas chromatograph and detected  using a mass
spectrometer,  which  is  used  to provide  both  qualitative and  quantitative
information.    The  chromatographic  conditions,  as  well  as  typical  mass
spectrometer operating parameters, are given.

      2.2    If  the  above  sample  introduction techniques  are not applicable, a
portion of the sample is dispersed in methane!  to dissolve the volatile organic
constituents. A portion of the methanolic solution is combined with organic-free
reagent water in a specially designed purging chamber.  It is then analyzed by
purge-and-trap GC/MS following the normal  water method.

      2.3   The purge-and-trap process  -  An inert gas is  bubbled  through the
solution at  ambient  temperature,  and the volatile  components  are  efficiently
transferred from  the aqueous  phase to  the  vapor phase.   The  vapor  is swept
through  a  sorbent column  where  the volatile  components  are trapped.   After
purging is  completed, the sorbent  column  is heated and backflushed with  inert gas
to  desorb  the  components onto  a  gas  chromatographic  column.    The  gas
chromatographic column is heated to elute the components, which are detected with
a mass spectrometer.


3.0   INTERFERENCES

      3.1   Interferences  purged or coextracted  from the  samples will  vary
considerably from source  to  source, depending upon the  particular  sample or
extract being tested.   The analytical  system, however,  should be  checked to
ensure freedom from  interferences, under the analysis  conditions,  by analyzing
method blanks.

      3.2   Samples  can  be  contaminated  by diffusion  of volatile  organics
(particularly methylene chloride and fluorocarbons)  through the septum  seal into
the sample  during shipment and  storage.  A trip blank, prepared from organic-free
reagent water and  carried through  the sampling  and handling protocol, can serve
as a check on such contamination.

      3.3   Cross contamination can occur whenever high-concentration and low-
concentration  samples are analyzed  sequentially.    Whenever  an  unusually
concentrated sample  is analyzed,  it  should  be followed  by  the  analysis  of
organic-free reagent water  to check for cross  contamination.  The purge-and-trap
system may require extensive  bake-out and cleaning  after  a high-concentration
sample.

      3.4   The  laboratory where  volatile   analysis  is   performed should  be
completely free of solvents.

      3.5   Impurities in the purge gas  and  from organic  compounds out-gassing
from the plumbing ahead of the trap account  for the majority of contamination
problems.   The analytical   system  must  be  demonstrated  to  be  free  from
contamination under  the conditions of the analysis  by running  calibration and
reagent blanks.  The  use of non-TFE plastic coating,  non-TFE thread sealants, or
flow controllers with rubber components in  the purging  device should be avoided.
                                  8240B - 4                         Revision 2
                                                                September 1994

-------
4.0   APPARATUS AND MATERIALS

      4,1    Microsyringes - 10 jiL, 25 jxL,  100 ^L, 250 ^L, 500 jxL, and 1,000 /it.
These syringes should be equipped with a 20 gauge (0.006 in.  ID) needle having
a length sufficient to extend from the sample inlet to within 1 cm of the glass
frit in the  purging device.  The needle length  will  depend upon the dimensions
of the purging device employed.

      4.2    Syringe valve - Two-way,  with  Luer  ends (three each), if applicable
to the purging device.

      4.3    Syringe - 5 ml, gas-tight with shutoff valve.

      4.4    Balances  - Analytical, 0.0001 g, and top-loading, 0.1 g.

      4.5    Glass scintillation vials -  20 ml, with screw caps and Teflon liners
or glass culture tubes with a screw cap and Teflon  liner.

      4.6    Volumetric flasks,  Class A -  10 ml and 100  ml,  with  ground-glass
stoppers.

      4.7    Vials - 2 ml, for GC autosampler.

      4.8    Spatula - Stainless steel.

      4.9    Disposable pipets - Pasteur.

      4.10   Heater or heated  oil  bath - Should be capable of  maintaining the
purging chamber to within 1°C  over  the temperature range  of ambient  to  100°C.

      4.11   Purge-and-trap device - The purge-and-trap device consists of three
separate pieces of equipment:  the  sample  purger,  the trap,  and the desorber.
Several  complete devices  are commercially  available.

             4.11.1     The  recommended purging chamber  is designed  to accept
      5 ml  samples  with  a  water  column  at least  3  cm deep.   The  gaseous
      headspace between the water column and the trap  must have a  total volume
      of less than 15 ml.  The purge  gas must pass through the  water column as
      finely divided  bubbles with  a  diameter of less than 3  mm  at  the  origin.
      The purge gas must be introduced no more than 5 mm from  the  base of the
      water  column.   The  sample purger,  illustrated  in  Figure  1,  meets  these
      design criteria. Alternate sample purge devices may be utilized, provided
      equivalent performance is demonstrated.

             4.11.2     The  trap must be at least 25 cm long and have an inside
      diameter of at least 0.105 in.   Starting  from the inlet,  the  trap should
      contain the following  amounts of adsorbents:  1/3 of 2,6-diphenylene oxide
      polymer,  1/3  of  silica  gel,   and  1/3  of coconut charcoal.    It  is
      recommended that 1.0 cm of methyl silicone coated packing be  inserted at
      the inlet to extend the  life of the  trap (see  Figure 2).  If  it is not
      necessary to analyze  for  dichlorodifluoromethane  or other fluorocarbons
      of similar  volatility,  the charcoal  can  be  eliminated and  the  polymer
      increased to fill  2/3 of the trap.  If only compounds boiling above 35°C


                                   8240B - 5                         Revision 2
                                                                September 1994

-------
are to  be  analyzed,  both  the silica gel and  charcoal  can  be eliminated
and the polymer  increased to fill the  entire  trap.   Before initial use,
the trap should be conditioned  overnight at  180°C by backflushing with an
inert gas flow of at  least 20 mL/min.  Vent the trap effluent to the room,
not to  the analytical  column.   Prior  to daily use,  the trap  should be
conditioned for  10 minutes at  180°C with backflushing.   The  trap may be
vented to the analytical column during daily conditioning.   However, the
column must be run through the  temperature  program prior to  analysis of
samples.

      4.11.3      The desorber  should be capable of  rapidly  heating the
trap to 180°C  for desorption.  The polymer section of the trap should not
be heated higher than 180°C, and the remaining sections should not exceed
220°C  during bake out mode.   The desorber design illustrated  in Figure 2
meets these criteria.

      4.11.4      The purge-and-trap device may be assembled as a separate
unit or  may be  coupled to  a gas chromatograph, as  shown  in  Figures 3
and 4.

      4,11,5      Trap  Packing  Materials

            4.11.5.1.   2,6-Diphenylene  oxide  polymer  -   60/80  mesh,
      chromatographic grade (Tenax GC or equivalent).

            4.11.5.2    Methyl   si 11 cone   packing   -    OV-1   (3%)   on
      Chromosorb-W, 60/80 mesh or equivalent.

            4.11.5.3    Silica  gel   -  35/60  mesh, Davison, grade  15  or
      equivalent.

            4.11.5.4    Coconut charcoal -  Prepare  from Barnebey Cheney,
      CA-580-26,  lot #M-2649,   by crushing  through  26 mesh screen  (or
      equivalent).

4.12  Gas chromatograph/mass spectrometer system

      4.12.1      Gas chromatograph  -  An analytical system  complete with
a temperature programmable gas chromatograph and al1  required accessories
including syringes, analytical  columns, and  gases.

      4.12.2      Column - 6 ft x 0.1 in. ID glass, packed with 1% SP-1000
on Carbopack-B (60/80 mesh)  or equivalent.

      4.IE.3      Mass  spectrometer  - Capable of scanning from 35-260 amu
every 3 seconds or less,  using  70  volts (nominal) electron  energy in the
electron impact  mode and  producing  a  mass  spectrum  that  meets  all  the
criteria in Table 3 when 50 ng of 4-bromofluorobenzene (BFB) are injected
through the gas chromatograph inlet.

      4.12.4      GC/MS interface -  Any GC-to-MS  interface that  gives
acceptable calibration points at 50  ng or less per  injection for each of
the  analytes   and  achieves  all acceptable   performance   criteria  (see


                            8240B - 6                         Revision 2
                                                          September 1994

-------
      Table 3) may  be  used.  GC-to-MS  interfaces constructed entirely of glass
      or of glass-lined materials are recommended. Glass can be deactivated by
      silanizing with dichlorodimethylsilane.

            4.12.5      Data  system  -   A   computer  system  that  allows  the
      continuous acquisition and storage on machine readable media of all mass
      spectra obtained throughout the  duration of the chromatographic program
      must  be interfaced  to the mass  spectrometer.  The  computer  must have
      software that allows searching any GC/MS data file for ions of a specified
      mass and plotting  such ion abundances versus time or  scan  number. This
      type  of plot  is  defined  as  an  Extracted  Ion  Current  Profile  {EICP}.
      Software must also be available that  allows  integrating the abundances in
      any EICP between  specified time  or  scan  number  limits.  The  most recent
      version of the EPA/NIST Mass  Spectral Library should also be available.


5.0   REAGENTS

      5.1   Reagent  grade  chemicals  shall  be  used   in  all  tests.    Unless
otherwise indicated,  it  is  intended  that  all  reagents  shall  conform  to  the
specifications of the Committee  on Analytical Reagents of the American Chemical
Society, where such  specifications  are  available.  Other  grades may be used,
provided it  is first  ascertained that the reagent is of  sufficiently high purity
to permit its  use without lessening  the accuracy of the determination.

      5.2   Organic-free reagent water -  All  references to  water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Stock solutions - Stock  solutions may be prepared  from pure standard
materials or purchased as certified solutions.  Prepare  stock standard solutions
in methanol, using assayed liquids or gases, as appropriate.

            5.3.1 Place about 9.8 ml of methanol in a 10 ml tared ground-glass-
      stoppered volumetric flask.   Allow the  flask to  stand,  unstoppered,  for
      about 10 minutes or until  all  alcohol wetted surfaces have dried.  Weigh
      the flask to the nearest 0.0001 g.

            5.3.2 Add the  assayed reference material,  as described below.

                  5.3.2.1     Liquids  - Using a  100 p,L syringe, immediately: add
            two or more drops of assayed reference material to the flask; then
            reweigh.  The  liquid must  fall directly into  the  alcohol  without
            contacting the neck of  the flask.

                  5.3.2.2     Gases  - To prepare standards for  any  compounds
            that   boil    below   30°C    (e.g.    bromomethane,    chloroethane,
            chloromethane,  or  vinyl chloride),  fill  a 5  ml  valved  gas-tight
            syringe with the reference standard to the 5.0 ml mark.  Lower the
            needle to 5 mm above  the methanol  meniscus.   Slowly introduce the
            reference standard above the surface of the liquid.  The heavy gas
            will  rapidly  dissolve  in  the  methanol.   Standards  may  also  be
            prepared by using a lecture bottle  equipped with a Hamilton Lecture
                                  8240B  -  7                         Revision 2
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             Bottle Septum  (#86600).  Attach Teflon tubing to the side-arm relief
             valve and direct a gentle stream of gas  into  the methanol meniscus.

             5.3.3 Reweigh, dilute to volume, stopper, and then mix  by inverting
       the  flask  several  times.   Calculate the concentration in milligrams per
       liter  (mg/L)  from the net gain in weight.  When compound  purity is  assayed
       to  be  96% or greater,  the  weight  may be  used without  correction to
       calculate  the concentration of the stock standard.  Commercially prepared
       stock  standards may  be used at any concentration if they  are  certified by
       the  manufacturer or  by an  independent  source.

             5.3.4 Transfer the  stock  standard solution  into  a  Teflon sealed
       screw  cap  bottle.   Store, with minimal  headspace,  at -10°C  to -20°C and
       protect from light.

             5.3.5 Prepare  fresh stock standards for gases weekly or sooner if
       comparison with check standards indicates a problem.  Reactive compounds
       such as 2-chloroethyl vinyl ether  and styrene may need to be prepared more
       frequently.   All  other standards must be replaced after  six months.  Both
       gas  and liquid standards  must be  monitored closely by comparison to the
       initial calibration curve and by comparison to QC check standards.  It may
       be necessary to  replace  the  standards more frequently  if  either check
       exceeds a  20% drift.

             5.3.6 Optionally, calibration  using a certified gaseous mixture can
       be accomplished  daily utilizing  commercially  available gaseous   analyte
       mixture  of  bromomethane,  chloromethane, chloroethane,   vinyl  chloride,
       dichlorodifluoromethane  and  trichlorofluoromethane  in   nitrogen. These
       mixtures  of  documented  quality  are  stable  for as  long as  six months
       without refrigeration.  (VOA-CYL  III, RESTEK Corporation, Cat.  120194 or
       equivalent),

       5.4    Secondary  dilution  standards  -  Using  stock  standard solutions,
prepare in methanol, secondary  dilution standards containing  the compounds of
interest, either singly or  mixed  together.  Secondary dilution  standards  must be
stored with  minimal headspace and  should  be checked  frequently for  signs of
degradation  or   evaporation, especially just  prior  to  preparing  calibration
standards from them.

       5.5    Surrogate standards  - The surrogates recommended  are  toluene-ti8,
 4-bromofluorobenzene,  and l,2-dichloroethane-d4.  Other  compounds may  be used
as surrogates,  depending upon the  analysis requirements.   A  stock surrogate
solution in methanol should be prepared as described in Sec.  5.3, and a surrogate
standard spiking  solution  should be prepared from the stock at a concentration
of 250 /itg/10  ml  in  methanol.  Each water sample undergoing GC/MS analysis must
be spiked with 10 juL of  the surrogate spiking  solution prior to analysis.

       5.6    Internal  standards   -  The  recommended   internal  standards  are
bromochloromethane, 1,4-difluorobenzene, and chlorobenzene-d6.  Other compounds
may be used as internal   standards as long  as they have retention times  similar
to the compounds  being detected  by GC/MS.  Prepare internal standard stock and
secondary dilution standards in methanol using the procedures described  in Sees.
5.3 and 5.4.  It  is recommended  that the secondary dilution standard should be


                                   8240B -  8                        Revision 2
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prepared  at a  concentration  of 25  mg/L  of each  internal  standard compound.
Addition of 10  /zL  of  this  standard to  5.0 ml of sample or calibration standard
would be the equivalent of 50 jug/L.

      5.7    4-Bromofluorobenzene (BFB) standard - A standard solution containing
25 ng/juL of BFB in methanol  should be  prepared.

      5.8    Calibration  standards  -  Calibration standards at a minimum of five
concentrations  should be prepared from  the secondary dilution of stock standards
(see Sees.  5.3 and  5.4).  Prepare these solutions in organic-free reagent water.
One of  the concentrations  should  be at a concentration near, but above,  the
method detection limit. The remaining  concentrations  should correspond to the
expected range of concentrations found  in real samples  but should not exceed the
working range of the GC/MS  system.  Each standard should contain each analyte for
detection  by this  method.   It  is EPA's intent  that all  target  analytes for a
particular analysis be included  in the  calibration standard(s).   However, these
target analytes may not include  the entire List of Analytes  (Sec. 1.1} for which
the method  has  been demonstrated.  However,  the laboratory shall  not report a
quantitative result for a target analyte that was not included in the  calibration
standard(s).  Calibration  standards must be prepared daily.

      5.9    Matrix spiking  standards   -  Matrix  spiking  standards  should  be
prepared from  volatile organic  compounds  which will  be  representative of the
compounds being investigated.   The suggested compounds are 1,1-dichloroethene,
trichloroethene, chlorobenzene,  toluene,  and benzene.   The standard should be
prepared  in  methanol, with each  compound  present   at a  concentration  of
250 /Ltg/10.0 ml.

      5.10   Great  care must be  taken to maintain the integrity of all standard
solutions.   It  is recommended that  all  standards in methanol  be stored  at -10°C
to -20°C in screw cap  amber bottles with Teflon liners.

      5.11  Methanol,  CH3OH.  Pesticide quality or equivalent. Store apart from
other solvents.

      5.12   Reagent Tetraglyme  - Reagent tetraglyme is defined as tetraglyme in
which interference is  not observed at the method detection limit of compounds of
interest.

             5.12.1      Tetraglyme  (tetraeihylene g~ycc~ c';,Tie thy" ether, A1dr:ch
      #17, 240-5 or equivalent), C8H180S. Purify by treatment  at reduced pressure
      in a  rotary  evaporator. The tetraglyme should have a peroxide content of
      less  than 5  ppm as  indicated  by EM  Quant  Test Strips  (available from
      Scientific Products  Co.,  Catalog No. P1126-8 or equivalent).

             CAUTION:    Glycol   ethers  are suspected carcinogens.  All  solvent
                        handling should be done in a  hood  while  using proper
                        protective  equipment  to  minimize  exposure to liquid and
                        vapor.

             Peroxides  may  be removed  by passing  the tetraglyme through a column
      of activated alumina.  The tetraglyme is placed  in a  round  bottom flask
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       equipped with a standard taper joint,  and the flask is affixed to a rotary
       evaporator. The flask is immersed in  a water bath at 90~10Q°C and a vacuum
       is  maintained  at <  10  mm Hg for  at  least two hours  using a two  stage
       mechanical  pump.  The vacuum system is equipped with  an all glass  trap,
       which  is  maintained in  a dry  ice/methanol bath.  Cool  the tetraglyme to
       ambient temperature and add 100 mg/L of 2,6-di-tert-butyl-4-methyl-phenol
       to  prevent  peroxide formation.  Store  the tetraglyme in a tightly sealed
       screw  cap bottle  in  an  area  that is not contaminated by solvent  vapors.

             5,12.2      In order to demonstrate that all interfering volatiles
       have   been   removed  from   the  tetraglyme,   an   organic-free  reagent
       water/tetraglyme  blank  must  be  analyzed.
      5.13   Polyethylene  glycol,
detection limit of the analytes.
H(OCH2CH2)nOH.   Free  of interferences at the
6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See  the  introductory material to  this  chapter,  Organic Analytes,
Sec. 4.1.
7.0   PROCEDURE

      Samples may be introduced into the GC by either direct  injection or purge-
and-trap procedures.  Whichever procedure is used, the instrument calibration and
sample introduction must be performed by the same procedure.

      Regardless of which sample introduction procedure is employed, establish
GC/MS operating conditions using the following recommendations as guidance.

      Recommended GC/MS operating conditions:
             Electron energy:
             Mass range:
             Scan time:

             Initial column temperature:
             Initial column holding time:
             Column temperature program:
             Final column temperature;
             Final column holding time:
             Injector temperature:
             Source temperature:

             Transfer line temperature:
             Carrier gas:
        70  volts  (nominal).
        35-260  amu.
        To  give  5 scans/peak,  but  not to
        exceed  1  sec/scan.
        45°C.
        w alt a ssU i-SS .
        8°C/minute.
        220°C.
        15  minutes.
        200-225°C,
        According    to     manufacturer's
        specifications.
        250-300°C.
        Hydrogen at 50 cm/sec or helium at 30
        cm/sec.
      7.1   Direct  injection  -  In  very limited  applications  (e.g.  aqueous
process wastes), direct injection of the  sample  into the GC/MS  system with a 10
/iL syringe may be appropriate.   One such  application is for verification of the
                                  8240B - 10
                                  Revision 2
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alcohol content  of an aqueous  sample  prior to  determining  if the  sample  is
ignitable (Methods 1010  or  1020).   In  this case, it  is  suggested  that direct
injection be used.  The detection limit is very high (approximately 10,000 /ig/L);
therefore, it is  only permitted when concentrations in  excess of 10,000 /ig/L are
expected or for water soluble compounds that do not purge.   The system must be
calibrated by direct  injection  using  the procedures described in Sec. 7.2,, but
bypassing the purge-and-trap device.

      7.2    Initial calibration for purge-and-trap procedure

             7.2.1  Establish   the  GC/MS   operating   conditions,    using   the
      recommendations in Sec. 7.0 as guidance.

             7.2.2  Each GC/MS system must be hardware tuned to meet the criteria
      in Table 3  for  a 50 ng  injection or purging of 4-bromofluorobenzene (2  pi
      injection  of the  BFB  standard).   Analyses must  not  begin  until  these
      criteria are met.

             7.2.3 Assemble a purge-and-trap device that meets the specification
      in Sec. 4.11.   Condition the trap  overnight at 180°C in the  purge  mode
      with an inert gas flow  of at least 20  mL/min.  Prior to use, condition the
      trap daily  for  10 min while backflushing at  180°C with the  column at 220°C.

             7.2.4 Connect the purge-and-trap device to a gas chromatograph.

            7.2.5 Prepare   the  final   solutions   containing   the   required
      concentrations  of  calibration  standards,  including surrogate standards,
      directly in the purging device  (use freshly prepared stock solutions when
      preparing the calibration  standards  for  the initial  calibration.)   Add
      5.0 ml of organic-free reagent  water  to the purging device.  The organic-
      free reagent water is added to  the  purging device using  a 5 mL  glass
      syringe fitted with a  15 cm, 20 gauge needle.   The needle  is  inserted
      through the sample  inlet  shown  in Figure  1.  The internal  diameter of the
      14 gauge needle that forms the sample inlet will permit  insertion of the
      20 gauge needle.  Next, using a 10 jiL or 25 /iL microsyringe equipped with
      a long  needle (Sec. 4.1), take a volume of the secondary dilution solution
      containing  appropriate concentrations of  the calibration  standards (Sec.
      5.6).   Add  the aliquot of calibration solution  directly  to  the  organic-
      free reagent water in  the purging device  by inserting  the needle through
      the sample  inlet.   When discharging the contents of the nncrosyringe,  be
      sure that the end of the syringe needle is well beneath the surface of the
      organic-free reagent water.  Similarly, add  10 jjL of the internal  standard
      solution (Sec.  5.4).   Close the 2 way syringe valve at  the  sample inlet.

            7.2.6 Carry out the purge-and-trap  analysis  procedure  as described
      in Sec. 7.4.1.

            7.2.7 Tabulate the  area  response  of the  characteristic  ions  (see
      Table  1)  against  concentration  for each  compound  and  each  internal
      standard.   Calculate response factors (RF)  for  each compound relative  to
      one of the  internal standards.   The  internal standard selected  for the
      calculation of  the  RF  for  a compound  should be the  internal  standard that
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has a retention time closest to the compound  being measured (Sec. 7.E.2).
The RF  is calculated as  follows:

      RF =  (AxCis)/(AisCJ

where:

      Ax     =     Area of the  characteristic  ion  for  the compound being
                  measured.
      AJS     =     Area of the characteristic ion for  the specific internal
                  standard.
      Cis     =     Concentration of the specific internal  standard.
      Cx     =     Concentration of the compound being  measured.

      7.2.8  The average  RF must be calculated for  each compound using the
5  RF  values calculated   for  each compound  from  the initial  (5-point)
calibration curve.  A system performance check should be made before this
calibration curve is used.  Five compounds (the System Performance Check
Compounds,  or SPCCs) are  checked for a minimum average relative response
factor. These compounds are chloromethane,  1,1-dichloroethane, bromoform,
1,1,2,2-tetrachloroethane,  and chlorobenzene.   The minimum  acceptable
average RF  for these  compounds  should  be 0.300  (>0.10  for  bromoform).
These compounds  typically  have  RFs of  0.4-0.6 and  are used  to  check
compound instability and  to check for degradation caused by contaminated
lines or active sites  in  the system.  Examples of these occurrences are:

             7.2,8.1     Chloromethane -  This compound  is the  most likely
      compound to be lost if the  purge flow  is too  fast.

             7.2.8.2     Bromoform - This compound  is one of the compounds
      most likely to be purged very poorly if the  purge flow is too slow.
      Cold spots and/or  active sites in the transfer lines may adversely
      affect response.   Response  of  the quantitation ion (m/'z  173}  is
      directly  affected  by the  tuning  of  BFB  at  ions  m/z  174/176.
      Increasing  the  m/z 174/176  relative to m/z  95 ratio may improve
      bromoform response.

             7.2.8.3     Tetrachloroethane and 1,1-dichloroethane - These
      compounds are degraded by contaminated transfer lines in purge-and-
      trap systems and/or active  sites In  trapping  materials.

      7.2.9  Using  the RFs  from  the initial  calibration,  calculate  and
record the  percent relative standard deviation (%RSD)  for all  compounds.
The percent RSD is calculated  as follows:

               SD
            ° " ................................ "" ........ °°°" J\  «l w \J
               RF
where:
      RSD   =     relative standard deviation.
      RF    =     mean of 5 initial RFs for a compound.
      SD    =     standard deviation of average RFs for  a compound.


                            8240B - 12                        Revision 2
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                  I   N  (RF, - RF)2
       SD  =           I  	
                  j  i=l N - 1

             where;

                  RFg    = RF for each of the 5 calibration levels
                  N     = Number of RF values (i.e.,  5)

       The percent relative standard deviation should  be less than 15% for
each compound.   However,  the %RSD for each individual  Calibration Check
Compound (CCC) must be less than 30%.  Late-eluting compounds usually have
much better  agreement.  The CCCs  are:

       1,1-Dichloroethene,
       Chloroform,
       1,2-Di chloropropane,
       Toluene,
       Ethyl benzene, and
       Vinyl  chloride.

             7.2.9.1     If a %RSD greater  than 30 percent is measured for
       any CCC, then corrective  action to  eliminate  a system leak and/or
       column  reactive  sites is required before reattempting calibration.

       7.2.10      Linearity -  If the %RSO  of  any compound is 15% or less,
then the  relative response  factor is assumed  to  be  constant  over  the
calibration  range, and the  average relative  response factor may be used
for quantisation (Sec. 7.5.2.2).

             7.2.10.1    If the %RSD of any compound  is greater than 15%,
       construct   calibration   curves  of  area  ratio   {A/Ais)   versus
       concentration using first or higher order regression fit of the five
       calibration points.  The  analyst should select  the regression order
       which  introduces the least calibration error into the quantitation
       (Sec.  7.5.2.4).   The use  of calibration curves is  a recommended
       alternative to  average  response factor calibration,  and  a useful
       diagnostic of standard preparation accuracy and absorption activity
       in the  chromatograph:c system.

       7.2.11      These curves  are  verified each  shift  by  purging  a
performance standard.   Recalibration is required only if calibration  and
on-going performance criteria cannot be met.

7.3    Daily  GC/MS calibration

       7.3.1  Prior to the analysis of samples, inject or purge 50 ng of the
4-bromofluorobenzene  standard.   The resultant mass   spectra for  the  BFB
must meet  all  of the  criteria  given  in  Table 3 before  sample  analysis
begins.  These criteria must be demonstrated each 12 hour shift.
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       7.3.2  The  initial calibration curve (Sec.  7,2) for each compound of
interest  must  be checked and verified  once  every 12 hours  of analysis
time.  This  is accomplished  by  analyzing  a calibration  standard that is
at a concentration near the midpoint concentration for the working range
of the GC/MS and checking the SPCC (Sec. 7.3.3} and CCC (Sec. 7.3.4).

       7.3.3  System   Performance  Check  Compounds  (SPCCs)  -  A  system
performance check must be made  each  12  hours.   If the SPCC criteria are
met, a comparison of relative response factors is made for all compounds.
This is  the  same check that is applied during  the  initial  calibration.
If the minimum relative response factors are  not met,  the system must be
evaluated, and  corrective  action must  be  taken before  sample  analysis
begins.  The  minimum relative response factor for volatile SPCCs is 0.300
(>0.10  for Bromoform).   Some  possible problems  are standard  mixture
degradation,   injection port  inlet  contamination,  contamination  at  the
front  end  of the analytical column, and  active sites in the  column or
chromatographic system.

       7.3.4  Calibration  Check  Compounds  (CCCs):    After  the  system
performance check is met, CCCs listed in Sec. 7.2.9 are used to check the
validity of the initial calibration.

       Calculate the percent drift using the following equation:

                  C, - Cc
       % Drift =	   x 100
where:

      C|  =   Calibration Check Compound standard concentration.
      Cc =   Measured concentration using selected quantitation method.

      If the percent difference for each CCC is  less than 20%, the initial
calibration is assumed to be valid.   If the criterion  is  not  met (> 20%
drift),   for  any one  CCC,  corrective  action  must be  taken.    Problems
similar to those listed under SPCCs could  affect  this  criterion.   If no
source of the problem can be determined after  corrective action has been
taken, a new  five  point  calibration  MUST be generated.   This criterion
MUST be  met before quantitative  sample analysis begins.  If the CCCs are
not required analytes  by the permit, then all required analytes must meet
the 20% drift criterion.

      7.3.5 The  internal  standard  responses and retention  times  in the
check calibration standard must  be  evaluated immediately after or during
data acquisition.  If the retention  time for any internal standard changes
by more than 30  seconds from the last  calibration check (12 hours), the
chromatographic system must  be inspected for malfunctions and corrections
must  be  made,  as required.    If  the  EICP  area  for  any of  the  internal
standards changes by a  factor of two (- 50% to +  100%) from the last daily
calibration check standard,  the mass  spectrometer must be inspected for
malfunctions  and  corrections  must   be  made,  as  appropriate.    When
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corrections are made,  reanalysis of samples analyzed while the system was
malfunctioning is necessary.

7.4   GC/MS analysis

      7.4.1 Water samples

            7.4.1.1     Screening  of  the sample prior to  purge-and-trap
      analysis  will   provide  guidance  on  whether  sample  dilution  is
      necessary  and  will  prevent  contamination of  the  purge-and-trap
      system.    Two  screening  techniques that  can be  used  are:    the
      headspace  sampler  (Method 3810)  using  a gas  chromatograph  (GC)
      equipped with a photo ionization detector (PID) in  series with an
      electrolytic conductivity detector  (HECD);  and  extraction of  the
      sample with hexadecane and analysis of the extract  on  a  GC with  a
      FID and/or an ECD (Method 3820).

            7.4.1.2    All samples and standard solutions must be allowed
      to warm  to ambient temperature  before  analysis.

            7.4.1.3    Set up the GC/MS system as outlined in Sec. 7.2.1.

            7.4.1.4    BFB tuning  criteria  and daily GC/MS  calibration
      criteria must be met (Sec.  7.3)  before analyzing samples.

            7.4.1.5    Adjust  the  purge gas (helium)  flow rate to  25-
      40 mL/min on the purge-and-trap  device.  Optimize  the flow rate to
      provide  the best response for chloromethane and bromoform, if  these
      compounds are analytes.   Excessive flow rate reduces chloromethane
      response, whereas insufficient flow reduces bromoform response (see
      Sec.  7.2.8),

            7.4.1.6    Remove the plunger from a 5  ml  syringe and attach
      a closed syringe valve.   Open the sample or standard bottle,  which
      has been allowed to come to ambient temperature,  and  carefully pour
      the sample  into the  syringe  barrel  to just short of  overflowing.
      Replace  the  syringe  plunger and  compress  the  sample.   Open  the
      syringe  valve and  vent  any residual air while adjusting the sample
      volume to 5.0 ml.   This process of taking an aliquot  destroys  the
      validity of the liquid sample  for future analysis;  therefore,  if
      there is only one VOA vial, the analyst should fill  a  second syringe
      at this  time to protect against  possible loss of sample integrity.
      This second  sample  is  maintained  only  until  such  time when  the
      analyst  has  determined  that the  first  sample  has  been  analyzed
      properly.  Filling one 20 ml  syringe would allow the use of only one
      syringe.  If a  second analysis is needed from a syringe, it must be
      analyzed within 24 hours.   Care must be taken to  prevent air from
      leaking  into the syringe.

            7.4.1.7    The   following   procedure   is   appropriate  for
      diluting purgeable samples.   All  steps  must  be performed without
      delays until the diluted  sample  is in  a  gas  tight  syringe.
                           8240B  -  15                         Revision  2
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            7.4.1.7.1   Dilutions may be made in volumetric flasks
       (10 to  100 ml).  Select the volumetric flask that will  allow
       for the necessary dilution.   Intermediate dilutions may be
       necessary for  extremely large  dilutions,

            7.4.1.7.2   Calculate the approximate volume of organic-
       free  reagent  water to  be  added  to  the volumetric  flask
       selected and add slightly less  than this quantity of organic-
       free  reagent water  to  the  flask.

            7.4.1.7.3   Inject the proper aliquot of  samples  from
       the   syringe   prepared  in  Sec.  7.4.1.6  into  the  flask.
       Aliquots of  less  than  1'mL are not  recommended.   Dilute the
       sample  to the  mark with organic-free reagent water.  Cap the
       flask,  invert, and shake three  times.  Repeat above procedure
       for additional dilutions.

            7.4.1.7.4   Fill  a 5  ml syringe with the diluted sample
       as in Sec. 7.4.1.6.

       7.4.1.8     Add 10.0 /zL of  surrogate  spiking  solution  (Sec.
5.5) and 10 /iL of  internal  standard spiking solution  (Sec.  5.6)
through the valve bore of the  syringe;  then  close the  valve.   The
surrogate and internal  standards  may  be mixed and added as a single
spiking solution.   The addition  of 10 /uL  of the surrogate spiking
solution to  5 ml of sample  is  equivalent  to  a concentration  of
50 /^g/L of  each surrogate standard.

       7.4.1,9     Attach the  syringe-syringe valve  assembly to the
syringe valve on the purging device.  Open  the  syringe valves and
inject the sample into the purging chamber.

       7.4.1.10    Close   both valves  and  purge  the  sample   for
11.0 + 0.1  minutes at ambient temperature.

       7.4.1.11    At  the conclusion of the purge time,  attach the
trap to the  chromatograph, adjust the device to the desorb mode, and
begin  the gas chromatographic temperature program and  GC/HS  data
acquisition.  Concurrently, introduce the trapped materials to the
gas chromatographic  column  by rapidly  heating  the trap  to  I80°C
while backflush ing the  trap with  inert gas between 20 and 60 mL/min
for 4  minutes. If this rapid heating  requirement cannot be met, the
gas chromatographic  column  must  be  used as a  secondary trap  by
cooling it  to 30°C (or  subambient, if problems  persist)  instead of
the recommended initial program temperature of 45°C.

       7.4.1.12    While  the  trap  is  being  desorbed  into the  gas
chromatograph, empty the purging chamber.   Wash the  chamber with a
minimum of  two 5  ml flushes  of organic-free  reagent water  (or
methane! followed  by organic-free reagent water) to avoid carryover
of pollutant compounds into subsequent analyses.
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             7.4.1.13    After  desorbing  the   sample   for   4  minutes,
      recondition the trap by returning the purge-and-trap device to the
      purge  mode.   Wait  15  seconds;  then  close the syringe  valve on the
      purging  device to  begin gas  flow through  the  trap.   The  trap
      temperature should be maintained at 180°C.  Trap temperatures up to
      220°C may be employed;  however,  the  higher temperature will  shorten
      the  useful  life of  the trap.   After approximately 7 minutes,  turn
      off the trap heater and open the syringe  valve to  stop the gas flow
      through the trap.  When cool, the trap is  ready for the next sample.

             7.4.1.14    If the initial analysis of  a sample or a dilution
      of  the sample has  a  concentration of  analytes  that  exceeds  the
      initial calibration range, the sample must be reanalyzed at a higher
      dilution.  Secondary ion quantitation is allowed  only when there are
      sample  interferences   with  the  primary  ion.   When  a sample  is
      analyzed that has  saturated  ions from a compound, this analysis must
      be followed by a blank organic-free  reagent water  analysis.  If the
      blank  analysis  is not  free  of  interferences,  the  system  must  be
      decontaminated.  Sample analysis may  not resume until  a blank can
      be analyzed that is free of interferences.

             7.4.1.15    For  matrix spike analysis,  add  10 /iL of the matrix
      spike  solution  (Sec.   5.9)  to   the  5  ml  of  sample  to  be  purged.
      Disregarding  any dilutions, this is equivalent  to a concentration
      of 50  ng/L  of each matrix spike standard.
            7.4.1.16    All  dilutions  should  keep  the  response of  the
      major constituents  (previously  saturated  peaks)  in  the  upper half
      of the linear range of the curve.   Proceed to Sees. 7.5.1 and 7.5.2
      for qualitative and quantitative analysis.

      7.4.2 Water miscible  liquids

            7.4.2.1     Water miscible  liquids  are  analyzed  as  water
      samples after first diluting them at least  50 fold with organic-free
      reagent water.

            7.4.2.2     Initial  and serial dilutions  can  be  prepared by
      pipetting  2  ml of  the sample  to  a 100  ml  volumetric  flask  and
      diluting  to  volume  with  organic-free  reagent  water.    Transfer
      immediately to a 5 ml gas tight syringe.

            7.4.2.3     Alternatively, prepare dilutions directly in  a 5
      ml syringe filled with organic-free reagent water by adding at least
      20 jiL,  but not  more than 100 ^L of  liquid sample.   The sample is
      ready for  addition of internal  and surrogate standards.

      7.4.3 Sediment/soil  and  waste samples  -  It is  highly  recommended
that all  samples of this type  be  screened prior to  the  purge-and-trap
GC/MS analysis.   The headspace  method  (Method  3810) or  the  hexadecane
extraction  and   screening  method  (Method  3820) may  be  used for  this
purpose.   These samples may  contain percent  quantities of  purgeable
organics that  will  contaminate  the  purge-and-trap  system,  and  require


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extensive cleanup  and  instrument  downtime.   Use  the screening data  to
determine whether to use the low-concentration  method {0.005-1  mg/kg)  or
the high-concentration method (> 1 mg/kg),

            7.4.3.1     Low-concentration method  - This is designed  for
      samples containing individual  purgeable compounds of < 1 mg/kg.   It
      is limited to sediment/soil  samples  and waste that  is of  a similar
      consistency (granular and  porous).  The low-concentration  method is
      based on purging a heated  sediment/soil sample mixed with organic-
      free reagent water containing the surrogate and internal standards.
      Analyze all reagent blanks and standards  under the  same conditions
      as the samples.   See  Figure 5 for an  illustration  of a  low  soils
      impinger.

                  7.4.3.1.1    Use   a  5   g   sample   if   the  expected
            concentration is  <  0.1  mg/kg  or a  1  g sample for expected
            concentrations between 0.1 and 1 mg/kg.

                  7.4.3.1.2    The  GC/MS  system  should  be set  up  as  in
            Sees.  7.4.1.2-7.4.1.4.   This should  be done  prior  to  the
            preparation  of  the  sample to avoid  loss of  volatiles from
            standards and samples, A heated purge calibration curve must
            be  prepared  and  used  for the quantitation  of  all samples
            analyzed  with the  low-concentration  method.    Follow  the
            initial and  daily calibration  instructions,  except for  the
            addition of a 40°C purge temperature.

                  7.4.3.1.3    Remove the plunger from a 5 ml Luerlock type
            syringe  equipped with  a  syringe  valve  and   fill   until
            overflowing  with  organic-free  reagent water.   Replace  the
            plunger and compress  the water to vent trapped air.  Adjust
            the volume to 5.0 ml.   Add  10 ^L each of surrogate spiking
            solution (Sec. 5.5)  and  internal  standard solution (Sec, 5.6}
            to  the  syringe   through  the  valve.    (Surrogate spiking
            solution  and  internal  standard  solution  may   be   mixed
            together.)  The addition  of 10  /iL  of the surrogate spiking
            solution to 5 g of sediment/soil  is  equivalent to  50 Mg/kg  of
            each surrogate standard.

                  7.4.3.1.4    The  sample (for vo~at:~e crganlcs; consists
            of  the  entire contents  of  the sample container.    Do  not
            discard any  supernatant  liquids.   Mix  the contents  of  the
            sample  container  with a  narrow  metal spatula.   Weigh  the
            amount  determined  in  Sec.  7.4,3.1.1  into  a tared   purge
            device.  Note and  record the actual  weight to  the  nearest  0.1
            9-

                  7.4.3.1.5    Determine  the  percent  dry  weight  of  the
            soil/sediment sample.   This includes waste samples that  are
            amenable to percent  dry weight determination.  Other wastes
            should be reported on  a wet-weight  basis.
                           8240B  -  18                        Revision  2
                                                         September  1994

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                  7.4.3.1.5.1  Immediately after weighing the sample
            for extraction, weigh 5-10 g of the sample into a tared
            crucible.   Determine  the %  dry weight  of the  sample by
            drying  overnight  at  105°C.    Allow  to  cool   in  a
            desiccator   before  re-weighing.     Concentrations  of
            individual  analytes  are reported  relative to the dry
            weight of sample.

                  WARNING :     The drying oven  should  be  contained
                              in  a  hood or  vented.   Significant
                              laboratory contamination may  result
                              from a heavily contaminated hazardous
                              waste  sample.

                  % dry weight =  q of dry  sample x 100
                                  g  of sample

            7.4.3.1.6    Add  the  spiked water to the purge  device,
      which contains the weighed  amount of sample, and connect the
      device to the purge-and-trap system.

            NOTE :  Prior to the attachment  of  the purge device, the
                  procedures in Sees. 7.4.3.1.4 and  7.4.3.1.6 must
                  be performed rapidly  and  without interruption to
                  avoid loss of  volatile  organics.   These  steps
                  must  be performed in a laboratory free of solvent
                  fumes.

            7.4.3.1.7    Heat the  sample  to  40°C ±  1°C and  purge the
      sample for  11.0 ± 0.1  minute.

            7.4.3.1.8    Proceed  with the  analysis as outlined  in
      Sees. 7.4.1.11-7.4.1.16.  Use 5 ml of  the same organic-free
      reagent water as in the  reagent  blank.  If saturated  peaks
      occurred or  would occur if a  1  g sample were analyzed,  the
      high-concentration method must be followed.

            7.4.3.1.9    For  low-concentration  sediment/soils  add
      10 pi of the matrix spike solution (Sec. 5.9)  to the 5 ml of
      organ 1c-£ree   reagent  wste^    'Ssc.   7.4.3.1.3).      The
      concentration for  a  5 g  sample would  be  equivalent  to  50
            of each matrix spike standard.
      7.4.3.2 •    High-concentration method - The method is based on
extracting the  sediment/soil  with methanol .   A  waste sample  is
either  extracted  or  diluted,  depending  on  its  solubility  in
methanol.   Wastes  (i.e.  petroleum   and  coke  wastes)  that  are
insoluble  in  methanol  are  diluted   with  reagent  tetraglyme  or
possibly polyethylene glycol (PEG).   An aliquot of  the extract  is
added to organic-free reagent water containing  internal  standards.
This is  purged at ambient temperature.  All samples with an expected
concentration of > 1.0 mg/kg should be analyzed by this method.
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      7.4.3,2.1    The sample  (for volatile organics)  consists
of  the  entire  contents  of  the  sample container.   Do  not
discard any  supernatant  liquids.   Mix the contents of  the
sample  container  with   a  narrow  metal  spatula.     For
sediment/soil   and   solid  wastes   that   are   insoluble   in
methanol,  weigh 4 g (wet weight) of  sample into a tared 20 ml
vial.  Use a  top loading balance.  Note and record the actual
weight to  0.1  gram and determine the  percent dry weight  of
the sample using the procedure in Sec.  7.4.3.1.5.  For  waste
that  is soluble in methanol, tetraglyme,  or PEG, weigh  1  g
(wet weight)  into a,tared  scintillation vial  or culture tube
or a 10 ml volumetric flask.   (If a vial  or tube is  used,  it
must be calibrated prior  to  use.   Pipet  10.0 ml of  solvent
into the vial and mark the bottom of the  meniscus.   Discard
this solvent.)

      7.4.3.2.2    Quickly  add 9.0 ml of appropriate  solvent;
then  add  1.0 ml  of  the  surrogate  spiking  solution to  the
vial.  Cap and  shake for 2 minutes.

      NOTE: Sees.  7.4.3.2.1 and 7.4.3.2.2 must  be performed
           rapidly and without interruption to avoid loss of
           volatile  organics.  These steps must be performed
           in  a laboratory free  from solvent fumes.

      7.4.3.2.3    Pipet approximately 1 ml of the extract  to
a  GC vial  for  storage,   using  a  disposable  pipet.    The
remainder  may be disposed  of.  Transfer approximately 1  ml of
appropriate  solvent  to a  separate  GC  vial for use as  the
method blank for each set  of  samples.   These extracts may be
stored at  4°C in the dark, prior to analysis.   The  addition
of  a 100  pi  aliquot  of  each of  these extracts  in Sec.
7.4.3,2.6  will  give a concentration equivalent to 6,200  Mi/kg
of each surrogate standard.

      7.4.3.2.4    The GC/MS  system  should be  set  up as  in
Sees. 7.4.1.2-7.4.1.4.   This  should  be  done  prior to  the
addition  of  the  solvent   extract   to  organic-free   reagent
water.

      7.4.3.2.5    Table 4 can be used to determine the volume
of solvent extract to add  to  the 5 ml of organic-free reagent
water for  analysis.   If  a screening procedure  was  followed
(Method 3810  or 3820), use  the  estimated concentration  to
determine  the  appropriate  volume.   Otherwise,   estimate  the
concentration range of the sample from  the low-concentration
analysis to determine the  appropriate volume.   If the sample
was  submitted   as  a  high-concentration  sample,  start with
100 /iL.   All  dilutions must  keep the response  of the  major
constituents (previously saturated  peaks)  in the upper half
of the linear range of the curve.
                8240B  -  20                         Revision  2
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                  7.4.3.2.6    Remove the plunger from  a  5.0 ml Luerlock
            type  syringe  equipped with a  syringe  valve and  fill  until
            overflowing with organic-free reagent  water.    Replace  the
            plunger  and compress  the water to  vent  trapped air.   Adjust
            the  volume  to 4.9 ml.  Pull  the  plunger back  to  5.0  ml to
            allow  volume  for the  addition of the sample extract  and of
            standards.  Add  10  fj,l of internal standard  solution.   Also
            add  the  volume  of  solvent  extract   determined  in  Sec.
            7.4.3.2.5 and a  volume  of extraction or dissolution  solvent
            to total 100 fj,l  (excluding methanol in  standards).

                  7.4.3.2.7    Attach the syringe-syringe valve assembly to
            the  syringe valve on  the  purging device.  Open the  syringe
            valve  and   inject the  organic-free  reagent  water/methanol
            sample into the  purging chamber.

                  7,4.3.2.8    Proceed  with the  analysis  as  outlined in
            Sec.  7.4.1.11-7.4.1.16.  Analyze  all  reagent  blanks  on  the
            same  instrument  as that use for the samples.   The standards
            and blanks should also contain 100 ^L  of solvent to simulate
            the sample conditions.

                  7.4.3.2.9    For  a matrix spike in the high-concentration
            sediment/soil  samples,  add  8.0 ml of  methanol,  1.0  ml of
            surrogate spike  solution  (Sec. 5.5),  and  1.0 ml  of  matrix
            spike solution (Sec. 5.9) as in Sec. 7.4.3.2.2.  This results
            in a 6,200  /ig/kg concentration of each matrix spike standard
            when  added  to a  4 g  sample.   Add  a 100 /zL aliquot of this
            extract to 5 ml of organic-free reagent water for purging (as
            per Sec- 7.4.3.2.6).

7.5   Data interpretation

      7.5.1 Qualitative analysis

            7.5.1.1     The   qualitative   identification   of   compounds
      determined  by  this method  is  based on  retention  time,  and  on
      comparison of the sample mass spectrum, after background correction,
      with  characteristic ions   in  a   reference  mass  spectrum.    The
      reference mass spectrum must >>e generated by  the  laboratory  using
      the conditions of this method.   The characteristic  ions from  the
      reference mass  spectrum are defined to be  the three ions of greatest
      relative intensity,  or  any ions over  30% relative intensity if less
      than three such ions occur  in the reference  spectrum.   Compounds
      should be identified as present  when the criteria below are met.

                  7.5.1.1.1    The  intensities  of the characteristic ions
            of a compound  maximize in the same scan or within one scan of
            each  other.   Selection of  a  peak by a data  system  target
            compound search  routine where the search  is  based on  the
            presence of  a target chromatographic  peak containing  ions
            specific for  the  target  compound at  a  compound-specific
            retention time will  be accepted as meeting this criterion.
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            7.5.1.1.2   The RRT of the  sample  component  is  within
      ± 0.06 RRT  units of  the  RRT of the standard component.

            7.5.1.1.3   The    relative    intensities    of    the
      characteristic  ions  agree  within   30%  of   the   relative
      intensities   of  these   ions   in   the  reference  spectrum.
      (Example:    For  an  ion  with  an   abundance  of  50% in  the
      reference spectrum,  the  corresponding abundance  in  a  sample
      spectrum can  range between 20% and 80%.)

            7.5.1.1.4   Structural isomers that produce very similar
      mass  spectra  should  be  identified as  individual isoraers  if
      they  have   sufficiently  different   GC   retention   times.
      Sufficient  GC resolution is achieved  if the  height of  the
      valley between two isomer peaks is less  than  25% of the  sum
      of the two  peak heights. Otherwise,  structural  isomers  are
      identified  as  isomeric pairs.

            7.5.1.1.5   Identification   is   hampered when  sample
      components  are not resolved chromatographically  and produce
      mass  spectra  containing  ions contributed  by  more than  one
      analyte.  When gas chromatographic peaks obviously  represent
      more  than one  sample component (i.e.,  a  broadened  peak with
      shoulder(s)  or  a   valley  between  two  or  more   maxima),
      appropriate  selection of  analyte  spectra  and  background
      spectra is  important.  Examination of extracted  ion current
      profiles of appropriate  ions  can aid  in  the selection  of
      spectra,  and  in  qualitative  identification  of compounds.
      When analytes coelute (i.e., only one chromatographic peak is
      apparent),   the identification criteria can  be met,  but each
      analyte spectrum will contain extraneous ions  contributed by
      the coeluting compound.

      7.5.1.2     For samples containing components  not associated
with the calibration standards, a library search may  be made for  the
purpose of tentative identification.  The necessity to perform this
type of identification will be determined by the  type  of  analyses
being conducted.   Guidelines  for making tentative  identification
are:

      (1)    Relative intensities  of  major  ions  in  the  reference
spectrum (ions >  10% of the most abundant ion) should be present in
the sample spectrum.

      (2)    The relative intensities of the major ions should agree
within + 20%.  (Example:  For an ion with  an  abundance of 50% in  the
standard  spectrum, the corresponding sample  ion  abundance must  be
between 30 and 70%).

      (3)    Molecular ions  present in the reference spectrum  should
be present in  the sample spectrum.
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       (4)   Ions present  in the  sample spectrum  but  not  in  the
reference  spectrum  should  be  reviewed  for possible  background
contamination or presence  of coeluting  compounds.

       (5)   Ions present in  the reference  spectrum but  not in the
sample spectrum should be reviewed for possible subtraction  from the
sample  spectrum because of  background  contamination  or coeluting
peaks.  Data system library reduction  programs can  sometimes create
these discrepancies,

      Computer  generated   library  search  routines  should  not  use
normalization  routines that would  misrepresent  the  library  or
unknown  spectra when compared to  each  other.   Only  after visual
comparison of sample with the nearest library searches will  the mass
spectral    interpretation    specialist    assign   a    tentative
identification,

7.5.2 Quantitative  analysis

      7.5.2.1     When  a   compound   has   been   identified,   the
quantitation  of that  compound  will  be based  on  the  integrated
abundance  from  the  EICP   of  the  primary  characteristic  ion.
Quantitation will take place using the internal standard technique.
The internal standard  used shall  be the one nearest the retention
time of that of a given analyte (e.g.  see Table  5).

      7.5.2.2     When  linearity   exists,   as  per  Sec.   7.2.10,
calculate the concentration of each identified analyte in the sample
as follows:

      Water
      concentration  (jjg/L)  =
                              (Ais)(RF)(V0)

where:

      Ax    =      Area of  characteristic ion  for compound  being
                  measured.
      Is    =      Amount  of internal  standard injected (ng).
      Ais    =      Area of   characteristic  ion  for  the  internal
      _          standard.
      RF    =      Mean relative  response factor for compound  being
                  measured  (Sec.  7.2.8).
      V0    =      Volume   of  water   purged   (ml),   taking   into
                  consideration  any dilutions made.
                      8240B - 23                        Revision 2
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                   Sediment/Soil   Sludge   (on  a  dry-weight  basis)   and   Waste
             (normally on a wet-weight  basis)

                                              (AJ(I$)(Vt)
                   concentration  (jug/kg)
                                           (A,S)(RF)(V,)(WS){D)
             where:

                   Ax>  Is> Ais, RF,  = Same  as for water.
                   V,    =     Volume of total extract (^L) (use 10,000 ^l  or  a
                              factor of this when dilutions are made).
                   V,    =     Volume of extract added (pi) for purging.
                   Ws    =     Weight of sample extracted or purged (g).
                   D    =     % dry weight of sample/100,  or  1 for a wet-weight
                              basis.

                   7.5.2.3    Where applicable, an estimate of concentration for
             noncal ibrated components in the sample should be made.  The formulae
             given  above should be used with  the  following modifications: The
             areas  Ax and Ajs should be  from the total ion chromatograms, and the
             RF  for the  compound  should be assumed to  be 1.  The concentration
             obtained  should be reported  indicating  (1)  that the value  is an
             estimate  and  (2)  which  internal standard  was used  to  determine
             concentration.     Use  the  nearest   internal  standard   free  of
             interferences.

                   7.5.2.4    Alternatively, the regression line fitted to the
             initial calibration  (Sec.  7.2.10.1)  may  be  used for determination
             of  analyte  concentration.


8.0   QUALITY CONTROL

      8.1    Each  laboratory that  uses these methods  is required  to  operate a
formal quality control program.  The minimum requirements of this program consist
of an initial demonstration of laboratory  capability and an ongoing analysis of
spiked  samples  to evaluate  and  document  data quality.    The  laboratory must
maintain records to document  the  quality  of  the  data  generated.   Ongoing data
quality checks are compared with establishec performance criteria to determine
if the results of analyses meet the performance characteristics of the method.
When results of sample  spikes indicate atypical  method  performance,  a quality
control reference sample must be  analyzed  to  confirm that  the measurements were
performed in an in-control mode of operation.

      8,2    Before  processing any samples,  the  analyst   should  demonstrate,
through the analysis of a method blank, that interferences from the analytical
system, glassware, and reagents are under  control.  Each time a set of samples
is extracted or  there is a change  in reagents, a method blank should be processed
as  a  safeguard  against chronic  laboratory contamination.  The  blank samples
should be carried through all stages of sample preparation and measurement.
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      8.3   The  experience  of  the  analyst  performing  EC/MS  analyses  is
invaluable to the success of the methods.  Each day that analysis is performed,
the  daily  calibration   standard  should  be  evaluated   to  determine  if  the
chromatographic system is operating properly.  Questions  that  should be asked
are:  Do  the  peaks look  normal?;  Is  the response obtained comparable  to the
response  from previous  calibrations?    Careful  examination  of the  standard
chromatogram can indicate whether the column is still  useable,  the injector is
leaking, the injector septum needs replacing,  etc.   If any changes are made to
the system (e.g.  column changed),  recalibration of the system  must take place.

      8.4   Required instrument QC is found in the following section:

            8.4.1  The GC/MS system must be tuned to meet the BFB specifications
      in Sec.  7.2.2.

            8.4.2  There  must be an initial  calibration  of the  GC/MS system as
      specified in Sec. 7.2.

            8.4.3  The GC/MS system must meet the SPCC criteria specified in Step
      7.3.3 and the CCC criteria in Sec.  7.3.4. each  12  hours.

      8.5   To  establish the  ability  to  generate  acceptable  accuracy  and
precision, the analyst  must  perform the following  operations.

            8.5.1  A  quality  control   (QC)  reference  sample  concentrate  is
      required  containing each  analyte  at a  concentration   of  10  mg/L  in
      methanol.  The QC reference sample concentrate may be  prepared from pure
      standard materials or purchased as  certified solutions.   If  prepared by
      the laboratory, the QC reference  sample concentrate must  be  made  using
      stock standards prepared  independently from  those  used for calibration.

            8.5.2  Prepare a  QC reference sample  to  contain 20  iJ.g/1 of each
      analyte  by adding 200  juL  of QC  reference sample  concentrate to 100 ml of
      water.

            8.5.3  Four 5-mL aliquots of the well mixed QC reference sample are
      analyzed according to  the method beginning  in Sec.  7.4.1.

            8.5.4  Calculate the average recovery (x)  in  fig/I,  and the standard
      deviation of the recovery  (s)  ir,  ^g/L,  for  each analyte using  the four
      results.

            8.5.5  For  each  analyte  compare s  and x with  the  corresponding
      acceptance criteria_for  precision  and accuracy,  respectively,  found in
      Table 6.  If s and x for all analytes meet the acceptance  criteria,  the
      system performance  is acceptable and analysis  of actual samples can_begin.
      If any individual  s exceeds the precision limit or any individual x falls
      outside   the  range  for  accuracy,   then  the  system   performance  is
      unacceptable for  that  analyte.

            NOTE:  The large number of analytes  in Table 6 present a substantial
                   probability that one  or more will  fail at least  one  of the
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                   acceptance  criteria  when  all  analytes  of a  given method are
                   determined.

            8.5.6  When  one or more of  the analytes tested fail at least one of
      the  acceptance criteria,  the  analyst  must proceed  according  to  Sec.
      8.5.6.1 or 8.5.6.2.

                   8.5.6.1     Locate  and correct the  source of the problem and
            repeat the  test for all analytes beginning with Sec. 8.5.2.

                   8.5.6.2     Beginning with Sec. 8.5.2, repeat  the  test  only
            for those analytes that failed to meet criteria.  Repeated failure,
            however, will confirm a general problem with the measurement system.
            If this  occurs,  locate and correct the source  of  the  problem and
            repeat the  test for  all compounds  of interest  beginning  with  Sec.
            8.5.2.

      8.6   The laboratory must,  on an ongoing basis,  analyze a method blank and
a  spiked  replicate   for each   analytical  batch  {up  to  a  maximum  of  20
samples/batch) to assess accuracy.  For soil and waste samples where detectable
amounts of organics are present,  replicate samples may be appropriate in place
of spiked replicates.   For laboratories analyzing one to ten samples per month,
at least one spiked sample per month  is required.

            8.6.1  The  concentration  of the  spike  in  the  sample should  be
      determined as follows:

                   8.6.1.1     If,  as in compliance monitoring, the concentration
            of a  specific analyte in  the sample is  being checked  against  a
            regulatory  concentration limit, the  spike should  be  at that limit
            or 1 to 5 times higher than  the background concentration determined
            in Sec. 8.6.2, whichever concentration would be larger.

                   8.6.1.2     If  the  concentration of a  specific  analyte  in  a
            water  sample  is  not  being  checked  against  a specific limit,  the
            spike  should be  at   20  ng/L  or  1  to 5  times  higher  than  the
            background  concentration  determined  in  Sec.   8.6.2,  whichever
            concentration would  be larger.   For other  matrices,  recommended
            spiking concentration is  10 times the EQL.

            8.6.2  Analyze one 5-mL sample aliquot to  determine the background
      concentration  (B)  of each  analyte.   If  necessary,  prepare  a  new  QC
      reference sample concentrate (Sec. 8.5.1) appropriate for the background
      concentration in  the sample.   Spike  a  second  5-mL sample  aliquot  with
      10 fj,L of the QC reference sample concentrate and analyze it to  determine
      the  concentration  after spiking  (A)  of each  analyte.   Calculate  each
      percent recovery  (p) as 100(A-B)%/T, where T is the  known  true  value  of
      the spike.

            8.6.3  Compare the percent  recovery (p) for each analyte in a water
      sample with  the  corresponding QC acceptance criteria found  in Table  6.
      These acceptance  criteria  were  calculated  to  include an  allowance  for
      error in measurement  of both the background  and  spike  concentrations,


                                  8240B -  26                        Revision 2
                                                                September 1994

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       assuming a spike to background ratio of 5:1.  This error will  be accounted
       for to the extent that the analyst's spike to  background ratio approaches
       5:1.  If spiking was performed at a concentration  lower than  20 Atg/L, the
       analyst must use either the QC  acceptance  criteria presented in Table 6,
       or  optional  QC  acceptance criteria  calculated  for the  specific spike
       concentration.  To calculate optional  acceptance criteria for  the recovery
       of  an  analyte:  (1) Calculate accuracy (x'} using the  equation found in
       Table  7,  substituting the spike  concentration  (T)  for C; (2)  calculate
       £verall precision  {$') using the equation in Table 7, substituting x' for
     •  x;  (3)  calculate the range for recovery  at  the  spike concentration as
       (100x'/T) ± 2.44{100S'/T)%.

            8.6.4  If  any individual  p  falls outside  the designated  range for
       recovery,  that  analyte  has   failed  the   acceptance  criteria.    A check
       standard containing each analyte that failed the criteria must be analyzed
       as described in Sec.  8,7.

       8.7   If any analyte  in a  water sample fails  the  acceptance  criteria for
recovery in Sec.  8.6,  a QC reference sample containing each analyte that failed
must be prepared and analyzed.

       NOTE: The  frequency for the  required analysis of a  QC reference sample
            will depend upon the number of analytes being simultaneously tested,
            the  complexity of the  sample  matrix,   and  the performance  of the
            laboratory.   If the entire list  of analytes  in Table  6  must be
            measured  in  the  sample  in Sec.  8.6,  the probability  that  the
            analysis of a QC reference sample will be required is high.   In this
            case, the QC reference sample should be  routinely analyzed with the
            spiked sample,

            8.7.1 Prepare the QC reference sample  by  adding 10 /nl  of the QC
       reference  sample  concentrate  (Sec.  8.5.1  or  8.6.2}  to 5  ml of  reagent
      water.  The QC  reference  sample needs only to contain  the analytes that
       failed criteria in the test in  Sec.  8,6,

            8.7.2 Analyze the QC reference sample to  determine the concentration
      measured (A) of each analyte.   Calculate  each  percent recovery   (ps) as
       1QQ(A/T)%,  where T is the  true  value  of  the standard concentration.

            8.7.3 Compare  the  percent recovery  (pj for each analyte with the
      corresponding QC acceptance criteria found  in Table 6.   Only analytes that
       failed the test in Sec.  8.6 need  to be compared with these criteria.  If
       the recovery of any such analyte  falls outside the designated range, the
       laboratory performance for that analyte  is judged to  be out  of control,
       and the problem must be  immediately identified and corrected.  The result
       for that analyte in the unspiked sample is suspect and may  not be reported
       for regulatory compliance  purposes.

      8.8   As part of the  QC  program for the  laboratory,  method accuracy for
each matrix studied must  be assessed and records  must be maintained.  After the
analysis of five  spiked samplesJof the same matrix) as in Sec.  8.6,  calculate
the average  percent  recovery  (p)  and  the  standard deviation  of  the  percent
recovery (sp).  Express  the accuracy assessment as a percent  recovery interval


                                  824GB - 27                        Revision 2
                                                                September 1994

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 from  p  -  2sp to p + 2sp.   If p = 90%  and  sp  =  10%,  for example, the accuracy
 interval  is expressed  as  70-110%.   Update  the accuracy  assessment  for each
 analyte  on  a  regular  basis  (e.g.,  after   each  five  to  ten new  accuracy
 measurements).

      8.9    To determine acceptable accuracy and precision  limits for surrogate
 standards the  following procedure should be performed.

             8.9.1 For each sample analyzed,  calculate the percent recovery of
      each  surrogate  in the  sample.

             8.9.2 Once  a minimum of thirty samples of the same matrix have been
      analyzed,   calculate  the  average  percent  recovery  (P)  and  standard
      deviation  of  the  percent recovery (s) for  each of the  surrogates.

             8.9.3 For a given matrix,  calculate the upper  and lower control
      limit for method performance for each surrogate standard.   This should be
      done  as  follows:

             Upper Control  Limit  (UCL)  = P  + 3s
             Lower Control  Limit  (LCL)  = P  - 3s

             8.9.4 For aqueous  and soil matrices, these laboratory established
      surrogate  control  limits  should,  if applicable,  be  compared  with  the
      control  limits listed in Table 8. The limits given in  Table 8 are multi-
      laboratory  performance based limits for  soil  and aqueous samples,  and
      therefore,  the  single-laboratory limits established in Sec.  8.9.3 must
      fall  within those given in Table 8 for these matrices.

             8.9.5 If  recovery is not within limits, the following procedures are
      required.

             *      Check to  be  sure  there  are  no   errors  in  calculations,
                   surrogate  solutions  and internal   standards.   Also,  check
                   instrument performance.

             •      Recalculate the  data and/or reanalyze the  extract if any of
                   the above  checks  reveal  a problem.

             •      Reextract  and  reanalyze  the sample if none of the above are
                   a problem  or flag  the data  as  "estimated concentration".

             8.9.6 At  a minimum, each laboratory should update  surrogate recovery
      limits on a matrix-by-matrix basis,  annually.

      8.10   It is  recommended  that the  laboratory  adopt additional  quality
assurance practices for use with this method.   The specific practices that are
most productive depend upon  the needs  of  the  laboratory and  the nature of the
samples.   Field  duplicates  may  be  analyzed  to assess  the  precision  of  the
environmental measurements.  When doubt exists over the identification of a peak
on the chromatogram, confirmatory techniques such as  gas chromatography with a
dissimilar column or a different  ionization mode  using a mass spectrometer must


                                  8240B -  28                        Revision 2
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be used.   Whenever  possible,  the laboratory should analyze standard reference
materials  and participate in relevant performance evaluation studies,


9.0   METHOD PERFORMANCE

      9.1   This method was tested by 15 laboratories using organic-free reagent
water, drinking water, surface water, and industrial wastewaters spiked at six
concentrations over the range 5-600  M9/L-   Single operator precision,  overall
precision,  and  method  accuracy  were  found  to  be  directly  related  to  the
concentration of the analyte and essentially independent of the sample matrix.
Linear equations to describe these relationships are presented in Table 7.


10.0  REFERENCES

1.    U.S. EPA 40  CFR  Part 136, "Guidelines Establishing Test Procedures for the
      Analysis  of  Pollutants   Under  the   Clean  Water  Act,  Method  624,"
      October 26,  1984.

2,    U.S.  EPA  Contract  Laboratory Program,  Statement of  Work  for  Organic
      Analysis, July  1985, Revision,

3.    Bellar, T.A., and J.J. Lichtenberg, J. Amer, Waterworks Assoc.,  66(12),
      739-744, 1974.

4.    Bellar, T.A., and J.J.  Lichtenberg,  "Semi-Automated Headspace Analysis of
      Drinking  Waters and  Industrial  Waters  for Purgeable  Volatile  Organic
      Compounds,"  in Van Hall, ed.,  Measurement of Organic Pollutants in Water
      and  Wastewater,  ASTM STP 686,  pp. 108-129,  1979.

5,    Budde, W.L.  and J.W. Eichelberger,  "Performance Tests for the Evaluation
      of   Computerized  Gas  Chromatography/Mass  Spectrometry  Equipment  and
      Laboratories,"  EPA-6QQ/4-79-Q20,  U.S. Environmental  Protection  Agency,
      Environmental Monitoring and Support Laboratory, Cincinnati,  Ohio 45268,
      April 1980.

6.    Eichelberger, J.W., L.E. Harris, and  W.L,  Budde,  "Reference  Compound to
      Calibrate   Ion   Abundance   Measurement   in  Gas   Chromatography-Mass
      Spectrometry Systems," Analytical Cnemistry, 47, 995-1000, 1975,

7.    "Method Detection Limit for Methods  624 and  625," Olynyk, P.,  W.L. Budde,
      and  J.W. Eichelberger, Unpublished report, October 1980.

8.    "Inter!aboratory Method Study for EPA Method 624-Purgeables," Final Report
      for  EPA Contract 68-03-3102.

9.    "Method Performance Data for Method 624,"  Memorandum  from R.  Slater and
      T.   Pressley,   U.S.   Environmental    Protection   Agency,   Environmental
      Monitoring  and  Support  Laboratory,  Cincinnati, Ohio 45268,  January 17,
      1984,
                                  8240B - 29                        Revision 2
                                                                September 1994

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10.    Gebhart, J.E.;  Lucas,  S.V.;  Naber,  S.J.;  Berry,  A.M.; Danison,  T.H,;
      Burkholder,  H.M.  "Validation of SW-846 Methods 8010, 8015, and 8020"; U.S.
      Environmental  Protection  Agency,  Environmental  Monitoring and  Support
      Laboratory,  Cincinnati,  Old 45268,  July 1987, Contract No.  68-03-1760.

11.    Lucas, S.V.; Kornfeld,  R.A. "GC-MS Suitability Testing  of  RCRA Appendix
      VIII and Michigan List Analytes  ";  U.S.  Environmental  Protection Agency,
      Environmental  Monitoring  and  Support  Laboratory, Cincinnati,  OH 45268,
      February 20, 1987,  Contract No,  68-03-3224.
                                 8240B  - 30                         Revision  2
                                                                September 1994

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                                  TABLE  1.
        RETENTION TIMES AND CHARACTERISTIC IONS FOR VOLATILE COMPOUNDS
Compound
Retention
Time (minutes)
Primary Ion  Secondary Ion(s)
Ethyl ene oxide
Chloromethane
Di chl orodi f 1 uoromethane
Bromomethane
Vinyl chloride
Acetonitrile
Chloroethane
Methyl iodide
Methylene chloride
Carbon distil fide
Tri chl orof 1 uoromethane
Propionitrile
Ally! chloride
1, 1-Dichloroethene
Bromochloromethane (I.S.)
Ally! alcohol
trans- 1,2-Di chl oroethene
1,2-Dichloroethane
Propargyl alcohol
Chloroform
1,2-Di chl oroethane-d4(surr)
2-Butanone
Methacrylonitrile
Dibromomethane
2-Chloroethanol
b-Propiolactone
Epichlorohydrin
1,1,1 -Tri chloroethane
Carbon tetrachloride
1,4-Dioxane
Isobutyl alcohol
Bromodi chloromethane
Chloroprene
1 , 2 ; 3 , 4 -Di epoxybutane
1 , 2-Di chl oropropane
Chloral hydrate (b)
cis-1 ,3-Dichloropropene
Bromoacetone
Trichloroethene
Benzene
trans-l,3-Dichloropropene
1 , 1 , 2-Tri chl oroethane
3-Chloropropionitrile
1,2-Dibromoethane
Pyridine
1.30
2.30
2.47
3.10
3.80
3.97
4.60
5.37
6.40
7.47
8.30
8.53
8.83
9.00
9.30
9.77
10.00
10.10
10.77
11.40
12.10
12.20
12.37
12.53
12.93
13.00
13.10
13.40
13.70
13.70
13.80
14. 3C
14.77
14.87
15.70
15,77
15.90
16.33
16.50
17.00
17.20
17.20
17.37
18.40
18.57
44
50
85
94
62
41
64
142
84
76
101
54
76
96
128
' 57
96
62
55
83
65
72
41
93
49
42
57
97
117
88
43
83
53
55
63
82
75
136
130
78
75
97
54
107
79
44, 43, 42
52, 49
85, 87, 101, 103
96, 79
64, 61
41, 40, 39
66, 49
142, 127, 141
49, 51, 86
76, 78, 44
103, 66
54, 52, 55, 40
76, 41, 39, 78
61, 98
49, 130, 51
57, 58, 39
61, 98
64, 98
55, 39, 38, 53
85, 47
102
43, 72
41, 67, 39, 52, 66
93, 174, 95, 172, 176
49, 44, 43, 51, 80
42, 43, 44
57, 49, 62, 51
99, 117
119, 121
88, 58, 43, 57
43, 41, 42, 74
85, 129
53, 88, 90, 51
55, 57, 56
62, 41
44, 84, 86, 111
77, 39
43, 136, 138, 93, 95
95, 97, 132
52, 71
77, 39
83, 85, 99
54, 49, 89, 91
107, 109, 93, 188
79, 52, 51, 50
                                  8240B -  31
                                        Revision  2
                                    September  1994

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                                   TABLE 1.
                                  (Continued)
Compound
Retention
Time (minutes)
Primary Ion  Secondary Ion(s)
2-Chloroethyl vinyl ether
2-Hydroxypropi oni tri 1 e
1,4-Difluorobenzene (I.S.)
Malononitrile
Methyl roethacrylate
Broraoform
1, 1, 1,2-Tetrachloroethane
l,3-Dichloro-2-propanol
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
1,2,3-Trichloropropane
l,4-Dichloro-2-butene
n-Propylattiine
2-Picoline
Toluene
Ethyl methacrylate
Chlorobenzene
Pentachl oroethane3
Ethyl benzene
1 , 2-Di bromo-3-chl oropropane
4-Bromofluorobenzene (surr.)
Benzyl chloride
Styrene
bis-(2-Chloroethyl) sulfide(b)
Acetone
Acrolein
Acrylonitrile
Chlorobenzene-d5 (I.S.)
Chi orodi bromomethane
1,1-Dichloroethane
Ethanol
2-Hexanone
lodomethane
4-Methyl -2-pentanone
Toluene-de {surr.)
Vinyl acetate .
Xylene (Total)
18.60
18.97
19.60
19.60
19.77
19.80
20.33
21.83
22.10
22.20
22.20
22.73
23.00
23.20
23.50
23.53
24.60
24.83
26.40
27.23
28.30
29.50
30.83
33.53
--
--
--
_.
--
--
--
--
--
--
--
--
_ —
63
44
114
66
69
173
131
79
83
164
75
75
59
93
92
69
112
167
106
157
95
91
104
109
43
56
53
117
129
63
31
43
142
43
98
43
106
65,106
44,43,42,53
63,88
66,39,65,38
69,41,100,39
171,175,252
131,133,117,119,95
79,43,81,49
85,131,133
129,131,166
75,77,110,112,97
75,53,77,124,89
59,41,39
93,66,92,78
91,65
69,41,99,86,114
114,77
167,130,132,165,169
91
157,75,155,77
174,176
91,126,65,128
104,103,78,51,77
111, 158, 160
58
55,58
52,51
82,119
208,206
65,83
45,27,46
58,57, IOC
127,141
58,57,100
70,100
86
91
a The base peak at m/e 117 was not used due to an interference  at that mass with
  a nearly coeluting  internal standard, chlorobenzene-d5.
b  Response factor judged to be too low (less than 0,02) for practical use.
(I.S.) = Internal Standard
(surr) = Surrogate
                                  8240B - 32
                                        Revision 2
                                    September 1994

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                        TABLE 2.
ESTIMATED QUANTITATION LIMITS (EQL)  FOR VOLATILE  ORGANICS
Volatiles
Acetone
Acetonitrile
Ally! chloride
Benzene
Benzyl chloride
Bromodichloromethane
Bromoform
Bromomethane
2-Butanone
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chi orodi bromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Chloroprene
1 ,2-Dibromo-3-chloropropane
1 , 2-Di bromoethane
Di bromomethane
l,4-Dichloro-2-butene
Dichl orodi f 1 uoromethane
1,1-Dichloroethane
1, 2-Di chloroethane
1,1 Dichl oroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
ci s- 1 ,3 -Dichl oropropene
trans-l,3-Dich1oropropene
Ethyl benzene
Ethyl methacrylate
2-Hexanone
Isobutyl alcohol
Methacryl onitri 1 e
Methylene chloride
Methyl iodide
Methyl methacrylate
4-Methyl -2-pentanone
Pentachloroethane
Estimated
Quantitation
Limits8
Ground water Low
M9/L
100
100
5
5
100
5
5
10
100
100
5
5
5
10
10
5
10
5
100
5
5
100
5
5
5
5
5
5
5
5
5
5
50
100
100
5
5
5
50
10

Soil/Sedimentb
M9A9
100
100
5
5
100
5
5
10
100
100
5
5
5
10
10
5
10
5
100
5
5
100
5
5
5
5
5
*%
5
5
5
5
50
100
100
5
5
50
50
10
                       8240B - 33                        Revision 2
                                                     September 1994

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                                   TABLE 2.
                                  (Continued)
                                     Estimated
                                    Quantitation
                                      Limits"
                            Ground water       Low Soil/Sediment
Volatiles
Propionitrile
Styrene
1,1, 1,2-Tetrachloroethane
1 , 1 , 2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,1,1-Trichloroethane
1 ,1,2-Trichloroethane
Trichloroethene
1,2,3-Trichloropropane
Vinyl acetate
Vinyl chloride
Xylene (Total)
100
5
5
5
5
5
5
5
5
5
50
10
5
100
5
5
5
5
5
5
5
5
5
50
10
5
a Sample EQLs are highly matrix dependent.  The EQLs listed herein are provided
  for guidance and may not always be achievable.

b EQLs listed  for  soil/sediment  are based on wet  weight.  Normally  data  are
  reported on a dry weight basis; therefore,  EQLs will  be higher, based on  the
  percent dry weight of each sample.
               Other Matrices                      Factor0
               Water miscible liquid waste             50
               High-concentration soil  and sludge     125
               Non-water miscible waste               500


  CEQL  =   [EQL for  low  soil/sediment  (see Table 2)]  X [Factor found  in  this
          table].   For non-aqueous samples, the factor is  on a wet weight basis.
                                  8240B -  34                        Revision 2
                                                                September 1994

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                                TABLE 3.
                     BFB KEY ION ABUNDANCE CRITERIA
    Mass              Ion Abundance Criteria
    50               15 to 40% of mass 95
    75               30 to 60% of mass 95
    95               base peak, 100% relative abundance
    96               5 to 9% of mass 95
   173               less than 2% of mass 174
   174               greater than 50% of mass 95
   175               5 to 9% of mass 174
   176               greater than 95% but less than 101% of mass 174
   177               5 to 9% of mass 176
                                TABLE 4.
          QUANTITY OF METHANOL  EXTRACT  REQUIRED  FOR ANALYSIS
                 OF HIGH-CONCENTRATION  SOILS/SEDIMENTS
       Approximate                               Volume of
   Concentration Range                        Methanol  Extract3
      500- 10,000 pg/kg                            100 pi
    1,000- 20,000 M9/kg                             50 /uL
    5,000-100,000 pg/kg                             10 fj.1
   25,000-500,000 pg/kg                            100 fj.1 of 1/50 dilution4*
Calculate  appropriate  dilution  factor for  concentrations exceeding  this
table.

a  The volume of methanol  added  to  5 mL of water being purged should be kept
   constant.  Therefore,  add to the 5 mL syringe whatever volume of methanol
   is necessary to maintain a volume of 100 juL added to the syringe,

b  Dilute  and  aliquot  of  the  methanol extract  and then  take  100 /jL  for
   analysis.


                               8240B - 35                        Revision 2
                                                             September 1994

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                                    TABLE  5.
       VOLATILE  INTERNAL STANDARDS  WITH CORRESPONDING ANALYTES ASSIGNED
                                FOR  QUANTITATION
Bromochloromethane

Acetone
Acrolein
Acrylonitrile
Bromomethane
Carbon disulfide
Chloroethane
Chloroform
Chioromethane
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
I,2-Dichloroethane-d4 (surrogate)
1,1-Dichloroethene
trans-1,2-Dichloroethene
lodomethane
Methylene chloride
Tri chl orof1uoromethane
Vinyl chloride
1.4-DJ f1uprobenzen e

Benzene
Bromodichloromethane
Bromoform
2-Butanone
Carbon tetrachloride
Chlorod i bromomethane
2-Chloroethyl  vinyl  ether
Dibromomethane
l,4-Dichloro-2-fautene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
1,1,1-Trichloroethane
1,1,2^Trichloroethane
Trichloroethene
Vinyl acetate
                        Chlorobenzene-dc
                        Bromof1uorobenzene (surrogate)
                        Chlorobenzene
                        Ethyl benzene
                        Ethyl  methacrylate
                        2-Hexanone
                        4-Methyl-2-pentanone
                        Styrene
                        1}1»2,2-Tetrachloroethane
                        Tetrachloroethene
                        Toluene
                        Toluene-d8  (surrogate)
                        1,2,3-Tri chloropropane
                        Xylene
                                  8240B - 36
                      Revision 2
                  September 1994

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                                   TABLE 6.
                    CALIBRATION AND QC ACCEPTANCE CRITERIA3
Parameter
Benzene
Bromodi chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
2-Chloroethyl vinyl ether
Chloroform
Chl oromethane
Di bromochl oromethane
1, 2 -Di chlorobenzene
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans- 1,2-Di chl oroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Ethyl benzene
Methyl ene chloride
1,1,2, 2 -Tetrachl oroethane
Tetrachl oroethene
Toluene
1,1, 1 -Trichl oroethane
1,1,2-Trichloroethane
Trichl oroethene
Tri chl orof 1 uoromethane
Vinyl chloride
Range
for Q
(M9/L)
12.8-27.2
13.1-26.9
14.2-25.8
2.8-37.2
14.6-25.4
13.2-26.8
D-44.8
13.5-26.5
D-40,8
13.5-26.5
12.6-27.4
14.6-25.4
12,6-27.4
14.5-25.5
13.6-26.4
10.1-29.9
13.9-26.1
6.8-33.2
4.8-35.2
10.0-30.0
11.8-28.2
12.1-27.9
12.1-27.9
14.7-25.3
14.9-25.1
15.0-25.0
14.2-25.8
13.3-26.7
9.6-30.4
0.8-39.2
Limit
for s
(M9/L)
6.9
6.4
5.4
17.9
5.2
6.3
25.9
6.1
19.8
6.1
7.1
5.5
7.1
5.1
6.0
9.1
5.7
13.8
15.8
10.4
7.5
7.4
7.4
5.0
4.8
4.6
5.5
6.6
10.0
20.0
Range
for x
(M9/U
15.2-26.0
10.1-28.0
11.4-31.1
D-41.2
17.2-23.5
16.4-27.4
D-50.4
13.7-24.2
D-45.9
13.8-26.6
11.8-34.7
17.0-28.8
11.8-34.7
14.2-28.4
14.3-27.4
3.7-42.3
13.6-28.4
3.8-36.2
1.0-39.0
7.6-32.4
17.4-26.7
D-41.0
13.5-27.2
17.0-26.6
16.6-26.7
13.7-30.1
14.3-27.1
18.5-27.6
8.9-31.5
D-43.5
Range
37-151
35-155
45-169
D-242
70-140
37-160
D-305
51-138
D-273
53-149
18-190
59-156
18-190
59-155
49-155
D-234
54-156
D-210
D-227
17-183
37-162
D-221
46-157
64-148
47-150
52-162
52-150
71-157
17-181
D-251
X

P. Ps =
D
Concentration measured in QC check sample, in fj.g/1.
Standard deviation of four recovery measurements, in jig/L.
Average recovery for four recovery measurements, in M9/L.
Percent recovery measured.
Detected; result must be greater than zero.
   Criteria from 40 CFR Part 136 for Method 624 and were calculated assuming a
   QC check sample concentration of 20  pg/L.   These criteria are based directly
   upon the method performance  data in Table 7,  Where  necessary, the limits for
   recovery  have  been  broadened  to  assure  applicability  of  the limits  to
   concentrations below those used to develop Table 7.
                                  8240B - 37
                                                        Revision 2
                                                    September 1994

-------
                                    TABLE  7.
          METHOD ACCURACY AND PRECISION AS FUNCTIONS OF  CONCENTRATION*
Parameter
Benzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethylvinyl ether6
Chloroform
Chlorotnethane
Di bromochl oromethane
1 , 2-Di chl orobenzeneb
1 , 3 - Di chl orobenzene
1 , 4-Dichl orobenzeneb
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans- 1 , 2 , -Di chloroethene
1 , 2-Di chl oropropane8
cis-l,3-Dichloropropenea
trans-1 ,3-Di chl oropropene"
Ethyl benzene
Methyl ene chloride
1,1,2,2-Tetrachloroethane
Tetrachl oroethene
Toluene
1 , 1 , 1 -Tr i chl oroethane
1 ,1 ,2-Trichloroethane
Tri chl oroethene
Tri chl orof 1 uoromethane
Vinyl chloride
Accuracy, as
recovery, x'
(M9/L)
0.93C+2.00
1.03C-1.58
1.18C-2.35
l.OOC
1.10C-1.68
0.98C+2.28
1.18C+0.81
l.OOC
0.93C+0.33
1.03C-1.81
1.01C-0.03
0.94C+4.47
1.06C+1.68
0.94C+4.47
1.05C+0.36
1.02C+0.45
1.12C+0.61
1.05C+0.03
l.OOC
l.OOC
l.OOC
Q.98C+2.48
0.87C+1.88
0.93C+1.76
1.06C+0.60
Q.98C+2.03
1.06C+0.73
0.95C+1.71
1.04C+2.27
0.99C4-0.39
l.OOC
Single analyst
precision, s/
(M9/L)
0.26X-1.74
O.lSx-j-0.59
0.12X-J-0.34
0,43x
O.lZx-f-0.25
0.16X-0.09
0.14X+2.78
0.62X
0.16X+0.22
0,37x+2,14
0.17X-0.18
0.22X-1.45
0.14X-0.48
0.22X-1.45
0.13x-0.05
O.Ux-0.32
0.17X+1.06
0.14X+0.09
0.33x
0.38X
0.25x
0.14X+1.00
O.lBx+1.07
0.16X+0.69
0.13X-0.18
0.15X-0.71
0.12X-0.15
0.14x-{-0.02
0.13X+0.36
0.33X-1.48
0.48x
Overall
precision,
S' (MA)
0.25x-1.33
fl.20x-H.13
0.17X+1.38
0.58x
O.llx+0.37
0.26X-1.92
0.29x^1.75
0.84x
O.lSx+0.16
0.58X+0.43
0.17x+0.49
0.30X-1.20
O.lSx-0.82
fl.30x-l.20
0.16X+0.47
0.21X-0.38
0.43X-0.22
0.19X+0.17
0,45x
0.52x
0.34x
0.26X-1.72
0.32X+4.00
0.20X+0.41
0.16X-0.45
0.22X-1.71
fl.21x-0.39
O.lSx-rO.OO
Q-.12x-f-0.59
0.34X-0.39
0.65x
S'

C
x

a
b
      Expected  recovery  for  one  or more  measurements  of  a  sample
      containing a concentration of C, in /ig/L.
      Expected  single  analyst  standard deviation of measurements  at an
      average concentration of x, in ^g/L.
      Expected  interlaboratory standard  deviation of measurements  at an
      average concentration found of x,  in fig/L.
      True value for the concentration,  in /ng/L.
=     Average recovery found for measurements  of samples  containing  a
      concentration of C, in jiig/L.
Estimates based upon the performance  in  a single laboratory.
Due to  chromatographic resolution problems, performance  statements for
these isomers are based upon the sums of their concentrations.
                                  8240B - 38
                                                              Revision 2
                                                          September 1994

-------
                                   TABLE 8.
      SURROGATE  SPIKE  RECOVERY  LIMITS  FOR WATER AND SOIL/SEDIMENT SAMPLES
                                 Low/High             Low/High
Surrogate Compound                Water             Soil/Sediment
4-Bromofluorobenzene             86-115               74-121
l,2-Dichloroethane-d4            76-114               70-121
To1uene-d0                       88-110               81-117
                                  8240B - 39                        Revision 2
                                                                September 1994

-------
                         FIGURE  1.
                     PURGING CHAMBER
                         "* M, OH,
EOT 1M IN, 0.0
IT CM 30 OMAE SYHINOf HEBX£

• MM O.B. RUMEM SEPTUM

**UT W4 M, Q.O.
MfDMM PQHOWTT        yC    J
                                                  VW IM O-O
                                               /'STAINUSSSTKL
                                                 ISC
                                                 MCXfCUUM SEVC
                                                 WJUBC GAS RtTBB
                                                   FLOW CQNTNOL
                         8240B - 40
                                   Revision  2
                               September  1994

-------
                  FIGURE 2.
   TRAP  PACKINGS AND  CONSTRUCTION  TO  INCLUDE
      DESORB CAPABILITY FOR METHOD 8240B
PACKING
OfTM.
                    8240B - 41
                Revision 2
            September 1994

-------
                               FIGURE  3.
   SCHEMATIC  OF PURGE-AND-TRAP DEVICE - PURGE MODE FOR METHOD 8240B
CARRIER GAS
ROW CONTROL
PRESSURE
REGULATOR
UOUIO INJECTION PORTS

      COLUMN OVEN
               CONFIRMATORY COLUMN


              TO DETECTOR
PURQEQAS  ^
FLOW CONTROL
t3X MOLECULAR
SIEVE RLTER
                                                 ANALYTICAL COLUMN
                               OPTIONAL **»ORT COLUMN
                               SELECTION VALVE
                                »»    /• TRAP INLET
                                       TRAP
                                       arc
                                Ai PURGING
                                "OCVICE
             NOTE;
             ALL UHiS BETWEEN TRAP
             ANO QC SHOULD K HiATEO
             TO arc.
                              8240B - 42
                               Revision 2
                           September 1994

-------
                            FIGURE  4.
SCHEMATIC OF PURGE-AND-TRAP DEVICE  - DESORB MODE FOR METHOD 8240B
CARWEBQAS
FLOWOOfCmOL
PRESSURE
REGULATOR
LJQUD fUiCrnON PORTS

    — COLUMN OVEN
                                     JIAJV-
               CONFIRMATORY COLUMN

              TO DETECTOR
                                                ANALYTICAL COLUMN
                              OPTWNAL 4-POPT COLUMN
                              SELECTION VALVE
                                       TRAP INLET
PURGE GAS
FLOW CONTROL
13* MOLECULAR
SIEVE FILTER
                                PURGING
                                OCVCE
             NOTE.
             AIL LINES BFTWEEN TRAP
             AMD QC SHOULD BE HEATED
                           8240B - 43
                            Revision  2
                        September 1994

-------
                    FIGURE 5.
                LOW SOILS IMPINGER
  PURGE INLfT FITTING
 SAMPLE OUTLET FITTING
I" s 6mm 0 D CLASS TUBING
                                     SEPTUM
                                        CAP
             40ml VIAL
                   8240B -  44
    Revision 2
September 1994

-------
                                 HETHOD 8240B
VOLATILE ORGANICS  BY  GAS  CHROMATOGRAPHY/MASS SPECTROMETRY  (6C/MS)
                                              Water
                                             Miscible
                                              Liquids
                                                                        Soil/Sediment
                                                                          and Waste
                                                                           Samples
    7.1
   Select
procedure for
 introducing
 cample into
  GC/MS.
     7,4
    Select
  screening
method for the
    waste
    matrix.
                              7.4.2.1
                            Dilute sample
                             at least 50
                             fold with
                               water.
                                                                                         7.4.3 Screen
                                                                                         sample using
                                                                                         Method 3810
                                                                                           or 3820.
 Direct
Injection
                                                    Water
                                                   Samples
rurge-and-trnp
                                                        7.4.1.1
                                                     Screen sample
                                                      using Method
                                                     3810 or 3820.
            7.2.1
          Set GC/MS
           operating
          conditions.
                                                        7.4.1.7
                                                        Perform
                                                       secondary
                                                       dilutions.
        7,2.4 Connect
        purge-0nd-trap
        device to GC.
 7.2,6 Perform
 purge-nnd-trap
    analysis.
                                                              7.4.1.8 Add
                                                            internal standard
                                                             and surrogate
                                                            •piking solutions.
     7.2.8
 Calculate RFs
 for S SPCCs.
                                                                7.4.1.10
                                                                Parform
                                                             purge-and-trap
                                                               procedure.
  7.3 Perform
     daily
   calibration
  using SPCCs
   and CCCs.
                                   8240B  - 45
                                                                                      Revision  2
                                                                                 September  1994

-------
                                       METHOD  B240B
                                        (continued)
 concentration
  > 1 ma/Kg?
   7.4,3,1.1
 Choose sample
 size based on
   estimated
 concentration.
 7.4.3.1.3 Add
internal standard
 and surrogate
spiking solutions.
   7.4.3,1.5
   Determine
  percent dry
   weight of
    sample.
    7.4.3.1.7
     Perform
  purge-and-trap
   procedure.
7.4.3.2 Choose
  solvent for
 extraction or
dilution. Weigh
    sample.
 7,4.3.2.2 Add
    solvent,
     shake.
   7.4.3.2.7
    Perform
 purge-and-trap
  procedure.
    7.4.1.11
   Attach trap
   to GC and
    perform
    analysis.
7.5.1.1  Indentify
   anaiytet by
 comparing the
sample retention
time and sample
 mass spectra.
7.5.2.2 Calculate
the concentration
of each identified
    analyte.
                                            7.5.2.4
                                           Report all
                                            results.
                                         (   St°p    I
                                        8240B  - 46
                                                 Revision  2
                                            September 1994

-------
                                 METHOD 8250A

SEHIVOLATILE ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY fGC/MS)


1.0   SCOPE AND APPLICATION

      1.1   Method 8250 is used to determine the concentration of semivolatile
organic compounds in extracts prepared from all  types of solid waste matrices,
soils, and ground water.  Direct  injection  of a  sample  may  be used in limited
applications.  The following compounds can be determined by  this method;
                                            Appropriate  Preparation  Techniques
Compounds
CAS No*   3510
                                  8250A - 1
3520  3540/   3550  3580
      3541
Acenaphthene
Acenaphthene-d10 (I.S.)
Acenaphthylene
Acetophenone
Aldrin
4-Aminobiphenyl
Aniline
Anthracene
Aroclor - 1016 (PCB-1016)
Aroclor - 1221 (PCB-1221)
Aroclor - 1232 (PCB-1232)
Aroclor - 1242 (PCB-1242)
Aroclor - 1248 (PCB-1248)
Aroclor - 1254 (PCB-1254)
Aroclor - 1260 (PCB-1260)
Benzidine
Benzoic acid
Benz( a) anthracene
Benzo(b)fl uoranthene
Benzo ( k) f 1 uoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzyl alcohol
a-BHC
£-BHC
5-BHC
•y-BHC (Lindane)
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl ) ether
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
83-32-9

208-96-8
98-86-2
309-00-2
92-67-1
62-53-3
120-12-7
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
92-87-5
65-85-0
56-55-3
205-99-2
207-08-5
191-24-2
50-32-8
100-51-6
319-84-6
319-85-7
319-86-8
58-89-9
111-91-1
111-44-4
108-60-1
117-81-7
101-55-3
85-68-7
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
X
X
X
V
A
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
ND
X
X
X
X
X
X
X
X
X
CP
X
X
X
V
A
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
ND
ND
X
X
X
X
X
X
X
X
CP
ND
X
X
V
A
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
ND
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
X
X
X
V
A
X
X
X
X
X
X
X
X
X
X
X
X
X
                                Revision 1
                            September 1994

-------
Compounds
        Appropriate Preparation Techniques

CAS Noa    3510      3520  3540/   3550  3580
                        3541
Chlordane (technical)
4-Chloroaniline
1 -Chi oronaphthal ene
2-Chloronaphthalene
4-Chloro-3-methyl phenol
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Chrysene-d12 (I.S.)
4,4'-DDD
4, 4' -DDT
4,4'-DDE
Dibenz(a,j)acridine
Dibenz (a, h) anthracene
Dibenzofuran
Di-n-butyl phthalate
1 , 2 -D i chl orobenzene
1 , 3-Di chl orobenzene
1 » 4-Di chl orobenzene
l,4-Dichlorobenzene-d4 (I.S)
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dieldrin
Diethyl phthalate
Dimethyl ami noazobenzene
7,12-Dimethylbenz(a)-
anthracene
a»a-Dimethylphenethylamine
2, 4-Dimethyl phenol
Dimethyl phthalate
4,6-Dinitro-2-inethy"!phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di phenyl ami ne
1,2-Di phenyl hydrazine
Di-n-octyl phthalate
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
Ethyl methanesulfonate
57-74-9
106-47-8
90-13-1
91-58-7
59-50-7
95-57-8
7005-72-3
218-01-9

72-54-8
50-29-3
72-55-9
224-42-0
53-70-3
132-64-9
84-74-2
95-50-1
541-73-1
106-46-7
3855-82-1
91-94-1
120-83-2
87-65-0
60-57-1
84-66-2
60-11-7

57-97-6
122-09-8
105-67-9
131-11-3
534-52-1
51-28-5
121-14-2
606-20-2
122-39-4
122-66-7
117-84-0
959-98-8
33213-65-9
1031-07-8
72-20-8
7421-93-4
53494-70-5
62-50-0
X
X
X
X

X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X

CP(45)
ND
X
X
V
A
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
X

X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
ND
X
X
ND

ND
ND
X
X
V
A
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
ND
X
X

X
X
X
X
X
X
X
ND
X
ND
X
X
X
X
X
X
X
ND
X
X
ND

ND
ND
X
X
V
A
X
X
X
X
X
X
X
X
X
X
X
ND
ND
X
ND
X
X

X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
ND
X
X
ND

ND
ND
X
X
V
A
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X

X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X

CP
X
X
X
V
A
X
X
X
X
X
X
X
X
X
X
X
X
V
A
                                  8250A -  2
                                Revision 1
                            September 1994

-------
Compounds
Fluoranthene
Fluorene
2-Fluorobiphenyl (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentad i ene
Hexachloroethane
Indeno(l,2,3-cd)pyrene
Isophorone
Methoxychlor
3-Methyl chol anthrene
Methyl methanesulfonate
2-Methyl naphtha! ene
2-Methyl phenol
4-Methyl phenol
Naphthalene
Naphthalene-d8 (I.S.)
1-Naphthyl amine
2-Naphthyl amine
2-Nitroaniline
3-Nitroanil ine
4-Nitroanil ine
Nitrobenzene
Nitrobenzene-d5 (surr.)
2-Nitrophenol
4-Nitrophenol
N- Ni trosod i butyl ami ne
N-Nitrosodi methyl amine
N-Ni trosod iphenyl amine
N-Nitrosodi -n-propyl amine
N-Nitrosopiperidine
Pentachl orobenzene
Pentachloronitrobenzene
Pentachl orophenol
Perylene-d12 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-d10 (I.S.)
Phenol
Phenol -d6 (surr.)
2- Pi col ine
Pronamide
j
CAS No*
206-44-0
86-73-7
321-60-8
367-12-4
76-44-8
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
193-39-5
78-59-1
72-43-5
56-49-5
66-27-3
91-57-6
95-48-7
106-44-5
91-20-3
1146-65-2
134-32-7
91-59-8
88-74-4
99-09-2
100-01-6
98-95-3
4165-60-0
'88-75-5
100-02-7
924-16-3
62-75-9
86-3C-5
621-64-7
100-75-4
608-93-5
82-68-8
87-86-5
198-55-0
62-44-2
85-01-8

108-95-2
13127-88-3
109-06-8
23950-58-5
Appropriate Preparation Techniques
3510
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
OS(44)
X
X
X
X
X
X
X
X
X
X
V
A
X
X
X
X
X
X
X
X
X
DC(28)
DC(28)
ND
X
3520
X
X
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
X
ND
ND
X
X
ND
ND
X
X
X
X
X
X
X
ND
X
V
A
X
ND
ND
ND
X
X
ND
X
X
X
X
ND
ND
3540/
3541
X
X
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
ND
ND
X
X
X
X
ND
X
V
A
X
ND
ND
ND
X
X
ND
X
X
X
X
ND
ND
3550
X
X
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
X
ND
ND
X .
X
ND
ND
X
X
X
X
X
X
X
ND
X
V
A
X
ND
ND
ND
X
X
ND
X
X
X
X
ND
ND
3580
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
V
A
X
X
X
X
X
X
X
X
X
X
X
ND
X
8250A - 3
    Revision 1
September 1994

-------
                                            Appropriate Preparation Techniques

Compounds                           CAS Noa   3510     3520  3540/  3550  3580
                                                             3541
Pyrene
Terphenyl-d14(surr.)
1 , 2 , 4, 5-Tetrachl orobenzene
2,3,4, 6-Tetrachl orophenol
Toxaphene
2 , 4 , 6~Tri bromophenol ( surr . )
1, 2, 4-Trichl orobenzene
2, 4, 5-Trichl orophenol
2, 4, 6-Trichl orophenol
129-00-0
1718-51-0
95-94-3
58-90-2
8001-35-2
118-79-6
120-82-1
95-95-4
88-06-2
X
X
X
X
X
X
X
X
X
X
X
ND
ND
X
X
X
X
X
X
ND
ND
ND
X
X
X
ND
X
X
X
ND
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
a     Chemical Abstract Service Registry Number,

CP    =     Nonreproducible chromatographic performance.
DC    =     Unfavorable  distribution  coefficient   (number  in  parenthesis  is
            percent recovery).
ND    -     Not determined.
OS    =     Oxidation  during   storage  (number  in  parenthesis  is  percent
            stability).
X     =     Greater than 70 percent  recovery by this technique.


      1.2   Method 8250  can be used to quantitate most  neutral,  acidic,  and
basic organic compounds that are  soluble  in  methylene  chloride and capable of
being eluted without derivatization  as sharp  peaks  from a gas chromatographic
packed  column.    Such compounds  include  polynuclear   aromatic  hydrocarbons,
chlorinated  hydrocarbons  and  pesticides,  phthalate   esters,  organophosphate
esters,   nitrosamines,  haloethers,   aldehydes,   ethers,   ketones,  anilines,
pyridines,  quinolines,  aromatic  nitro  compounds,  and  phenols,  including
nitrophenols.   See Table 1 for a list of compounds and their characteristic ions
that have been evaluated on the specified GC/MS system.

      1.3   The following  compounds may require special  treatment when being
determined by this method.   Benzidine can  be subject to  oxidative losses during
solvent   concentration.   Also,  chromatography  is  poor.   Under the  alkaline
conditions of the  extraction step, a-BHC, 7-BHC, endosulfan I  and II, and endrin
are subject to decomposition.   Neutral extraction should be performed if these
compounds  are  expected  and   are   not  being  determined   by  Method  8080.
Hexachlorocyclopentadiene is subject  to thermal  decomposition in the  inlet of the
gas chromatograph, chemical  reaction  in  acetone solution,  and photochemical
decomposition. N-nitrosodimethylamine is difficult to separate from the solvent
under  the  chromatographic  conditions  described.     N-nitrosodiphenylamine
decomposes  in  the gas chromatographic inlet  and  cannot  be  separated  from
diphenylamine. Pentachlorophenol,  2,4-dinitrophenol,4-nitrophenol, 4,6-dinitro-
2-methylphenol,   4-chloro-3-methylphenol,   benzoic    acid,    2-nitroaniline,


                                  8250A -  4                         Revision 1
                                                                September 1994

-------
3-nitroaniline,  4-chloroaniline,  and  benzyl  alcohol  are  subject  to  erratic
chromatographic behavior, especially if the EC system is contaminated with high
boil ing material.

      1.4   The   estimated   quantitation   limit  (EQL)  of  Method  8250  for
determining an  individual  compound  is approximately  1 mg/kg  (wet weight) for
soil/sediment samples, 1-200 mg/kg for wastes  (dependent on  matrix  and method of
preparation),  and 10 jig/L for ground water samples (see Table  2).  EQLs will be
proportionately  higher for  sample  extracts  that require  dilution to  avoid
saturation of the detector.

      1.5   This  method  is restricted to  use by or  under the  supervision of
analysts experienced  in  the  use  of gas chromatograph/mass  spectrometers and
skilled in  the interpretation of mass spectra.  Each analyst  must demonstrate the
ability to generate acceptable results with this method.


2.0   SUMMARY OF METHOD

      2.1   Prior  to  using this  method,  the  samples should be  prepared for
chromatography using  the  appropriate sample  preparation and  cleanup  methods.
This . method  describes  chromatographic  conditions   that  will  allow  for  the
separation of the compounds in the extract.


3.0   INTERFERENCES

      3.1   Raw  GC/MS data  from  all   blanks,   samples,  and  spikes  must  be
evaluated for  interferences.  Determine if  the source of interference is in the
preparation and/or cleanup of the samples and take corrective action to eliminate
the problem.

      3.2   Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially analyzed.   To  reduce carryover, the
sample syringe must be rinsed out  between samples with solvent.   Whenever an
unusually  concentrated  sample is encountered,  it should  be followed by the
analysis of solvent to check for cross contamination.


4.0   APPARATUS AND MATERIALS

      4.1   Gas chromatograph/mass spectrometer system

            4.1.1 Gas  chroraatograph -  An  analytical  system  complete with  a
      temperature-programmable  gas   chromatograph    suitable   for   splitless
      injection and all  required accessories,  including syringes,  analytical
      columns,  and gases.

            4.1.2 Columns

                  4.1.2.1      For base/neutral  compound  detection  -  2 m  x  2
            mm ID stainless or glass,  packed with 3%  SP-2250-DB on 100/120 mesh
            Supelcoport or equivalent.


                                  8250A  -  5                         Revision 1
                                                                September 1994

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                   4.1.2.2      For acid compound detection - 2 m x 2 mm ID glass,
             packed with 1% SP-1240-DA on 100/120 mesh Supelcoport or equivalent.

             4.1,3  Mass  spectrometer -  Capable of scanning from 35  to  500 amu
       every  1  second  or less,  using 70  volts (nominal)  electron energy in the
       electron  impact  ionization  mode.  The  mass spectrometer must  be  capable
       of  producing a mass  spectrum for  decaf!uorotriphenylphosphine  (DFTPP)
       which  meets  all of the criteria in Table 3 when 1  pi of the GC/MS tuning
       standard  is  injected through  the GC {50 ng of DFTPP).

             4.1.4  GC/MS interface - Any GC-to-MS interface that gives acceptable
       calibration  points at  50  ng per  injection  for each compound of interest
       and achieves acceptable tuning performance criteria may  be used.  GC-to-MS
       interfaces  constructed entirely  of glass  or glass-lined materials are
       recommended.      Glass   may  be   deactivated    by   silanizing   with
       dichlorodimethyl si lane.

             4.1.5  Data system - A computer system must be interfaced to the mass
       spectrometer.   The  system must  allow the  continuous acquisition  and
       storage on machine-readable media  of all mass  spectra obtained throughout
       the  duration of the  chroraatographic  program.  The computer must  have
       software that can search any  GC/MS data file for ions of a specific mass
       and that  can plot  such  ion  abundances  versus  time or scan  number.   This
       type  of plot  is  defined as  an  Extracted  Ion  Current Profile  (EICP).
       Software must also be available that allows integrating the abundances in
       any EICP  between  specified  time or  scan-number  limits.   The most recent
       version of the EPA/NIH Mass Spectral  Library should also be available.

       4.2    Syringe - 10 pi.


5.0    REAGENTS

       5.1    Reagent grade chemicals shall be used in all  tests. Unless otherwise
indicated, it is intended that  all  reagents shall conform to the specifications
of the Committee on Analytical  Reagents of the American Chemical  Society,  where
such specifications are available. Other grades may be used, provided it is first
ascertained  that the reagent is of  sufficiently  high  purity  to  permit  its use
without lessening the accuracy of the determination.

       5.2    Organic-free reagent water.  All  references  to water in this method
refer  to organic-free reagent water, as defined in Chapter One.

       5.3    Stock  standard  solutions (1000  mg/L} - Standard  solutions  can be
prepared from pure standard materials or purchased as certified solutions.

             5,3.1  Prepare stock standard solutions by accurately weighing about
       0.0100 g  of  pure  material.    Dissolve the material  in  pesticide  quality
       acetone  or other  suitable  solvent  and dilute  to volume  in a 10  ml
       volumetric flask.  Larger volumes can  be used at  the convenience of the
       analyst.  When  compound purity is assayed to be 96% or greater, the weight
      may be used without correction to calculate  the concentration of the stock
       standard.   Commercially  prepared  stock standards may be  used  at  any


                                   8250A - 6                         Revision 1
                                                                September 1994

-------
       concentration   if  they  are  certified  by  the  manufacturer  or  by  an
       independent  source.

             5.3.2  Transfer the stock standard solutions into bottles with Teflon
       lined  screw-caps or crimp  tops.   Store  at  -10°C  to  ~20°C  or less and
       protect from light.  Stock standard solutions should be  checked frequently
       for  signs  of  degradation   or  evaporation,  especially  just  prior  to
       preparing calibration  standards from  them.

             5.3.3  Stock  standard   solutions  must  be replaced after  I  year or
       sooner  if comparison  with   quality  control  check samples  indicates  a
       problem.

       5.4    Internal  standard solutions  - The  internal standards  recommended are
1,4-dichlorobenzene-d4,  naphthalene-ds,   acenaphthene-d10,   phenanthrene-d10,
chrysene-d12, and perylene-d12.  Other compounds may be used as  internal standards
as long as  the requirements given in Sec. 7.3.2 are met.  Dissolve 200  mg of each
compound with a  small  volume of carbon disulfide. Transfer to a 50 ml volumetric
flask  and dilute to volume  with methylene chloride so that the final solvent is
approximately 20% carbon disulfide.  Most of  the compounds are also soluble in
small  volumes of methane!, acetone,  or  toluene, except  for  perylene-d12.  The
resulting solution  will contain each standard  at a  concentration  of 4,000 ng/^L.
Each 1 ml sample extract  undergoing analysis should  be spiked with 10 pL of the
internal standard  solution,  resulting  in a concentration of 40  ng/^L  of each
internal standard.   Store  at -10°C to -20°C or  less when not being used.

       5.5   EC/MS  tuning standard - A  methylene  chloride solution containing
50 ng/jiL  of decafluorotriphenylphosphine   (DFTPP)  should be  prepared.    The
standard should also  contain 50 ng/^L each of 4,4'-DDT,  pentachlorophenol, and
benzidine to verify injection port inertness  and GC column performance.  Store
at 4°C or less when not being used.

       5.6   Calibration  standards  - Calibration standards at a minimum of five
concentrations should  be prepared.  One of the  calibration standards should be
at a  concentration near, but above,  the method  detection limit; the others should
correspond to the range of concentrations found in real   samples but should not
exceed the  working  range  of the GC/MS system.  Each standard should contain each
analyte for detection  by this method (e.g. some or all of the compounds listed
in Table 1  may be included).  Each 1 ml aliquot of calibration standard should
be spiked with 1C JUL  of the  interne" standard sc'uticr: pfior tc analysis.  AT!
standards should be stored  at -10°C to -20°C and should be freshly prepared once
a year, or  sooner if check  standards  indicate a  problem.  The daily calibration
standard should be prepared weekly and stored at 4°C.

       5.7   Surrogate  standards   -  The  recommended surrogate standards are
phenol-d6,    2-fluorophenol,    2,4,6-tribroraophenol,    nitrobenzene-d5,    2-
fluorobiphenyl,  and p-terphenyl-d,4.   See Method  3500  for the  instructions on
preparing the surrogate standards.  Determine what concentration should be  in the
blank  extracts after  all  extraction, cleanup, and concentration steps.   Inject
this concentration into the GC/MS  to determine  recovery  of surrogate standards
in all blanks,  spikes, and  sample  extracts.   Take  into account all dilutions of
sample extracts.
                                   8250A -  7                         Revision 1
                                                                September 1994

-------
      5.8    Matrix  spike  standards  -  See Method  3500  for  instructions  on
preparing the matrix spike standard.  Determine what concentration should be in
the  blank  extracts  after all  extraction,  cleanup,  and  concentration  steps.
Inject this  concentration into the GC/MS to determine recovery of standards in
all matrix spikes.  Take  into account all dilutions of sample extracts.


6.0   SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

      6.1    See  the  introductory material  to this chapter,  Organic Analytes,
Sec. 4.1.
7.0   PROCEDURE

      7.1   Sample  preparation  -  Samples  must  be  prepared  by  one  of  the
following methods prior to GC/MS analysis.

      Matrix                                Methods
      Water                                 3510, 3520
      Soil/sediment                         3540, 3541,  3550
      Waste                                 3540, 3541,  3550,  3580

            7.1.1 Direct  injection  -   In  very  limited  applications  direct
      injection of the sample into  the GC/MS system with a 10 ^L syringe may be
      appropriate.     The  detection   limit   is  very   high   (approximately
      10,000 M9/L);  therefore,  it  is only  permitted where concentrations  in
      excess of  10,000  ^9/L are expected.  The  system must be  calibrated  by
      direct injection.

      7.2   Extract cleanup - Extracts may be cleaned up  by any of the following
methods prior to GC/MS analysis.

      Compounds                                Methods
      Phenols                                  3630, 3640,  8040*
      Phthalate esters                         3610, 3620,  3640
      Nitrosamines                             3610, 3620,  3640
      Organochlorine pesticides & PCBs          3620, 3640,  3660
      Nitroaromatics and cyclic ketones         3620, 3640
      Polynuclear aromatic hydrocarbons         3611, 363C,  354C
      Haloethers                               3620, 3640
      Chlorinated hydrocarbons                 3620, 3640
      Organophosphorus pesticides              3620
      Petroleum waste                          3611, 3650
      All basic, neutral, and acidic
      Priority Pollutants                      3640


"Method 8040 includes a derivatization technique followed by GC/ECD analysis,  if
interferences are encountered on GC/FID.
                                  8250A  - 8                         Revision 1
                                                                September 1994

-------
7.3    Recommended  GC/MS operating  conditions

Electron energy;               70 volts (nominal)
Mass range;                    35-500 amu
Scan time:                     1  sec/scan
Injector temperature:          250-300°C
Transfer line temperature:     250-300°C
Source temperature:            According  to manufacturer's specifications
Injector:                      Grob-type, splitless
Sample volume:                 1-2  ^L
Carrier gas:                   Helium at  30  mL/min

Conditions for base/neutral analysis  (3% SP-225Q-DB):

Initial column temperature and hold time:       50°C for 4 minutes
Column temperature program:                     50-300°C at 8°C/min
Final column temperature hold:                  300°C for 20 minutes

Conditions for acid analysis (1% SP-1240-DA):

Initial column temperature and hold time:       70°C for 2 minutes
Column temperature program:                     70-200°C at 8°C/min
Final column temperature hold:                  200°C for 20 minutes

7.4 Initial calibration

      7.4.1 Each GC/MS system must be hardware-tuned to  meet  the criteria
in Table 3  for  a 50 ng injection  of DFTPP.  Analyses  should not begin
until  all  these criteria  are met.    Background  subtraction  should be
straightforward and designed only to  eliminate column bleed or instrument
background ions.  The GC/MS tuning  standard  should also  be used to assess
GC column performance and  injection  port inertness.   Degradation of DDT
to DDE and  ODD  should not  exceed  20% (See Sec. 7.4.5  of Method 8080).
Benzidine  and  pentachlorophenol   should be  present   at  their  normal
responses,  and  no  peak tailing  should  be  visible.   If degradation is
excessive and/or poor  chromatography  is noted,  the injection  port may
require cleaning.

      7.4.2 The internal  standards  selected in Sec.  5.1 should permit most
of the components  of interest  in a chromatogram to  have retention times
of 0.80-1.20 relative to one of the internal  standards.   Use  the base peak
ion  from  the  specific  internal   standard  as  the  primary  ion  for
quantitation (see Table 1).  If interferences are noted,  use  the next most
intense ion as the quantitation ion  (i.e. for l,4-dichlorobenzene-d4 use
m/z 152 for quantitation).
                            8250A  -  9                         Revision 1
                                                          September 1994

-------
       7.4.3 Analyze 1 juL of each calibration standard (containing internal
standards) and tabulate the area of the primary characteristic  ion against
concentration  for  each compound  (as  indicated in  Table  1).   Calculate
response factors (RFs) for each compound relative to the  internal standard
as follows:

       RF « (A,Cis)/(A,sCx)

where:

Ax     =     Area  of  the  characteristic  ion  for  the compound  being
            measured.
AJS     =     Area  of  the  characteristic  ion  for the  specific internal
            standard.
Cx     =     Concentration  of the  compound being measured  (ng/^l).
Cis     =     Concentration  of the  specific internal  standard
      7.4.4 A system  performance  check must be performed to ensure that
minimum  average  response  factors,  calculated  as  the  mean  of  the  5
individual relative response factors, are met before  the calibration curve
is  used.    For  semivolatiles,  the System  Performance  Check  Compounds
(SPCCs)  are:    N-nitroso-di-n-propylamine;  hexachlorocyclopentadiene;
2,4-dinitrophenol ; and 4-nitrophenol .  The minimum acceptable average RF
for these compounds  is  0.050.   These  SPCCs typically have  very low RFs
(0.1-0.2) and tend to decrease in response as the chromatographic system
begins to deteriorate or the  standard material begins  to  deteriorate.
They are  usually the first to show poor performance.  Therefore, they must
meet the minimum requirement when the  system is calibrated.

            7.4.4.1     The percent relative standard deviation should be
      less  than 15%  for  each  compound.    However, the %RSD  for each
      individual Calibration Check  Compound (CCC)  (see  Table 4) must be
      less than 30%.   The  relative retention  times of  each compound in
      each calibration  run  should agree within  0.06  relative retention
      time  units.     Late-eluting  compounds  usually  have  much  better
      agreement.
                        SO
            %RSD = - — -   x 100
                        RF
      where:
            RSD   =      relative  standard  deviation.
            RF    =      mean of 5  initial  RFs  for a compound.
            SD    =      standard deviation of average  RFs  for a compound.
                            8250A - 10                        Revision 1
                                                          September 1994

-------
                            N   (RF; - RF}2
            SD =         II   	
                         J  i=I  N - I

      where:

            RFj     =      RF for each of the  5  calibration  levels
            N      =      Number of RF values (i.e.,  5}

            7.4.4.2      If the %RSD of any CCC is 30% or greater, then the
      chromatographic system is too reactive for analysis  to begin.  Clean
      or replace the injector  liner  and/or capillary column, then repeat
      the calibration procedure beginning with Sec. 7.4.

      7.4.5 Linearity -  If the %RSD  of  any compound is 15% or lesss then
the  relative   response  factor  is  assumed  to  be  constant  over  the
calibration range, and the average relative response factor may be used
for quantitation (Sec. 7.7.2).

            7.4.5.1      If the %>RSD  of  any compound is greater than 15%,
      construct   calibration   curves   of   area  ratio   (A/Ais)   versus
      concentration using first or higher order regression fit of the five
      calibration points.  The analyst should  select the regression order
      which introduces the  least calibration error into the quantitation
      (Sees. 7.7.2.2  and 7.7.2.3).  The use  of  calibration  curves is a
      recommended alternative to average response factor calibration, and
      a useful  diagnostic of standard preparation accuracy and absorption
      activity in the chromatographic system.

7.5   Daily GC/MS calibration

      7.5.1 Prior to analysis  of samples, the GC/MS tuning standard must
be analyzed.  A 50 ng injection of DFTPP must result in  a mass spectrum
for DFTPP which  meets the criteria given in  Table 3,  These criteria must
be demonstrated during each 12 hour  shift.

      7.5.2 A calibration standard(s) at mid-concentration containing all
semivolatile  analytes,   including   all  required  surrogates,   must  be
analyzed every  12  hours during  analysis.  Compare the instrument response
factor from the standards  every 12 hours with the  SPCC (Sec. 7.5.3) and
CCC (Sec. 7.5.4) criteria.

      7.5.3 System  Performance  Check  Compounds  (SPCCs)  -  A  system
performance check must be  made during  every 12  hour shift.   If the SPCC
criteria  are  met,  a comparison  of  response  factors  is  made for all
compounds.  This  is the same  check that is  applied during  the  initial
calibration. If the minimum response factors are not met, the system must
be evaluated,  and corrective action must be taken before  sample analysis
begins.   The minimum RF  for semivolatile SPCCs  is  0.050.   Some possible
problems  are   standard   mixture  degradation,  injection   port   inlet
contamination,  contamination at the  front end of the analytical  column,
                            8250A - 11                        Revision 1
                                                          September 1994

-------
and active sites in the column or chromatographic system.  This check must
be met  before analysis begins.

      7.5.4  Calibration  Check  Compounds   (CCCs):    After  the  system
performance  check  is  met,  CCCs  listed in Table 4  are  used  to  check the
validity of  the initial calibration.

      Calculate the percent drift using:

                c,   -  cc
      % Drift = 	  x 100
where:

      C, =  Calibration Check Compound standard concentration.
      C0 =  Measured concentration using selected quantitation method.

      If the percent difference  for each CCC is less  than  or equal to 20%,
the initial calibration is assumed to be valid.  If the criterion is not
met  (>  20%  drift)  for  any one CCC,  corrective  action must  be taken.
Problems similar to those  listed under SPCCs could affect this criterion.
If no source of the problem  can  be determined after corrective action has
been  taken, a  new  five-point   calibration  must  be  generated.    This
criterion must be met before sample analysis begins.  If the CCCs are not
analytes required by the permit,  then all required analytes must meet the
20% drift criterion.

      7.5.5 The  internal  standard  responses  and retention times  in the
calibration check standard must be evaluated immediately after or during
data acquisition.  If the retention time for any internal standard changes
by more than 30  seconds from the last  daily calibration  (Sec.  7.4), the
chromatographic system must  be inspected for malfunctions and corrections
must  be  made,  as required.    If the EICP  area for  any of  the internal
standards changes by a factor of two (-50% to  +100%) from the last daily
calibration check standard,  the  mass spectrometer must be  inspected for
malfunctions and corrections must be made,  as  appropriate.

7.6   GC/MS analysis

      7.6.1 It  is  highly  recommended  that  the extract be  screened  on a
GC/FID  or GC/PID using the same type  of  column.   This will  minimize
contamination of the GC/MS  system from unexpectedly high concentrations
of organic compounds.

      7.6.2 Spike the 1 ml extract obtained from sample preparation with
10 fj,l of the internal standard solution (Sec. 5.4) just  prior to analysis.

      7.6.3 Analyze the 1  ml extract by GC/MS using the  appropriate column
(as specified in Sec.  4,1.2).  The recommended GC/MS operating conditions
to be used are specified in  Sec. 7.3.
                            8250A - 12                        Revision 1
                                                          September 1994

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      7.6.4 If the response for any quantitation  ion  exceeds  the initial
calibration curve range of the GC/MS system, extract dilution must  take
place.  Additional  internal standard must be added to  the diluted extract
to maintain  the required  40 ng/^L  of  each  internal   standard in  the
extracted volume.  The diluted extract  must  be  reanalyzed.

      7.6.5 Perform  all  qualitative  and quantitative  measurements  as
described in Sec. 7.7.  Store the extracts  at 4°C, protected  from  light
in screw-cap vials  equipped with  unpierced Teflon  lined  septa.

7.7   Data interpretation

      7.7.1 Qualitative analysis

            7.7.1.1     The  qualitative  identification  of  compounds
      determined by  this  method is  based  on  retention time,  and  on
      comparison of the sample mass spectrum, after background  correction,
      with  characteristic  ions  in  a   reference  mass  spectrum.    The
      reference mass spectrum must be generated by the  laboratory  using
      the conditions of this  method.   The  characteristic ions  from  the
      reference mass  spectrum are defined to  be the three ions  of  greatest
      relative intensity, or any  ions over 30% relative  intensity if less
      than three such  ions occur in  the reference spectrum.   Compounds
      should be identified  as  present when the  criteria  below are met.

                  7.7.1.1.1   The intensities of the  characteristic  ions
            of a compound maximize in the same scan or within  one scan of
            each other.   Selection  of  a peak  by a  data system  target
            compound  search  routine  where   the  search   is based on  the
            presence  of  a  target chromatographic peak  containing  ions
            specific  for  the  target   compound  at a compound-specific
            retention time  will be accepted  as  meeting this criterion.

                  7.7.1.1.2   The RRT of the sample  component is  within
            ±0.06  RRT units  of the  RRT of the  standard  component.

                  7.7.1.1.3   The    relative    intensities    of    the
            characteristic   ions   agree  within  30%  of  the   relative
            intensities  of  these  ions  in  the  reference  spectrum.
            (Example:   For  an   ion  with an  abundance  of  50% in  the
            reference spectrum,  the corresponding abundance in  a  sample
            spectrum can range between  20% and  80%.)

                  7.7.1.1.4   Structural  isomers  that  produce   very
            similar  mass  spectra  should be  identified  as   individual
            isomers  if  they   have  sufficiently different  GC retention
            times.   Sufficient GC resolution is  achieved  if the height of
            the valley between two isonter peaks is less than 25%  of  the
            sum of  the two peak heights.  Otherwise,  structural  isomers
            are identified  as  isomeric  pairs.

                  7.7.1.1.5   Identification  is   hampered when  sample
            components are  not resolved chromatographically and  produce
                           8250A  -  13                        Revision  1
                                                         September  1994

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      mass  spectra  containing  ions  contributed  by more  than  one
      analyte.  When gas chromatographic peaks obviously represent
      more than one  sample  component (i.e.,  a broadened peak with
      shoulder(s)  or  a  valley  between  two  or  more  maxima),
      appropriate  selection  of  analyte spectra  and  background
      spectra is  important.   Examination of  extracted ion current
      profiles  of appropriate  ions  can aid  in  the  selection  of
      spectra, and in qualitative identification of compounds.  When
      analytes  coelute  (i.e.,  only one  chromatographic peak  is
      apparent),  the identification  criteria  can  be  met,  but each
      analyte spectrum will contain extraneous ions contributed by
      the coeluting compound.

      7.7.1.2     For samples containing components not associated
with the calibration  standards,  a library search may be made for the
purpose of tentative  identification.  The necessity to perform this
type of  identification  will be determined  by the purpose  of  the
analyses  being   conducted.    Computer  generated  library  search
routines  should  not   use  normalization  routines   that   would
misrepresent the library or unknown  spectra when  compared to each
other.   For example, the RCRA permit  or waste delisting requirements
may require the  reporting of nontarget analytes.  Only after visual
comparison of sample  spectra with the nearest library searches will
the  mass  spectral interpretation  specialist  assign a  tentative
identification.  Guidelines  for making tentative identification are:

      (1)   Relative  intensities  of major ions  in  the  reference
spectrum (ions > 10%  of the  most abundant ion) should be present in
the sample spectrum.

      (2)  The relative intensities of the major  ions should agree
within  + 20%.  (Example:  For an  ion  with an abundance  of 50% in the
standard spectrum, the corresponding sample ion  abundance must be
between 30 and 70%.)

      (3)  Molecular  ions  present  in the reference spectrum should
be present in sample  the spectrum.

      (4)   Ions  present  in the  sample spectrum  but not  in. the
reference  spectrum   should  be  reviewed for  possible  background
contamination or presence  of coeluting compounds.

      (5)  Ions present in  the  reference spectrum but not  in  the
sample  spectrum  should be reviewed  for possible subtraction from the
sample  spectrum because of background  contamination  or  coeluting
peaks.   Data  system library  reduction programs can sometimes create
these discrepancies.

7.7.2 Quantitative Analysis

      7.7.2.1     When  a   compound  has  been   identified,   the
quantitation   of that compound  will  be based on the  integrated
abundance from the EICP of the primary characteristic ion.
                      8250A -  14                        Revision 1
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       7.7.2.2      If the %RSD  of a  compound's  relative response
factor is 15% or less, then the concentration in  the extract may be
determined  using the  average  response  factor  (RF)  from initial
calibration data  (Sec.  7.4.3)  and  the following  equation:

                     (Ax x C(J
       C.x (mg/L)  =
                     (Ais  x  RF)

      where Cex  is the concentration of the compound  in the extract,
and the other terms  are  as defined  in Sec. 7.4.3.

      7.7.2.3     Alternatively,  the regression line fitted to the
initial calibration  (Sec. 7.4.6.1) may  be  used for determination of
the extract concentration.

      7.7.2.4     Compute  the concentration  of  the  analyte in the
sample using the equations in Sees. 7.7. 2.4. 1 and 7.7,2.4.2.

            7.7.2.4.1    The  concentration of  the  analyte  in the
      liquid  phase   of  the  sample   is   calculated   using  the
      concentration  of the analyte in the  extract  and the volume of
      liquid extracted,  as follows:

            Concentration  in  liquid (M9/L)  = (Ce!t x  VCT)
                                                  Vo

      where:

            Vex    =      extract  volume, in  ml
            V0    =      volume of liquid  extracted,  in  L.

            7.7.2.4.2    The  concentration of  the  analyte  in the
      solid  phase   of  the   sample   is   calculated   using  the
      concentration  of the pollutant in the extract and the weight
      of the solids, as  follows:
            Concentration  in  solid  (/ig/kg) =  (Ceit x Ve,)
                                                  X.

      where:

            Vex    =      extract  volume,  in ml
            Ws    =      sample weight,  in kg.

      7.7.2.5     Where applicable, an estimate of concentration for
noncal ibrated components in the sample should be made.  The formulae
given above should be  used with  the following  modifications:  The
areas Ax and Ajs  should be from the total ion chromatograms and the
RF for the compound  should be assumed  to be  1.   The concentration
obtained should  be  reported  indicating  (1)  that the value  is  an
estimate and  (2) which  internal standard  was  used  to  determine
                      8250A - 15                        Revision 1
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             concentration.     Use   the  nearest  internal   standard  free  of
             interferences.

                   7.7.2.6      Quantitation  of  multicomponent  compounds  (e.g.
             Aroclors)   is  beyond  the  scope   of  Method  8250A.    Normally,
             quantitation is  performed  using a GC/ECD by Method 8080.


8.0   QUALITY CONTROL

      8.1    Each  laboratory  that uses these methods is  required  to operate a
formal quality control program.  The minimum requirements of  this program consist
of an initial demonstration of laboratory  capability and an ongoing analysis of
spiked  samples  to evaluate  and document data  quality.   The  laboratory  must
maintain records  to document  the quality  of the data generated.   Ongoing  data
quality checks are compared with established performance criteria to determine
if the results of analyses meet the performance characteristics of the method.
When  results of sample  spikes indicate atypical method performance, a quality
control  check standard  must  be  analyzed to  confirm  that  the  measurements  were
performed in an in-control  mode of operation.

      8.2    Before  processing  any  samples,  the  analyst  should  demonstrate,
through the  analysis  of a  reagent water blank,  that  interferences  from  the
analytical system, glassware, and reagents are under control.  Each time  a set
of samples is extracted  or  there is a  change in  reagents, a reagent water  blank
should be  processed as a  safeguard against chronic laboratory contamination.  The
blank samples should be  carried  through all stages of the sample preparation and
measurement steps.

      8.3   The   experience   of  the  analyst  performing  GC/MS  analyses  is
invaluable to the  success of  the methods.  Each  day that analysis is performed,
the  daily  calibration  standard should  be  evaluated  to   determine  if  the
chromatographic system  is operating properly.   Questions that  should  be  asked
are:  Do  the peaks look normal?;  Is  the  response obtained  comparable to  the
response  from  previous calibrations?   Careful examination  of the  standard
chromatogram can  indicate  whether  the column  is still good, the  injector is
leaking, the injector septum needs  replacing,  etc.  If  any  changes are made to
the system (e.g.  column  changed), recalibration of the  system must take place.

      8.4   Required instrument  QC is found in  the following section:

            8.4.1 The   GC/MS  system  must  be  tuned  to  meet   the   DFTPP
      specifications in  Sec.  7.3.1  and 7.4.1.

            8.4.2 There must  be an  initial  calibration of  the  GC/MS system as
      specified in Sec.  7.4.

            8.4.3 The GC/MS system  must meet the SPCC criteria specified in Sec.
      7.5.3 and the CCC  criteria in Sec. 7.5.4, each 12 hr.

      8.5   To  establish   the  ability  to  generate  acceptable  accuracy  and
precision, the analyst must perform the following operations.
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             8.5.1  A quality control  (QC) check sample concentrate is required
       containing each  analyte  at  a concentration of 100 mg/L in acetone.  The
       QC  check  sample  concentrate  may be prepared from pure  standard materials
       or  purchased  as  certified solutions.   If prepared by the laboratory, the
       QC  check  sample  concentrate  must  be  made using stock standards prepared
       independently  from those used for  calibration.

             8.5.2  Using a pipet, prepare QC check samples  at  a concentration of
       100 fjtg/L  by adding 1.00 mi of QC check sample  concentrate to each of four
       1-L aliquots of  organic-free reagent water.

             8.5.3 Analyze  the well-mixed  QC check  samples  according  to  the
       method beginning in Sec. 7.1 with  extraction of the samples.

             8.5.4 Calculate  the average  recovery (x) in M9/L, and the standard
       deviation of  the recovery  (s)  in /ig/L, for each  analyte  using the four
       results.

             8.5.5 For  each  analyte  compare  s  and  x  with  the  corresponding
       acceptance criteria  for  precision and  accuracy,  respectively,  found in
       Table  6.   If s  and x  for  all  analytes of interest  meet  the acceptance
       criteria, the  system  performance  is  acceptable and analysis  of actual
       samples can begin.   If any individual s exceeds the precision limit or any
       individual x   falls  outside the  range  for  accuracy,  then the  system
       performance is unacceptable  for that analyte.

             NOTE: The  large  number of analytes in Table  6 present a substantial
                  probability  that one  or more will fail at  least  one of the
                  acceptance criteria when  all  analytes of a given method are
                  analyzed.

             8.5.6 When one or more of the analytes tested fail at least one of
       the  acceptance criteria, the  analyst  must  proceed  according  to  Sees.
       8.5.6.1 or 8.5.6.2.

                  8.5.6.1      Locate  and correct the source of the problem and
             repeat the  test for  all  analytes of interest  beginning  with Sec.
             8.5.2.

                  8.5.6.2      Beginning  with Sec.  8.5.2,  repeat  the  test on'y
             for those analytes that failed  to meet criteria.  Repeated failure,
             however, will  confirm a general problem with  the measurement system.
             If  this  occurs,  locate and correct the  source of the problem and
             repeat the test  for all  compounds of interest  beginning  with Sec.
             8.5.2.

       8.6    The laboratory  must, on  an  ongoing  basis,  analyze a  method blank,
a matrix spike,  and a matrix spike/duplicate  for  each analytical batch (up to a
maximum of 20 samples/batch)  to assess accuracy.   For  laboratories analyzing one
to ten samples per  month,  at least one spiked sample per month is required.
                                  8250A - 17                        Revision 1
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       8.6.1 The  concentration  of  the  spike  in  the  sample  should  be
determined as follows:

            8.6.1.1      If, as in compl iance monitoring, the concentration
       of  a specific analyte  in the sample  is being  checked  against a
       regulatory concentration  limit, the  spike  should be at that limit
       or 1 to 5 times higher than the background concentration determined
       in Sec. 8.6.2, whichever  concentration would be  larger.

            8.6.1.2      If the  concentration of a specific analyte in the
       sample  is not  being checked  against  a limit  specific  to  that
       analyte, the spike should  be at 100 /ig/L or 1 to 5 times higher than
       the  background  concentration  determined in  Sec.  8.6.2,  whichever
       concentration would be larger.

            8.6.1.3      If  it  is  impractical  to determine  background
       levels  before  spiking   (e.g.,  maximum  holding  times  will  be
       exceeded), the spike concentration should be at  (1) the regulatory
       concentration limit, if any; or,  if  none (2)  the larger of either
       5  times  higher   than  the  expected   background   concentration  or
       100 Mg/L.

       8.6.2,Analyze  one  sample  aliquot   to   determine   the  background
concentration (B) of each analyte.   If necessary, prepare a new QC check
sample  concentrate   (Sec.   8.5.1)   appropriate  for   the   background
concentration in the sample.   Spike a second sample aliquot with 1.00 ml
of the QC  reference  sample  concentrate  and analyze  it to determine the
concentration after spiking (A)  of each  analyte.   Calculate each percent
recovery (p)  as  100(A-B)%/T, where T is the  known  true value of the spike.

       8.6.3 Compare the percent recovery  (p) for each  analyte  with the
corresponding QC acceptance criteria found  in Table 6.  These acceptance
criteria were calculated to include an allowance for error in measurement
of both  the  background  and  spike concentrations,  assuming  a  spike  to
background ratio of 5:1.  This error will  be accounted for to the extent
that the analyst's spike to background ratio approaches 5:1.   If spiking
was performed at  a concentration lower than  100  /ig/L,  the analyst must use
either the QC acceptance  criteria  presented in Table  6,  or  optional  QC
acceptance criteria calculated for the specific spike concentration.  To
calculate optional  acceptance criteria for the recovery of an analyte: (I)
Calculate accuracy (x')  using the equation  found in Table 75  substituting
the spike concentration  (T) for C;  (2)  calculate  overall  precision  ($')
using  the equation in Table 7,  substituting  x'  for x;  (3) calculate the
range   for   recovery   at   the   spike   concentration   as   (lOOx'/T)
± 2.44(100S'/T)%.

       8.6.4 If any  individual p falls outside the designated  range for
recovery,   that  analyte  has  failed  the  acceptance  criteria.    A  check
standard containing each analyte that failed the criteria must be analyzed
as described  in Sec. 8.7.
                            8250A - 18                        Revision 1
                                                          September 1994

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      8.7    If  any  analyte  fails  the acceptance criteria for recovery in Sec,
8.6, a QC check  standard containing each analyte that failed must be prepared and
analyzed.

      NOTE:  The frequency for the required analysis of a  QC check  standard will
             depend upon the number of analytes being simultaneously tested, the
             complexity  of  the  sample matrix,  and  the  performance of  the
             laboratory.   If the  entire list  of  analytes  in Table  6 must be
             measured  in the  sample  in Sec.  8.6, the  probability  that  the
             analysis of a QC check standard will be required is high.  In this
             case, the QC check  standard should be routinely analyzed with the
             spiked sample,

             8.7.1 Prepare the  QC  reference sample by  adding 1.0  ml  of the QC
      check  sample concentrate  (Sec.  8.5.1  or 8.6.2)  to  1  L of reagent water.
      The  QC check standard  needs  only to  contain  the analytes that failed
      criteria  in the test in Sec. 8.6.

             8,7.2 Analyze the QC check  standard to determine the  concentration
      measured  (A) of  each  analyte.    Calculate each  percent recovery (PJ  as
      100(A/T)%, where T is the true value of  the standard concentration.

             8.7.3 Compare the  percent recovery (Ps) for  each analyte with the
      corresponding QC acceptance  criteria  found in Table 6.   Only  analytes that
      failed the test in Sec.  8.6 need to be compared with these  criteria.  If
      the recovery of any such analyte falls outside the designated range, the
      laboratory performance for  that  analyte is  judged  to  be  out of control,
      and the problem must  be  immediately  identified and  corrected.  The result
      for that analyte  in the unspiked sample is suspect and may not be reported
      for regulatory compliance purposes.

      8.8    As  part of the QC  program for  the laboratory,  method accuracy for
each matrix studied must  be  assessed  and records must be  maintained.  After the
analysis of five spiked samplesjof the same matrix) as  in Sec. 8.6,  calculate
the average  percent  recovery  (p)  and the  standard  deviation  of the percent
recovery (sp).   Express  the  accuracy assessment as a percent recovery interval
from p  - 2sp to p +  2sp.   If  p = 90% and  $p = 10%, for  example,  the accuracy
interval  is  expressed  as 70-110%.   Update  the accuracy assessment  for each
analyte  on  a   regular  basis  (e.g.  after  each  five  to   ten   new  accuracy
measurements).

      8.9    To determine acceptable accuracy and precision limits  for surrogate
standards the following procedure should be performed.

             8.9.1 For each sample  analyzed,  calculate the  percent recovery of
      each surrogate in the sample.

             8.9.2 Once a minimum of thirty samples of  the same matrix  have been
      analyzed,   calculate   the  average percent   recovery   (P)   and  standard
      deviation of the percent recovery (s) for each of  the surrogates.
                                  8250A - 19                        Revision 1
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             8,9.3  For a given matrix,  calculate the upper  and  lower control
       limit  for method performance for each surrogate standard.  This should be
       done as  follows:

             Upper  Control  Limit  (UCL) =  P  +  3s
             Lower  Control  Limit  (LCL) =  P  -  3s

             8.9.4  For aqueous  and soil  matrices, these laboratory established
       surrogate  control  limits  should,  if  applicable,  be compared  with  the
       control  limits  listed in Table 8,   The  limits given in Table 8 are multi-
       laboratory  performance  based limits  for  soil  and aqueous  samples,  and
       therefore,  the  single-laboratory  limits established in  Step  8.9.3 must
       fall within  those given  in Table 8 for these matrices.

             8.9.5  If  recovery is not within limits, the following procedures are
       required.

             *      Check  to  be  sure  there  are  no   errors  in  calculations,
                   surrogate  solutions and internal   standards.   Also,  check
                   instrument performance.

             •      Recalculate  the  data  and/or  reanalyze the  extract if any of
                   the above checks  reveal  a  problem.

             »      Reextract and  reanalyze  the  sample if none of  the above are
                   a problem or flag the  data as  "estimated concentration".

             8.9.6  At  a minimum, each laboratory should update surrogate recovery
       limits on a  matrix-by-matrix basis,  annually.

       8.10   It  is recommended  that the  laboratory  adopt additional  quality
assurance practices for use with this method.  The specific practices that are
most productive depend upon the  needs of the laboratory and  the  nature of the
samples.   Field duplicates may  be analyzed to  assess  the  precision  of  the
environmental measurements. When doubt exists over the identification of a peak
on the chromatogram,   confirmatory techniques such as  gas chromatography with a
dissimilar column or mass spectrometry using other ionization modes must be used.
Whenever possible,  the laboratory should analyze standard reference materials and
participate  in relevant performance evaluation studies.


9.0    METHOD PERFORMANCE

     ,9.1    Method 8250 was tested by 15 laboratories  using organic-free reagent
water, drinking water, surface water,  and  industrial  wastewaters  spiked at six
concentrations  over  the range  5-1,300  M9/L-    Single  operator  accuracy  and
precision, and method  accuracy  were  found  to  be  directly  related  to  the
concentration of the  analyte and essentially independent of the sample matrix.
Linear equations to describe these relationships are  presented in Table 7.
                                  8250A - 20                        Revision 1
                                                                September 1994

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10.0  REFERENCES

1.    U.S. EPA 40 CFR Part  136, "Guidelines Establishing Test Procedures  for the
      Analysis of Pollutants Under the Clean Water Act,  Method 625," October 26,
      1984,

2.    U.S.  EPA Contract  Laboratory Program,  Statement  of Work  for  Organic
      Analysis, July  1985,  Revision,

3.    Eichelberger, J.W.,  I.E. Harris,  and W.L.  Budde, "Reference Compound to
      Calibrate   Ion   Abundance   Measurement   in  Gas   Chromatography-Mass
      Spectroraetry Systems," Analytical Chemistry, 47, 995-1000, 1975.

4.    "Method Detection Limit for Methods 624  and  625," Qlynyk,  P., W.L. Budde,
      and J.W. Eichelberger, Unpublished report, October  1980.

5.    "Interlaboratory Method Study for EPA Method 625-Base/Neutrals, Acids, and
      Pesticides," Final Report  for  EPA  Contract  68-03-3102 (in preparation).

6.    Burke,  J,A.  "Gas  Chromatography  for  Pesticide  Residue  Analysis;  Some
      Practical Aspects,"  Journal of  the  Association of  Official  Analytical
      Chemists, 48, 1037,  1965.
                                  8250A - 21                        Revision 1
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                        TABLE 1.
CHROHATOGRAPHIC CONDITIONS,  METHOD DETECTION LIMITS,  AND
     CHARACTERISTIC IONS FOR SEMIVOLAT1LE COMPOUNDS
Compound
Acenaphthene
Acenaphthene-d10 (I.S.)
Acenaphthylene
Acetophenone
Aldrin
4-Aminobiphenyl
Aniline
Anthracene
Aroclor-1016b
Aroclor-1221b
Aroclor-I232b
Aroclor-1242b
Aroclor-1248b
Aroclor-1254b
Aroclor-1260b
Benzidine"
Benzole acid
Benzo(a) anthracene
Benzo(b)fl uoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzyl alcohol
Q-BHCB
iS-BHC
5-BHC
7-BHC (Lindane)8
Bis(2-chloroethoxy) methane
Bis(2-chloroethyl) ether
Bis(2-ch1oroisopropyl) ether
Bis(2-ethylhexy1) phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
Chlordaneb
4-Chloroaniline
1 -Chi oronaphthal ene
2-Chlorortaphthalene
4- Chi oro-3 -methyl phenol
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Chrysene-d12 (I.S.)
4,4'~DDD
Method
Retention Detection Primary Secondary
Time (min) limit (M9/L) Ion Ion(s)
17,8
--
17.4
--
24.0
._
.,
22.8
18-30
15-30
15-32
15-32
12-34
22-34
23-32
28.8
..
31.5
34.9
34,9
45.1
36.4
__
21.1
23.4
23.7
22.4
12.2
8.4
9.3
30.6
21.2
29.9
19-30
__
._
15.9
13.2
5.9
19.5
31.5
--
28.6
1.9
—
3.5
..
1.9
--
--
1.9
--
30
--

__
36
--
44
__
7.8
4.8
2.5
4.1
2.5
__
._
4.2
3.1
--
5.3
5.7
5 7
2.S
1.9
2.5
__
--
__
1.9
3.0
3.3
4.2
2.5
--
2.8
154
164
152
105
66
169
93
178
222
190
190
222
292
292
360
184
122
228
252
252
276
252
108
183
181
183
183
93
93
45
149
248
149
373
127
162
162
107
128
204
228
240
235
153,
162,
151,
77,
263,
168,
66,
176,
260,
224,
224,
256,
362,
362,
362,
92,
105,
229,
253,
253,
138,
253,
79,
181,
183,
181,
181,
95,
63,
77
167,
250,
91,
375,
129
127,
127,
144,
64,
206,
226,
120,
237,
152
160
153
51
220
170
65
179
292
260
260
292
326
326
394
185
77
226
125
125
277
125
77
109
109
109
109
123
95
!2!
279
141
206
377

164
164
142
130
141
229
236
165
                      8250A  - 22
    Revision 1
September 1994

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                                   TABLE 1.
                                  (Continued)
Compound
             Method
Retention   Detection
Time (min)  Limit (jug/L)
Primary  Secondary
Ion        Ion(s)
4, 4' -DDT
4,4'-DDE
Dibenz(a, jjacridine
Di benz( a, h) anthracene
Dibenzofuran
Di-n-butyl phthalate
1,2-DichTorobenzene
1 , 3 -Di chl orobenzene
1 ,4-Di chl orobenzene
l,4-Dichlorobenzene-d4 (I.S.)
3,3' -Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dieldrin
Diethyl phthalate
p-Dimethyl aminoazobenzene
7, 12-Dimethyl benz(a) anthracene
a- , a-Di methyl phenethyl ami ne
2,4-Dimethylphenol
Dimethyl phthalate
4,6-Di ni tro-2-methyl phenol
2,4-Dinitrophenol
2,4-Dihitrotoluene
2,6-Dinitrotoluene
Diphenylamine
1 , 2 -Di phenyl hydrazi ne
Di-n-octyl phthalate
Endosulfan Ia
Endosulfan IT
Endosulfan sulfate
Endrina
Endrin aldehyde
Endrin ketone
Ethyl methanesulfonate
Fluoranthene
Fluorene
2-Fluorobiphenyl (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachl orobutadiene
Hexachl orocycl opentad i enea
Hexachl oroethane
29
27

43

24
8
7
7

32
9

27
20



9
18
16
15
19
18


32
26
28
29
27



26
19


23
25
21
11
13
8
.3
.2
--
.2
--
.7
.4
.4
.8
--
.2
.8
--
.2
.1
--
__
--
.4
.3
.2
.9
.8
.7
._
--
.5
.4
.6
.8
.B
--
--
--
.5
.5
_.
--
.4
.6
.0
.4
.9
.4
4


2

2
1
1
4

16
2

2
1



2
1
24
42
5
1


2


5




2
1


1
2
1
0

i
,7
__
--
.5
--
.5
.9
.9
.4
--
.5
.7
--
.5
.9
--
--
--
.7
.6


.7
.9
--
--
.5
--
--
.6
..
--
--
--
.2
.9
--
--
.9
.2
.9
.9
--
.6
235
246
279
278
168
149
146
146
146
152
252
162
162
79
149
120
256
58
122
163
198
184
165
165
169
77
149
195
337
272
263
67
317
79
202
166
172
112
100
353
284
225
237
117
237,
24,
280,
139,
139
150,
148,
148,
148,
150,
254,
164,
164,
263,
177,
225,
241,
91,
107,
194,
51,
63,
63,
63,
168,
105,
167,
339,
339,
387,
82,
345,
67,
109,
101,
165,
171
64
272,
355,
142,
223,
235,
201,
165
176
277
279

104
111
111
111
115
126
98
98
279
150
77
257
42
121
164
105
154
89
89
167
182
43
341
341
422
81
250
319
97
203
167


274
351
249
227
272
199
                                  8250A - 23
                                   Revision  1
                              September 1994

-------
TABLE 1.
(Continued)
Compound
Indeno ( 1 , 2 , 3 -cd ) pyrene
Isophorone
Methoxychlor
3-Methy] chol anthrene
Methyl methanesulfonate
2-Methyl naphthalene
2-Methyl phenol
4-Methyl phenol
Naphthalene
Naphtha! ene-d8 (I.S.)
1-Naphthylamine
2-Naphthylamine
2-Nitroaniline
3-Nitroaniline
4-N1troaniline
Nitrobenzene
Nitrobenzene-dg (surr.)
2-Nitrophenol
4-Nitrophenol
N-Nitroso-di -n-butyl amine
N-Nitrosodi methyl ami nea
N-Ni trosodi phenyl ami nea
N-Nitroso-di -n-propyl amine
N-Ni trosopi peri dine
Pentachl orobenzene
Pentachl oroni trobenzene
Pentachl orophenol
Perylene-d12 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-d.c (I.S.)
Phenol
Phenol -de (surr.)
2-Picoline
Pronamide
Pyrene
Terphenyl-d14 (surr.)
1,2,4,5-Tetrachlorobenzene
2,3,4,6-Tetrachlorophenol
Method
Retention Detection Primary Secondary
Time (min) Limit (fj,g/L) Ion Ion(s)
42.7
11.9
--
--
._
-_
..
--
12.1
--
--
,-
._
_.
--
11.1
--
6.5
20.3
--
--
20.5
--
--
--
--
17.5
--
--
22.8
--
8.0
--
--
--
27.3
--
--
--
3.7
2.2
--
--
_.
--
..
--
1.6
..
--
--

--
--
1.9
--
3.6
2.4
--
--
1.9
--
--
_.
--
3.6
__
--
5.4
--
1.5
--
--
--
1.9
--
--
--
276
82
227
268
80
142
108
108
128
136
143
143
65
138
138
77
82
139
139
84
42
169
70
42
250
295
266
264
108
178
188
94
99
93
173
202
244
216
232
138,
95,
228
253,
79,
141
107,
107,
129,
68
115,
115,
92,
108,
108,
123,
128,
109,
109,
57,
74,
168,
130,
114,
252,
237,
264,
260,
109,
179,
94,
65,
42,
66,
175,
200,
122,
214,
230,
227
138

267
65

79
79
127

116
116
138
92
92
65
54
65
65
41
44
167
42
55
248
142
268
265
179
176
80
66
71
92
145
203
212
218
131
8250A - 24
    Revision 1
September 1994

-------
TABLE 1.
(Continued)


Compound
Toxapheneb
2,4,6-Tribromophenol (surr.)
1,2,4-Trichlorobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol

Retention
Time (min)
25-34
-- .
11.6
..
11.8
Method
Detection
Limit (jug/L)
*. -
__
1.9
__
2.7

Primary
Ion
159
330
180
196
196

Secondary
Ion(s)
231, 233
332, 141
182, 145
198, 200
198, 200
aSee Sec.  1.3
bThese compounds are mixtures  of various isomers.
(I.S.)  = Internal Standard
(surr}, = Surrogate
                                   TABLE 2.
             DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQL)
                             FOR  VARIOUS MATRICES3
Matrix
  Factor
Ground water                                                           10
Low-concentration soil by ultrasonic extraction with GPC cleanup      670
High-concentration soil and sludges by ultrasonic extraction       10,000
Non-water miscible waste                                          100,000
    EQL = [Method detection limit (see iable I}j  X  [Factor found in this tablej.
    For non-aqueous  samples,  the factor  is on a wet-weight  basis.  Sample EQLs
    are highly matrix-dependent.  The EQLs  to be determined herein are provided
    for guidance  and  may  not  always  be achievable.
                                  8250A - 25
    Revision 1
September 1994

-------
                                   TABLE 3.
                  DFTPP  KEY  IONS AND  ION ABUNDANCE CRITERIA41
       Mass              Ion Abundance  Criteria
       51                30-60% of mass  198

       68                <  2%  of mass 69
       70                <  2%  of mass 69

      127                40-60% of mass  198

      197                <  1%  of mass 198
      198                Base  peak, 100% relative abundance
      199                5-9%  of mass 198

      275                10-30% of mass  198

      365                >  1%  of mass 198

      441                Present but less than mass 443
      442                >  40% of mass 198
      443                17-23% of mass 442
"See Reference 3,
                                  8250A - 26                        Revision 1
                                                                Seotember 1994

-------
                             TABLE 4.
                    CALIBRATION CHECK COMPOUNDS
Base/Neutral Fraction                   Acid Fraction
Acenaphthene                            4-Chloro-3-methylphenol
1,4-Dichlorobenzene                     2,4-Dichlorophenol
Hexachlorobutadiene                     2-Nitrophenol
N-Nitroso-di-n-phenylamine              Phenol
Di-n-octyl phthalate                    Pentachlorophenol
Benzo(a)pyrene                          2,4,6-Trichlorophenol
Fluoranthene
                            8250A -  27                        Revision 1
                                                          September 1994

-------
                                   TABLE 5.
          SEMIVOLATILE  INTERNAL  STANDARDS WITH  CORRESPONDING  ANALYTES
                           ASSIGNED  FOR  QUANTITATION
1,4-Di chlorobenzene-D4
Naphtha!ene-dE
Acenaphthene-d
                                                                       10
Aniline
Benzyl alcohol
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl )ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
Ethyl methanesulfonate
2-Fluorophenol (surr.)
Hexachloroethane
Methyl methanesulfonate
2-Methylphenol
4-Methylphenol
N-Nitrosodimethylami ne
N-Nitroso-di-n-propylamine
Phenol
Phenol-d6 (surr.)
2-Picoline
Acetophenone
Benzoic acid
Bis(2-chloroethoxy)methane
4-Chloroaniline
4-Chloro-3-methyl phenol
2,4-Dichlorophenol
2,6-Dichlorophenol
a,a-Dimethylphenethylamine
2,4-Dimethylphenol
Hexachlorobutadiene
Isophorone
2-Hethylnaphthalene
Naphthalene
Nitrobenzene
Nitrobenzene-d8 (surr.)
2-Nitrophenol
N-Nitroso-di-n-butylamine
N-Nitrosopiperi dine
1,2,4-Trichlorobenzene
Acenaphthene
Acenaphthylene
1-Chloronaphthalene
2-Chloronaphthalene
4-Chlorophenyl
  phenyl  ether
Dibenzofuran
Diethyl phthalate
Dimethyl  phthalate
2,4-Dinitrophenol
2,4-Dinitrotoluene
2.6-Dinitrotoluene
Fluorene
2-Fluorobiphenyl
  (surr.)
Hexachlorocyclo-
  pentadiene
I-Naphthylamine
2-Naphthylamine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
4-Nitrophenol
Pentachlorobenzene
1,2,4,5-Tetrachloro-
  benzene
2,3,4,6-Tetrachloro-
  phenol
2,4,6-Tribromophenol
  (Surr.)
2,456-Trichlorophenol
2,455-Trichloropheno1
(surr.) = surrogate
                                  8250A - 28
                                        Revision 1
                                    September 1994

-------
                                   TABLE 5,
          SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
                           ASSIGNED FOR QUANTITATION
                                  (Continued)
Phenanthrene-d,
                            Chrysene-d
                                      12
                             Perylene-d
                                                                   12
4-Aminobiphenyl
Anthracene
4-Bromophenyl phenyl ether
Di-n-butyl phthalate
4,6-Dinitro-2-methylphenol
Diphenylamine
1,2-Di phenylhydrazi ne
Fluoranthene
Hexachlorobenzene
N-Nitrosodiphenylamine
Pentachlorophenol
Pentachloron i trobenzene
Phenacetin
Phenanthrene
Pronamide
Benzidine
Benzo(a)anthracene
Bis(Z-ethylhexyl) phthalate
Butyl benzyl phthalate
Chrysene
3,3'-Dichlorobenzidine
p-Dimethylaminoazobenzene
Pyrene
Terphenyl-d14  (surr.)
                                                         Benzo(b}fluoranthene
                                                         Benzo(k)fluoranthene
                                                         Benzo(g,h,ijperylene
                                                         Benzo(a)pyrene
                                                         Dibenz(a,j)acridine
                                                         Di benz(a,h)anthracene
                                                         7,12-Dimethylbenz-
                                                           (a)anthracene
                                                         Di-n-octyl  phthalate
                                                         Indeno(l,2,3-cd)pyrene
                                                         3-Methylcholanthrene
(surr,} = surrogate
                                  8250A - 29
                                        Revision  1
                                    September  1994

-------
       TABLE 6.
QC ACCEPTANCE CRITERIA8
Compound
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benzo(a)anthracene
Benzo(b)fl uoranthene
Benzo(k)fl uoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Butyl benzyl phthalate
8-BHC
<5-BHC
Bis(2-ehloroethyl) ether
Bis(2-chloroethoxy)methane'
Bis(2-ehloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4, 4' -DDT
Dibenzo( a, h) anthracene
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3' -Dichlorobenzidine
Dieldnr.
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfan sulfate
Endrin aldehyde
Fl uoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Test
cone.
(M9/L)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(M9/L)
27.6
40.2
39.0
32.0
27.6
38.8
32.3
39.0
58.9
23.4
31.5
21.6
55.0
34.5
46.3
41.1
23.0
13.0
33.4
48.3
31.0
32.0
61.6
70.0
16.7
30.9
41.7
32.1
71.4
30. 7
26.5
23.2
21.8
29.6
31.4
16.7
32.5
32.8
20.7
37.2
54.7
24.9
26.3
Range
for x
(M9/U
60.1-132.3
53.5-126.0
7.2-152.2
43.4-118.0
41.8-133.0
42.0-140.4
25.2-145.7
31.7-148.0
D-195.0
D-139.9
41.5-130.6
D-100.0
42.9-126.0
49.2-164.7
62.8-138.6
28.9-136.8
64.9-114.4
64.5-113.5
38.4-144.7
44.1-139.9
D-134.5
19.2-119.7
D-170.6
D-199.7
8.4-111.0
48.6-112.0
16.7-153.9
37.3-105.7
8.2-212.5
44.3-119.3
D-100.0
D-100.0
47.5-126.9
68.1-136.7
18.6-131.8
D-103.5
D-188.8
42.9-121.3
71.6-108.4
D-172.2
70.9-109.4
7.8-141.5
37.8-102.2
Range
P, Ps
(%)
47-145
33-145
D-166
27-133
33-143
24-159
11-162
17-163
D-219
D-152
24-149
D-110
12-158
33-184
36-166
8-158'
53-127
60-118
25-158
17-168
D-145
4-136
D-203
D-227
1-118
32-129
D-172
20-124
D-262
29-136
D-114
D-112
39-139
50-158
4-146
D-107
D-209
26-137
59-121
D-192
26-155
D-152
24-116
      8250A - 30
    Revision 1
September 1994

-------
                             TABLE 6.
                      QC ACCEPTANCE CRITERIA8
                            (Continued)


Compound
Hexachl oroethane
Indeno ( 1 , 2 , 3 - cd } pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Nitroso-di -n-propylamine
PCB-1260
Phenanthrene
Pyrene
1 ,2,4-Trichlorobenzene
4-Chl oro-3 -methyl phenol
2-Chlorophenol
2,4-Chlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl -4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Test
cone.
(M9A)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(M/L)
24.5
44.6
63.3
30.1
39.3
55.4
54.2
20.6
25.2
28.1
37.2
28.7
26.4
26.1
49.8
93.2
35.2
47.2
48.9
22.6
31.7
s = Standard deviation of four recovery
x = Average recovery
p, ps = Percent recovery
D = Detected; result
a r »• -i 4- n •. -i -* £Vnin A f\ TCD D
for four
measured
must be
-.*.¥ T3C 4
recovery
•
Range
for x
(jig/L)
55.2-100.0
D-150.9
46.6-180.2
35.6-119.6
54.3-157.6
13.6-197.9
19.3-121.0
65.2-108.7
69.6-100.0
57.3-129.2
40.8-127.9
36.2-120.4
52.5-121.7
41.8-109.0
D-172.9
53.0-100.0
45.0-166.7
13.0-106.5
38.1-151.8
16.6-100.0
52.4-129.2
measurements,
measurements,

Range
P» Ps
(%)
40-113
D-171
21-196
21-133
35-180
D-230
D-164
54-120
52-115
44-142
22-147
23-134
39-135
32-119
D-191
D-181
29-182
D-132
14-176
5-112
37-144
in M9/L-
in fxg/L.

greater than zero.
• f\ v* M^4" r*^^i
Tkri ^ r\ r-i
^^nhf^v*^*! *a%r* ri*'3C'^\/H
directly on the method performance data  in Table 7.  Where necessary, the
limits for  recovery  have  been broadened to assure  applicability  of the
limits to concentrations below those used to develop Table 7.
                            8250A - 31
    Revision 1
September 1994

-------
                          TABLE  7.
METHOD ACCURACY AND PRECISION AS FUNCTIONS  OF  CONCENTRATION3
Parameter
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benzo( a) anthracene
Chloroethane
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Butyl benzyl phthalate
B-BHC
£-BHC
Bis{2-chloroethyl) ether
Bis{2-chloroethoxy)methane
Bis{2-chloroisopropyl ) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
Di benzo ( a, h) anthracene
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
Dieldrin
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfan sulfate
Endrin aldehyde
Fluoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachloroethane
Accuracy, as
recovery, x'
(W3A)
0.96C+0.19
0.89C+0.74
0.78C+1.66
0.80C+0.68
0.88C-0.60
0.99C-1.53
0.93C-1.80
0.87C-1.56
0.90C-0.13
0.98C-0.86
0.66C-1.68
0.87C-0.94
0.29C-1.09
0.86C-1.54
1.12C-5.04
1.03C-2.31
0.84C-1.18
0.91C-1.34
0.89C+0.01
0.91C+0.53
0.93C-1.00
0.56C-0.40
0.70C-0.54
0.79C-3.28
0.88C+4.72
0.59C+0.71
0.8QC+0.28
0.86C-0.70
0.73C-1.47
1.23C-12.65
0.82C-0.16
0.43C+I.OO
0.20C+1.03
0.92C-4.81
1.06C-3.60
0.76C-0.79
0.39C+0.41
0.76C-3.86
0.81C+1.10
0.90C-0.00
0.87C-2.97
0.92C-1.87
0.74C+0.66
0.71C-1.01
0.73C-0.83
Single analyst
precision, s/
(M9/L)
0.15x-0.12
0.24x-1.06
0.27x-1.28
0.21x-0.32
0.15x+0.93
0.14x-0,13
0,22x+0.43
0.19X+1.Q3
0.22X+0.48
0,29x+2,40
0.18x+0,94
0.20X-0.58
CK34X+Q.86
fl.35x-0.99
0.16X+1.34
0.24x^0.28
0.26X+0.73
0.13x+0.66
0.07X+0.52
0.20x-0.94
0.28x^0,13
0.29X-0.32
0.26X-1.17
0.42x+0,19
0.30x+8.51
O.lSx+1.16
0.20X+0.47
0.25X+0.68
0.24X+0.23
0.28X+7.33
0.20X-0.16
0.28x+i.44
0.54x+0'.19
0.12x+1.06
0.14x+1.26
0.21x+1.19
0.12X+2.47
0.18x+3.91
0.22x-0,73
0.12X+0.26
0.24X-0.56
0.33X-0.46
O.lSx-0.10
0.19X+0.92
0.17x+0.67
Overall
precision,
s' Ug/U
0.21X-0.67
0.26X-0.54
0.43X+1.13
0.27X-0.64
0.26X-0.21
0.17x-0.28
0.29X+0.96
0.35x+0.40
0.32X+1.35
0.51x-0.44
0.53X+0.92
O.SOx+1.94
0.93X-0.17
0.35X+0.10
0.26X+2.01
0.25X+1.04
0.36X+0.67
0.16X+0.66
0.13X+0.34
O.SOx-0.46
0.33x-0.09
0.66x^0.96
0.39x-1.04
0.65X-0.58
0.59x+0.25
0.39x+0.60
0.24X+0.39
0.41X+0.11
0.29X+0.36
0.47X+3.45
0.26X-0.07
0.52x^0.22
l.OSx-0.92
0.21X+1.50
0.19X+0.35
0.37x+1.19
0.63X-1.03
0.73x-0.62
0.28x-0.60
0.13X+0.61
0.50x-0.23
0.28X+0.64
0.43X-0.52
0.26X+0.49
0.17X+0.80
                        8250A - 32
    Revision 1
September 1994

-------
                                   TABLE 7.
         METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION8
                                  (Continued)
Parameter
Indeno(l,2,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Nitroso-di-n-propylamine
PCB-1260
Phenanthrene
Pyrene
1 , 2 , 4-Tr i chl orobenzene
4-Ch1oro-3 -methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2 ,4 , 6-Tri chl orophenol
Accuracy, as
recovery, x?
(M9A)
0.78C-3.10
1.12C+1.41
0.76C+1.58
1.09C-3.05
1.12C-6.22
0.81C-10.86
0.87C+0.06
0.84C-0.16
0.94C-0.79
0.84C+0.35
0.78C+0.29
0.87C-0.13
0.71C+4.41
0.81C-18.04
1.04C-28.04
0.07C-1.15
•0.61C-1.22
0.93C+1.99
0.43C+1.26
0.91C-0.18
Single analyst
precision, s/
(M9/L)
0.29X+1.46
Q.27X+Q.77
0.21X-0.41
0.19x+0.92
0,27x+0.68
0.35X+3.61
0.12X+0.57
0.16X+0.06
O.lSx+0.85
0.23X+0.75
O.lSx+1.46
O.lBx+1.25
O.lGx+1.21
0.38X+2.36
O.lOx+42.29
O.lSx+1.94
0.38X+2.57
0.24X+3.03
0.26X+0.73
0.16X+2.22
Overall
precision,
S' (M9/L)
0.50X-0.44
0.33X+0.26
0.30X-0.68
0.27X+0.21
0.44X+0.47
0.43X+1.82
0,15x+0.25
0.15X+0.31
0.21X+0.39
0.29X+1.31
0.28X+0.97
0.21X+1.28
0.22x+1.31
0.42x+26.29
0.26X+23.10
0.27x+2,60
0.44X+3.24
0.30x^4,33
0,35x+0.58
0.22x+1.81
S'


c

x
            Expected  recovery  for  one  or  more  measurements  of  a   sample
            containing a concentration of C,  in /ug/L.

            Expected  single  analyst standard deviation  of  measurements at  an
            average concentration of x, in
Expected inter! aboratory standajd deviation  of measurements at an
average concentration found of x, in
True value for the concentration, in /Lig/L.

Average recovery  found for measurements  of samples  containing a
concentration of C, in
                                  8250A - 33
                                                        Revision 1
                                                    September 1994

-------
                                   TABLE 8,
      SURROGATE  SPIKE  RECOVERY  LIMITS  FOR  WATER  AND  SOIL/SEDIMENT  SAMPLES
                                    Low/Medium             Low/Medium
Surrogate Compound                     Water              Soil/Sediment


Nitrobenzene-ds                       35-114                23-120
2-Fluorobiphenyl                      43-116                30-115
Terpheny]-du                          33-141                18-137

Phenol-de                             10-94                 24-113
2-Fluorophenol                        21-100                25-121
2,4,6-Tribromophenol                   10-123                19-122
                                  8250A -  34                        Revision 1
                                                                September 1994

-------
                                        METHOD  82BOA
SEMIVOLATILE  ORGANIC COMPOUNDS  BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/HS)
                 7.1 Prepero «ampl«
                 u»ing Method 354O,
                  3541, or 3550
7.1 Prepare lample
u*ine Method 3510
    or 3520
                                            7,1 Prepare lamole
                                            u*ing Mnthod 3540,
                                           3541, 3550, or 3580
                                               7.2 Cleanup
                                                 extract
                                                   7.3
                                               Recommended
                                                 GC/MS
                                                operating
                                                condition*.
                                                  7,4
                                                  Initial
                                               Calibration.
                                                 7.5 Daily
                                              calibration - Tune
                                             GC/MS with TFTPP
                                             and check SPCC &
                                                  CCC.
                                         8250A -  35
           Revision  1
      September 1994

-------
       METHOD  S250A
         continued
 7.8.1 Screen extract
in QC/FID or GC/PID to
  eliminate loo High
   concentrations.
     7.8.2 Spike
     sample with
       internal
      standard.
     7.6.3 Analyze
   extract by QC/MS
  yting -ecommendod
  column and operating
      condition*.
                                     7.6,4 Dituta
                                       extract.
     7,7.1 Identify
     compounds by
   comparing sample
   retention time and
  sample mast spectra
     to itandarde.
1
r
7.7.2
Quantitate
samples yiing
internal std.
technique.
1
r
7.7.2.4 Report
results.
•*
r
     (   Stop   J
         8250A  -  36
     Revision  1
September  1994

-------
                                 METHOD 8260A

  VOLATILE ORGANIC COMPOUNDS BY GAS CHROHATOGRAPHY/HASS SPECTRQHETRY  CGC/HS;
                          CAPILLARY COLUMN TECHNIQUE
1.0   SCOPE AND APPLICATION

      1.1   Method 8260 is  used  to  determine volatile organic compounds  in  a
variety of solid waste  matrices.  This method is applicable to nearly all types
of samples, regardless of water content, including ground water, aqueous sludges,
caustic  liquors,  acid  liquors,  waste  solvents,- oily  wastes
fibrous  wastes,  polymeric emulsions,  filter  cakes,  spent
catalysts, soils, and sediments.   The following compounds  can
this method:
 mousses,  tars,
 carbons,  spent
be determined by
Appropriate Technique
Analyte
Acetone
Acetonitrile
Acrolein (Propenal)
Acrylonitrile
Ally! alcohol
Ally! chloride
Benzene
Benzyl chloride
Bromoacetone
Bromochloromethane (I.S.)
Bromodichloromethane
4-Bromofluorobenzene (surr.)
Bromoform
Bromomethane
n-Butanol
2-Butanone (MEK)
Carbon disuifide
Carbon tetrachloride
Chloral hydrate
Chlorobenzene
2 - Chi oro- 1,3 -butadiene
Chlorodibromomethane
Chloroethane
2-Chloroethanol
bis-(2-Chloroethyl) sulfide
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Chloroprene
CAS No,b Purge- and-Trap
67-64-1
75-05-8
107-02-8
107-13-1
107-18-6
107-05-1
71-43-2
100-44-7
598-31-2
74-97-5
75-27-4
460-00-4
75-25-2
74-83-9
71-36-3
78-93-3
75-I5-C
56-23-5
302-17-0
108-90-7
126-99-8
124-48-1
75-00-3
107-07-3
505-60-2
110-75-8
67-66-3
74-87-3
126-99-8
PP
PP
PP
PP
ht
a
a
a
pp
a
a
a
a
a
ht
PP
PP
a
PP
a
a
a
a
PP
PP
a
a .
a
a
Direct
Injection
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
2
a
a
a
a
a
a
a
a
a
a
a
pc
                                  8260A  -  1
      Revision 1
  September 1994

-------
   Appropriate Technique
Analyte
3-Chloropropene
3-Chloropropionitrile
l,2-Dibromo-3-chloropropane
1 ,2-Dibromoethane
Dibromomethane
1 , 2-Di chl orobenzene
1 ,3-Dichl orobenzene
1 ,4-Dichl orobenzene
cis-l,4-Dichloro-2-butene
trans-l,4-Dichloro-2-butene
Di chl orodi f 1 uoromethane
1 ,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans -1, 2-Di chl oroethene
1 , 2-Dichl oropropane
1 ,3-Dichl oro-2-propanol
cis-l,3-Dichloropropene
trans- 1 , 3-Di chl oropropene
1,2,3,4-Diepoxybutane
Di ethyl ether
1,4-Difluorobenzene (I.S.)
1,4-Dioxane
Epichlorohydrin
Ethanol
Ethyl acetate
Ethyl benzene
Ethyl ene oxide
Ethyl methacrylate
Hexachl orobutad i ene
Hexachloroethane
2-Hexanone
2-Hydroxypropionitrile
lodomethane
Isobutyl alcohol
Isopropyl benzene
Malononitrile
Methacrylonitrile
Methanol
Methylene chloride (DCM)
Methyl methacrylate
4-Methyl-2-pentanone (MIBK)
Naphthalene
Nitrobenzene
2-Nitropropane
CAS No.fa
107-05-1
542-76-7
96-12-8
106-93-4
74-95-3
95-50-1
541-73-1
106-46-7
1476-11-5
110-57-6
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
78-87-5
96-23-1
10061-01-5
10061-02-6
1464-53-5
60-29-7
540-36-3
123-91-1
106-89-8
64-17-5
141-78-6
100-41-4
75-21-8
97-63-2
87-68-3
67-72-1
591-78-6
7S-S7-7
74-88-4
78-83-1
98-82-8
109-77-3
126-98-7
67-56-1
75-09-2
80-62-6
108-10-1
91-20-3
98-95-3
79-46-9
Purge-and-Trap
a
i
pp
a
a
a
a
a
a
PP
a
a
a
a
a
a
PP
a
a
a
a
a
PP
i
i
i
a
PP
a
a
i
pp
-.
a
PP
a
PP
PP
i
a
a
PP
a
a
a
Direct
Injection
a
pc
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
pc
a
a
a
a
a
a
a
a
a
a
a
a
8260A - 2
    Revision 1
September 1994

-------
Aooropriate Technique

.Analyte
Pentachl oroethane
2-Picoline
Propargyl alcohol
R-Propiolactone
Propionitrile (ethyl cyanide)
n-Propylamine
Pyridine
Styrene
1,1, 1 ,2-Tetrachloroethane
1, 1,2, 2 -Tetrachl oroethane
Tetrachl oroethene
Toluene
1 , 2 , 4-Trl chl orobenzene
1,1,1 -Tri chl oroethane
1, 1,2 -Tri chl oroethane
Tri chl oroethene
Tri chl orof 1 uoromethane
1,2, 3 -Tri chl oropropane
Vinyl acetate
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
a Adequate response by thi

CAS No,b
76-01-7
109-06-8
107-19-7
57-57-8
107-12-0
107-10-8
110-86-1
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
120-82-1
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
108-05-4
75-01-4
95-47-6
108-38-3
106-42-3
s technique.

Purge-and-Trap
i
PP
PP
PP
ht
a
i
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a

Direct
Injection
a
a
a
a
pc
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a

b Chemical Abstract Services Registry Number.
ht Method analyte only when
i Inappropriate technique
purged at 80QC
for this analyte.




pc Poor chromatographic behavior.
pp Poor purging efficiency
surr Surrogate
I.S. Internal Standard
resulting in high


EQLs.





      1.2  Method 8260 can be used to quantitate most volatile organic compounds
that have boiling points  below  200°C and that are insoluble or slightly soluble
in water.  Volatile water-soluble compounds can be included in this analytical
technique.  However,  for  the  more soluble compounds, quantitation  limits  are
approximately ten  times  higher  because  of poor  purging  efficiency.    Such
compounds  include  low-molecular-weight  halogenated  hydrocarbons,  aromatics,
ketones, nitriles,  acetates, acrylates, ethers,  and sulfides.  See Tables 1  and
2 for lists of analytes and retention times that have  been  evaluated on a purge-
                                  8260A - 3                         Revision 1
                                                                September 1994

-------
 and-trap  GC/MS system.   Also,  the method  detection limits  for  25 ml  sample
 volumes are presented.  The following analytes are also amenable to  analysis  by
 Method 8260:

      Bromobenzene                  1-Chlorohexane
      n-Butylbenzene                2-Chlorotoluene
      sec-Butyl benzene              4-Chlorotoluene
      tert-Butylbenzene             Crotonaldehyde
      Chloroacetonitrile            Dibromofluoromethane
      1-Chlorobutane                cis-l,2-Dichloroethene
      1,3-Dichloropropane           Methyl-t-butyl  ether
      2,2-Di chl oropropane           Pentaf 1 uorobenzene
      1,1-Dichloropropene           n-Propylbenzene
      Fluorobenzene                 1,2,3-Tri chlorobenzene
      p-Isopropyltoluene            1,2,4-Trimethylbenzene
      Methyl acrylate               1,3,5-Tritnethylbenzene

      1.3   The estimated  quantisation  limit  (EQL)  of  Method  8260  for   an
 individual compound is somewhat instrument dependent. Using  standard quadrupole
 instrumentation,  limits  should  be  approximately  5 /ig/kg  (wet  weight)  for
 soil/sediment samples, 0.5 mg/kg (wet  weight)  for wastes, and  5  /ig/L for ground
 water (see Table 3).   Somewhat  lower  limits may be achieved using an ion trap
 mass spectrometer or other instrumentation of improved  design.   No matter which
 instrument is used, EQLs will  be  proportionately higher for  sample extracts and
 samples that require dilution  or reduced  sample size to avoid  saturation of the
 detector.

      1,4   Method  8260  is based upon a purge-and-trap,  gas chromatographic/mass
 spectrometric (GC/MS) procedure.   This method is restricted  to use by, or under
 the supervision of, analysts experienced in the use of purge-and-trap  systems and
 gas chromatograph/mass spectrometers,  and skilled in the interpretation of mass
 spectra and their use as a quantitative tool.

      1.5   An  additional method for  sample  introduction  is direct injection.
 This technique  has been  tested  for  the analysis  of  waste  oil  diluted with
 hexadecane  1:1  (vol/vol) and may  have  application  for the  analysis  of some
 alcohols and aldehydes in aqueous samples,


 2.C   SUMMARY OF METHOD

      2.1    The volatile compounds are introduced into  the gas chromatograph  by
 the purge-and-trap  method or by  direct  injection  (in limited applications).
 Purged sample  components are trapped in  a  tube  containing  suitable sorbent
materials.  When purging  is complete, the sorbent tube is heated  and backflushed
with helium  to  desorb trapped sample components.    The analytes  are  desorbed
directly to  a  large bore capillary or cryofocussed on a  capillary precolumn
 before being flash  evaporated to a narrow bore capillary  for  analysis.   The
column is temperature programmed to separate the analytes which are then detected
with a mass spectrometer  (MS) interfaced  to  the gas chromatograph.   Wide bore
capillary  columns require a jet separator, whereas narrow bore capillary columns
can be directly interfaced to the ion source.
                                   8250A -  4                         Revision 1
                                                                September 1994

-------
      2.2   If the above sample  introduction  techniques  are  not applicable,  a
portion of the sample is dispersed in solvent to dissolve the volatile organic
constituents.  A portion of the  solution is combined with organic-free reagent
water  in  the  purge chamber.    It  is then  analyzed  by  purge-and-trap  GC/MS
following the normal water method.

      2.3   Analytes eluted from the  capillary  column  are introduced into the
mass spectrometer via a  jet separator  or a direct connection.  Identification of
target analytes is accompl ished by comparing their mass spectra with the electron
impact (or electron impact-like) spectra of authentic standards.  Quantisation
is accomplished by comparing the  response of a major (quantitation) ion relative
to an internal standard with a five-point calibration curve.

      2.4   The method includes specific calibration and quality control  steps
that replace the general requirements in Method 8000.


3.0   INTERFERENCES

      3.1    Major  contaminant  sources  are volatile materials  in the laboratory
and impurities in the  inert purging gas and  in  the sorbent trap.   The use of non-
polytetrafluoroethylene  (PTFE)  thread  sealants,  plastic  tubing,   or  flow
controllers with rubber components should be avoided since such materials out-gas
organic compounds  which will  be concentrated  in the  trap  during  the  purge
operation.  Analyses of calibration and reagent blanks provide information about
the presence of contaminants.   When  potential  interfering peaks are noted in
blanks,  the  analyst  should  change the  purge  gas  source and  regenerate  the
molecular sieve purge gas  filter  (Figure  1).  Subtracting  blank  values  from
sample results is not permitted.  If  reporting values not corrected for blanks
result in  what the laboratory feels is  a false positive for a sample, this should
be fully explained in text  accompanying the uncorrected data.

      3.2    Interfering  contamination  may  occur when  a  sample  containing  low
concentrations of volatile  organic  compounds is  analyzed  immediately  after  a
sample containing  high  concentrations  of  volatile organic  compounds.    The
preventive technique is rinsing of the  purging apparatus and sample syringes with
two portions of organic-free reagent water between samples.   After analysis of
a sample containing high concentrations  of volatile organic  compounds,  one or
more calibration blanks  should be analyzed to check for cross contamination.  For
samples containing large amounts of water soluble .Tiaterlals,  suspended solids,
high boiling compounds or high  concentrations  of compounds being determined, it
may be necessary to  wash the  purging device with a  soap solution, rinse it with
organic-free reagent water,  and then dry the purging device in an oven at 105°C.
In extreme situations, the whole purge and trap device may require dismantling
and cleaning.  Screening of the  samples prior to purge and trap GC/MS analysis
is highly  recommended  to prevent contamination of the system.   This is especially
true for soil and waste samples.  Screening may be accomplished with an automated
headspace  technique or  by Method 3820 (Hexadecane Extraction and  Screening of
Purgeable  Organics).

            3.2.1  The low  purging efficiency  of many  analytes  from a 25 ml
      sample often results in significant concentrations remaining in  the sample
      purge vessel after analysis.  After removal of the  analyzed sample aliquot


                                   8260A  -  5                        Revision 1
                                                                September 1994

-------
       and  three rinses  of the  purge  vessel  with  analyte  free water,  it  is
       required  that the empty vessel be subjected to a  heated  purge cycle prior
       to  the analysis of  another sample  in  the same purge  vessel  to reduce
       sample to sample carryover.

       3.3   Special  precautions must be taken to analyze for methylene chloride.
 The  analytical  and  sample  storage area should be  isolated from all atmospheric
 sources of methylene chloride.  Otherwise random background levels will result.
 Since   methylene  chloride  will  permeate  through   PTFE   tubing,   all   gas
 chromatography  carrier gas lines and  purge gas  plumbing should be constructed
 from stainless  steel or copper tubing.   Laboratory clothing worn by the analyst
 should  be clean since  clothing previously exposed to methylene chloride fumes
 during   liquid/liquid  extraction   procedures    can   contribute  to   sample
 contamination.

       3.4   Samples  can  be  contaminated  by  diffusion  of  volatile  organ ics
 (particularly methylene chloride and fluorocarbons) through the septum seal  into
 the  sample during shipment  and storage.  A trip blank prepared  from organic-free
 reagent water and carried  through the sampling and handling protocol  can serve
 as a check on such contamination.

      3.5   Use  of sensitive mass spectrometers to achieve lower detection level
 will increase the potential to detect laboratory  contaminants  as interferences.

      3.6   Direct injection - Some contamination  may be eliminated by baking out
 the  column  between analyses.    Changing  the  injector  liner  will  reduce  the
 potential for cross-contamination.  A  portion  of  the  analytical column may  need
 to be removed in the case of extreme  contamination.  Use of direct injection  will
 result  in the need for more frequent instrument maintenance.

      3.7   If hexadecane is added to samples or  petroleum samples are analyzed,
 some chromatographic  peaks will  elute  after  the  target analytes.    The   oven
 temperature program must  include a post-analysis  bake out  period to ensure  that
 semi -vol atile hydrocarbons are volatilized.


 4.0   APPARATUS AND MATERIALS

      4.1   Purge-and-trap  device -  aqueous samples,  described in Method 5030.

      4.2   Purge-and-trap  device -  solid  samples,  described  in Method  5030.

      4.3   Injection port  liners (HP catalogue #18740-80200, or equivalent) are
modified for  direct  injection analysis by  placing  a 1-cm plug of pyrex   wool
 approximately 50-60  mm down the length
 of  the  injection   port  towards  the
oven.  An 0.53 mm  ID column is mounted    s«j>t*a.*n
1 cm into the liner from the oven side
of  the  injection  port,  according  to
manufacturer's  specifications.                       Modified Injector
                                  8260A  -  6                         Revision 1
                                                                September 1994

-------
4,4   Gas chromatography/mass spectrometer/data  system

      4.4.1  Gas  chromatograph  - An  analytical   system  complete  with a
temperature-programmable  gas   chromatograph   suitable   for  splitless
injection or interface to purge-and-trap apparatus.  The system includes
all  required  accessories,  including  syringes,  analytical  columns,   and
gases.  The  GC  should be equipped with variable constant differential flow
controllers so that the column flow rate will remain constant throughout
desorption  and   temperature  program  operation.    For   some  column
configurations,  the column  oven must be cooled  to  <  30°C,  therefore, a
subambient oven controller may be required.  The capillary column should
be directly coupled to the source,

            4.4.1.1     Capillary precolurnn interface when using cryogenic
      cooling  - This device  interfaces the purge and trap concentrator to
      the capillary  gas  chromatograph.    The  interface condenses   the
      desorbed  sample components and focuses them into a narrow band on an
      uncoated  fused  silica  capillary precoluran.   When  the  interface is
      flash  heated, the sample  is transferred to the analytical  capillary
      column.

                  4.4.1.1.1   During   the    cryofocussing    step,   the
            temperature of the  fused silica in the  interface is maintained
            at -150°C  under a  stream of  liquid nitrogen.   After  the
            desorption period,  the  interface must  be  capable  of rapid
            heating to  250°C  in  15  seconds or  less  to  complete  the
            transfer  of analytes.

      4.4.2  Gas chromatographic columns

            4.4.2.1     Column 1  -  60 m  x 0.75 mm ID  capillary column
      coated with  VOCOL (Supelco), 1.5 ^m film thickness, or equivalent.

            4.4.2.2     Column 2 -  30 - 75 m x 0.53 mm ID capillary column
      coated with DB-624  (J&W  Scientific),  Rtx-502.2 (RESTEK),  or VOCOL
      (Supelco),  3 Mffl  film thickness,  or equivalent.

            4.4.2.3     Column 3  -  30 m  x  0.25 - 0.32  mm  ID  capillary
      column coated with  95% dimethyl - 5%  diphenyl  polysiloxane (DB-5,
      Rtx-5,  SPB-5, or equivalent},  1 y,~, ~i~~. thickness.

            4.4.2.4     Column 4  -  50 m  x  0.32 mm ID  capillary column
      coated with  DB-624  (J&W  Scientific),  1.8 pm  film thickness,  or
      equivalent.

      4.4.3  Mass  spectrometer  - Capable of  scanning from 35 to  300  amu
every 2  sec or  less,  using 70 volts  (nominal)  electron energy  in  the
electron impact ionization mode. The mass spectrometer must be capable of
producing a  mass  spectrum for p-Bromofluorobenzene (BFB)  which  meets all
of the criteria in Table 4 when 5-50 ng of  the GC/MS tuning standard (BFB)
is injected  through  the  GC.   To  ensure  sufficient  precision  of  mass
spectral data,  the desirable MS scan rate  allows acquisition of at least
five  spectra while a  sample  component elutes from the  GC.


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                  4.4.3.1      The  ion  trap  mass  spectrometer may be used if it
            is capable of axial  modulation to reduce  ion-molecule reactions and
            can produce  electron impact-like  spectra that match those  in  the
            EPA/NIST Library.   In  an ion  trap  mass spectrometer,  because ion-
            molecule reactions with water and methanol may produce interferences
            that coelute with chloromethane  and chloroethane, the base peak for
            both of these analytes  will be at m/z 49.  This ion should be used
            as the  quantisation  ion in this case.   The mass  spectrometer must be
            capable of producing a  mass spectrum  for  BFB which meets all  of the
            criteria in Table 3  when  5  or  50 ng  are introduced.

            4.4.4 GC/MS interface - Two alternatives are used to interface  the
      GC to the mass spectrometer.

                  4.4.4.1     Direct coupling by inserting the column into the
            mass spectrometer is generally used  for 0.25-0.32 mm id  columns.

                  4.4.4.2     A separator including  an all-glass transfer line
            and glass  enrichment  device or split interface  is  used with  an
            0.53 mm column.

                  4.4.4.3     Any enrichment device or transfer line can be used
            if  all  of  the   performance specifications  described   in  Sec.  8
            (including  acceptable calibration at 50 ng or less) can be achieved.
            GC-to-MS interfaces  constructed  entirely  of glass or of glass-lined
            materials are recommended.   Glass can be deactivated by silanizing
            with dichlorodimethylsilane.

            4.4.5 Data system -  A  computer  system that allows  the  continuous
      acquisition  and  storage  on machine-readable  media  of all mass  spectra
      obtained throughout the duration  of the  chromatographic  program must be
      interfaced to the mass  spectrometer.  The computer must have software that
      allows  searching  any  EC/MS data  file  for  ions of a specified mass  and
      plotting such  ion  abundances versus  time or scan number.  This type of
      plot is defined as an Extracted Ion Current  Profile (EICP).  Software must
      also  be available that allows  integrating  the  abundances  in any  EICP
      between specified time or  scan-number  limits.   The most recent version of
      the EPA/NIST Mass Spectral Library should also be available.

      4.5   Microsyringes -  1C,  25, ICO, 25C, 500,  ar.c 1,000 ^1.

      4.6   Syringe valve - Two-way, with Luer ends (three each),  if applicable
to the purging device.

      4.7   Syringes -  5,  10, or 25 ml,  gas-tight with shutoff valve.

      4.8   Balance -  Analytical, 0.0001 g,  and top-loading, 0,1 g.

      4.9   Glass scintillation  vials  - 20 ml,  with Teflon lined  screw-caps or
glass culture tubes with Teflon lined screw-caps.

      4.10  Vials -  2  rnL,  for GC autosampler.
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      4.11  Disposable pipets - Pasteur.

      4.12  Volumetric flasks, Class  A  -  10 ml and  100  ml,  with ground-glass
stoppers.

      4.13  Spatula -  Stainless steel.


5.0   REAGENTS

      5.1   Reagent grade inorganic chemicals shall  be used in all  tests.  Unless
otherwise indicated,  it is  intended that all inorganic reagents  shall conform to
the  specifications of the  Committee on  Analytical  Reagents  of  the  American
Chemical Society, where such specifications are available.  Other grades may be
used, provided it is  first  ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the  accuracy of the determination.

      5.2   Organic-free  reagent  water - All references to water in this method
refer to organic-free reagent water,  as defined in Chapter One.

      5.3   Methanol,  CH3OH  -  Pesticide  quality or equivalent,  demonstrated to
be free of analytes.   Store apart from other solvents.

      5.4   Reagent Hexadecane -  Reagent hexadecane is defined  as hexadecane in
which interference is  not observed at  the method detection Limit of compounds of
interest.

            5.4.1  In  order to  demonstrate  that all  interfering volatiles have
      been  removed from  the  hexadecane,  a  direct  injection  blank  must  be
      analyzed.

      5.5   Polyethylene  glycol,  H(OCH2CH2)nOH  - Free of  interferences  at the
detection limit of the target analytes.

      5.6   Hydrochloric  acid  (1:1  v/v), HC1  - Carefully  add a measured volume
of concentrated HC1 to an equal volume of organic-free reagent water.

      5.7   Stock solutions -  Stock solutions may be prepared from pure standard
materials or purchased as certified solutions.   Prepare stock standard solutions
in methane"!, using assayed liquids or gases, as appropriate.

            5.7.1  Place about 9,8 ml  of  methanol in a 10 ml tared ground-glass-
      stoppered volumetric flask.  Allow  the  flask to  stand,  unstoppered, for
      about 10 minutes or until all alcohol-wetted surfaces have dried.  Weigh
      the flask to the nearest 0.0001 g.

            5.7.2  Add  the assayed reference material, as  described below.

                  5.7.2.1      Liquids - Using a 100 pi syringe, immediately add
            two or  more drops of  assayed reference material  to the flask; then
            reweigh.   The liquid must fall directly into the  alcohol  without
            contacting the  neck of  the flask.
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            5.7.2.2      Gases  - To prepare  standards  for any compounds
      that boil below 30°C (e.g. bromomethane,  chloroethane, chloromethane,
      or vinyl chloride), fill  a 5  ml  valved gas-tight syringe with the
      reference standard to the  5.0 ml mark.  Lower the  needle  to 5 mm
      above the methanol meniscus. Slowly introduce the  reference standard
      above the surface of the liquid.  The heavy gas will rapidly dissolve
      in the methanol.   Standards may also be prepared  by using a lecture
      bottle  equipped  with  a  Hamilton  Lecture Bottle  Septum (#86600).
      Attach Teflon tubing to the side arm relief valve and  direct a gentle
      stream of gas  into the methanol meniscus.

      5.7.3 Reweigh, dilute to  volume,  stopper, and  then mix by inverting
the flask  several times.   Calculate the concentration  in  milligrams per
liter (mg/L) from the net gain  in weight.  When compound purity  is assayed
to  be 96%  or greater,  the weight  may be  used  without  correction  to
calculate the concentration of the stock standard.   Commercially prepared
stock standards may be  used at  any concentration if  they are certified by
the manufacturer or by an independent source.

      5.7.4 Transfer the stock standard solution  into a  bottle with  a
Teflon lined screw-cap.  Store, with minimal  headspace, at -10°C to  -2Q°C
and protect from light,

      5.7.5 Prepare  fresh   standards   for  gases  weekly  or   sooner  if
comparison with check standards indicates a problem.  Reactive compounds
such as 2-chloroethyl vinyl  ether and styrene may need to be prepared more
frequently.   All  other standards must  be replaced  after  six  months,  or
sooner if comparison with check standards indicates a problem.  Both gas
and  liquid standards  must  be  monitored  closely   by comparison to the
initial calibration curve and by comparison to QC check  standards.  It may
be  necessary  to  replace the standards  more  frequently if  either  check
exceeds a 20% drift.

      5.7.6 Optionally  calibration  using a certified gaseous mixture can
be  accomplished  daily  utilizing commercially  available gaseous  analyte
mixture  of bromomethane,  chloromethane,  chloroethane, vinyl  chloride,
dichlorodifluoromethane  and trichlorofluoromethane  in nitrogen.  These
mixtures  of documented quality  are stable  for as  long  as  six  months
without refrigeration.   (VOA-CYL  III, RESTEK  Corporation,  Cat. #20194 or
equivalent).

            5.7.6.1       Preparation of Calibration  Standards  From  a Gas
      Mixture

                  5.7,6.1.1  Before removing the  cylinder shipping cap,
            be sure the-valve  is  completely closed  (turn clockwise).  The
            contents are under pressure and  should be used  in  a  well-
            ventilated  area.

                  5.7.6.1.2  Wrap the pipe thread  end of the Luer fitting
            with Teflon tape.   Remove the shipping cap from the cylinder
            and replace it  with the  Luer fitting.
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       5.7.6.1.3   Transfer half the working standard containing
other  analytes,  internal standards,  and surrogates  to the
purge  apparatus.

       5.7.6.1.4   Purge  the  Luer fitting  and stem on the gas
cylinder prior to  sample removal using the following sequence:

       a)     Connect  either  the  100 ^iL or 500 pL  Luer syringe
             to the  inlet fitting of  the  cylinder.

       b)     Make  sure  the  on/off valve  on the syringe  is in
             the open position.

       c)     Slowly   open  the   valve  on  the  cylinder  and
             withdraw a  full  syringe  volume.

       d)     Be sure  to close the valve on the cylinder before
             you withdraw the syringe from the  Luer  fitting.

       e)     Expel  the  gas   from the syringe  into  a  well-
             ventilated  area.

       f)     Repeat  steps a  through e one more time to fully
             purge the fitting.

       5.7.6.1.5  Once the fitting and stem have  been purged,
quickly withdraw  the volume of gas you  require  using  steps
5.6.6.1.4(a) through (d).  Be sure  to close the  valve on the
cylinder and syringe  before  you  withdraw  the syringe from the
Luer fitting.

       5.7.6.1.6  Open the syringe on/off valve for 5 seconds
to reduce the syringe pressure  to atmospheric pressure.  The
pressure in the cylinder is -30 psi .

       5.7.6.1.7  The gas mixture should be quickly transferred
into the reagent water through the female  Luer fitting located
above the purging  vessel .
      NOTE: Hake  s^re  the  arrow  on   the  4 -way  valve  :s
            pointing  toward  the  female  Luer   fitting  when
            transferring the sample from the syringe. Be sure
            to  switch the  4-way  valve  back  to  the  closed
            position  before removing  the syringe  from the
            Luer  fitting.

      5.7.6.1.8   Transfer the  remaining  half of the working
standard into  the  purging vessel.  This  procedure insures that
the  total  volume of  gas mix  is  flushed  into the  purging
vessel,  with none remaining  in the valve or lines.

      5.7.6.1.9   Concentration  of   each   compound  in  the
cylinder is typically 0.0025
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                        5.7.6.1.10 The fol 1 owing are the recommended gas vol umes
                  spiked  into  5  ml  of  water  to  produce  a typical  5-point
                  calibration:

                        Gas                     Calibration
                        Volume                  Concentrat ion
                         40 ML                      20 M9/L
                        100 ML                      50 M9/L
                        200 ML                     100 M9/L
                        300 ML                     150 M9/L
                        400 ML                     200 M9/L

                        5.7.6.1.11 The following are the recommended gas volumes
                  spiked  into  25 ml  of water  to produce  a typical  5-point
                  calibration:

                        Gas                     Calibration
                        Volume                  Concentration
                         10 ML                       1 M9/L
                         20 ML                       2 M9/L
                         50 ML                       5 M9/L
                        100 ML                      10 M9/L
                        250 ML                      25 M9/L

      5.8   Secondary  dilution  standards  -  Using stock  standard  solutions,
prepare in methanol, secondary dilution standards  containing the  compounds of
interest,  either singly  or mixed together.  Secondary dilution standards must be
stored with minimal  headspace  and should be  checked  frequently  for  signs of
degradation or  evaporation,  especially  just  prior  to preparing  calibration
standards from them.  Store in  a vial  with no  headspace for one  week only.

      5.9   Surrogate  standards - The  surrogates  recommended are toluene^ds,
4-bromofluorobenzene,  l,2-dichloroethane-d4,  and dibromofluoromethane.   Other
compounds may be used as surrogates,  depending upon the analysis requirements.
A stock surrogate solution in methanol should be prepared as described above,  and
a surrogate standard spiking solution  should  be prepared from  the  stock at a
concentration of 50-250 M9/1Q  ml in methanol.   Each water  sample undergoing
GC/MS analysis must  be spiked with 10  ML of the surrogate spiking solution prior
to analysis.

            5.9.1  If a  more sensitive mass spectrometer is employed to achieve
      lower detection levels,  more dilute  surrogate solutions may be required.

      5.10  Internal  standards   -  The  recommended   internal   standards   are
fluorobenzene, chlorobenzene-d5, and l,4-dichlorobenzene-d4.  Other compounds may
be used as  internal standards as long as they have retention times similar to the
compounds being  detected by GC/MS.  Prepare internal  standard stock and secondary
dilution  standards in methanol  using  the procedures described in Sees. 5.7  and
5.8.   It  is recommended  that the secondary dilution standard  should be prepared
at a concentration of 25 mg/L of each internal  standard compound.   Addition of
10 ML of this standard  to 5.0 ml of sample or calibration  standard would be the
equivalent of 50 M9/L.
                                  8260A - 12                        Revision 1
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            5.10,1       If  a more sensitive mass  spectrometer  is employed to
      achieve lower  detection  levels,  more dilute internal standard solutions
      may  be  required.   Area counts of  the  internal  standard peaks should be
      between 50-200% of the  area  of the  target  analytes  in  the mid-point
      calibration analysis.

      5.11  4-Bromofluorobenzene (BFB)  standard - A standard solution containing
25 ng/jiL of BFB  in methanol  should be  prepared.

            5.11.1       If  a more sensitive mass  spectrometer  is employed to
      achieve lower detection levels, a more dilute BFB standard  solution may be
      required,

      5.12  Calibration  standards -  Calibration standards at a minimum of five
concentrations should be prepared from  the secondary dilution of  stock standards
(see Sees.  5.7 and 5.8).  Prepare these solutions in organic-free reagent water.
One of  the concentrations should be  at  a concentration near,  but  above, the
method detection limit.   The remaining concentrations should correspond to the
expected range of concentrations  found  in real samples but should not exceed the
working range  of  the GC/MS system. Each standard should contain each analyte for
detection  by  this method.   It is EPA's  intent that  all  target  analytes  for a
particular analysis be included in the  calibration  standard(s).  However, these
target analytes  may  not  include the entire List of Analytes  (Sec. 1.1) for which
the method has been demonstrated.  However,  the laboratory shall  not report a
quantitative result  for a target analyte that was not included in  the calibration
standard(s).  Calibration standards must be prepared daily.

      5.13  Matrix spiking  standards  -  Matrix  spiking  standards  should  be
prepared from volatile  organic compounds which will  be  representative  of the
compounds being  investigated.  At a minimum, the matrix spike should include 1,1-
dichloroethene,   trichloroethene,  chlorobenzene,  toluene, and benzene.   It is
desirable  to  perform  a  matrix spike  using  compounds found in  samples.   Some
permits may require spiking specific compounds of interest, especially if they
are polar  and would not  be  represented  by  the  above listed compounds.   The
standard should  be  prepared in  methanol,  with  each compound  present  at  a
concentration of 250 ^ig/10.0 ml.

            5.13.1       If a  more sensitive mass  spectrometer  is employed to
      achieve lower detection levels, more dilute matrix spiking solutions may
      be required.

      5.14  Great care must  be taken  to maintain the integrity of all  standard
solutions.   It is recommended  all  standards  in methanol  be stored at -10°C to
-20°C  in amber bottles with  Teflon lined  screw-caps.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the introductory material  to this chapter,  Organic Analytes, Sec.
4.1.
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7.0   PROCEDURE

      7.1   Three  alternate  methods  are  provided for sample introduction.   All
internal standards,  surrogates, and matrix spikes (when applicable) must be added
to samples before introduction.

            7.1.1  Direct  injection   -   in  very  limited  application,   {e.g.,
      volatiles in  waste  oil  or  aqueous  process  wastes) direct injection  of
      aqueous  samples  or  samples diluted  according  to Method 3585  may  be
      appropriate.  Direct injection has been used  for the analysis of volatiles
      in waste oil  (diluted 1:1 with hexadecane)  and for determining  1f  the
      sample is ignitable  (aqueous  injection,  Methods 1010 or  1020).   Direct
      injection is  only  permitted for  the  determination of volatiles  at  the
      toxicity characteristic  (TC)   regulatory limits,  at concentrations  in
      excess of 10,000  ng/l, or for water-soluble compounds that do not purge.
           7.1.2  Purge-and-trap for  aqueous  samples,   see  Method  5030  for
      details.

           7.1.3  Purge-and-trap for solid samples, see Method 5030 for details.

      7.2  Recommended Chromatographic conditions

           7.2.1  General:

                  Injector  temperature:          200-225°C
                  Transfer  line  temperature:     250-300°C

           7.2.2  Column  1  (A  sample chromatogram  is  presented  in  Figure  5)

                  Carrier gas  (He)  flow rate:    15 mL/min
                  Initial temperature:           10°C,  hold for  5 minutes
                  Temperature  program:           6°C/min to 160°C
                  Final temperature:             160°C, hold until  all  expected
                                                compounds have  eluted.

           7.2.3  Column  2,   Cryogenic   cooling  (A   sample  chromatogram  is
      presented in Figure 6)

                  Carrier gas  (He)  flow rate:    15 mL/min
                  Initial temperature:           10°C,  hold for  5 minutes
                  Temperature  program:           6°C/min to 160°C
                  Final temperature:             160°C, hold until  all  expected
                                                compounds have  eluted.

           7.2.4  Column  2, Non-cryogenic  cooling (A  sample   chromatogram  is
      presented in Figure 7),  It is recommended  that  carrier gas flow and  split
      and make-up  gases be  set using performance of standards as guidance.  Set
      the carrier  gas head  pressure to « 10 psi and  the  split  to  * 30  mL/min.
      Optimize  the make-up  gas flow for the separator (approximately 30  mL/min)
      by  injecting BFB,  and determining the optimum  response when varying the
      make-up  gas.  This will require  several  injections of BFB.   Next,  make
      several  injections  of the  volatile  working standard with  all analytes  of

                                  8260A -  14                         Revision 1
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interest.  Adjust the carrier and split to  provide optimum chromatography
and response.  This is an especially critical  adjustment  for the volatile
gas analytes.  The head pressure should optimize  between  8-12 psi  and  the
split  between  20-60 mL/min.   The  use  of  the splitter  is   important  to
minimize the effect  of water on analyte response,  to allow  the use of a
larger volume of helium during  trap desorption,  and to slow  column flow.
      Initial  temperature:
      Temperature program:
      Final  temperature:
                        45°C,  hold  for  2  minutes
                        8°C/m;in  to  200°C
                        200°C, hold for 6 minutes,
      A trap preheated to 150°C prior to  trap  desorption is required  to
provide adequate chromatography of the gas analytes.

      7.2.5 Column 3 (A sample chromatogram is presented in Figure 8)
            Carrier gas (He) flow rate:
            Initial temperature:
            Temperature program:

            Final  temperature:
      7.2.6  Direct injection - Column 2
            Carrier gas (He) flow rate:
            Column:
            Initial temperature:
            Temperature program:
            Final  temperature:
                                     4  mL/min
                                     10°C, hold for 5 minutes
                                     6°C/niin to  70°C,  then 15°C/min
                                     to 145°C
                                     145°C, hold until  all  expected
                                     compounds  have eluted.
                                     4 mL/min
                                     J&W  DB-624,  70m  x  0.53  mm
                                     40C
hold for 3 minutes
                                    8°C/nrin
                                    260°C, hold until  all  expected
                                    compounds  have  eluted.
      Column Bake out  (direct inj): 75 minutes
      Injector temperature:         200-225°C
      Transfer line temperature:    250-300°C

7.2,7 Direct Split Interface - Column 4
            Carrier gas (He) flow rate:
            Initial temperature:
            Temperature program:

            Final  temperature:

            Split  ratio:
            Injector temperature:
                                     1.5 mL/min
                                     35°C, ho'td  for  2  iinnutes
                                     4°C/min to  50°C
                                     10°C/min to 220°C
                                     220°C, hold until  all  expected
                                     compounds have  eluted
                                     100:1
                                     125'C
7.3   Initial  calibration   -  the recommended  MS  operating  conditions
      Mass  range:
      Scan  time:
      Source  temperature:
                        35-260 amu
                        0.6-2 sec/scan
                        According to manufacturer's specifications
                            8260A - 15
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      Ion trap only:           Set axial modulation, manifold temperature,
                              and   emission   current   to  manufacturer's
                              recommendations

      7.3.1 Each GC/MS system must  be  hardware-tuned to meet the criteria
in  Table 4 for a  5-50  ng injection  or  purging  of 4-bromofluorobenzene
(2  jiL injection of the BFB standard).  Analyses must not begin until these
criteria are met.

      7.3.2 Set up the purge-and-trap  system as outlined  in Method 5030 if
purge-and-trap  analysis  is  to  be  utilized.   A set of  at least  five
calibration  standards containing  the method analytes  is  needed.   One
calibration  standard should  contain  each  analyte  at  a  concentration
approaching but greater than the method detection  limit (Table 1) for that
compound;  the other  calibration  standards  should  contain analytes  at
concentrations that define the range of the method.  Calibration should be
done  using the  sample  introduction  technique  that  will  be  used  for
samples.   For  Method 5030,  the  purging efficiency for 5 ml of water is
greater  than  for  25 ml.   Therefore, develop the  standard curve  with
whichever volume of  sample that will be analyzed.

            7.3.2.1      To prepare  a  calibration standard for purge-and-
      trap  or aqueous direct  injection,  add an  appropriate volume  of a
      secondary dilution  standard  solution to an  aliquot of organic-free
      reagent  water in a volumetric flask.  Use a  microsyringe and rapidly
      inject  the alcoholic standard into  the expanded  area of  the filled
      volumetric flask.   Remove the needle  as quickly as  possible after
      injection.  Mix by inverting the  flask three  times only.  Discard the
      contents  contained  in the neck of the flask.  Aqueous standards are
      not stable and  should be prepared daily.  Transfer 5.0 ml (or 25 ml
      if lower detection  limits are required) of each standard  to  a gas
      tight syringe along with 10 /iL of internal  standard.  Then transfer
      the contents  to a purging device  or  syringe.  Perform purge-and-trap
      or direct injection as  outlined  in  Method 5030.

            7.3.2.2      To  prepare a calibration standard  for  direct
      injection analysis  of oil, dilute standards in hexadecane.

      7.3.3 Tabulate the area response  of the characteristic  ions  {see
Table 5)   against  concentration for  each  compound   and  each  internal
standard.  Calculate response factors (RF) for each compound relative to
one of  the  internal  standards.   The  internal standard  selected  for the
calculation of the RF for a compound should be the internal  standard that
has a retention time  closest  to the  compound being measured (Sec. 7.6.2).
The RF is calculated as follows:
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                         RF  =  (AxCis)/(AfeCx)

where:

      Ax     -     Area of the  characteristic  ion  for the compound being
                  measured.
      Aj,.     =     Area  of  the  characteristic  ion  for  the  specific
                  internal  standard.
      Cto     =     Concentration of the specific internal standard.
      Cx     =     Concentration of the compound being measured.

      7.3.4  The  average  RF must  be  calculated and  recorded  for  each
compound using the five RF  values calculated  for  each compound from the
initial (5-point) calibration curve.  A system performance check  should be
made before this calibration curve  is  used.   Five  compounds (the System
Performance Check Compounds, or SPCCs) are checked for a minimum average
relative  response factor.    These  compounds  are  chloromethane;  1,1-
dichloroethane; bromoform;  1,1,2,2-tetrachloroethane; and chlorobenzene.
These compounds are used to check compound  instability  and to check for
degradation caused by contaminated  lines or  active  sites in the system.
Examples of these occurrences  are:

            7.3.4.1      Chloromethane  - This compound is the most likely
      compound  to  be  lost  if the purge  flow  is  too fast.

            7.3.4.2      Bromoform - This compound  is  one  of the compounds
      most likely to  be purged  very poorly if the purge flow is too" slow.
      Cold spots  and/or  active  sites in the  transfer lines may adversely
      affect  response.    Response  of the quantitation ion  (tn/z  173)  is
      directly  affected  by the  tuning  of  BFB  at   ions  m/z  174/176,
      Increasing  the  m/z  174/176  ratio relative to  m/z 95 may improve
      bromoform response.

            7.3.4.3      Tetrachloroethane and  1,1-dichloroethane - These
      compounds are degraded by contaminated transfer lines in purge-and-
      trap systems and/or  active sites  in trapping materials.

      7.3.5  Using the RFs   from the  initial  calibration,  calculate  and
record the percent relative standard deviation (%RSD) for all  compounds.
The percent  RSD is calculated  as  follows:


                   % RSD =  -JB- x 100%
                            RFx
where:
      RSD    =     Relative standard deviation.
      RFX    =     mean of 5 initial RFs for a compound.
      SD     =     standard deviation of the 5 initial RFs for a compound.
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                          ^  (RF.-RF):
                    SD    ^    '
            where:

                  RFj    =  RF  for  each  of the  5  calibration  levels
                  N      =  number  of  RF values (i.e., 5)

      The percent relative  standard deviation  should be less than 15% for
each compound.   However, the  %RSD for  each individual  Calibration Check
Compound  (CCC) must be less than 30%.  The CCCs are:

      1,1-Dichloroethene,
      Chloroform,
      1,2-Dichloropropane,
      Toluene,
      Ethyl benzene,  and
      Vinyl  chloride.

            7,3.5.1       If a %RSD greater than 30 percent is measured for
      any CCC,  then  corrective action  to  eliminate  a  system leak and/or
      column reactive sites is required before reattempting  calibration.

      7.3.6  Linearity -  If the %RSD of any compound is 15% or less, then
the  relative  response   factor  is   assumed   to  be  constant  over  the
calibration range, and the average relative  response  factor may be used
for quantitation.

            7.3.6.1       If the %RSD  of any compound is greater than 15%,
      construct  calibration   curves  of   area  ratio   (A/Ajs)   versus
      concentration  using first or higher order regression fit of the five
      calibration points.   The  analyst  should  select the regression order
      which  introduces the  least calibration error into the quantitation.
      The use of calibration curves is a recommended  alternative to average
      response  factor calibration  (Sec. 7.6.2.4), and a useful diagnostic
      of standard preparation  accuracy and  absorption  activity  in  the
      chromatographic system.

      7.3.7  These curves  are verified each shift by purging a performance
standard.   Recalibration  is  required  only if calibration  and  on-going
performance criteria cannot be met.

7.4   GC/MS  calibration verification

      7.4.1  Prior to the  analysis of samples,  inject or purge 5-50 ng of
the 4-bromofluorobenzene standard following Method  5030.   The resultant
mass spectra for the BFB must meet all of the criteria  given in Table 4
before sample analysis begins.  These  criteria must be demonstrated each
12-hour shift.
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      7.4.2 The initial calibration curve (Sec.  7.3)  for each compound of
 interest must be checked and verified once every 12 hours during analysis
 with the introduction technique used  for  samples.  This is accomplished by
 analyzing  a  calibration  standard  that  is  at  a  concentration  near the
 midpoint concentration for the working range of  the GC/MS by checking the
 SPCC and CCC.

      7.4.3 System  Performance  Check   Compounds  (SPCCs)   -  A  system
 performance check must  be made  each  12 hours.   If the SPCC criteria are
 met, a comparison of relative response factors is made-for all compounds.
 This is the same  check that  is applied during the initial calibration.  If
 the minimum  relative response  factors  are  not  met,   the system  must be
 evaluated, and  corrective action  must be taken  before  sample analysis
 begins.    Some  possible problems  are   standard  mixture  degradation,
 injection port inlet contamination, contamination at  the front end of the
 analytical column,  and  active  sites  in the column  or  chromatographic
 system.

            7.4.3.1       The minimum relative response factor for volatile
      SPCCs are  as follows:

            Chloromethane                              0.10
            1,1-Dichloroethane                         0.10
            Bromoform                                 >0.10
            Chlorobenzene                              0.30
            1,1,2,2-Tetrachloroethane                  0.30

      7.4.4 Calibration  Check  Compounds  (CCCs)  -   After  the  system
 performance check is met, CCCs listed in  Sec. 7,3.5 are used to check the
 validity of the initial calibration.

      Calculate  the  percent  drift  using the  following equation:

                    % Drift  = (C, - CC)/C, x 100

where:

      C, =   Calibration Check Compound standard  concentration.
      Cc =   Measured concentration using selected quantitation  method.

      If  the percent  drift  for each  CCC is  less than 20%,  the  initial
 calibration is assumed to be  valid.   If  the  criterion is not met (> 20%
drift),  for  any one  CCC,   corrective action must be taken.   Problems
 similar to those listed  under SPCCs  could affect this criterion.   If no
 source of the problem can be determined  after corrective action has been
taken, a new  five point calibration  MUST be generated.  This  criterion
MUST be met before quantitative sample analysis  begins.  If the CCCs are
not required analytes by the permit,  then all required analytes must meet
the 20% drift criterion.

      7.4.5 The internal standard  responses  and retention times  in the
check calibration standard must be evaluated immediately after or during
data acquisition.  If  the retention time for any  internal standard changes


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by more  than  30  seconds  from the last calibration check (12 hours), the
chromatographic system must be inspected for malfunctions and corrections
must  be  made, as  required.   If the  EICP  area for any of  the internal
standards changes  by a factor of two  (-50%  to +100%) from the last daily
calibration check  standard,  the  mass  spectrometer must be inspected for
malfunctions  and  corrections  must  be made,   as  appropriate.    When
corrections are made, reanalysis of samples  analyzed while the system was
malfunctioning is  necessary.

7.5   GC/MS  analysis

      7.5.1  It is  highly  recommended  that   the extract  be screened  on a
headspace-GC/FID   (Methods  3810/8015),  headspace-GC/PID/ELCD  (Methods
3810/8021), or waste dilution-GC/PID/ELCD  (Methods  3585/8021)  using the
same type of  capillary column.   This  will  minimize contamination of the
GC/MS system from  unexpectedly high concentrations of organic compounds.
Use of screening  is particularly important when  this  method  is  used to
achieve  low detection levels,

      7.5.2  All  samples and standard solutions  must  be  allowed to warm to
ambient temperature before analysis.  Set up the purge-and-trap system as
outlined in Method 5030 if purge-and-trap introduction will  be used,

      7,5.3  BFB  tuning  criteria  and  GC/MS  calibration  verification
criteria must be met before analyzing samples.

            7.5.3.1     Remove the plunger  from a 5  ml  syringe and attach
      a closed syringe valve.  If lower detection  limits  are required,- use
      a 25 ml syringe.  Open the sample or standard bottle, which has been
      allowed to come to ambient temperature, and carefully pour the sample
      into the  syringe  barrel  to just  short of overflowing.   Replace the
      syringe  plunger and compress the sample.   Open  the  syringe valve and
      vent any residual air while adjusting  the sample  volume to  5.0  ml.

      7.5.4  The  process of taking  an  aliquot  destroys the  validity of
aqueous and  soil  samples  for future  analysis; therefore, if there is only
one VGA vial,  the analyst  should  prepare a second  aliquot for analysis at
this time to  protect against possible  loss of sample  integrity.   This
second sample  is  maintained only until  such  time when the  analyst  has
determined that the first  sample  has been analyzed properly.   For aqueous
samples,  filling  one 20 ml  syringe would   require  the use  of only  one
syringe.    If a  second  analysis  is  needed  from  a  syringe,  it  must be
analyzed  within 24 hours.   Care must be  taken to prevent air from leaking
into the  syringe.

            7.5.4.1     The   following   procedure  is   appropriate  for
      diluting  aqueous  purgeable  samples.   All steps  must  be  performed
      without  delays  until  the diluted sample  is  in  a gas-tight syringe.

                   7.5.4.1.1  Dilutions  may  be  made  in  volumetric flasks
            (10  to 100  ml).  Select the volumetric flask that will  allow
            for  the necessary dilution.  Intermediate  dilutions may be
            necessary for  extremely large dilutions.
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                  7.5.4.1.2  Calculate the approximate volume of organic-
            free  reagent water  to  be  added  to  the volumetric  flask
            selected and add slightly less than this quantity of organic-
            free reagent water to the flask,

                  7.5.4.1.3  Inject the proper aliquot of sample from the
            syringe into the flask.   Aliquots of  less than  1  ml are not
            recommended.  Dilute  the  sample to the mark with organic-free
            reagent water.   Cap the flask, invert, and shake three times.
            Repeat above procedure for additional  dilutions.

                  7.5.4.1.4  Fill a 5 ml syringe with  the diluted sample.

            7.5.4.2      Compositing   aqueous   samples  prior   to  GC/MS
      analysis

                  7.5.4.2,1  Add  5  ml  or equal  larger amounts  of each
            sample (up to 5  samples are allowed)  to a 25 ml glass syringe.
            Special  precautions must be made to maintain zero headspace in
            the syringe.

                  7.5.4.2.2  The samples must  be cooled at 4°C during this
            step to minimize volatilization  Tosses.

                  7.5.4.2.3  Mix  well  and draw out  a 5 ml aliquot  for
            analysis.

                  7.5.4.2.4  Follow  sample  introduction,  purging,  and
            desorption steps described in  Method 5030.

                  7.5.4.2.5  If  less than  five  samples  are  used  for
            compositing, a  proportionately  smaller syringe may  be used
            unless a 25 ml  sample is  to  be purged.

      7.5.5  Add  10.0  /uL  of surrogate  spiking solution  and   10  juL  of
internal standard  spiking  solution to  each sample.   The  surrogate  and
internal standards may  be mixed  and  added as  a  single spiking  solution.
The addition of 10 juL of the surrogate spiking solution to 5 ml of sample
is equivalent to  a  concentration  of  50  jtig/L of  each  surrogate  standard.
The addition of 10 JUL of the surrogate spiking solution to  5 g  of sample
is equivalent to a concentration  of 50 /ug/kg of each  surrogate  standard.

            7.5.5.1       If  a more sensitive mass spectrometer is employed
      to achieve lower detection levels, more dilute surrogate and internal
      standard  solutions may be required.

      7.5.6  Perform purge-and-trap or direct injection by Method 5030.  If
the  initial  analysis  of  sample or  a dilution  of  the  sample  has  a
concentration of analytes that exceeds the initial calibration range, the
sample  must  be  reanalyzed  at   a  higher dilution.    Secondary  ion
quantitation is allowed only when there  are sample interferences with the
primary ion.   When  a  sample is  analyzed that  has  saturated ions  from a
compound,  this analysis must be followed by a  blank organic-free reagent


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water analysis.  If the blank analysis is not free of interferences,  the
system must be decontaminated.   Sample analysis  may not resume until  the
blank analysis is demonstrated  to be free of interferences.

            7.5.6.1,     All  dilutions should keep  the response of  the
     major constituents (previously saturated peaks)  in the upper half of
     the linear range of the curve.   Proceed  to Sees. 7.6.1 and 7.6.2  for
     qualitative  and quantitative analysis.

     7.5.7  For matrix  spike  analysis,  add  10  #L  of  the matrix  spike
solution {Sec.  5.13) to  the 5 ml of sample  to  be purged.  Disregarding  any
dilutions,  this is equivalent to a concentration of 50 /xg/L of each matrix
spike standard.

7.6  Data  interpretation

     7.6.1  Qualitative  analysis

            7.6.1.1      The  qualitative   identification  of  compounds
     determined  by this  method  is  based  on  retention  time,  and  on
     comparison of the sample mass spectrum,  after background correction,
     with characteristic ions in a reference mass  spectrum.  The reference
     mass  spectrum  must  be  generated   by  the  laboratory  using  the
     conditions  of this  method.    The   characteristic   ions  from  the
     reference mass spectrum are defined  to be the three ions of greatest
     relative  intensity, or any ions over 30% relative intensity if less
     than  three  such  ions occur  in  the  reference spectrum.   Compounds
     should be identified as present when  the criteria below  are met.

                  7.6.1.1.1   The intensities of  the  characteristic ions
            of a  compound maximize in the same scan or within one scan of
            each  other.    Selection  of a  peak by  a  data  system target
            compound  search  routine  where the  search  is  based on  the
            presence  of a  target chromatographic  peak containing ions
            specific  for  the  target compound   at  a  compound-specific
            retention time will  be  accepted as meeting  this  criterion.

                  7.6.1.1.2   The RRT  of  the  sample component  is within
            ±0.06  RRT units  of the  RRT of the standard component.

                  7.6.1.1.3   The    relative    intensities     of    the
            characteristic   ions  agree   within   30%   of  the  relative
            intensities   of   these  ions    in  the   reference  spectrum.
            (Example:    For   an  ion  with  an abundance of   50% in  the
            reference  spectrum,  the corresponding abundance  in  a sample
            spectrum can range  between 20% and 80%.)

                  7.6.1.1.4   Structural isomers that produce very similar
            mass  spectra should be  identified  as individual  isorners  if
            they   have  sufficiently  different   GC  retention  times.
            Sufficient  GC resolution  is  achieved if  the  height of  the
            valley between two isomer peaks is less than 25% of the sum of
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       the  two  peak heights.   Otherwise,  structural  iseiners  are
       identified  as isomeric pairs.

             7.6.1.1.5  Identification  is  hampered  when   sample
       components  are not resolved chromatographically and  produce
       mass  spectra  containing  ions  contributed by  more than  one
       analyte.  When gas  chromatographic  peaks  obviously  represent
       more  than one sample component (i.e., a  broadened  peak  with
       shoulder(s)   or   a   valley   between  two   or   more  maxima),
       appropriate   selection  of  analyte  spectra  and   background
       spectra  is  important.   Examination of extracted ion  current
       profiles  of  appropriate  ions  can  aid  in  the selection  of
       spectra,  and in qualitative  identification of compounds.  When
       analytes  coelute  (i.e.,  only  one chromatographic  peak  is
       apparent),  the identification  criteria  can be met, but  each
       analyte spectrum  will  contain  extraneous  ions  contributed by
       the coeluting  compound.

       7.6.1.2      For samples containing  components  not  associated
with the calibration standards,  a  library  search may be made  for the
purpose of tentative identification.   The  necessity to perform  this
type of  identification  will  be  determined by  the type of analyses
being conducted. Guidelines for making tentative identification  are:

       (1)    Relative intensities  of major ions  in  the  reference
             spectrum (ions > 10% of the  most abundant ion)  should
             be  present  in the sample spectrum.

       (2)    The relative  intensities of the major ions should agree
             within + 20%.   (Example:  For an ion with an  abundance
             of  50%  in  the  standard spectrum,  the  corresponding
             sample ion  abundance  must be  between 30  and  70%).

       (3)    Molecular ions present in the reference spectrum should
             be  present  in the sample spectrum,

       (4)    Ions  present  in the   sample  spectrum but not  in  the
             reference  spectrum  should  be  reviewed  for possible
             background  contamination   or  presence  of   coeluting
             compounds.

       (5)    Ions  present  in  the reference spectrum but not  in  the
             sample  spectrum  should  be  reviewed  for  possible
             subtraction  from  the  sample  spectrum  because   of
             background  contamination  or coeluting  peaks.     Data
             system library reduction programs can sometimes  create
             these  discrepancies.

       Computer  generated  library  search  routines should  not  use
normalization routines that would misrepresent the library or  unknown
spectra when compared to each other.   Only  after visual comparison
of sample with the nearest library searches will the mass spectral
interpretation specialist assign a tentative identification.
                      8260A  - 23                        Revision  1
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7.6.2  Quantitative analysis

       7.6.2.1      When   a   compound  has  been   identified,   the
quantisation  of  that  compound  will  be  based  on the  integrated
abundance  from   the   EICP   of   the  primary   characteristic  ion.
Quantitation will  take place using the internal standard technique.
The  internal standard  used  shall be the one  nearest  the retention
time of that of  a  given analyte,

       7.6.2.2      When MS response is  linear  and passes through the
origin, calculate the concentration of each identified  analyte in the
sample as follows:

       Water

                                 (AX) (i.)
       concentration  (^ig/L)  = - 33 -
                              (Ais)(RF)(V0)

where:

       Ax     =      Area of  characteristic  ion for compound being
                   measured.
       Is     =      Amount of internal  standard injected  (ng).
       Ais     =      Area  of  characteristic ion  for  the  internal
       _           standard.
       RF     =      Mean relative response factor for compound being
                   measured.
       V0     =      Volume  of   water  purged   (ml),   taking  into
                   consideration any dilutions made.

       Sediment/Soil  Sludge   (on a  dry-weight  basis)  and  Waste
{normally on a wet-weight basis)
      concentration  (jig/kg)  =
                               (Ak)(RF)(Vi)(WJ(D)

where:

      Ax> Is>  Au,  RF,  = Same as for water.
      Vt     =     Volume of total extract (juL) (use 10,000 ^L or a
                   factor-of this when dilutions are made).
      Vj     =     Volume of extract added (juL) for  purging.
      Ws     =     Weight of sample extracted or purged  (g).
      D     =     % dry weight of sample/100,  or 1 for a wet-weight
                   basis.

      7.6.2.3      Where appl icable, an estimate of concentration for
noncal ibrated components in the sample  should be made.  The formulae
given above  should be  used  with the following modifications:  The
areas Ax and A!s should be from the total  ion  chromatograms, and the
RF for  the  compound  should be assumed to be 1.  The concentration

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            obtained should  be  reported indicating  (1)  that  the value  is an
            estimate and  (2) which  internal  standard was  used  to  determine
            concentration.     Use  the  nearest   internal   standard   free  of
            interferences.

                  7.6.2.4     Alternatively, the  regression line fitted to the
            initial  calibration  (Sec.  7,3.6.1) may be used for determination of
            analyte  concentration.


8.0   QUALITY CONTROL

      8.1   Refer to Chapter One  and  Method 8000 for general  quality control
procedures.

      8.2   Additional  required  instrument QC is found in  the Sees. 7.3 and 7.4:

            8.2.1 The SC/MS system must be tuned to meet the BFB specifications.

            8.2.2 There must be  an initial  calibration of the  GC/MS  system

            8.2.3 The  GC/MS  system  must meet  the SPCC  criteria  and the  CCC
      criteria, each 12 hours.

      8.3   To  establish  the  ability  to   generate  acceptable  accuracy  and
precision, the analyst must perform the following operations.

            8.3.1 A   quality control   (QC)  reference  sample  concentrate  is
      required containing each analyte at a  concentration of 10 mg/L or less in
      methane!.  The QC reference sample concentrate  may  be  prepared from pure
      standard materials or  purchased as certified solutions.   If prepared by
      the laboratory,  the  QC reference sample  concentrate must be made  using
      stock standards prepared independently from those  used for calibration.

            8.3.2 Prepare a QC reference sample to contain 20 /ig/L  or less of
      each analyte by adding  200 ^L of QC reference sample concentrate to 100 ml
      of organic-free reagent water.

            8.3.3 Four 5-mL aliquots  of the well  mixed QC reference  sample are
      analyzed according to the  method beg:nr:ng -.r.  Sec.  7.5.1.

            8.3.4 Calculate the  average recovery (x)  in M9/L,  and  the standard
      deviation of the  recovery  (s)  in M9/L,  for each analyte  using  the four
      results.

            8.3.5 Tables  7  and 8  provide  single  laboratory  recovery  and
      precision  data  obtained  for the  method  analytes  from  water.    Similar
      results from dosed water should be expected by any experienced laboratory.
      Compare s  and x   (Sec. 8.3.4) for each analyte to  the  single  laboratory
      recovery and precision data.   Results are comparable if  the  calculated
      standard deviation of the  recovery does  not exceed  2.6 times the single
      laboratory RSD or 20%, whichever  is greater, and the  mean recovery lies
      within the interval x ± 3s or  x  ± 30%, whichever is greater,


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            NOTE:  The  large  number of  analytes  in Tables  7  and  8  present a
                  substantial probability that one  or  more  will  fail at least
                  one of the acceptance  criteria when  all  analytes of a given
                  method are determined.

            8.3.6  When one or more of  the analytes tested are not comparable to
      the  data  in Table 6  or  7, the  analyst  must proceed according  to Sec.
      8.3,6.1 or 8.3.6.2.

                  8.3,6.1      Locate  and correct the source of the problem and
            repeat the test  for all  analytes  beginning  with  Sec.  8.3.2.

                  8.3.6.2      Beginning  with Sec.  8.3.2,  repeat  the test only
            for  those  analytes  that  are not  comparable.   Repeated failure,
            however, will confirm a general problem with the measurement system.
            If this occurs,   locate  and  correct the source of  the  problem and
            repeat the test  for all compounds  of interest  beginning with Sec.
            8.3.2.

      8.4   For  aqueous  and  soil  matrices,  laboratory established  surrogate
control limits should be compared with the control  limits listed in Table 8.

            8.4.1  If recovery is not within limits,  the  following procedures are
      required.

                  8.4.1.1      Check to be sure that there are no errors in the
            calculations,  surrogate  solutions or internal standards.  If errors
            are  found,  recalculate  the  data accordingly.

                  8.4.1.2      Check instrument performance.   If  an  instrument
            performance problem is identified, correct the problem and re-analyze
            the  extract.

                  8.4.1.3      If no problem is  found, re-extract and re-analyze
            the  sample.

                  8.4.1.4      If,  upon  re-analysis,  the recovery is again not
            within  limits, flag  the  data  as "estimated  concentration".

            8.4.2  At a mini mum, each laboratory  shou'c update surrogate recovery
      limits on a matrix-by-matrix basis, annually.


9.0   METHOD PERFORMANCE

      9.1   The  method   detection  limit  (MDL)  is  defined  as  the  minimum
concentration of  a  substance   that  can  be  measured  and  reported with  99%
confidence that the value is above zero.  The MDL actually achieved in a given
analysis will vary depending on instrument sensitivity  and matrix effects.

      9.2   This  method has  been  tested  in  a  single  laboratory  using  spiked
water.  Using a wide-bore capillary column,  water was spiked at concentrations
between 0.5  and  10 /ug/L.   Single  laboratory accuracy  and  precision data are


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presented for the method analytes in Table 6.   Calculated MDLs  are presented in
Table 1.

      9.3   The method was  tested  using water spiked  at  0.1 to 0.5  ^g/L and
analyzed on a cryofocussed narrow-bore column.  The accuracy  and precision data
for these compounds are presented in Table 7.  MDL values were also calculated
from these data and are presented in Table 2.

      9.4   Direct injection has been used for the analysis of waste motor oil
samples using  a wide-bore column.   The accuracy  and  precision data for these
compounds are presented in Table 10.


10.0  REFERENCES

1.    Methods for the Determination  of Organic Compounds  in  Finished Drinking
      Water and Raw  Source MaterMethod  524.2;  U.S.  Environmental  Protection
      Agency.  Office  of  Research  Development,  Environmental  Monitoring  and
      Support Laboratory,  Cincinnati, OH 1986.

2.    U.S.  EPA Contract  Laboratory Program,  Statement of  Work for  Organic
      Analysis, July 1985, Revision.

3.    Bellar, T.A.;  J.J. Lichtenberg.  J. Amer.  Water Works Assoc. 1974, 66(12),
      739-744.

4.    Bellar,  T.A.;  J.J,   Lichtenberg.  "Semi-Automated Headspace Analysis  of
      Drinking Waters  and  Industrial  Waters  for Purgeable Volatile  Organic
      Compounds";  in Van Hall,  Ed.; Heasur ernent of 0rgan ic Po11u t an ts in Wa t e r
      and Wastewater,  ASTM STP 686, pp 108-129, 1979.

5.    Budde, W.L.; J.W.  Eichelberger.   "Performance Tests for the Evaluation of
      Computerized   Gas    Chromatography/Mass    Spectrometry   Equipment   and
      Laboratories";  U.S.  Environmental   Protection   Agency.    Environmental
      Monitoring and Support Laboratory, Cincinnati, OH 45268, April 1980; EPA-
      600/4^79-020.

6.    Eichelberger,  J.W.;   I.E.  Harris;  W.L.  Budde.   "Reference Compound  to
      Calibrate   Ion   Abundance   Measurement   in   Gas   Chromatography-Mass
      Spectrometry Systems"; Analytical Chem'stry 1S75, 47, 995-IOCC.

7.    Olynyk,  P.;  W.L. Budde;  J.W.  Eichelberger. "Method  Detection  Limit  for
      Methods 624  and 625"; Unpublished report, October 1980.

8.    Non   Cryogenic   Temperatures   Program   and   Chromatogram,   Private
      Communications;   Myron  Stephenson   and  Frank   Allen,   EPA   Region  IV
      Laboratory,  Athens,  GA.

9.    Marsden, P.; C.L. Helms, B.N. Colby.  "Analysis  of Volatiles  in Waste Oil";
      report for B.  Lesnik, OSW/EPA under EPA contract 68-W9-001, 6/92.
                                  8260A - 27                        Revision 1
                                                                September 1994

-------
10.    Methods for  the  Determination of  Organic  Compound^^ 1,ri  DHjjking  Water,
      Supplement II Method 524.2;  U.S.  Environmental  Protection Agency.  Office
      of Research and Development, Environmental Monitoring Systems Laboratory,
      Cincinnati, OH   1992.
                                  8260A  -  28                         Revision  1
                                                                September  1994

-------
                                   TABLE 1.
       CHROMATOGRAPHIC  RETENTION  TIMES  AND  METHOD  DETECTION  LIMITS  (HDL)
         FOR  VOLATILE ORGANIC  COMPOUNDS ON  WIDE-BORE  CAPILLARY  COLUMNS
ANALYTE
RETENTION TIME
  (minutes)
MDL

Dichlorodifl uoromethane
Chl oromethane
Vinyl Chloride
Bromomethane
Chloroethane
Trichl orof 1 uoromethane
Acrolein
lodomethane
Acetonitrile
Carbon disulfide
Ally! chloride
Methyl ene chloride
1,1-Dichloroethene
Acetone
trans- 1, 2-Di chl oroethene
Acrylonitrile
1, 1-Di chl oroethane
Vinyl acetate
2, 2-Di chl oropropane
2-Butanone
ci s- 1 , 2-Di chl oroethene
Propionitrile
Chloroform
Bromochl oromethane
Hethacryl oni tr i 1 e
1,1,1 -Tri chl oroethane
Carbon tetrachloride
1 , 1 -Di chl oropropene
Benzene
1, 2-Di chl oroethane
Trichl oroethene
1 , 2-Di chl oropropane
Bromodi chl oromethane
Dibromotnethane
Methyl methacrylate
1,4-Dioxane
2-Chloroethyl vinyl ether
4-Methyl -2-pentanone
trans- 1 , 3-Di chl oropropene
Toluene
cis-1, 3-Di chl oropropene
1 ,1,2 -Tri chl oroethane
Column la
1.35
1.49
1.56
2.19
2.21
2.42
3.19
3.56
4.11
4.11
4.11
4.40
4.57
4.57
4.57
5.00
6.14
6.43
8.10
__
8.25
8.51
9.01
--
9.19
10.18
11.02
--
11.50
12.09
14.03
14.51
15.39
15.43
15.50
16.17
--
17.32
17.47
18.29
19.38
19.59
Column 2b
0.70
0.73
0.79
0.96
1.02
1.19





2.06
1.57

2.36

2.93

3.80

3.90

4.80
4.38

4.84
5.26
5.29
5.67
5.83
7.27
7.66
8.49
7.93




--
10.00
--
11.05
Column 2'e
3.13
3.40
3.93
4.80
--
6.20





9.27
7.83

9.90

10.80

11.87

11.93

12.60
12.37

12.83
13.17
13.10
13 .50
13.63
14.80
15.20
15.80
15.43




16.70
17.40
17.90
18.30

0.10
0.13
0.17
0.11
0.10
0.08





0.03
0.12

0.06

0.04

0.35

0.12

0.03
0.04

0.08
0.21
0.10
0.04
0.06
0.19
0.04
0.08
0.24




--
0.11
--
0.10
                                  8260A - 29
                       Revision 1
                   September 1994

-------
TABLE 1,
(Continued)
ANALYTE


Ethyl methacryl ate
2-Hexanone
Tetrachloroethene
1,3-Dichloropropane
Di bromochl oromethane
1,2-Dibromoethane
1-Chlorohexane
Chlorobenzene
1,1,1, 2-Tetrachl oroethane
Ethyl benzene
p-Xylene
m-Xylene
o-Xylene
Styrene
Bromoform
Isopropyl benzene (Cumene)
cis-l,4-Dichloro-2-butene
1,1,2, 2-Tetrachl oroethane
Bromobenzene
1 , 2 , 3 -Tri chl oropropane
n-Propyl benzene
2-Chlorotoluene
trans -1,4-Di chl oro-2-butene
1 , 3 , 5-Tri methyl benzene
4-Chlorotoluene
Pentachl oroethane
1 , 2 , 4-Trimethyl benzene
sec-Butyl benzene
tert-Butyl benzene
p- Isopropyl tol uene
1,3-Dichl orobenzene
1,4-Dichlorobenzene
Benzyl chloride
n- Butyl benzene
1 , 2-Dichl orobenzene
1, 2 -Dibromo-3-chl oropropane
1, 2, 4-Tri chl orobenzene
Hexachl orobutadi ene
Naphthalene
1,2, 3 -Tri chl orobenzene
RETENTION TIME

Column 1B
20.01
20.30
20.26
20.51
21.19
21.52
_.
23.17
23.36
23.38
23.54
23.54
25.16
25.30
26.23
26.37
27.12
27.29
27.46
27.55
27.58
28.19
28.26
28.31
28.33
29.41
29.47
30.25
30.59
30.59
30.56
31.22
32.00
32.23
32.31
35.30
38.19
38.57
39.05
40.01
(minutes)
Column 2B


11.15
11.31
11.85
11.83
13.29
13.01
13.33
13.39
13.69
13.68
14.52
14.60
14.88
15.46

16.35
15.86
16.23
16.41
16.42

16.90
16.72

17.70
18.09
17.57
18.52
18.14
18.39

19.49
19.17
21.08
23.08
23.68
23.52
24.18

Column 2/c


18.60
18.70
19.20
19.40
__
20.67
20.87
21.00
21.30
21.37
22.27
22.40
22.77
23.30

24.07
24.00
24.13
24.33
24.53

24.83
24.77

31.50
26.13
26.60
26. 5C
26.37
26.60

27.32
27.43
--
31.50
32.07
32.20
32.97
MDLd
(MA)



0.14
0.04
0.05
0.06
0.05
0.04
0.05
0.06
0.13
0.05
0.11
0.04
0.12
0.15

0.04
0.03
0.32
0.04
0.04

0.05
0.06

0.13
0.13
0.14
G.I2
0.12
0.03

0.11
0.03
0.26
0.04
0.11
0.04
0.03
8260A - 30
    Revision 1
September 1994

-------
                                   TABLE 1.
                                  (Continued)
ANALYTE
                                    Column I1
RETENTION TIME
  (minutes)
   Column 2    Column 2'c
             MDLd
            (M9/L)
INTERNAL STANDARDS/SURROGATES

1,4-Difluorobenzene                 13.26
Chlorobenzene-d5                    23.10
l,4-Dichlorobenzene-d4              31.16

4-Bromofluorobenzene                27.83
l,2-Dichlorobenzene-d4              32.30
Dichloroethane-d4                   12.08
01bromof1uoromethane
To1uene-d8                          18.27
Pentaf1uorobenzene
Fluorobenzene                       13.00
   15,71
   19.08
23.63
27.25
    6.27
14.06
"  Column 1 - 60 meter x 0.75 mm ID VOCOL capillary.  Hold at 10DC for 8 minutes,
   then program to 180°C at 4°/min.

b  Column 2-30 meter x 0.53 mm ID DB-624 wide-bore capillary  using cryogenic
   oven.  Hold at 10°C  for 5 minutes,  then program to 160°C at 6D/min.

c  Column 2' - 30 meter x 0.53 mm ID DB-624 wide-bore capillary,  cooling  GC oven
   to ambient  temperatures.   Hold  at  10°C  for 6 minutes,  program to  70°C  at
   10°/niin,  program to  120°C  at  5°/min,  then program to 180°C at 8°/min.

d  MDL based on a 25 mL sample volume.
                                  8260A - 31
                       Revision 1
                   September 1994

-------
                            TABLE 2.
CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (HDL)
 FOR VOLATILE ORGANIC COMPOUNDS ON NARROW-BORE CAPILLARY COLUMNS
ANALYTE
Di chl orod i f 1 uoromethane
Chl oromethane
Vinyl chloride
Bromomethane
Chloroethane
Tr i chl orof 1 uoromethane
1,1-Di chl oroethene
Methyl ene chloride
trans- 1 , 2-Di chl oroethene
1,1-Dichloroethane
cis-1, 2-Di chl oroethene
2 , 2-Di chl oropropane
Chloroform
Bromochl oromethane
1, 1,1 -Tri chloroethane
1, 2-Di chloroethane
1,1-Dichloropropene
Carbon tetrachloride
Benzene
1 ,2-Dichloropropane
Tri chl oroethene
Dibromomethane
Bromodi chl oromethane
Toluene
1 , 1 ,2-Trichloroethane
1 , 3 -Di chl oropropane
Di bromochl oromethane
Tetrachl oroethene
1,2-Dibromoethane
Cnlorobenzene
1 , 1 , 1 , 2-Tetrachl oroethane
Ethyl benzene
p-Xylene
m-Xylene
Bromoform
o-Xylene
Styrene
1,1,2 , 2-Tetrachl oroethane
1,2, 3 -Tri chl oropropane
I sopropyl benzene
RETENTION TIME
(minutes)
Column 3a
Q.8S
0.97
1.04
1.29
1.45
1.77
2.33
2.66
3.54
4.03
5.07
5.31
5.55
5.63
6,76
7.00
7.16
7.41
7.41
8.94
9.02
9.09
9.34
11.51
11.99
12.48
12.80
13.20
13.60
14.33
14.73
14.73
15.30
15.30
15.70
15.78
15.78
15.78
16.26
16.42
MDLb
(M9A)
0.11
0.05
0.04
0.06
0.02
0.07
0.05
0.09
0.03
0.03
0.06
0.08
0.04
0.09
0.04
0.02
0.12
0.02
0.03
0.02
0.02
0.01
0.03
0.08
0.08
0.08
0.07
0.05
0.10
0.03
0.07
0.03
0.06
0.03
0.20
0.06
0.27
0.20
0.09
0.10
                           8260A - 32
    Revision 1
September 1994

-------
                                   TABLE 2.
                                  (Continued)
ANALYTE
                                     RETENTION TIME
                                       (minutes)
                                       Column 3a
HDL
Bromobenzene
2-Chlorotoluene
n-Propyl benzene
4-Chlorotoluene
1,3,5-Trimethyl benzene
tert- Butyl benzene
1 , 2 ,4-Trimethyl benzene
sec - Butyl benzene
1 ,3-Dichl orobenzene
p - 1 sopropyl to! uene
1 , 4-Di chl orobenzene
1 , 2 -Di chl orobenzene
n -Butyl benzene
l,2~Dibromo-3-chloropropane
1,2, 4-Tri chl orobenzene
Naphthalene
Hexachlorobutadiene
1,2,3 -Tri chl orobenzene
16.42
16.74
16.82
16.82
16.99
17.31
17.31
17.47
17.47
17.63
17.63
17.79
17.95
18.03
18.84
19.07
19.24
19.24
0.11
0.08
0.10
0.06
0.06
0.33
0.09
0.12
0.05
0.26
0.04
0.05
0.10
0.50
0.20
0.10
0.10
0.14
a  Column 3-30 meter x 0.32 mm  ID DB-5 capillary with 1

b  MDL based on a 25 ml sample volume.
                                                             film thickness.
                                  8260A -' 33
                                                                    Revision 1
                                                                September  1994

-------
                                 TABLE 3.
           ESTIMATED QUANTITATION LIMITS FOR VOLATILE ANALYTES8
                                     Estimated Quantitation Limits
                                       (All Analytes in Table 1)
                                  Ground water         Low Soil/Sedimentb
    Purging 5 mL of water              5

    Purging 25 mL of water             1

    Soil/Sediment
   Estimated Quantitation Limit (EQL) - The lowest concentration that can be
   reliably  achieved within specified limits of precision and accuracy during
   routine   laboratory  operating  conditions. The  EQL  is  generally  5  to 10
   times the MDL.  However, it may be nominally  chosen within these guidelines
   to simplify data  reporting. For many analytes the EQL is selected from the
   lowest non-zero standard in the calibration  curve.  Sample EQLs are highly
   matrix-dependent.  The EQLs  listed herein  are  provided for guidance and may
   not always be achievable.

   EQLs listed for soil/sediment are based  on  wet  weight.  Normally data are
   reported on a dry weight basis;  therefore,  EQLs will be higher, based on
   the percent dry weight in  each  sample.
             Other Matrices                      ractor0
             Water miscible liquid waste             50
             High-concentration soil  and sludge     125
             Non-water miscible waste               500
CEQL  =   [EQL for low soil/sediment  (see Table 3}] X [Factor]. For non-aqueous
        samples, the factor is on a wet-weight  basis.
                                8260A - 34                        Revision 1
                                                              September 1994

-------
                             TABLE 4.
    BFB MASS -  INTENSITY SPECIFICATIONS (4-BRQMQFLUQROBENZENE)1
Mass              Intensity Required (relative abundance)
 50               15 to 40% of mass 95
 75               30 to 60% of mass 95
 95               base peak, 100% relative abundance
 96               5 to 9% of mass 95
173               less than 2% of mass 174
174               greater than 50% of mass 95
175               5 to 9% of mass 174
176               greater than 95% but less than 101% of mass 174
177               5 to 9% of mass 176
     Alternate tuning criteria may  be used (e.g. CLP, Method  524.Z,  or
     manufacturers'  instructions), provided that method performance is not
     adversely affected.
                            8260A - 35                        Revision 1
                                                          September 1994

-------
                             TABLE 5.
    CHARACTERISTIC MASSES  (M/Z) FOR  PURGEABLE ORGANIC COMPOUNDS
Analyte
  Primary
Characteristic
    Ion
  Secondary
Characteristic
    Ion(sJ
Acetone
Acetonitrile
Acrolein
Acrylonitrile
Ally! alcohol
Allyl chloride
Benzene
Benzyl chloride
Broioacetone
Bromobenzene
Bromochl oromethane
Bromodi chl oromethane
Bromoform
Bromomethane
iso-Butanol
n-Butanol
2-Butanone
n-Butyl benzene
sec-Butyl benzene
tert- Butyl benzene
Carbon disulfide
Carbon tetrachloride
Chloral hydrate
Chloroacetonitrile
Chlorobenzene
1-Chlorobutane
Chlorodibromomethane
Chloroethane
2-Chloroethanol
bis-(2-chloroelhy1} su"!f:de
2-Chloroethyl vinyl ether
Chloroform
Chl oromethane
Chloroprene
3-Chloropropionitrile
Z-Chlorotoluene
4-Chlorotoluene
1 , 2-Di bromo-3-chl oropropane
Dibromochl oromethane
1,2-Dibromoethane
Dibromome thane
1 , 2-Dichl orobenzene
1 , 2-Dichl orobenzene-d4
58
41
56
53
57
76
78
91
136
156
128
83
173
94
74
56
72
91
105
119
76
117
82
48
112
56
129
64(49*)
49
:os
63
83
50(49*}
53
54
91
91
75
129
107
93
146
152
43
41, 40, 39
55, 58
52, 51
57, 58, 39
76, 41, 39, 78
_
91, 126, 65, 128
43, 136, 138, 93, 95
77, 158
49, 130
85, 127
175, 254
96
43
41
43, 72
92, 134
134
91, 134
78
119
44, 84, 86, 111
75
77, 114
49
208, 206
66(51*)
49, 44, 43, 51, 80
111, 158, ISC
65, 106
85
52(51*)
53, 88, 90, 51
54, 49, 89, 91
126
126
155, 157
127
109, 188
95, 174
111, 148
115, 150
                            8260A  -  36
                                Revision 1
                            September 1994

-------
                       TABLE 5.(continued)
Analyte
  Primary
Characteristic
    Ion
  Secondary
Characteristic
    Ion(s)
1,3-Dichlorobenzene
1 ,4-Dichlorobenzene
cis-l,4-Dichloro-2-butene
trans-l,4-Dichloro-2-butene
Di chl orod i f 1 uoromethane
1 , 1-Dichloroethane
1,2-Dichloroethane
1, 1-Dichloroethene
cis-1, 2-Di chl oroethene
trans- 1 , 2 -Di chl oroethene
1 , 2-Di chl oropropane
1 ,3-Dichloropropane
2 , 2-Di chl oropropane
1 ,3-Dichloro-2-propanol
1 , 1 -Di chl oropropene
cis-1, 3- Di chl oropropene
trans-1 ,3-Dichloropropene
1 ,2,3,4-Diepoxybutane
Diethyl ether
1,4-Dioxane
Epichlorohydrin
Ethanol
Ethyl acetate
Ethyl benzene
Ethyl ene oxide
Ethyl methacrylate
Hexachlorobutadiene
Hexachloroethane
2-Hexanone
2-Hydroxypropi oni tri 1 e
lodomethane
Isobutyl alcohol
Isopropyl benzene
p-Isopropyl toluene
Malononitrile
Methacrylonitrile
Methyl acrylate
Methyl -t-butyl ether
Methyl ene chloride
Methyl ethyl ketone
Methyl iodide
Methyl methacrylate
4-Methyl -2-pentanone
Naphthalene
Nitrobenzene
146
146
75
53
85
63
62
96
96
96
63
76
77
79
75
75
75
55
74
88
57
31
88
91
44
69
225
201
43
44
•>£?
"43
105
119
66
41
55
73
84
72
142
69
100
128
123
111,
111,
75,
88,
87
65,
98
61,
61,
61,
112
78
97
79,
110,
77,
77,
55,
45,
88,
57,
45,
43,
106
44,
69,
223,
166,
58,
44,
1 '75
"43^
120
134,
66,
41,
85
57
86,
43
142,
69,
43,
-
51,
148
148
53,
75

83

63
98
98



43,
77
39
39
57,
59
58,
49,
27,
45,

43,
41,
227
199,
57,
43,
141
ii;

91
39,
67,


49

127,
41,
58,

77


77, 124,










81, 49



56

43, 57
62, 51
46
61

42
99, 86,

203
100
42, 53

42, 74


65, 38
39, 52,




141
100, 39
85




89






















114









66









                            8260A -  37
                                Revision 1
                            September 1994

-------
                        TABLE 5.(continued)
Analyte
  Primary
Characteristic
    Ion
  Secondary
Characteristic
    Ion(s)
2-Nitropropane
2-Picoline
Pentachl oroethane
Propargyl alcohol
6-Propiolactone
Propionitrile (ethyl cyanide)
n-Propylamine
n-Propyl benzene
Pyridine
Styrene
1,2,3-Trichlorobenzene
1,2, 4-Tri chl orobenzene
1,1,1 , 2-Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachl oroethene
Toluene
1, 1,1-Tri chl oroethane
1 , 1, 2 -Tri chl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
1,2,3-Trichloropropane
1 , 2 , 4-Trimethyl benzene
1 ,3,5-Trimethylbenzene
Vinyl acetate
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
INTERNAL STANDARDS/SURROGATES
1 5 4-Di f 1 uorobenzene
Chlorobenzene-d5
1,4-Di chl orobenzene -d4
4-Bromof 1 uorobenzene
Di bromof 1 uoromethane
Dichloroethane-d4
To"!uene-d8
Pentaf 1 uorobenzene
Fl uorobenzene
46
93
167
55
42
54
59
91
79
104
180
180
131
83
164
92
97
83
95
151
75
105
105
43
62
106
106
106

114
117
152
95
113
102
98
168
96

93,
167,
55,
42,
54,
59,
120
52
78
182,
182,
133,
131,
129,
91
99,
97,
97,
101,
77
120
120
86
64
91
91
91



115,
174,




77

66, 92, 78
130, 132, 165, 169
39, 38, 53
43, 44
52, 55, 40
41, 39



145
145
119
85
131, 166

61
85
130, 132
153











150
176





* - characteristic ion for an  ion  trap mass spectrometer (to be used when
ion-molecule reactions are observed)
                            8260A - 38
                                Revision  1
                            September  1994

-------
                         TABLE 6.
SINGLE LABORATORY ACCURACY AND PRECISION DATA FOR VOLATILE
    ORGANIC COMPOUNDS IN WATER DETERMINED WITH A WIDE-
                   BORE  CAPILLARY COLUMN
Analyte
Benzene
Bromobenzene
Bromochl oromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert - Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chi oromethane
2-Chlorotoluene
4-Chlorotoluene
l,2-Dibromo-3-Chloropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1, 2 -Di chlorobenzene
1 ,3-Dichl orobenzene
1 , 4-Dichl orobenzene
Di chl orodi f 1 uoroniethane
1 ,1-Dichlorobenzene
1,2-Dichlorobenzene
1,1-Dichloroethene
ci s-1 , 2-Di chl oroethene
trans-l,2-Dichloroethene
1 ,2-Dichloropropane
1 , 3-Di chl oropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
Isopropyl benzene
p- I sopropyl toluene
Methyl ene chloride
Naphthalene
n-Propyl benzene
Styrene
Cone. Number
Range, of Recovery8
jug/L Samples %
0.1
0.1
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.5
0.5
0.5
0.1
0.1
0.5
0.1
0.5
0.5
0.1
0.5
0.2
0.5
0.5
0.1
0.1
0.5
0.1
0.1
0.1
0.5
0.5
0.1
0.5
0.5
0.1
0.1
0.1
0.1
0.1
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 20
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
-100
- 10
-100
31
30
24
30
18
18
18
16
18-
24
31
24
24
23
31
31
24
31
24
24
31
24
31
18
24
31
34
18
30
30
31
12
18
31
18
16
23
30
31
31
39
97
100
90
95
101
95
100
100
102
84
98
89
90
93
90
99
83
92
102
100
93
99
103
90
96
95
94
101
93
97
96
86
98
99
100
101
99
95
104
100
102
Standard
Deviation Percent
of Recoveryb RSD
6.5
5.5
5.7
5.7
6.4
7.8
7.6
7.6
7.4
7.4
5.8
8.0
5.5
8.3
5.6
8.2
16.6
6.5
4.0
5,6
5.8
6.8
6.6
6.9
5.1
5.1
6.3
6.7
5.2
5.9
5.7
14.6
8.7
8.4
6.8
7.7
6.7
5.0
8.6
5.8
7.3
5.7
5.5
6.4
6.1
6.3
8.2
7.6
7.6
7.3
8.8
5.9
9.0
6.1
8.9
6.2
8.3
19.9
7.0
3.9
5.6
6.2
6.9
6.4
7.7
5.3
5.4
6.7
5.7
5.6
6.1
6.0
15.9
8.9
8.6
6.8
7.6
6.7
5.3
8.2
5.8
7.2
                        8260A  -  39
    Revision 1
September 1994

-------
                                   TABLE 6.
                                  (Continued)


Analyte
Cone.
Range,
M9A
Number
of Recovery8
Samples %
Standard
Deviation Percent
of Recovery13 RSD
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,2,3-Tri chlorobenzene
1,2,4-Trichlorobenzene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chlorof1uoromethane
1,2,3-Tri chloropropane
1,2,4-Trimethyl benzene
1,3,5-Tri methyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.5
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 31
- 10
- 10
24
30
24
18
18
18
18
18
24
24
16
18
23
18
18
31
18
 90
 91
 89
102
109
108
 98
104
 90
 89
108
 99
 92
 98
103
 97
104
  6.1
 5.7
 6.0
 8.1
 9.4
 9.0
 7.9
 7.6
 6.5
 7.2
15.6
 8.0
 6.8
 6.5
 7.4
 6.3
 8.0
 6.8
 6.3
 6.8
 8.0
 8.6
 8.3
 8.1
 7.3
 7.3
 8.1
14.4
 8.1
 7.4
 6.7
 7.2
 6.5
 7.7
   Recoveries were calculated using  internal  standard method. Internal standard
   was fluorobenzene.

   Standard deviation was calculated by  pooling data from three concentrations.
                                  8260A - 40
                          Revision 1
                      September 1994

-------
                    TABLE 7.
SINGLE LABORATORY ACCURACY AND PRECISION  DATA FOR
 VOLATILE ORGANIC COMPOUNDS IN WATER DETERMINED
       WITH A NARROW-BORE CAPILLARY  COLUMN
Analyte
Benzene
Bromo benzene
Bromochl oromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chi oromethane
2-Chlorotoluene
4-Chlorotoluene
1 , 2 -Di bromo-3-chl oropropane
Di bromochl oromethane
1,2-Dibromoethane
Di bromomethane
1 , 2-Di chl orobenzene
1 , 3 -Di chl orobenzene
1 , 4 -Di chl orobenzene
Dichlorodifluoromethane
1, 1-Di chloroethane
1,2-Diehloroethane
1, 1-Dichloroethene
cis-I,2-Dich]oroethene
t ran s-1, 2-Di chl oroethene
1 , 2-Di chl oropropane
1 ,3-Dichl oropropane
2 , 2-Dichl oropropane
1 , 1 -Di chl oropropene
Ethyl benzene
Hexachlorobutadiene
Isopropyl benzene
p- I sopropyl to! uene
Methylene chloride
Naphthalene
n-Propyl benzene
Cone.
M9/L
0.1
0.5
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.5
0.1
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.1
0.1
y . i
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
Number
of
Samples
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Recovery8
%
99
97
97
100
101
99
94
110
110
108
91
100
105
101
99
96
92
99
97
93
97
101
106
99
98
100
95
- r\f\
iUl/
98
96
99
99
102
99
100
102
113
97
98
99
Standard
Deviation
of Recovery
6.2
7.4
5.8
4.6
5.4
7.1
6.0
7.1
2.5
6.8
5.8
5.8
3.2
4.7
4.6
7.0
10.0
5.6
5.6
5.6
3.5
6.0
6.5
8.8
6.2
6.3
9.0
3.7
7.2
6.0
5.8
4.9
7.4
5.2
5.7
5.4
13.0
13.0
7.2
6.6
Percent
RSD
6.3
7.6
6.0
4.6
5.3
7.2
6.4
6.5
2.3
6.3
6.4
5.8
3.0
4.7
• 4.6
7.3
10.9
5.7
5.8
6.0
3.6
5.9
6.1
8.9
6.3
6.3
9.5
3.7
7.3
6.3
5.9
4.9
7.3
5.3
6.7
6.3
11.5
13.4
7.3
6.7
                   8260A - 41
    Revision 1
September 1994

-------
TABLE 7.
(Continued)


Analyte
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1 , 2,3-Tri chl orobenzene
1,2,4-Trichlorobenzene
1,1,1 -Tri chl oroethane
1,1, 2 -Tri chl oroethane
Trichloroethene
Trichlorof 1 uoromethane
1,2,3-Trichloropropane
1, 2, 4-Trimethyl benzene
1, 3, 5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene

Cone.
M9A
0.5
0.5
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.5
0.5
0.5
0.1
0.5
0.5
0.5
Number
of
Samples
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7

Recovery"
%
96
100
100
96
100
102
91
100
102
104
97
96
96
101
104
106
106
97
Standard
Deviation
of Recovery
19.0
4.7
12.0
5.0
5.9
8.9
16.0
4.0
4.9
2.0
4.6
6.5
6.5
4.2
0.2
7.5
4.6
6.1

Percent
RSD
19.8
4.7
12.0
5.2
5.9
8.7
17.6
4.0
4.8
1.9
4.7
6.8
6.8
4.2
0.2
7.1
4.3
6.3
Recoveries were calculated  using  internal standard method. Internal standard
was fluorobenzene.
                               8260A - 42
    Revision 1
September 1994

-------
                                   TABLE 8.
      SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
Surrogate Compound
4-Bromof 1 uorobenzene"
Di bromof 1 uoromethane"
Toluene-dg"
Dich1oroethane-d4a
Percent
Low/High
Water
86-115
86-118
88-110
80-120
Recovery
Low/High
Soil /Sediment
74-121
80-120
81-117
80-120
"  Single laboratory data, for guidance only.
                                   TABLE 9.
                 QUANTITY OF EXTRACT REQUIRED FOR ANALYSIS OF
                          HIGH-CONCENTRATION SAMPLES
Approximate                                     Volume of
Concentration Range                             Extract"
   500 -  10,000 ug/kg                          100 uL
 1,000 -  20,000 /itg/kg                           50 ML
 5,000 - 100,000 jutg/kg                           10 ML
25,000 - 500,000 M9A§                          100 y,L of 1/50 dilution13
Calculate appropriate dilution factor for concentrations exceeding this table.

"     The volume of solvent added to 5 mL of water being purged should be kept
      constant.  Therefore, add to the 5 mL syringe whatever volume of solvent
      is necessary to maintain a volume of 100 ^L added to the syringe.

b     Dilute  an  aliquot  of the  solvent  extract  and  then  take  100 p,L  for
      analysis.
                                  8260A - 43                        Revision 1
                                                                September  1994

-------
                  TABLE 10
DIRECT INJECTION ANALYSIS  OF NEW OIL AT 5
PPM

Compound
Acetone
Benzene
n-Butanol*,**
iso-Butanol*,**
Carbon tetrachloride
Carbon disulfide**
Chlorobenzene
Chloroform
1, 4 -Di chlorobenzene
1 , 2-Di chl oroethane
1, 1-Dichloroethene
Diethyl ether
Ethyl acetate
Ethyl benzene
Hexachl oroethane
Methyl ene chloride
Methyl ethyl ketone
MIBK
Nitrobenzene
Pyridine
Tetrachloroethene

Recovery (%)
91
86
107
95
86
'53
81
84
98
101
97
76
113
83
71
98
79
93
89
31
82
Trichlorofluoromethane 76
l,l,2-Cl3F3ethane
Toluene
Trichloroethene
Vinyl chloride
o-Xylene
m/p-Xylene
* Alternate mass
** 1s? nuantit at inr
69
73
66
63
83
84
employed
i

%RSD
14.8
21.3
27.8
19.5
44.7
22.3
29.3
29.3
24.9
23.1
45.3
24.3
27.4
30.1
30.3
45.3
24.6
31.4
30,3
35.9
27.1
27.6
29.2
21.9
28.0
35.2
29.5
29.5

Blank
(ppm)
1.9
0.1
0.5
0.9
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.2
0.0
0.0
0.4
0.0
0.0
0.0
0.0
0.0
0.0
0.6
0.0
0.0
0.4
0.6

Spike
(ppm)
5.0
0.5
5.0
5.0
0.5
5.0
5.0
6.0
7.5
0.5
0.7
5,0
5.0
5.0
3.0
5.0
5.0 •
5.0
2.0
5.0
0.7
5.0
5.0
5.0
0.5
0.2
5.0
10.0

                 8260A - 44
         Revision 1
     September 1994

-------
      FIGURE  1.
   PURGING  DEVICE
   BUT m m. OO.
— 14MMO.CI.
   U*L£T 1M IN O.O.
          1? CM 20 GAUGf SrWNQE NEEX£


          8 MM O 0 WMEK SEPTUM


              1M IN. 00
                               in« IN. 00
                              is
                              MOt£CUOR S4EVE
                                     iFiura
    8260A -  45
     Revision 1
September  1994

-------
                          FIGURE  2.
TRAP PACKING AND CONSTRUCTION TO INCLUDE DESORB CAPABILITY
     PACKING DETAIL



        Zl-a MM ouun WOOL
CONSTRUCTION DCTAJL
          7.7 CM SRJCA Q£L
                                              TUtMOSCM
                                                   LO
                                              ate «. OLD,
                                              IT.
                        8260A - 46
                          Revision  1
                      September 1994

-------
                             FIGURE 3.
          SCHEMATIC OF PURGE-AND-TRAP DEVICE - PURGE MODE
CAfWiRGAS
FLOW CONTROL
PRESSURE
RfGULATO*
               uouo wuecnoN POATS
                    COLUMN OVEN
                              CONPlRMATOffY COtUMM

                             TO
PURGE QAS
FLOW CONTROL
13X MOLECULAR
SEVt FILTER
                                                 AMAUTICAI. COLUMN
                               OFTXDNAL *^O«T COLUMN
                               SaJECTTON VALVI
S.PORT
VALVi
                        ViNT
            lj PURGING
             loevics
                                               NOTE
                                               ALL UN€S BTTWCEh TRAP
                                               AMO OC SHOULD K HCATB3
                             8260A  -  47
                                           Revision 1
                                       September 1994

-------
                           FIGURE 4,
        SCHEMATIC OF PURGE-AND-TRAP DEVICE  - DESORB MODE
PRESSURE
REGULATOR
                                UQUIO INJECTION PORTS
                                   — COLUMN OVEN
Jl/U*-,
JUUV-
                                              CONFIRMATORY COLUMN
                                             TO DETECTOR
                                              ANALYTICAL COLUMN
PURGE GAS
FLOW CONTROL
1» MOLECULAR
SIEVE FILTER
                             OPTIONAL «^ORT COLUMN
                             SELECT**! VALVE
                                     TRAP INLET
                                    HUP
                                    330-C
                             l PURGING
                              "oevcf
         NOTE-
         ALL LINES BETWEEN TRAP
         AND GC SHOULD BE HEATED
         TOBTC.
                           8260A - 48
                       Revision 1
                    September 1994

-------
                                          FIGURE 5.
                            GAS CHROMATOGRAM OF VOLATILE ORGANICS
•400
                    I 1C
                            808
                                    _L
1288
	I

'ILLRRV      Z
1688
. . I  ..
                                                            2909
                                                                                        2400
COLUMNi 60 MEIER N O.73 MM X.D. VOCOL  CAPILLARY



PROORHMi 1O C FOR 3 MIN., THEN 6 /MIN  TO ISO C
                                      HiTENIIOM TMMI. MIN.
                                          8260A  - 49
                                                 Revision 1
                                             September 1994

-------
                                              FIGURE 6.
                                GAS CHROMATOGRAM OF VOLATILE ORGANICS
Column 2 - 30m long * O.SJnw ID 06-624
           nega-bore coluM
PAOOROHi  IO C FOR 3 MIN. ,
        1HEN 6 /MIN 10  160 C
                                      18     12      14      16      18     28
                                         ME1IMIION IIMI. MM.
                                             8260A -  50
    Revision 1
September 1994

-------

-

vj 'is «.

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£. £: ~


si-
«•
oo
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o
5* ,3^ 'd!! _
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cn
fc--' w

•? >n
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—
£8-

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-
CO g^
_
C"ilS
c^.,5^
f

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^^=-
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ID
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3 ro
.0- <
ft* ->•
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"— O
ID 3
(0
dilorcraethane
vai^lehloride 3? 2 K £ 2
broacmethane *?«*'" °
chloroethar.e R 5 r1 [^
c, " " "'
11 TV* r^-H*»nr» /Ar«at"^rip T* «?
, ^. ij^ Z^>— I*^Ilt^/ mjK IAJI Kr ^« ^<
mmm— fv «-.y-a^,C 1 ? rTf"1 K'+"H|Cllf>*S ^'-1 ^* *"** "*
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•*• J tn1 o it1

	 r5?' '•'•Sl/BT^pjijSVi^iri TCijjjane^^^
111 1 1,2 DC Ethane/ (ft m r"i


— Clj Ethane £2
1,2 DC Pixpane "^S
BT2Q-2 eC C5
BrCl2CH IS II
— £ cis 1, 3 DC Propene 55" ^ ^ ^
txarl°i^Bc Propene ?P £2
1,1,2 TC Etnane - _b wu.


BT2C10-: <- * 55
l/*4 4-»
e? E tv«





^* Q!
sr_ w
3 " g

^5»Z5SC5ilQrotoluene
•jp

— 	 	 § 0*1.4 Cl, A (IS5/1.4 Cljd>
'«D ^ * *• *
Irpurity
g 1,2 C12 A
r-i
m
i
»5
*















!75
3>
Crt
O
=r
7?
o
s»
—1
o
sn
33
3> -n
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-------
                                            FIGURE 8,
                             GAS CHROMATOGRAM OF TEST MIXTURE
               u
             f
            M
n
u
iL_L
                                                  u
                                 21
 «M*
 «~       ««*       IIS.
                                                                  t««*»
                                                     0,5  g/L PER COHPOUND

                                                     1.   1,1-DlCHLQRQETHYLENE
                                                     2.   HETHYLENE CHLORIDE
                                                     3.   TRANS-1.2-DICHLOROETHYLENE
                                                     4.   1,1 DICHLQROETHANE
                                                     5,   ISOPROPTLETHER
                                                     6.   CHLOROFORM
                                                     7.   1,1.1-TRICHLOROETHANE
                                                     8.   1,2-DICHLORORETHYLENE
                                                     9.   CARBON TETRACHLORIDE
                                                     10.  BENZENE
                                                     11.  FLOUROBENZENE (INT.  STD.)
                                                     12.  TRICHLOROETHfENE
                                                     13.  1,2-DICHLOROPROPANE
                                                     14.  BROWDICHLOROMETKANE
                                                     15.  TOLUENE
                                                     16.  BROHQCHLOROPROPANE INT. STD.
                                                     17.  DIBRONOCHLOROMETHANE
                                                     IS.  TETRACHLOROETHYLENE
                                                     19.  CHLOROBENZENE
                                                     20.  ETHYLBENZENE
                                                     21.  1.3-XYLENE
                                                     22.  BROMOFORH
                                                     23.  BROHOBENZENE
                                                     24.  1.4-DICHLOROBENZENE
                                                     25.  1,2,4-TRICHLOROBENZENE
                                                     26.  NAPHTHALENE
                                           8260A - 52
                                                                                   Revision  1
                                                                              September  1994

-------
                    FIGURE 9.
                LOW  SOILS  IMPINGER
  PURGf
3"«6rr,mOD CLASS TUBING
                                      SIPTUM
                                         CAP
                 8260A - 53
                                                  Revision  1
                                              September 1994

-------
                                       METHOD  8260A
VOLATILE ORGANIC COMPOUNDS  BY GAS CHROMATOGRAPHY/MASS  SPECTROMETRY {GC/MS)
                              CAPILLARY  COLUMN TECHNIQUE
                   Purge-and-trap
                               7.1
                              Select
                             procedure
                           for introducing
                            sample into
                              GC/MS,
 Direct
Injection
   x
                           7.2 Set GC/MS
                             operating
                             conditions.
                             7,3.1 Tune
                           GC/MS system
                              with BFB.
                           7.3.2 Assemble
                            purge-arsd-trap
                          device and prepare
                         calibration standards
                           7.3.2.1 Perform
                            purge-and-trap
                              analysis.
7,3.4 Calculate
   RFs for
  5 SPCCs.
              7.3.5 Calculate
                %RSD of RF
                 for CCCs.
               7.4 Perform
               calibration
               verification.
            7.5 Perform GC/MS
              analysis utilizing
               Methods 5030
                 or 8260.
               7.6.1 identify
               analytes by
              comparing the
            sample  and standard
               mass spectra.
                                        8260A -  54
                                                         7.6.2 Calculate the
                                                          concentration of
                                                          each identified
                                                              analyte.
                                                           7.6.2.3 Report
                                                             all results.
                                                               Stop
                           j
                                      Revision  1
                                 September  1994

-------
                                 METHOD 8270B

                       SEMIVOLATILE  ORGANIC  COMPOUNDS  BY
   GAS CHROMATOGRAPHY/HASS SPECTROMETRY (GC/MS): CAPILLARY COLUMN TECHNIQUE
1.0   SCOPE AND APPLICATION

      1.1   Method 8270 is used to determine the concentration of semivolatile
organic compounds in extracts prepared from all  types of solid waste matrices,
soils, and ground water.  Direct  injection  of a  sample  may be used in limited
applications.  The following compounds can be determined by this method:
Compounds
        Ajiproprjale Preparation Techniques


CAS No"      3510
      354Q/
3520  3541  3550  3580
Acenaphthene
Acenaphthene-d10 (l.S.)
Acenaphthylene
Acetophenone
2-Acetyl aminof 1 uorene
1-Acetyl -2-thiourea
Aldrin
2-Aminoanthraquinone
Aminoazobenzene
4-Aminobiphenyl
3-Amino-9-ethylcarbazole
Anil azine
Anil ine
o-Anisidine
Anthracene
Aramite
Aroclor - 1016
Aroclor - 1221
Aroclor - 1232
Aroclor - 1242
Aroclor - 1248
Aroclor - 1254
Aroclor - 1260
Azinphos -methyl
Barban
Benzidine
Benzoic acid
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo ( k) f 1 uoranthene
Benzo (g , h , i ) peryl ene
Benzo(a)pyrene
83-32-9

208-96-8
98-86-2
53-96-3
591-08-2
309-00-2
117-79-3
60-09-3
92-67-1
132-32-1
101-05-3
62-53-3
90-04-0
120-12-7
140-57-8
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
86-50-0
101-27-9
92-87-5
65-85-0
56-55-3
205-99-2
207-08-9
191-24-2
50-32-8
X
X
X
X
X
LR
X
X
X
X
X
X
X
X
X
HS(43)
X
X
V
A
X
X
X
X
HS(62)
LR
CP
X
X
X
X
X
X
X
X
X
ND
ND
ND
X
ND
ND
ND
X
ND
X
ND
X
ND
X
X
V
A
X
X
X
X
ND
ND
CP
X
X
X
X
X
X
X
X
X
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
X
ND
X
X
V
A
X
X
X
X
ND
ND
CP
ND
X
X
X
X
V
A
X
X
X
ND
ND
ND
X
ND
ND
ND
ND
ND
X
ND
X
ND
X
X
V
A
X
X
X
X
ND
ND
CP
X
X
X
X
X
V
A
X
X
X
X
X
LR
X
X
X
X
ND
X
X
X
X
X
X
X
V
A
X
X
X
X
X
LR
CP
X
X
X
X
X
X
                                  8270B - 1
                                   Revision 2
                               September 1994

-------
Appropriate Preparation Techniques
Compounds
p-Benzoquinone
Benzyl alcohol
a-BHC
0-BHC
S-BHC
7-BHC (Lindane)
Bis{2-chloroethoxy)methane
Bis{2-chloroethyl) ether
Bis{2~ehloroisopropyl) ether
Bis(2~ethylhexyl) phthalate
4-Bromophenyl phenyl ether
Bromoxynil
Butyl benzyl phthalate
2-sec-Butyl -4,6-dinitrophenol
Captafol
Captan
Carbaryl
Carbofuran
Carbophenothion
Chlordane
Chlorfenvinphos
4-Chloroaniline
Chi orobenzi late
5-Chloro-2-methylanil ine
4- Chi oro-3 -methyl phenol
3-(Chloromethyl )pyridine
hydrochloride
1-Chloronaphthalene
2-Chloronaphthalene
2-Chlorophenol
4-Chloro-l ,2-phenylenediamine
4-Chl oro- 1 , 3 -phenyl enedi ami ne
4-Chlorophenyl phenyl ether
Chrysene
Chrysene-d12 (I.S.)
Coumaphos
p-Cresidine
Crotoxyphos
2-Cyclohexyl -4,6-dinitro-phenol
4,4'-DDD
4,4'-DDE
4,4'-DDT
Demeton-0
Demeton-S
Diallate (cis or trans)
2,4-Diaminotoluene
CAS Noa
106-51-4
100-51-6
319-84-6
319-85-7
319-86-8
58-89-9
111-91-1
111-44-4
108-60-1
117-81-7
101-55-3
1689-84-5
85-68-7
88-85-7
2425-06-1
133-06-2
63-25-2
1563-66-2
786-19-6
57-74-9
470-90-6
106-47-8
510-15-6
95-79-4
59-50-7

6959-48-4
90-13-1
91-58-7
95-57-8
95-83-0
5131-60-2
7005-72-3
218-01-9

56-72-4
120-71-8
7700-17-6
131-89-5
72-54-8
72-55-9
50-29-3
298-03-3
126-75-0
2303-16-4
95-80-7
3510
OE
X
X
X
X
X
X
X
X
X
X
X
X
X
HS(55)
HS(40)
X
X
X
X
X
X
X
X
X

X
X
X
X
X
X
V
A
X
X
X
X
X
X
X
X
X
HS(68)
X
X
DC,QE(42)
3520
ND
X
X
X
X
X
X
X
X
X
X
ND
X
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
X

ND
X
X
X
X
X
V
A
X
X
ND
ND
ND
ND
X
X
X
ND
ND
ND
ND
3540/
3541
ND
ND
X
X
X
X
X
X
X
X
X
ND
X
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
X

ND
X
X
X
ND
ND
V
A
X
X
ND
ND
ND
ND
X
X
X
ND
ND
ND
ND
3550
ND
X
X
X
X
X
X
X
X
X
X
ND
X
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
X

ND
X
X
X
ND
ND
V
A
X
X
ND
ND
ND
ND
X
X
X
ND
ND
ND
ND
3580
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
x-
X
X
X
X
X

X
X
X
X
ND
ND
V
A
X
X
X
X
X
LR
X
X
X
X
X
X
X
8270B - 2
    Revision 2
Seotember 1994

-------
Compounds
        Appropriate Preparation Techniques


CAS Noa       3510
      3540/
3520  3541 3550   3580
Dibenz(a,j)acridine
Dibenz( a, h) anthracene
Dibenzofuran
Dibenzo(a,e)pyrene
l,2-Dibromo-3-chloropropane
Di-n-butyl phthalate
Dichlone
1 , 2-Di chl orobenzene
1,3-Dichlorobenzene
1,4-Di chl orobenzene
l,4-Dichlorobenzene-d4 (I.S)
3,3' -Di chl orobenzi dine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos
Dicrotophos
Dieldrin
Di ethyl phthalate
Diethylstilbestrol
Diethyl sulfate
Di hydro saf fro! e
Dimethoate
3,3'-Dimethoxybenzidine
Dimethyl aminoazobenzene
7,12-Dimethylbenz(a)-
anthracene
3 , 3 ' -Di methyl benzidi ne
a,a-Dimethylphenethylamine
2, 4-Dimethyl phenol
Dimethyl phthalate
1,2-Dinitrobenzene
I ,3-0 i nitrobenzene
1,4-Di nitrobenzene
4,6-Dinitro-2~methylphenol .
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap
Dinoseb
Dioxathion
Diphenylamine
5,5-Diphenylhydantoin
1,2-Diphenylhydrazine
Di-n-octyl phthalate
Disulfoton
224-42-0
53-70-3
132-64-9
192-65-4
96-12-8
84-74-2
117-80-6
95-50-1
541-73-1
106-46-7

91-94-1
120-83-2
87-65-0
62-73-7
141-66-2
60-57-1
84-66-2
56-53-1
64-67-5
56312-13-1
60-51-5
119-90-4
60-11-7
57-97-6

119-93-7
122-09-8
105-67-9
131-11-3
528-29-0
99-65-C
100-25-4
534-52-1
51-28-5
121-14-2
606-20-2
39300-45-3
88-85-7
78-34-2
122-39-4
57-41-0
122-66-7
117-84-0
298-04-4
X
X
X
ND
X
X
OE
X
X
X
X
X
X
X
X
X
X
X
AW, OS (67)
LR
ND
HE,HS(31)
X
X
CP(45)

X
ND
X
X
X
V
A
HE(14)
X
X
X
X
CP,HS(28)
X
ND
X
X
X
X
X
ND
X
X
ND
X
X
ND
X
X
X
X
X
X
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND

ND
ND
X
X
ND
ND
ND
X
X
X
X
ND
ND
ND
X
ND
X
X
ND
ND
X
ND
ND
ND
X
ND
X
X
X
X
X
X
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND

ND
ND
X
X
ND
NC
ND
X
X
X
X
ND
ND
ND
X
ND
X
X
ND
ND
X
X
ND
ND
X
ND
X
X
X
X
X
X
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND

ND
ND
X
X
ND
ND
ND
X
X
X
X
ND
ND
ND
X
ND
X
X
ND
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
ND
X
LR
X
CP

X
X
X
X
X
V
A
X
X
X
X
X
CP
X
ND
X
X
X
X
Y
                                  8270B - 3
                                   Revision 2
                               September 1994

-------
                                         Appropriate P.reparation Techniques
Compounds
CAS No"
3510
      3540/
3520  3541 3550
3580
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
EPN
Ethion
Ethyl carbamate
Ethyl methanesulfonate
Ethyl parathion
Famphur
Fensulfothion
Fenthion
Fluchloralin
Fluoranthene
Fluorene
2-Fluorobiphenyl (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachloroethane
Hexachl orophene
Hexachl oropropene
Hexamethyl phosphorami de
Hydroquinone
Indeno(l,2s3-cd)pyrene
Isodrin
Isophorone
Isosafrole
Kepone
Leptophos
Malathion
Maleic anhydride
Mestranol
Methapyrilene
Methoxychlor
3-Methylcholanthrene
4,4'-Methylenebis
(2-chloroanil ine)
4,4'-Methylenebis
(N,N -dimethyl anil ine)
959-98-8
33213-65-9
1031-07-8
72-20-8
7421-93-4
53494-70-5
2104-64-5
563-12-2
51-79-6
62-50-0
56-38-2
52-85-7
115-90-2
55-38-9
33245-39-5
206-44-0
86-73-7
321-60-8
367-12-4
76-44-8
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
680-31-9
123-31-9
193-39-5
465-73-6
78-59-1
120-58-1
143-50-0
21609-90-5
121-75-5
108-31-6
72-33-3
91-80-5
72-43-5
56-49-5

101-14-4

101-61-1
X
X
X
X
X
X
X
X
DC(28)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
AW,CP(62)
X
X
ND
X
X
V
A
DC(46)
X
X
HS(5)
HE
X
X
X
X

OE,OS(0)

X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
V
A
ND
ND
ND
ND
ND
ND
ND
ND
ND

ND

X
X
X
X
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND

ND

ND
X
X
X
X
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
V
A
ND
ND
ND
ND
ND
ND
ND
ND
ND

ND

ND
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
V
A
X
X
X
X
X
X
X
X
X

LR

ND
                                  8270B
                                   Revision 2
                               September 1994

-------
Compounds
        Appropriate Preparation. Techniques

                           3540/
CAS No"       3510     3520  3541 3550   3580
Methyl methanesulfonate
2-Methyl naphthalene
2-Methyl -5-nitroani line
Methyl parathion
2 -Methyl phenol
3-Methyl phenol
4-Methyl phenol
2-Methyl pyridine
Mevinphos
Mexacarbate
Mi rex
Monocrotophos
Naled
Naphthalene
Naphthalene-d8 (I.S.)
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthyl amine
Nicotine
5-Nitroacenaphthene
2-Nitroani line
3-Nitroanil ine
4-Nitroaniline
5-Nitro-o-anisidine
Nitrobenzene
Nitrobenzene-d5 (surr.J
4-Nitrobiphenyl
Nitrofen
2-Nitrophenol
4-Nitrophenol
5-Nitro-o-toluidine
Nitroquinol ine-1 -oxide
N-Nitrosodibutyl amine
N-Nitrosodiethyl amine
N-Nitrosodimethyl amine
N-N i trosomethyl ethyl ami ne
N-Nitrosodiphenyl amine
N-Nitrosodi -n-propyl amine
N-Nitrosomorphol ine
N-N itrosopi peri dine
N-Nitrosopyrrol idine
Octamethyl pyrophosphoramide
4?4'-Oxydianil ine
Parathion
Pentachlorobenzene
66-27-3
91-57-6
99-55-8
298-00-0
95-48-7
108-39-4
106-44-5
109-06-8
7786-34-7
315-18-4
2385-85-5
6923-22-4
300-76-5
91-20-3

130-15-4
134-32-7
91-59-8
54-11-5
602-87-9
88-74-4
99-09-2
100-01-6
99-59-2
98-95-3

92-93-3
1836-75-5
88-75-5
100-02-7
99-55-8
56-57-5
924-16-3
55-18-5
62-75-9
10595-95-6
86-30-6
621-64-7
59-89-2
100-75-4
930-55-2
152-16-9
101-80-4
56-38-2
608-93-5
X
X
X
X
X
X
X
X
X
HE,HS(68)
X
HE
X
X
X
X
05(44}
X
DE{67)
X
X
X
X
X
X
X
X
X
X
X
X
V
A
X
X
X
X
X
X
ND
X
X
LR
X
X
X
ND
X
X
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
X
X
ND
ND
ND
ND
ND
X
X
X
ND
X
X
ND
ND
X
X
ND
ND
ND
ND
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
X
X
ND
ND
ND
ND
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
ND
ND
X
X
X
ND
X
X
ND
ND
X
X
ND
ND
ND
ND
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
X
X
ND
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
V
A
X
X
X
X
X
X
X
X
X
LR
X
X
\J
A
                                  8270B - 5
                                   Revision  2
                               September 1994

-------
                                         Appropri ate  Preparat ion Techn1ques
Compounds
CAS No"
3510
      3540/
3520  3541 3550
3580
Pentachloronitrobenzene
Pentachlorophenol
Pery1ene-d12 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-d10 (I.S.)
Phenobarbital
Phenol
Phenol -d6 (surr.)
1,4-Phenylenediamine
Phorate
Phosalone
Phosraet
Phosphamidon
Phthalic anhydride
2-Picoline
Piperonyl sulfoxide
Pronamide
Propylthiouracil
Pyrene
Pyridine
Resorcinol
Safrole
Strychnine
Sul fall ate
Terbufos
Terphenyl -d14(surr, )
1,2,4,5-Tetrachlorobenzene
2,3,4,6-Tetrachlorophenol
Tetrachlorvinphos
Tetraethyl dithiopyrophosphate
Tetraethyl pyrophosphate
Thionazine
Thiophenol (Benzenethiol)
Toluene diisocyanate
o-Toluidine
Toxaphene
2,4,6-Tribromophenol (surr.)
1 ,2,4-Trichlorobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Triflural in
2,4,5-Trimethylaniline
Trimethyl phosphate
82-68-8
1 87-86-5

62-44-2
85-01-8

50-06-6
108-95-2

106-50-3
298-02-2
2310-17-0
732-11-6
13171-21-6
85-44-9
109-06-8
120-62-7
23950-58-5
51-52-5
129-00-0
110-86-1
108-46-3
94-59-7
60-41-3
95-06-7
13071-79-9
1718-51-0
95-94-3
58-90-2
961-11-5
3689-24-5
107-49-3
297-97-2
108-98-5
584-84-9
95-53-4
8001-35-2

120-82-1
95-95-4
88-06-2
1582-09-8
137-17-7
512-56-1
X
X
X
X
X
X
X
DC(28)
DC{28)
X
X
HS(65)
HS(15)
HE(63)
CP,HE(1)
ND
X
X
LR
X
ND
DC,OE(10)
X
AW, 05(55}
X
X
X
X
X
X
X
X
X
X
HE(6)
X
X
X
X
X
X
X
X
HE(60)
ND
X
X
ND
X
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
X
ND
ND
ND
ND
ND
X
X
X
X
X
ND
ND
ND
ND
X
X
ND
X
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
ND
X
ND
ND
ND
ND
X
X
ND
X
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
ND
X
X
LR
X
ND
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
                                  8270B - 6
                                   Revision 2
                               Seotember 1994

-------
                                         Appropriate Preparat1 on Techn1ques

                                                             3540/
Compounds                        CAS No"      3510      3520   3541 3550   3580
1,3,5-Trinitrobenzene 99-35-4
Tris(2,3-dibromopropyl) phosphate 126-72-7
Tri-p~tolyl phosphate 78-32-0
0,0,0-Triethyl phosphorothioate 126-68-1
X
X
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
LR
X
X
a     Chemical Abstract Service Registry Number.

AW =  Adsorption to walls of glassware during extraction and storage.
CP =  Nonreproducible chromatographic performance,
DC =  Unfavorable distribution  coefficient  (number in  parenthesis  is percent
      recovery).
HE =  Hydrolysis during  extraction  accelerated  by acidic  or  basic  conditions
      (number in parenthesis is percent recovery),
HS =  Hydrolysis during storage (number in parenthesis  is percent stability).
LR =  Low response.
ND =  Not determined.
OE =  Oxidation during  extraction  accelerated by basic  conditions  (number in
      parenthesis is percent recovery).
OS =  Oxidation during storage (number in parenthesis is percent stability).
X =   Greater than 70 percent recovery by this technique.


      1.2   Method 8270  can be used  to  quantitate most neutral,  acidic,  and
basic organic compounds that are soluble  in methylene  chloride and  capable of
being eluted without derivatization as sharp  peaks  from a  gas chromatographic
fused-silica capillary  column  coated with  a  slightly  polar  silicone.   Such
compounds include polynuclear aromatic hydrocarbons, chlorinated hydrocarbons and
pesticides,  phthalate esters, organophosphate  esters, nitrosamines, haloethers,
aldehydes, ethers,  ketones, anilines, pyridines,  quinolines,  aromatic  nitro
compounds, and  phenols,  including nitrophenols.   See  Table  1 for a  list of
compounds and their characteristic ions that have been eva'uatec on the specified
GC/MS system,

      1,3   The following  compounds  may  require special treatment  when  being
determined by this  method.   Benzidine  can  be subject to oxidative losses during
solvent  concentration.   Also,  chromatography  is  poor.   Under  the  alkaline
conditions of the extraction step, a-BHC,  y-BHC,  Endosulfan  I and II, and Endrin
are subject  to decomposition.  Neutral extraction should be performed if these
compounds are  expected.    Hexachlorocyclopentadiene  is  subject  to  thermal
decomposition in the inlet of the gas chromatograph, chemical reaction in acetone
solution, and  photochemical  decomposition.  N-nitrosodimethylamine is difficult
to separate from the  solvent under the chromatographic conditions  described.
N-nitrosodiphenylamine decomposes  in the gas chromatographic inlet  and cannot be
separated   from   diphenylamine.       Pentachlorophenol,   2,4-dinltrophenol.


                                  8270B - 7                         Revision 2
                                                                September 1994

-------
4-nitrophenol, 4,6-dinitro-2-methylphenol,4-chloro-3-methylpheno1,benzoicacid,
2-nitroaniline, 3-nitroaniline, 4-chloroaniline,  and benzyl  alcohol are subject
to erratic chromatographic behavior, especially if the GC system is contaminated
with high boiling material.

       1.4    The   estimated  quantitation  limit   (EQL)   of  Method  8270  for
determining  an individual  compound is approximately  1  mg/kg  (wet  weight) for
soil/sediment samples, 1-200 mg/kg  for wastes (dependent on matrix and method of
preparation), and 10 pg/L for ground water samples  (see  Table 2),  EQLs will be
proportionately  higher for  sample extracts  that  require  dilution to  avoid
saturation of the detector,

       1.5    This  method  is restricted to  use  by or  under  the  supervision of
analysts experienced  in  the  use  of gas  chromatograph/mass  spectrometers and
skilled in  the interpretation of mass spectra.  Each analyst must demonstrate the
ability to generate acceptable results with this method.


2,0    SUMMARY OF METHOD

       2.1    Prior  to  using  this  method, the  samples should be prepared for
chromatography using  the  appropriate sample preparation  and  cleanup  methods.
This method  describes  chromatographic  conditions  that  will   allow  for  the
separation of  the  compounds in  the extract  and   for  their qualitative  and
quantitative analysis by mass spectrometry.


3.0    INTERFERENCES

      3.1    Raw  GC/MS data  from  all  blanks,   samples,  and spikes  must  be
evaluated for interferences.  Determine  if the  source  of  interference is in the
preparation and/or cleanup of the samples  and take corrective action to eliminate
the problem.

      3.2    Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially analyzed.  To reduce  carryover, the
sample  syringe must be rinsed out between samples  with  solvent.   Whenever an
unusually concentrated  sample is  encountered,  it  should  be followed by the
analysis of solvent to check for cross contamination.


4.0   APPARATUS AND MATERIALS

      4.1    Gas chromatograph/mass spectrometer  system

             4.1.1 Gas  chromatograph  -  An analytical  system complete with  a
      temperature-programmable   gas   chromatograph    suitable   for   split!ess
       injection and  all  required  accessories, including syringes,  analytical
      columns, and gases.   The  capillary column  should  be directly coupled to
      the source.
                                   8270B  -  8                         Revision 2
                                                                September 1994

-------
             4.1.2 Column -  30 m x 0.25 mm ID  (or 0.32 mm ID)  1 /itm film thickness
       sili cone-coated  f used-si "I ica capillary  column  (J&W  Scientific  DB-5 or
       equivalent).

             4.1.3 Mass spectrometer - Capable of  scanning  from 35 to 500 amu
       every  1  sec or  less, using  70  volts  (nominal)  electron energy  in the
       electron  impact  ionization  mode.   The  mass spectrometer must be capable
       of  producing a  mass  spectrum  for decafluorotriphenylphosphine (DFTPP)
       which meets  all  of the criteria in Table 3 when 1 pi of the GC/MS tuning
       standard  is  injected  through  the GC  (50  ng of DFTPP).

             4.1.4 GC/MS interface - Any GC-to-MS interface that gives acceptable
       calibration  points at 50 ng per injection  for each compound of interest
       and achieves acceptable tuning  performance criteria may  be  used.   For a
       narrow-bore  capillary column,  the  interface  is usually capillary-direct
       into the mass spectrometer  source.

             4.1.5 Data system - A computer system must be interfaced to the mass
       spectrometer.    The  system  must  allow  the  continuous acquisition  and
       storage on machine-readable media of all  mass spectra obtained throughout
       the duration of  the  chromatographic program.   The computer must  have
       software that can search any GC/MS data  file for ions of a specific mass
       and that  can plot  such  ion  abundances  versus time  or scan  number.   This
       type  of  plot  is defined as  an Extracted  Ion Current  Profile (EICP).
       Software must also be available that allows integrating the abundances in
       any EICP  between specified  time or scan-number limits.   The most recent
       version of  the EPA/NIST Mass  Spectral  Library should also be available.

             4.1.6 Guard  column  (optional)  (J&W Deactivated Fused  Silica,  0.25
       mm ID x 6 m, or equivalent)  between the injection port and the analytical
       column joined  with  column  joiners  (Hewlett  Packard No. 5062-3556,  or
       equivalent).

       4.2    Syringe  -  10 pi.

       4.3    Volumetric flasks,  Class A  - Appropriate sizes  with  ground  glass
stoppers.

       4,4    Balance  -  Analytical,  0.0001 g.

       4.5    Bottles  -  glass with  Teflon-lined  screw caps  or crimp tops.


5.0    REAGENTS

       5.1    Reagent  grade  inorganic  chemicals shall  be  used  in all  tests.
Unless otherwise indicated,  it is intended that  all reagents shall conform to the
specifications of the Committee on Analytical  Reagents of the American Chemical
Society, where  such  specifications are available.   Other grades  may  be  used,
provided it  is  first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
                                   8270B  -  9                         Revision 2
                                                                September 1994

-------
       5.2    Organic-free reagent water - All references to water  in this method
 refer  to organic-free reagent water, as defined in Chapter One.

       5.3    Stock standard solutions (1000 mg/L)  -  Standard  solutions can be
 prepared from pure standard materials or purchased as certified solutions,

             5.3.1 Prepare stock standard solutions by accurately weighing about
       0.0100 g  of pure material.   Dissolve the material  in  pesticide quality
       acetone  or  other  suitable  solvent  and dilute to  volume in  a  10 ml
       volumetric  flask.   Larger volumes  can  be used  at the convenience of the
       analyst.  When compound purity  is assayed to be  96% or greater, the weight
       may be used without correction to calculate the  concentration of the stock
       standard.    Commercially  prepared  stock  standards may  be  used  at  any
       concentration  if  they  are  certified  by  the  manufacturer  or by  an
       independent source.

             5.3,2 Transfer the stock standard solutions into bottles with Teflon
       lined screw-caps.  Store at -10°C to -20°C or less and protect from light.
       Stock  standard  solutions  should  be checked  frequently  for signs  of
       degradation or evaporation, especially just prior to preparing calibration
       standards from them.

             5.3.3 Stock  standard  solutions must  be  replaced after 1  year or
       sooner  if  comparison  with  quality  control check  samples indicates  a
       problem.

       5.4    Internal standard solutions - The internal standards recommended are
 l,4-dichlorobenzene-d4,   naphthalene-d8,    acenaphthene-d10,   phenanthrene~d10,
 chrysene-d12,  and perylene-d12  (see Table 5).   Other compounds may  be  used as
 internal standards as  long as the requirements given in Sec. 7.3.2  are met.
 Dissolve 0.200  g of each  compound  with  a  small  volume  of  carbon  disulfide.
 Transfer to  a 50 ml volumetric flask and dilute to volume with methylene chloride
 so that the final  solvent  is  approximately  20% carbon  disulfide.   Most of the
 compounds are also soluble in  small  volumes of methanol,  acetone, or toluene,
 except for perylene-d12.   The resulting  solution will contain each standard at
 a concentration of 4,000 ng/^L,  Each  1  ml sample extract undergoing analysis
 should be spiked  with 10 y.L  of the internal  standard solution,  resulting in a
 concentration of  40 ng/jxL  of  each  internal  standard.   Store  at  -10°C to -20°C
 or less when not  being used.

       5.5   GC/MS tuning standard  -  A methylene  chloride solution  containing
 50 ng/^iL  of decafluorotriphenylphosphine  (DFTPP) should be  prepared.    The
 standard should also  contain  50 ng/^ii each of 4,4'-DDT, pentachlorophenol,  and
 benzidine to verify injection port  inertness and GC column performance.  Store
 at -1Q*C to -20"C or less when not  being  used.

       5.6   Calibration  standards  -  A minimum of five  calibration  standards
 should  be   prepared.     One  of  the   calibration   standards   should  be  at  a
concentration near, but  above,  the  method detection limit; the  others should
correspond to the range of concentrations found in real samples but  should not
exceed the working range  of the GC/MS  system.  Each standard should contain each
 analyte for detection by this method  (e.g.  some or all of the compounds listed
 in Table 1  may be included).   Each  1  ml aliquot of calibration standard should


                                  8270B - 10                        Revision 2
                                                                September 1994

-------
be spiked with 10 pi of the internal standard solution prior to analysis.  All
standards  should  be stored at  -10°C to  -2Q°C  or  less,  and should  be freshly
prepared once a year, or sooner if check standards indicate a problem.  The daily
calibration standard should be prepared weekly and stored at 4°C.

      5.7    Surrogate  standards  -  The  recommended  surrogate standards  are
phenol-de,     2-fluorophenol,    2,4,6-tribromophenol,    nitrobenzene-d5,
2-fluorobiphenyl,  and p-terphenyl-d14.  See Method 3500 for the instructions on
preparing the surrogate standards. Determine what concentration should be  in the
blank extracts after all  extraction, cleanup,  and  concentration steps.  Inject
this concentration into the GC/MS to determine recovery  of surrogate standards
in all  blanks, spikes,  and  sample extracts.  Take into account all  dilutions of
sample extracts.

      5.8   Matrix  spike  standards -  See  Method  3500  for   instructions  on
preparing the matrix spike  standard. Determine what concentration should be in
the  blank  extracts after  all  extraction, cleanup,  and  concentration  steps.
Inject this  concentration  into the GC/MS to  determine  recovery  of  surrogate
standards  in  all  matrix  spikes.   Take into  account  all  dilutions  of  sample
extracts.

      5.9   Acetone, hexane, methylene chloride,  isooctane, carbon  disulfide,
toluene,  and other appropriate solvents -  Pesticide quality or equivalent


6.0   SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

      6.1   See the  introductory material  to this  chapter, Organic  Analytes,
Sec.  4.1.
7.0   PROCEDURE

      7.1   Sample  preparation  -  Samples  must be  prepared  by  one  of  the
following methods prior to GC/MS analysis.

      Matrix                              Methods
      Water                               3510, 3520
      Soil/sediment                       3540, 3541, 3550
      Waste                               3540, 3541, 3550, 358G

            7.1.1 Direct  injection  -  In   very  limited  applications  direct
      injection of the sample into  the GC/MS system with a 10 /^L syringe may be
      appropriate.     The  detection   limit   is  very  high   (approximately
      10,000 M9/L);  therefore,  it  is only  permitted where concentrations  in
      excess of  10,000 fj.g/1 are expected.  The  system must be  calibrated  by
      direct injection.
                                  8270B -  11                        Revision 2
                                                                September 1994

-------
      7.2   Extract cleanup - Extracts  may be cleaned up by any of the following
methods prior to GC/MS analysis.

      Compounds                           Methods
      Phenols                             3630, 3640, 8040"
      Phthalate esters                    3610, 3620, 3640
      Nitrosamines                        3610, 3620, 3640
      Organochlorine pesticides & PCBs    3620, 3660
      Nitroaromatics and cyclic ketones   3620, 3640
      Polynuclear aromatic hydrocarbons   3611, 3630, 3640
      Haloethers                          3620, 3640
      Chlorinated hydrocarbons            3620, 3640
      Organophosphorus pesticides         3620
      Petroleum waste                     3611, 3650
      All priority pollutant base,
          neutral, and acids              3640

      8     Method 8040 includes a derivatization technique followed by GC/ECD
            analysis,   if interferences  are encountered on GC/FID.

      7.3   Initial calibration - The recommended GC/MS operating conditions:

      Mass range:             35-500 amu
      Scan time:              1 sec/scan
      Initial  temperature:    40DC,  hold  for 4  minutes
      Temperature program:    40-270°C  at 10°C/min
      Final  temperature:      270°C,  hold until benzo[g,h,i]perylene has eluted
      Injector temperature:   250-300°C
      Transfer line temperature: 250-300°C
      Source temperature:      According to  manufacturer's specifications
      Injector:               Grob-type,  split!ess
      Sample volume:           1-2 /uL
      Carrier gas:            Hydrogen  at 50 cm/sec or helium at 30 cm/sec

      (Split injection is allowed if the sensitivity  of the mass spectrometer
      is sufficient).

            7.3.1 Each GC/MS system must  be  hardware-tuned to meet the criteria
      In Table  3  for a 50 ng  injection  o^  DFTPP.  Analyses should  not begir?
      until  all  these  criteria are met.    Background  subtraction  should  be
      straightforward and  designed only to eliminate column bleed or instrument
      background ions.   The GC/MS  tuning  standard  should also be used to assess
      GC column performance and injection port inertness.   Degradation of DDT
      to DDE and ODD  should not exceed  20%.   (See  Sec. 8.3.1 of Method 8081 for
      the percent  breakdown  calculation).    Benzidine and  pentachlorophenol
      should be present at their  normal  responses,  and  no peak  tailing should
      be visible.  If  degradation is excessive and/or  poor  chromatography  is
      noted, the injection port may  require  cleaning.  It may also be necessary
      to break  off the  first  6-12 in.  of the  capillary column.  The use of a
      guard  column (Sec. 4,1.6) between  the injection  port and  the analytical
      column may help prolong analytical  column performance.
                                  82708 - 12                        Revision 2
                                                                September 1994

-------
       7.3.2  The internal standards selected in Sec. 5.4 should permit most
of the components  of  interest  in  a chromatogram to have retention times
of 0.80-1.20 relative  to one of the internal  standards.  Use  the base peak
ion  from  the  specific  internal  standard  as  the  primary  ion  for
quantitation (see Table 1).  If interferences are noted, use  the next most
intense ion as the quantitation ion (i.e. for l,4-dichlorobenzene-d4, use
152 m/z for quantitation).

       7.3.3 Analyze 1  ^L of each calibration  standard  (containing internal
standards) and tabulate the area of the primary characteristic ion against
concentration for each compound  (as indicated in Table 1).  Figure 1 shows
a chromatogram of a calibration  standard containing base/neutral and acid
analytes.  Calculate response  factors  (RFs) for each compound relative to
one of the internal standards as follows:

                         RF =  (A^CJ/WJ

where:

      Ax    =     Area of the characteristic ion  for  the  compound being
                  measured.
      Ais    =     Area of the characteristic  ion  for the specific internal
                  standard.
      Cis    =     Concentration of the specific internal standard (ng/jitL).
      Cx    =     Concentration  of the compound  being measured
      7.3.4 A system performance  check must  be  performed to ensure that
minimum average RFs are  met  before the calibration curve  is  used.   For
semivolatiles,   the System  Performance  Check  Compounds   (SPCCs)  are;
N-nitroso-di-n-propylamine;hexachlorocyclopentadiene;2,4-dinitro-phenol ;
and 4-nitrophenol .   The minimum acceptable average RF for these compounds
is 0.050.   These SPCCs  typically have very low RFs (0.1-0.2) and tend to
decrease in response as the chromatographic system begins to deteriorate
or the  standard material  begins  to  deteriorate.   They  are usually the
first to show poor performance.   Therefore,  they must  meet the minimum
requirement when the system is calibrated.

            7.3.4.1     The percent  relative standard  deviation  (%RSD)
      should be less than  15% for each compound.   However, the %RSD for
      each individual Calibration  Check Compound (CCC) (see  Table 4) must
      be less than  30%.  The  relative retention times of each compound in
      each calibration run should agree within 0.06  relative retention
      time  units.    Late-eluting  compounds   usually  have much  better
      agreement.

              SD
      %RSD =  _   x 100
              RF
where:

      RSD   =    relative  standard deviation.
      RF    =    mean  of 5 initial  RFs for a compound.
      SD    =    standard  deviation  of average  RFs  for  a compound.


                            8270B  - 13                         Revision. 2
                                                          September 1994

-------
                     N  (RFj - RF)
      SD «      •  I   Z  —	
                    i=l N - 1

             where:

                  RFj    = RF for each of the 5 calibration levels
                  N     = Number of RF values (i.e., 5}

             7.3.4,2     If the %RSD of any CCC is 30% or greater, then the
      chromatographic system is too reactive for analysis  to begin.  Clean
      or replace the injector  liner and/or capillary column,  then repeat
      the calibration  procedure beginning with  section 7.3.

      7.3.5  Linearity  -  If  the %RSD of any compound is 15% or less, then
the  relative  response  factor  is  assumed  to  be  constant  over  the
calibration range, and the  average relative  response  factor  may be used
for quantitation (Sec.  7.6.2).

             7.3.5.1     If the %RSD of any compound is greater than 15%,
      construct   calibration   curves  of   area  ratio   {A/Ais}   versus
      concentration using first or  higher order regression fit of the five
      calibration points. The  analyst should select the regression order
      which introduces the  least calibration error into the quantitation
      (Sec.  7.6.2.2  and  7.6.2.3).   The  use  of calibration curves  is  a
      recommended alternative to average  response factor calibration, and
      a useful diagnostic of standard preparation accuracy and absorption
      activity in the  chromatographic system.

7.4   Daily GC/MS calibration

      7.4.1  Prior to analysis  of samples, the GC/MS tuning standard must
be analyzed.  A 50 ng  injection of DFTPP must  result  in  a mass spectrum
for DFTPP which meets the criteria  given  in Table 3.  These criteria must
be demonstrated during  each 12 hour shift.

      7.4.2 A calibration standard(s) at  mid-concentration containing all
semivolatile  analytes,  including  all   required  surrogates,   must  be
analyzed every 12  hours during  analysis.  Compare the instrument response
factor from the standards every  12 hours with  the  SPCC (Sec.  7.4.3) and
CCC (Sec. 7.4.4) criteria.

      7.4.3 System   Performance  Check  Compounds   (SPCCs):    A  system
performance check must  be made during every 12  hour  shift.  For each SPCC
compound in the daily calibration a minimum response factor of 0.050 must
be obtained.  This is  the same check that  is  applied  during  the initial
calibration.  If the  minimum response factors  are not met, the system must
be evaluated, and corrective action must be taken before  sample analysis
begins.   The minimum RF  for semivolatile SPCCs  is  0.050.   Some possible
problems  are   standard   mixture  degradation,  injection   port   inlet
contamination, contamination at the  front end  of the  analytical  column,
                            8270B - 14                        Revision 2
                                                          September 1994

-------
and active sites In the column or chrotnatographic system.   This check must
be met before  analysis  begins.

      7.4.4  Calibration  Check   Compounds   (CCCs):    After  the  system
performance  check  is met, CCCs listed in Table 4  are  used to  check the
validity of  the  initial calibration.

      Calculate  the  percent  drift  using:

                              C,   -  Cc
                    % Drift = 	  x 100
                                 C,

where:

      C|  =    Calibration Check Compound standard concentration.
      Cc =   Measured concentration  using selected  quantitation method.

      If the percent difference for each CCC is less than  or equal to 20%,
the initial  calibration is assumed  to be valid.  If the criterion is not
met  (>  20%  drift)  for any one  CCC,  corrective  action  must  be taken.
Problems similar to those  listed under SPCCs could affect this criterion.
If no source of the problem can  be determined after corrective action has
been  taken,  a  new  five-point  calibration  must  be  generated.    This
criterion must be met before sample analysis begins.  If the CCCs are not
analytes required by the permit,  then all required analytes must meet the
20% drift criterion.

      7.4.5  The  internal  standard responses and retention times  in  the
calibration check standard must be evaluated immediately after or during
data acquisition.  If the retention time for  any internal standard changes
by more than 30  seconds from the  last  calibration  check  (12  hours),  the
chromatographic system must be  inspected for malfunctions and corrections
must be  made,  as required.   If the EICP area for any of the  internal
standards changes by a  factor of two (-50% to +100%) from the last daily
calibration  check standard,  the mass spectrometer  must  be inspected  for
malfunctions  and  corrections   must be  made,  as  appropriate.    When
corrections are made, reanalysis of samples analyzed while the system was
malfunctioning is required.

7.5   GC/MS  analysis

      7.5.1  It  is  highly  recommended  that the extract be screened on a
GC/FID or  GC/PID using the  same type of capillary column.   This  will
minimize  contamination of  the  GC/MS  system from  unexpectedly  high
concentrations of organic  compounds.

      7.5.2  Spike the  1 ml extract obtained from sample preparation with
10 /iL of the internal  standard solution just prior to analysis.

      7.5.3  Analyze  the 1 ml extract by GC/MS  using a 30 m x 0.25 mm (or
0.32 mm)  silicone-coated fused-silica capillary column.  The volume to be
injected should ideally contain  100 ng of base/neutral and 200 ng of acid


                            8270B - 15                         Revision 2
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surrogates  (for  a  1  ^L  injection).   The  recommended GC/MS  operating
conditions to be used are specified in Sec,  7.3.

      7.5.4  If the  response for any quantitation  ion exceeds the initial
calibration curve range of the GC/MS  system, extract  dilution  must  take
place.  Additional  internal  standard must be added to the diluted extract
to  maintain  the required  40 ng/jLtL  of  each  internal  standard  in  the
extracted volume.  The diluted extract must  be  reanalyzed.

      7,5.5  Perform  all  qualitative  and quantitative  measurements  as
described in Sec. 7.6.  Store the extracts at  4°C,  protected from  light
in screw-cap vials equipped with unpierced Teflon lined septa.

7.6   Data interpretation

      7.6.1 Qualitative analysis

            7.6.1.1     The  qualitative  identification  of   compounds
      determined by this  method  is  based  on  retention time,  and  on
      comparison of the sample mass spectrum, after background correction,
      with  characteristic   ions   in  a  reference mass  spectrum.    The
      reference mass spectrum must be generated  by  the  laboratory using
      the conditions of this  method.   The characteristic ions  from  the
      reference mass spectrum  are defined to  be the three ions of greatest
      relative intensity,  or any ions over 30% relative intensity if less
      than three such  ions  occur  in  the reference  spectrum.   Compounds
      should be identified as  present when the  criteria below are met.

                 7.6.1.1.1    The  intensities of  the characteristic  ions
            of a compound maximize in  the same scan or within one scan of
            each other.   Selection of  a peak  by  a data system  target
            compound  search  routine  where  the  search  is  based  on  the
            presence  of  a target  chromatographic  peak containing  ions
            specific  for  the  target  compound   at  a  compound-specific
            retention time will  be accepted  as  meeting this criterion.

                 7.6.1.1.2    The  RRT of the sample component  is  within
            ± 0.06 RRT units of the RRT of the  standard component.

                 7.5.1.1.3    rhe    relative     f^ter.s'ties    o~    the
            characteristic  ions  agree  within  30%   of  the   relative
            intensities  of  these  ions  in  the   reference   spectrum.
             (Example:   For  an  ion  with an  abundance  of  50%  in  the
            reference spectrum,  the corresponding abundance  in  a  sample
            spectrum can range between 20% and  80%.)

                 7.6.1.1.4    Structural isomers that produce very similar
            mass spectra should be identified  as individual isomers  if
            they   have   sufficiently   different   GC  retention   times.
            Sufficient GC  resolution  is achieved  if  the height  of  the
            valley between two isomer peaks is less than 25% of the  sum
            of the two peak heights.  Otherwise, structural  isomers  are
            identified as isomeric pairs.


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            7.6.1.1.5    Identification  is  hampered  when  sample
      components are not  resolved  chromatographically and produce
      mass  spectra  containing ions contributed  by more  than  one
      analyte.  When gas chromatographic peaks obviously represent
      more  than one sample component  {i.e.,  a broadened peak with
      shoulder(s)  or  a  valley  between  two  or  more  maxima),
      appropriate  selection  of analyte  spectra  and  background
      spectra is important.   Examination  of  extracted ion current
      profiles  of  appropriate  ions can aid  in  the  selection  of
      spectra,  and  in  qualitative identification  of  compounds.
      When analytes  coelute (i.e.,  only  one chromatographic peak is
      apparent), the identification criteria  can  be met,  but each
      analyte spectrum will contain extraneous ions contributed by
      the coeluting compound.

      7.6.1.2     For  samples containing components not associated
with the calibration standards, a library search may be made for the
purpose of tentative identification.  The necessity to perform this
type of  identification  will  be determined by the purpose of  the
analyses  being  conducted.    Computer  generated  library  search
routines  should  not   use  normalization  routines   that   would
misrepresent the library or  unknown spectra when  compared to each
other.   For  example, the RCRA permit or waste delisting  requirements
may require the  reporting  of  nontarget analytes.  Only after visual
comparison of sample spectra  with the nearest library searches will
the  mass  spectral  interpretation  specialist  assign  a  tentative
identification.  Guidelines for making tentative identification are:

      (1)   Relative  intensities of major ions  in the  reference
spectrum (ions > 10% of  the most abundant ion) should be present in
the sample spectrum.

      (2)   The relative intensities of the major ions  should agree
within  + 20%,  (Example:  For an ion with an abundance of 50% in the
standard spectrum,  the corresponding sample  ion abundance must be
between 30 and 70%.)

      (3)   Molecular ions present  in the reference spectrum should
be present in the sample spectrum.

      (4)   Ions  present  in  the sample  spectrum  but  not in  the
reference  spectrum  should  be  reviewed  for  possible  background
contamination or presence of coeluting compounds.

      (5)   Ions present  in the reference spectrum but  not  in  the
sample  spectrum  should be reviewed for possible subtraction from the
sample  spectrum because  of background contamination  or coeluting
peaks.   Data system library reduction programs can sometimes create
these discrepancies.
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7,6,2 Quantitative analysis

      7.6.2.1     When  a  compound   has  been   identified,   the
quantitation  of that  compound will  be based  on the  integrated
abundance from the EICP of the primary characteristic ion.

      7.6.2.2     If the  %RSD of  a  compound's relative  response
factor is 15% or less,  then the concentration in the extract may be
determined  using the  average response  factor  (RF)  from  initial
calibration data (7.4.5.2) and the following equation:.

                      (A,  x CJ
      Cflx (mg/L)  =
                      (A.  x  RF)

where CBX  is  the  concentration  of the compound  in  the extract,  and
the other terms are as defined in Sec. 7.4.3.

      7.6.2.3     Alternatively,  the regression line fitted to  the
initial  calibration (Sec.  7.3.5.1) may be used for determination of
the extract concentration.

      7.6.2.4     Compute  the concentration of the  analyte in  the
sample using the equations in Sees.  7.6.2,4.1 and 7.6.2.4.2.

           7.6.2.4.1    The   concentration  of the  analyte  in  the
      liquid  phase   of   the  sample  is  calculated   using   the
      concentration of the analyte in the extract and the volume of
      liquid extracted, as follows:

           Concentration  in  liquid  (ng/L)  =  iCex_x_Vexl
      where:

            Vex    =     extract volume,  in ml
            VQ     =     volume of liquid extracted,  in L.

            7.6.2.4.2    The concentration  of the  analyte in  the
      solid   phase  of  the   sample   is  calculated  using   the
      concentration of the pollutant in the extract and the weight
      of the solids, as follows:

            Concentration  in solid  (tig/kg)  = (C^ x V^,)
                                                W
                                                 s
      where:

            Vex    =     extract volume,  in ml
            Ws     =     sample weight,  in kg.

      7.6.2.5     Where applicable, an estimate of concentration for
noncalibrated components in the sample should be made.  The formulae

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             given  above should be used with the following modifications:  The
             areas  Ax and A.  should be from the total  ion chromatograms and the
             RF  for the compound should be assumed to be 1.  The concentration
             obtained  should be  reported  indicating  (1) that the  value  is an
             estimate  and  (2)  which  internal  standard  was  used  to determine
             concentration.     Use  the  nearest  internal   standard  free  of
             interferences.

                   7,6.2.6     Quantitation  of multicomponent  compounds  (e.g.
             Aroclors)   is   beyond  the  scope  of  Method  8270.     Normally,
             quantitation is performed using  a GC/ECD  by Method  8081.


8.0   QUALITY CONTROL

      8.1    Each laboratory that uses these  methods  is required  to operate a
formal quality control  program.  The minimum requirements of this  program consist
of an initial demonstration of laboratory  capability and an ongoing analysis of
spiked  samples  to  evaluate  and document   quality  data.  The  laboratory must
maintain records to document the quality  of  the data  generated.  Ongoing data
quality checks are compared with established performance criteria to determine
if the results of analyses meet  the performance characteristics of the method.
When results of sample  spikes  indicate atypical  method  performance,  a quality
control  reference  sample  (Sec.  8.5.1) must  be  analyzed  to confirm  that  the
measurements were performed in an in-control mode of operation.

      8.2    Before  processing  any  samples,   the  analyst   should  demonstrate,
through the analysis of a method blank, that  interferences from the analytical
system,  glassware,  and reagents  are under control.  Each time a set of samples
is extracted or there is a change in  reagents,  a method blank should be processed
as a safeguard against chronic laboratory contamination.  The blanks should be
carried through  all stages of sample preparation and measurement.

      8.3   The  experience  of  the   analyst  performing  GC/MS  analyses  is
invaluable to the  success of the methods.   Each day that analysis is performed,
the  daily  calibration  standard should  be  evaluated  to   determine  if  the
chromatographic  system  is  operating properly.   Questions  that  should  be  asked
are:  Do  the peaks look normal?;  Is  the  response obtained  comparable to  the
response  from  previous  calibrations?   Careful   examination  of the  standard
chromatogram can indicate  whether the co'iumr.  ^s  st"i~~  good, the  injector is
leaking, the injector septum needs replacing, etc.  If any changes are made to
the system (e.g.  column changed], recalibration of the system must take place.

      8.4   Required instrument  QC  is  found  in the following sections

            8.4.1  The   GC/MS  system  must   be   tuned   to  meet   the   DFTPP
      specifications in Sees. 7.3.1 and 7.4.1.

            8.4.2  There must  be an  initial  calibration  of the  GC/MS system as
      specified in Sec. 7.3.

            8.4.3  The GC/MS system must meet  the SPCC criteria specified in Sec.
      7.4.3 and the CCC criteria in Sec. 7.4.4, each 12 hours.


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      8.5    To  establish  the  ability  to  generate  acceptable accuracy  and
precision, the analyst must perform the following operations.

             8.5.1  A  quality  control  (QC)  reference  sample   concentrate  is
      required containing  each  base/neutral  analyte at  a concentration of 100
      mg/L and each  acid  analyte  at  a concentration of  200 mg/L in acetone or
      methane!.  (See Sec, 5.5.1 of Method 3500  for  minimum requirements.)  The
      QC  reference  sample concentrate  may  be prepared  from pure  standard
      materials  or  purchased  as  certified  solutions.    If  prepared  by  the
      laboratory,  the QC reference sample concentrate must be made using stock
      standards prepared independently from those used for calibration.

             8.5.2  Using a pipet, prepare QC reference samples at  a concentration
      of 100 jig/L  by  adding 1.00 ml of QC reference sample concentrate to each
      of four 1-L  aliquots of water.

             8.5.3  Analyze  the well-mixed  QC reference samples according to the
      method beginning in  Sec. 7.1 with extraction of the samples.

             8.5.4  Calculate the average recovery (x) in  /ig/L, and the standard
      deviation of the recovery (s) in /ig/L,  for each analyte of interest using
      the four results,

             8.5.5  For each analyte  compare  s  and x with  the corresponding
      acceptance criteria^for  precision  and accuracy,  respectively,  found in
      Table  6.   If s  and  x for  all  analytes  meet  the  acceptance criteria,  the
      system performance is acceptable and analysis of actual  samples can_begin.
      If any individual s exceeds the precision  limit or  any  individual x falls
      outside  the   range   for   accuracy,   then  the  system  performance  is
      unacceptable for that analyte.

             NOTE:  The large number of analytes in Table 6 present a substantial
                   probability  that one  or more will fail at least  one of the
                   acceptance criteria when  all  analytes  of a given method are
                   analyzed.

             8.5.6  When one or more of the analytes tested fail  at least one of
      the  acceptance criteria,  the  analyst  must   proceed  according  to  Sec.
      8.5.6.1 or 8.5.6.2.

                   8.5.6.1     Locate and  correct the source of the problem and
             repeat  the  test  for all  analytes of interest  beginning  with  Sec.
             8.5.2.

                   8.5.6.2     Beginning with Sec. 8.5.2, repeat the  test  only
             for those analytes that failed to meet criteria.  Repeated failure,
             however, will confirm a general problem with the measurement system.
             If this  occurs,  locate and correct the source of  the  problem and
             repeat  the test for  all  compounds  of  interest  beginning  with  Sec.
             8.5.2.

      8.6    The laboratory must,  on  an ongoing  basis, analyze  a method blank,
a matrix spike, and a  replicate for each analytical  batch  (up  to  a maximum of 20


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samples/batch) to assess accuracy.  For soil and waste samples where detectable
amounts of organics are present,  replicate samples  may be  appropriate in place
of matrix spiked  samples.   For laboratories  analyzing one to ten  samples  per
month, at least one spiked sample per month is  required.

            8.6,1 The  concentration   of  the spike in  the  sample  should  be
      determined as follows:

                  8.6.1.1     If, as in compliance monitoring, the concentration
            of  a  specific analyte in  the sample  is  being checked  against  a
            regulatory concentration limit, the spike should be  at  that limit
            or 1 to 5  times  higher than the background concentration determined
            in Sec. 8.6.2, whichever concentration  would be larger.

                  8.6.1.2     If  the  concentration  of a specific analyte  in  a
            water sample is not being checked against  a  limit specific  to  that
            analyte, the spike  should be at 100  M9/L or 1 to 5 times  higher than
            the background  concentration  determined in Step 8.6.2,  whichever
            concentration would  be  larger.  For  other matrices,  recommended
            spiking concentration is  20 times the EQL.

                  8.6.1.3     If   it  is  impractical  to  determine   background
            levels before spiking (e.g. maximum  holding times will be exceeded),
            the   spike   concentration  should   be   at   (1)   the   regulatory
            concentration limit,  if any; or,  if none  {2}  the larger  of either
            5 times higher  than  the  expected background concentration  or  100
            ng/L.  For other matrices, recommended  spiking concentration is 20
            times the EQL.

            8.6.2 Analyze  one sample aliquot  to  determine the   background
      concentration (B)  of each  analyte.   If necessary,  prepare  a  new  QC
      reference sample concentrate (Sec.  8.5.1}  appropriate for  the  background
      concentration in the sample.  Spike a second  sample  aliquot with  1.00 ml
      of the QC reference sample concentrate and  analyze  it to determine  the
      concentration after spiking (A)  of  each analyte.   Calculate each  percent
      recovery (p) as  1QQ(A-B)%/T, where T is the known true value of the spike.

            8.6.3 Compare the percent recovery  (p)  for each analyte in  a water
      sample with the corresponding QC acceptance  criteria found in Table  6.
      These  acceptance  criteria  were  calculated to  Include  an  allowance  for
      error  in  measurement  of  both the  background and spike concentrations,
      assuming a spike to background ratio of 5:1.  This error will be accounted
      for to the extent that the analyst's spike to  background ratio  approaches
      5:1.   If spiking was performed at a concentration lower than 100 M9/L,  the
      analyst must use either the QC  acceptance  criteria presented  in Table 6,
      or optional  QC  acceptance   criteria  calculated  for  the  specific  spike
      concentration.  To calculate optional  acceptance criteria for the recovery
      of an  analyte:  (1)  Calculate accuracy (x') using  the equation found  in
      Table  7, substituting the  spike concentration  (T)  for  C;   (2)  calculate
      overall  precision  ($'} using the equation  in Table 7,  substituting x'  for
      x;  (3) calculate  the  range for recovery   at  the  spike  concentration  as
      (lOOx'/T)  ± 2.44(100S'/T)%.
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            8.6.4  If  any individual  p falls outside  the  designated range for
      recovery,  that  analyte  has  failed  the  acceptance  criteria.    A check
      standard containing each analyte that failed the criteria must be analyzed
      as described in Sec. 8.7.

      8.7   If  any analyte  in  a  sample  fails  the  acceptance  criteria  for
recovery in Sec.  8.6,  a  QC reference  sample containing each analyte that failed
must be prepared and analyzed.

      NOTE: The  frequency for the  required analysis of a  QC reference sample
            will depend upon  the number of analytes  being simultaneously tested,
            the  complexity of the sample  matrix,  and the performance  of the
            laboratory.   If the entire  list of analytes  in Table  6  must be
            measured  in  the sample  in  Sec.  8.6, the  probability that  the
            analysis of a QC  reference sample will be required is high.   In this
            case, the QC reference  sample should  be routinely  analyzed with the
            spiked sample.

            8.7.1  Prepare the  QC  reference sample by adding  1.0  ml  of the QC
      reference sample concentrate (Sec.  8.5.1  or 8.6.2) to 1 L of water.  The
      QC  reference sample  needs  only  to contain the  analytes that  failed
      criteria in the test in Sec.  8.6.

            8.7.2 Analyze the QC reference sample to determine the concentration
      measured (A) of  each analyte.   Calculate  each  percent recovery  (ps) as
      100(A/T)%,  where T  is the true value of the standard concentration.

            8.7.3  Compare the  percent  recovery (ps)  for each analyte with the
      corresponding QC acceptance criteria found in Table 6.   Only analytes that
      failed the test in  Sec. 8.6 need to be  compared with these criteria.  If
      the recovery of any such analyte falls  outside the designated range, the
      laboratory performance for that analyte  is judged to be out of control,
      and  the  problem  must   be  immediately  identified  and  corrected.   The
      analytical  result for that analyte in the unspiked sample is suspect and
      may not be reported for regulatory compliance purposes.

      8.8   As part of  the QC  program for the  laboratory,  method accuracy for
each matrix studied must be assessed  and  records must be maintained.  After the
analysis of five spiked samplesJof the  same  matrix) as in Sec. 8.6, calculate
the average percent  recovery  (p)  and  the standard  deviation  of the  percent
recovery (sp).   Express  the accuracy  assessment as  a percent  recovery interval
from p - 2sp to p + 2sp.   If p = 90% and sp  = 10%,  for example,  the accuracy
interval  is expressed  as  70-110%.   Update  the  accuracy  assessment  for each
analyte  on a  regular  basis  (e.g.   after  each  five  to   ten  new  accuracy
measurements).

      8.9   The following procedure should be performed to determine acceptable
accuracy and precision limits for surrogate standards.

            8.9.1  For each sample  analyzed,  calculate the  percent recovery of
      each surrogate in the  sample.
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             8.9.2  Once a minimum of thirty samples of the same matrix  have been
       analyzed,  calculate  the  average  percent  recovery  (P)  and  standard
       deviation  of the percent  recovery  (s)  for  each  of  the  surrogates.

             8.9.3  For a  given  matrix,  calculate the upper  and  lower control
       limit  for method performance for each surrogate standard. This  should be
       done as  follows:

             Upper  Control  Limit (UCL)  =  P  +  3s
             Lower  Control  Limit (LCL)  =  P  -  3s

             8.9,4  For aqueous and soil matrices, these  laboratory-established
       surrogate  control   limits  should,  if  applicable,  be  compared  with  the
       control  limits  listed in Table 8.  The  limits given in  Table 8 are multi-
       laboratory  performance-based limits for  soil  and  aqueous  samples,  and
       therefore, the  single-laboratory limits established in Sec.  8.9.3 must
       fall within  those  given in Table 8 for  these matrices.

             8.9.5  If  recovery is not within limits, the following procedures are
       required.

             •      Check  to  be  sure   there   are  no  errors   in  calculations,
                   surrogate  solutions  and  internal  standards.   Also,  check
                   instrument  performance.

             •      Recalculate the  data and/or reanalyze  the  extract if any of
                   the above checks reveal  a  problem.

             »      Reextract and reanalyze  the sample if  none of the above are
                   a problem or  flag the  data as  "estimated concentration".

             8.9.6  At  a minimum,  each laboratory should update  surrogate recovery
       limits on a  matrix-by-matrix basis, annually.

       8.10   It  is   recommended  that the  laboratory adopt additional  quality
assurance practices for use with this method.  The specific practices that are
most productive depend upon the  needs  of the laboratory  and  the  nature of the
samples.   Field duplicates may be analyzed to  assess  the   precision  of  the
environmental measurements. When doubt exists over the identification  of a peak
on the chromatograni, confirmatory techniques  sucn as gas chromatography with a
dissimilar column,  specific element  detector, or  a mass spectrometer must be
used.   Whenever possible,  the  laboratory should analyze standard  reference
materials and participate in relevant performance evaluation studies.


9.0    METHOD PERFORMANCE

       9.1    Method 8250  (the  packed column version of Method 8270)  was tested
by 15  laboratories using organic-free reagent water,  drinking water, surface
water, and industrial  wastewaters spiked at six concentrations over the range 5-
1,300 jig/L.  Single operator  accuracy  and  precision,  and method  accuracy were
found to be directly related to the concentration of the analyte and essentially
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 independent  of   the   sample  matrix.   Linear  equations  to  describe  these
 relationships are presented  in Table 7.

       9.2    Chromatograms from calibration standards analyzed with Day 0 and Day
 7  samples  were compared  to  detect possible deterioration  of  GC performance.
 These  recoveries  (using Method 3510 extraction) are presented in Table 9.

       9.3    Method  performance  data  (using  Method 3541  Automated  Soxhlet
 extraction) are presented in  Table  10.  Single laboratory  accuracy and precision
 data were  obtained  for semivolatile organics  in  a clay soil by spiking at a
 concentration of 6 mg/kg for  each compound.  The spiking solution  was mixed into
 the soil during addition and  then  allowed to equilibrate  for approximately 1 hr
 prior  to  extraction.   The spiked  samples were then extracted by  Method 3541
 (Automated Soxhlet).  Three  determinations were performed and each extract was
 analyzed by gas chromatography/ mass spectrometry following Method 8270.  The low
 recovery of the more volatile compounds is probably due to volatilization losses
 during equilibration.   These data are listed in Table 11  and  were taken from
 Reference 9.
10.0  REFERENCES

1.    U.S. EPA 40 CFR Part  136, "Guidelines Establishing Test  Procedures for the
      Analysis of Pollutants Under the Clean Water Act,  Method 625," October 26,
      1984.

2.    U.S.  EPA Contract  Laboratory Program,  Statement of  Work for  Organic
      Analysis, July  1985,  Revision.

3.    Eichelberger, J.W.,  L.E. Harris,  and  W.L.  Budde, "Reference Compound to
      Calibrate   Ion   Abundance   Measurement   in  Gas   Chromatography-Mass
      Spectrometry Systems," Analytical Chemistry, 47, 995-1000,  1975.

4.    "Method Detection Limit for Methods  624 and  625," Olynyk, P., W.L. Budde,
      and J.W. Eichelberger, Unpublished report, October 1980.

5.    "Interlaboratory Method Study for EPA Method 625-Base/Neutrals, Acids, and
      Pesticides," Final Report for EPA Contract 68-03-3102  (in preparation).

6.    Burke,  J.A.  "Gas  Chromatography  for  Pesticide  Residue Analysis;  Some
      Practical  Aspects,"  Journal of the  Association of  Official  Analytical
      Chemists, 48, 1037,  1965.

7.    Lucas, S.V.; Kornfeld,  R.A,  "GC-MS  Suitability Testing of RCRA Appendix
      VIII and Michigan List Analytes "; U.S. Environmental Protection Agency,
      Environmental Monitoring  and Support  Laboratory,  Cincinnati,  OH 45268,
      February 20, 1987, Contract  No. 68-03-3224.

8.    Engel, T.M.; Kornfeld,  R.A.; Warner,  J.S.;  Andrews,  K.D.   "Screening of
      Semivolatile Organic  Compounds for  Extractabil ity and  Aqueous Stability
      by  SW-846,     Method  3510";  U.S.   Environmental  Protection  Agency,
      Environmental Monitoring  and Support  Laboratory,  Cincinnati,  OH 45268,
      June 5, 1987, Contract 68-03-3224.


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9.    Lopez-Avila, V.  (W. Beckert,  Project Officer);  "Development  of a Soxtec
      Extraction Procedure for Extraction of Organic  Compounds  from Soils and
      Sediments";    U.S.  Environmental   Protection  Agency.     Environmental
      Monitoring and  Support Laboratory.   Las Vegas,  NV,  October  1991;  EPA
      600/X-91/140.
                                  8270B  - 25                         Revision  2
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                                   TABLE 1.
                CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS
Compound
Retention    Primary   Secondary
Time (min.)  Ion       Ion(s)
2-Picoline
Aniline
Phenol
Bis(2-chloroethyl) ether
2-Chlorophenol
1 ,3-Dichl orobenzene
l,4-Dichlorobenzene-d4 {I.S.)
1 , 4 -Dichl orobenzene
Benzyl alcohol
1,2 -Dichl orobenzene
N-Ni trosoraethyl ethyl ami ne
Bis(2-chloroisopropyl) ether
Ethyl carbamate
Thiophenol (Benzenethiol)
Methyl methanesulfonate
N-Ni trosodi-n-propyl ami ne
Hexachloroethane
Maleic anhydride
Nitrobenzene
Isophorone
N-Nitrosodiethylamine
2-Nitrophenol
2,4-Dimethylphenol
p-Benzoquinone
Bis{2-chloroethoxy)methane
Benzole acid
2,4-Dichlorophenol
Trimethyl phosphate
Ethyl methanesulfonate
1,2, 4 -Trichl orobenzene
Naphthalene-d8 (I.S.)
Naphthalene
Hexachlorobutadiene
Tetraethyl pyrophosphate
Diethyl sulfate
4-Chl oro-3-niethyl phenol
2-Methyl naphthalene
2-Methyl phenol
Hexachl oropropene
Hexachlorocyclopentadiene
N-Nitrosopyrrolidine
Acetophenone
4-Methyl phenol
2,4,6-Trichlorophenol
o-Toluidine
3-Methyl phenol
3.75°
5.68
5.77
5.82
5.97
6.27
6.35
6.40
6.78
6.85
6.97
7.22
7.27
7.42
7.48
7,55
7.65
7.65
7.87
8.53
8.70
8.75
9.03
9.13
9.23
9.38
9.48
9.53
9.62
9.67
9.75
9.82
10.43
11.07
11.37
11.68
11,87
12.40
12.45
12.60
12.65
12.67
12.82
12.85
12.87
12.93
93
93
94
93
128
146
152
146
108
146
88
45
62
110
80
70
117
54
77
82
102
139
122
108
93
122
162
110
79
180
136
128
225
99
139
107
142
107
213
237
100
105
107
196
106
107
66,92
66,65
65,66
63,95
64,130
148,111
150,115
148,111
79,77
148,111
42,88,43,56
77,121
62,44,45,74
110,66,109,84
80,79,65,95
42,101,130
201,199
54,98,53,44
123,65
95,138
102,42,57,44,56
109,65
107,121
54,108,82,80
95,123
105,77
164,98
110,79,95,109,140
79,109,97,45,65
182,145
68
129,127
223,227
99,155,127,81,109
139,45,59,99,111,125
144,142
141
107,108,77,79,90
213,211,215,117,106,141
235,272
100,41,42,68,69
71,105,51,120
107,108,77,79,90
198,200
106,107,77,51,79
107,108,77,79,90
                                 8270B - 26
                                  Revision  2
                              September  1994

-------
                                   TABLE  1.
                                  (Continued)
Compound
  Retention
  Time  (min.)
Primary
Ion
Secondary
Ion(s)
2-Chloronaphthalene
N-Nitrosopiperidine
1,4-Phenylened i ami ne
1-Chloronaphthalene
2-Nitroaniline
5-Chioro-2-methyl anil ine
Dimethyl phthalate
Acenaphthylene
2,6-Dinitrotoluene
Phthalic anhydride
o-Anisidine
3-Nitroaniline
Acenaphthene-d10  (I.S.)
Acenaphthene
2,4-Dinitrophenol
2,6-Dinitrophenol
4-Chloroaniline
Isosafrole
Dibenzofuran
2,4-Diaminotoluene
2,4-Dinitrotoluene
4-Nitrophenol
2-Naphthylamine
1,4-Naphthoquinone
p-Cresidine
Dichlorovos
Diethyl phthalate
Fluorene
2,4,5-Trimethylaniline
N-Nitrosodibutylamine
4-Chlorophenyl phenyl ether
Hydroquinone
4,6-Dinitro-2-methylphenol
Resorcinol
N-Nitrosodiphenylamine
Safrole
Hexamethyl phosphoramide
3-(Chioromethyl}pyridine hydrochl
Diphenylamine
1,2,4,5-Tetrachlorobenzene
1-Naphthylamine
l-Acetyl-2-thiourea
4-Bromophenyl phenyl ether
Toluene diisocyanate
2,4,5-Trichlorophenol
Hexachlorobenzene
      13.30      162     127,164
      13.55      114     42,114,55,56,41
      13.62      108     108,80,53,54,52
      13.653     162     127,164
      13.75       65     92,138
      14.28      106     106,141,140,77,89
      14.48      163     194,164
      14,57      152     151,153
      14.62      165     63,89
      14,62      104     104,76,50,148
      15.00      108     80,108,123,52
      15.02      138     108,92
      15.05      164     162,160
      15.13      154     153,152
      15.35      184     63,154
      15.47      162     162,164,126,98,63
      15.50      127     127,129,65,92
      15.60      162     162,131,104,77,51
      15.63      168     139
      15.78      121     121,122,94,77,104
      15.80      165     63,89
      15.80      139     109,65   •
      16.00a     143     115,116
      16.23      158     158,104,102,76,50,130
      16.45      122     122,94,137,77,93
      16.48      109     109,185,79,145
      16.70      149     177,150
      16.70      166     165,167
      16.70      120     120,135,134,91,77
      16.73       84     84,57,41,116,158
      16.78      204     206,141
      16.93      110     110,81,53,55
      17.05      198     51,105
      17.13      110     110,81,82,53,69
      17.17      169     168,167
      17,23      162     162,162,104,77,103,135
      17.33      135     135,44,179,92,42
oride!7.50       92     92,127,129,65,39
      17.543     169     168,167
      17.97      216     216,214,179,108,143,218
      18,20      143     143,115,89,63
      18.22      118     43,118,42,76
      18.27      248     250,141
      18.42      174     174,145,173,146,132,91
      18.47      196     196,198,97,132,99
      18.65      284     142,249
                                  8270B - 27
                                   Revision 2
                               September 1994

-------
                                    TABLE  1.
                                  (Continued)
 Compound
Retention
Time (min.)
Primary   Secondary
Ion       Ion(s)
 Nicotine
 Pentachlorophenol
 5-Nitro-o-toluidine
 Thionazine
 4-Nitroaniline
 Phenanthrene-d1Q(i .s.}
 Phenanthrene
 Anthracene
 1,4-Di ni trobenzene
 Mevinphos
 Naled
 1,3-Dinitrobenzene
 Diallate  (cis or trans)
 1,2-Di nitrobenzene
 Diallate  (trans or cis)
 Pentachlorobenzene
 5-Nitro-o-anisidine
 Pentachloronitrobenzene
 4-Nitroquinoline-l-oxide
 Di-n-butyl phthalate
 2,3,4,6-Tetrachlorophenol
 Dihydrosaffrole
 Deraeton-0
 Fluoranthene
 1,3,5-Trinitrobenzene
 Dicrotophos
 Benzidine
 Triflural in
 Bromoxynil
 Pyrene
 Monocrotophos
 Phorate
 Sulfall ate
 Demeton-S
 Phenacetin
 Dimethoate
 Phenobarbital
 Carbofuran
Qctamethyl pyrophosphoramide
 4-Aminobiphenyl
 Dioxathion
Terbufos
 Q,Q-Dimethylphenylamine
 Pronamide
Aminoazobenzene
Dichlone
    18.70      84     84,133,161,162
    19.25     266     264,268
    19.27     152     77,152,79,106,94
    19.35     107     96,107,97,143,79,68
    19.37     138     138,65,108,92,80,39
    19.55     188     94,80
    19.62     178     179,176
    19.77     178     176,179
    19.83     168     168,75,50,76,92,122
    19.90     127     127,192,109,67,164
    20.03     109     109,145,147,301,79,189
    20.18     168     168,76,50,75,92,122
    20.57      86     86,234,43,70
    20.58     168     168,50,63,74
    20.78      86     86,234,43,70
    21.35     250     250,252,108,248,215,254
    21.50     168     168,79,52,138,153,77
    21.72     237     237,142,214,249,295,265
    21.73     174     174,101,128,75,116
    21.78     149     150,104
    21.88     232     232,131,230,166,234,168
    22.42     135     135,64,77
    22.72      88     88,89,60,61,115,171
    23.33     202     101,203
    23.68      75     75,74,213,120,91,63
    23.82     127     127,67,72,109,193,237
    23.87     184     92,185
    23.88     306     306,43,264,41,290
    23.90     277     277,279,88,275,168
    24.02     202     200,203
    24.08     127     127,192,67,97,109
    24.10      75     75,121,97,93,260
    24.23     188     188,88,72,60,44
    24.30      88     88,60,81,89,114,115
    24.33     108     180,179,109,137,80
    24.70      87     87,93,125,143,229
    24.70     204     204,117,232,146,161
    24.90     164     164,149,131,122
    24.95     135     135,44,199,286,153,243
    25.08     169     169,168,170,115
    25,25      97     97,125,270,153
    25.35     231     231,57,97,153,103
    25.43      58     58,91,65,134,42
    25.48     173     173,175,145,109,147
    25.72     197     92,197,120,65,77
    25.77     191     191,163,226,228,135,193
                                  8270B - 28
                                 Revision 2
                             September 1994

-------
                                   TABLE 1.
                                  (Continued)
Compound
Retention
Time (min.)
Primary
Ion
Secondary
Ion(s)
Dinoseb
Disulfoton
Fluchloralin
Mexacarbate
4,4/-Oxydianiline
Butyl benzyl phthalate
4-Nitrobiphenyl
Phosphamidon
2-Cyclohexyl-4,6-Dinitrophenol
Methyl parathion
Carbaryl
Dimethyl ami noazobenzene
Propylthiouracil
Benz(a)anthracene
Chrysene-d12 (I.S.)
3,3'-Dichlorobenzidine
Chrysene
Malathion
Kepone
Fenthion
Parathion
Anilazine
Bis(2-ethylhexyl) phthalate
3,3'-Dimethylbenzidine
Carbophenothion
5-Nitroacenaphthene
Methapyrilene
Isodrin
Captan
Chlorfenvinphos
Crotoxyphos
Phosmet
EPN
Tetrachlorvinphos
Di-n-octyl phthalate
2-Aminoanthraquinone
Barban
Aramite
Benzo(b)f1uoranthene
Nitrofen
Benzo{k)f 1uoranthene
Chlorobenzilate
Fensulfothion
Ethion
Diethylstilbestrol
Famphur
    25.83     211     211,163,147,117,240
    25.83      88     88,97,89,142,186
    25.88     306     306,63,326,328,264,65
    26.02     165     165,150,134,164,222
    26.08     200     200,108,171,80,65
    26.43     149     91,206
    26.55     199     199,152,141,169,151
    26.85     127     127,264,72,109,138
    26.87     231     231,185,41,193,266
    27.03     109     109,125,263,79,93
    27.17     144     144,115,116,201
    27.50     225     225,120,77,105,148,42
    27.68     170     170,142,114,83
    27.83     228     229,226
    27.88     240     120,236
    27.88     252     254,126
    27.97     228     226,229
    28.08     173     173,125,127,93,158
    28.18     272     272,274,237,178,143,270
    28.37     278     278,125,109,169,153
    28.40     109     109,97,291,139,155
    28.47     239     239,241,143,178,89
    28.47     149     167,279
    28.55     212     212,106,196,180
    28.58     157     157,97,121,342,159,199
    28.73     199     199,152,169,141,115
    28.77      97     97,50,191,71
    28.95     193     193,66,195,263,265,147
    29.47      79     79,149,77,119,117
    29.53     267     267,269,323,325,295
    29.73     127     127,105,193,166
    30.03     160     160,77,93,317,76
    30.11     157     157,169,185,141,323
    30.27     329     109,329,331,79,333
    30.48     149     167,43
    30.63     223     223,167,195
    30.83     222     222,51,87,224,257,153
    30.92     185     185,191,319,334,197,321
    31.45     252     253,125
    31.48     283     283,285,202,139,253
    31.55     252     253,125
    31.77     251     251,139,253,111,141
    31.87     293     293,97,308,125,292
    32.08     231     231,97,153,125,121
    32.15     268     268,145,107,239,121,159
    32.67     218     218,125,93,109,217
                                  8270B - 29
                                  Revision 2
                              September 1994

-------
                                    TABLE  1.
                                  (Continued)
 Compound
Retention
Time (min.)
Primary
Ion
Secondary
Ion(s)
Tri-p-tolyl phosphate"                 32.75      368
Benzo(a)pyrene                         32,80      252
Pery1ene-d12 (I.S.)                    33.05      264
7,12-Dimethylbenz(a)anthracene         33.25      256
5,5-Diphenylhydantoin                  33.40      180
Captafol                               33.47       79
Dinocap                                33.47       69
Methoxychlor                           33.55      227
2-Acetylaminofluorene                  33.58      181
4,4'-Methylenebis(2-ehloroaniline)     34.38      231
3,3'-Dimethoxybenzidine                34.47      244
3-Methylcholanthrene                   35.07      268
Phosalone                              35.23      182
Azinphos-methyl                        35.25      160
Leptophos                              35.28      171
Mi rex                                  35.43      272
Tris(2,3-dibromopropyl) phosphate      35.68      201
Dibenz{a,j)acridine                    36.40      279
Mestranol                              36.48      277
Coumaphos                              37.08      362
Indeno(l,2,3-cd)pyrene                 39.52      276
Dibenz(a,hjanthracene                  39.82      278
Benzo(g,h,i)perylene                   41.43      276
l,2:4,5-Dibenzopyrene                  41.60      302
Strychnine                             45.15      334
Piperonyl sulfoxide                    46.43      162
Hexachlorophene                        47.98      196
Aldrin                                  --         66
Aroclor-1016                            --        222
Aroclor-1221                            --        190
Aroclor-1232                            --        190
Aroclor-1242                            --        222
Aroclor-1248                            --        292
Aroclor-1254                            --        292
Aroclor-1260                            --        360
a-BHC                                   --        183
/S-BHC                                   --        181
<5-BHC                                   --        183
7-BHC (Lindane)                         --        183
4,4'-DDD                                --        235
4,4'-DDE                                --        246
4,4'-DDT                                --        235
Dieldrin                                --         79
1,2-Diphenylhydrazine                   --         77
Endosulfan I                                     195
Endosulfan II                           --        337
                      368,367,107,165,198
                      253,125
                      260,265
                      256,241,239,120
                      180,104,252,223,209
                      79,77,80,107
                      69,41,39
                      227,228,152,114,274,212
                      181,180,223,152
                      231,266,268,140,195
                      244,201,229
                      268,252,253,126,134,113
                      182,184,367,121,379
                      160,132,93,104,105
                      171,377,375,77,155,379
                      272,237,274,270,239,235
                      137,201,119,217,219,199
                      279,280,277,250
                      277,310,174,147,242
                      362,226,210,364,97,109
                      138,227
                      139,279
                      138,277
                      302,151,150,300
                      334,335,333
                      162,135,105,77
                      196,198,209,211,406,408
                      263,220
                      260,292
                      224,260
                      224,260
                      256,292
                      362,326
                      362,326
                      362,394
                      181,109
                      183,109
                      181,109
                      181,109
                      237,165
                      248,176
                      237,165
                      263,279
                      105,182
                      339,341
                      339,341
                                  8270B - 30
                                 Revision  2
                             September  1994

-------
                                   TABLE 1.
                                  (Continued)
                                   Retention     Primary    Secondary
Compound                           Time  (min.)   Ion        Ion(s)
Endosulfan sulfate                      --        272     387,422
Endrin                                  --        263     82,81
Endrin aldehyde                         --         67     345,250
Endrin ketone                           --        317     67,319
2-Fluorobiphenyl {surr.)                --        172     171
2-Fluorophenol  {surr.)                  --        112     64
Heptachlor                              ~        100     272,274
Heptachlor epoxide                      --        353     355,351
Nitrobenzene-d5 (surr.)                 --         82     128,54
N-Nitrosodimethylamine                  --         42     74,44
Phenol-d6 (surr.)                        --         99     42,71
Terphenyl-d14 {surr.)                    --        244     122,212
2,4,6-Tribromophenol (surr.)            --        330     332,141
Toxaphene                               --        159     231,233
I.S.  = internal.standard.
surr, = surrogate.
"Estimated retention times.
Substitute for the non-specific mixture,  tricresyl  phosphate.
                                  82708 - 31                        Revision 2
                                                                September 1994

-------
                           TABLE  2.
ESTIMATED QUANTITATION LIMITS (EQLs)  FOR SEMIVOLATILE ORGANICS

                                       Estimated
                                     Quantitation
                                          Limits*
Ground water
Semi vol at lies /ig/L
Acenaphthene
Acenaphthylene
Acetophenone
2-Acetylaminofluorene
1-Acetyl -2-thiourea
2-Aminoanthraquinone
Aminoazobenzene
4-Aminobi phenyl
Anilazine
o-Anisidine
Anthracene
Aramite
Azinphos-methyl
Barban
Benz(a)anthracene
Benzo(b) f 1 uoranthene
Benzo(k)fluoranthene
Benzoic acid
Benzo(g,h,i)perylene
Benzo(a)pyrene
p-Benzoquinone
Benzyl alcohol
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
4-broraophenyl phenyl ether
Bromoxyn i 1
Butyl benzyl phthal ate
Captafol
Captan
Carbaryl
Carbofuran
Carbophenothion
Chlorfenvinphos
4-Chloroaniline
Chlorobenzilate
5-Chloro-2-methyl ani 1 ine
4-Chloro-3-methyl phenol
3-(Chloromethyl }pyridine hydrochloride
2-Chl oronaphthal ene
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Coumaphos
10
10
10
20
1000
20
10
20
100
10
10
20
100
200
10
10
10
50
10
10
10
20
10
10
10
10
10
10
20
50
10
10
10
20
20
10
10
20
100
10
10
10
10
40
Low Soil /Sediment"3
660
660
ND
ND
ND
ND
ND
ND
ND
ND
660
ND
ND
ND
660
660
660
3300
660
660
ND
1300
660
660
660
660
ND
660
ND
ND
ND
ND
ND
ND
1300
ND
ND
1300
ND
660
660
660
660
ND
                          8270B  -  32                         Revision  2
                                                        September 1994

-------






Semivolatiles
p-Cresidine
Crotoxyphos
2-Cyclohexyl -4,6-dinitrophenol
Demeton-0
Demeton-S
Diallate (cis or trans)
Diallate (trans or cis)
2,4-Diaminotoluene
Dibenz(a,j)acridine
Di benz ( a , h ) anthracene
Dibenzofuran
Dibenzo(a,e)pyrene
Di-n-butyl phthalate
Dichlone
1 ,2-Dichlorobenzene
1 ,3-Dichlorobenzene
1 , 4-Di chl orobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos
Dicrotophos
Diethyl phthalate
Diethyl stilbestrol
Diethyl sulfate
Dimethoate
3,3'-Dimethoxybenzidine
Dimethyl aminoazobenzene
7, 12-Di methyl benz (a) anthracene
3, 3' -Dimethyl benzi dine
a, a-Dimethyl phenethyl amine
2,4-Dimethylphenol
Dimethyl phthalate
1, 2-Dinitrobenzene
1,3-Dinitrobenzene
1,4-Dinitrobenzene
4, 6-Dinitro-2-methyl phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap
Dinoseb
5,5-Diphenylhydantoin
Di-n-octyl phthalate
TABLE 2.
(Continued)



Ground
M9/1
10
20
100
10
10
10
10
20
10
10
10
10
10
NA
10
10
10
20
10
10
10
10
10
20
100
20
100
10
10
10
ND
10
10
40
20
40
50
50
10
10
100
20
20
10


Estimated
Quantitation
Limits"
water Low Soil/Sediment&
pg/kg
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
660
ND
ND
ND
660
660
660
1300
660
ND
ND
ND
660
ND
ND
ND
ND
ND
ND
ND
ND
660
660
ND
ND
ND
3300
3300
660
660
ND
ND
ND
660
8270B - 33
    Revision 2
September 1994

-------






Semivolatiles
Disulfoton
EPN
Ethion
Ethyl carbamate
Bis(2-ethylhexyl) phthalate
Ethyl methanesulfonate
Famphur
Fensulfothion
Fenthion
Fluchloralin
Fluoranthene
Fluorene
Hexachl orobenzene
Hexachl orobutadiene
Hexachl orocycl opentadi ene
Hexachl oroethane
Hexachl orophene
Hexachl oropropene
Hexaraethyl phosphorami de
Hydroquinone
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
Isosafrole
Kepone
Leptophos
Malathion
Maleic anhydride
Mestranol
Methapyrilene
Methoxychlor
3-Methylcholanthrene
4,4'-Methylenebis(2-chloroaniline)
Methyl methanesulfonate
2-Methyl naphtha! ene
Methyl parathion
2-Methylphenol
3-Methylphenol
4-Methylpheno!
Mevinphos
Mexacarbate
Mi rex
Monocrotophos
Naled
TABLE 2.
(Continued)



Ground
M9/L
10
10
10
50
10
20
20
40
10
20
10
10
10
10
10
10
50
10
20
ND
10
20
10
10
20
10
50
NA
20
100
10
10
NA
10
10
10
10
10
10
10
20
10
40
20


Estimated
Quantitation
Limits"
water Low Soil/Sediment13
ml kg
ND
ND
ND
ND
660
ND
ND
ND
ND
ND
660
660
660
660
660
660
ND
ND
ND
ND
660
ND
660
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
ND
660
ND
660
ND
ND
ND
ND
ND
8270B - 34
    Revision 2
September 1994

-------






Semi vol at iles
Naphthalene
1,4-Naphthoquinone
1-Naphthyl amine
2-Naphthyl amine
Nicotine
5-Nitroacenaphthene
2-Nitroanil ine
3-Nitroanil ine
4-Nitroanil ine
5-Nitro-a-anisidine
Nitrobenzene
4-Nitrobiphenyl
Nitrofen
2-Nitrophenol
4-Nitrophenol
5-Nitro-o-toluidine
4-Nitroquinol ine-1-oxide
N-Nitrosodi butyl amine
N-Nitrosodiethyl amine
N-Nitrosodiphenyl amine
N-Nitroso-di -n-propyl amine
N-Nitrosopi peri dine
N-Nitrosopyrrol idine
Octamethyl pyrophosphoramide
4,4'-Oxydianiline
Parathion
Pentachl orobenzene
Pentachl oron i tro benzene
Pentachl orophenol
Phenacetin
Phenanthrene
Phenobarbital
Phenol
1 5 4- Phenyl ened i ami ne
Phorate
Phosalone
Phosmet
Phosphamidon
Phthalic anhydride
2-Picoline
Piperonyl sulfoxide
Pron amide
Propylthiouracil
Pyrene
TABLE 2.
(Continued)
Estimated
Quantitation
Limits"
Ground water Low Soi
M9/L
10
10
10
10
20
10
50
50
20
10
10
10
20
10
50
10
40
10
20
10
10
20
40
200
20
10
10
20
50
20
10
10
10
10
10
100
40
100
100
ND
100
10
100
10





"l/$edimentb
M9/kg
660
ND
ND
ND
ND
ND
3300
3300
ND
ND
660
ND
ND
660
3300
ND
ND
ND
ND
660
660
ND
ND
ND
ND
ND
ND
ND
3300
ND
660
ND
660
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
8270B - 35
    Revision 2
September 1994

-------
                                   TABLE 2.
                                   (Continued)
                                               Estimated
                                              Quantitation
                                                 Limits"
                                      Ground waterLow Soil/Sedimentb
Semivolatiles
Pyridine
Resorcinol
Safrole
Strychnine
Sul fall ate
Terbufos
1,2,4 , 5-Tetrachl orobenzene
2,3,4,6-Tetrachlorophenol
Tetrachlorvinphos
Tetraethyl pyrophosphate
Thionazine
Thiophenol (Benzenethiol )
Toluene diisocyanate
o-Toluidine
1 , 2 , 4-Trichl orobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Trifluralin
2, 4, 5-Tri methyl aniline
Trimethyl phosphate
1, 3, 5-Tri nitrobenzene
Tr i s ( 2 , 3 - di bromopropyl ) phosph ate
Tri-p-tolyl phosphate(h)
0,0,0-Triethyl phosphorothioate
ND
100
10
40
10
20
10
10
20
40
20
20
100
10
10
10
10
10
10
10
10
200
10
NT
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
660
660
ND
ND
ND
ND
ND
ND
ND
a Sample EQLs are highly matrix-dependent.   The EQLs listed herein are provided
  for guidance and may not always be achievable.
b EQLs  listed  for soil/sediment are based  on  wet weight.   Normally data are
  reported on  a  dry weight basis, therefore,  EQLs will  be higher based on the
  % dry weight of each  sample.   These  EQLs  are based  on a 30 g sample and gel
  permeation chromatography cleanup,
ND = Not determined.
NA = Not applicable,
NT = Not tested.
Other Matrices                                       Factor"

High-concentration soil and sludges by sonicator      7.5
Non-water miscible waste                             75

CEQL  =  (EQL  for Low Soil/Sediment  given  above in Table 2) X (Factor).


                                  8270B - 36                        Revision 2
                                                                September 1994

-------
                                   TABLE 3.
                  DFTPP KEY IONS AND ION ABUNDANCE CRITERIA"'"
       Mass
Ion Abundance Criteria
       51

       68
       70

      127

      197
      198
      199

      275

      365

      441
      442
      443
30-60% of mass 198

< 2% of mass 69
< 2% of mass 69

40-60% of mass 198

< 1% of mass 198
Base peak, 100% relative abundance
5-9% of mass 198

10-30% of mass 198

> 1% of mass 198

Present but less than mass 443
> 40% of mass 198
17-23% of mass 442
   8  See Reference 3.

   b  Alternate  tuning  criteria  may   be  used  (e.g.,  CLP,  Method  525,   or
      manufacturers'  instructions),  provided that  method performance is  not
      adversely affected.
                                   TABLE 4.
                          CALIBRATION CHECK COMPOUNDS
Base/Neutral Fraction
                  Acid  Fraction
Acenaphthene
1,4-Di chlorobenzene
Hexachlorobutadi ene
N-Ni trosodi phenylami ne
Di-n-octyl phthalate
Fluoranthene
Benzo(a)pyrene
                  4-Chloro-3-methyl phenol
                  2,4-Dichlorophenol
                  2-Nitrophenol
                  Phenol
                  Pentachlorophenol
                  2,4,6-Trichlorophenol
                                  8270B - 37
                                            Revision 2
                                        September 1994

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                                    TABLE  5.
          SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
                           ASSIGNED FOR QUANTITATION
l,4-Dichlorobenzene-d4    Naphthalene-dg
                                Acenaphthene-d
                                                                        10
Aniline
Benzyl alcohol
Bis(2-chloroethyl) ether
Bis(2-ehloraisopropyl)
                ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
Ethyl  methanesulfonate
2-Fluorophenol (surr.)
Hexachloroethane
Methyl methanesulfonate
2-Methylphenol
4-Methylphenol
N-Nitrosodimethylamine
N-Nitroso-di-n-propyl-
               amine
Phenol
Phenol-dg (surr.)
2-Picoline
Acetophenone
Benzole acid
Bis(2-chloroethoxy}methane
4-Chloroam'l ine
4-Chloro-3-methyl phenol
2,4-Dichlorophenol
2,6-Dichlorophenol
a,a-Dimethyl-
      phenethylamine
2,4-Dimethyl phenol
Hexachlorobutadiene
Isophorone
2-Methylnaphthalene
Naphthalene
Nitrobenzene
Nitrobenzene-d8 (surr.)
2-Nitrophenol
N-Nitrosodibutyl amine
N-Nitrosopiperidine
1,2,4-Tri chlorobenzene
Acenaphthene
Acenaphthylene
1-Chloronaphthalene
2-Chloronaphthalene
4-Chlorophenyl
  phenyl ether
Dibenzofuran
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Fluorene
2-Fluorobiphenyl
        {surr.)
Hexachlorocyclo-
      pentadiene
1-Naphthylamine
2-Naphthylamine
2-Nitroaniline
3-Nitroaniline
4-NHroaniline
4-Nitrophenol
Pentachlorobenzene
1,2,4,5-Tetra-
   chlorobenzene
2,3,4,6-Tetra-
   chlorophenol
2,4,6-Tribromo-
   phenol  (surr.)
2,4,6-7ricrf«oro-
   phenol
2.4,5-Trichloro-
   phenol
(surr.)  = surrogate
                                  827DB - 38
                                           Revision  2
                                      September  1994

-------
                                   TABLE 5.
                                  (Continued)
Phenanthrene-d
              10
Chrysene-d
                                    12
Pery1ene-d12
4-Aminobiphenyl
Anthracene
4-Bromophenyl phenyl
                ether
Di-n-butyl phthalate
4,6-Dinitro-2-methyl-
                phenol
Diphenylamine
Fluoranthene
Hexachlorobenzene
N-Nitrosodiphenylamine
Pentachlorophenol
Pentachloronitrobenzene
Phenacetin
Phenanthrene
Pronamide
Benzidine
Benzo(a)anthracene
Bis(2-ethylhexyl)
       phthalate
Butyl benzyl  phthalate
Chrysene
3,3'-Dichlorobenzidine
p-Dimethylaminoazobenzene
Pyrene
Terphenyl-d14  (surr.)
Benzo(b)fluor-
    anthene
Benzo(k)fluor-
    anthene
Benzo(g,h,i)-
    perylene
Benzo(a)pyrene
Dibenz(a,j)acridine
Dibenz(a,h)-
     anthracene
7,12-Dimethylbenz-
    (a)anthracene
Di-n-octyl phthalate
Indeno(l,2,3-cd)
     pyrene
3-Methylchol-
     anthrene
(surr.) = surrogate
                                  8270B - 39
                                          Revision  2
                                      September  1994

-------
    TABLE 6.
ACCEPTANCE CRITERIA8
Compound
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benz(a) anthracene
Benzo ( b) f 1 uoranthene
Benzo(k)fl uoranthene
Benzo(a)pyrene
Benzofghijperylene
Benzyl butyl phthalate
0-BHC
5-BHC
Bis(2-chloroethyl) ether
Bi s {2-chl oroethoxy)methane
Bis(2-chloroisopropyl } ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4»4'-DDD
4»4'-DDE
4,4'-DDT
Dibenzo( a, h) anthracene
Di-n-butyl phthalate
1,2-Dichl orobenzene
1,3-Dichl orobenzene
1 ,4-Dichl orobenzene
3,3'-Dichlorobenzidine
Dieldrin
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfan sulfate
Endrin aldehyde
Fl uoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachlorobutadiene
Test
cone.
100
100
100
100
100
100
100
100
^ 100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
27.6
40.2
39.0
32.0
27.6
38.8
32.3
39.0
58.9
23.4
31.5
21.6
55.0
34.5
46.3
41.1
23.0
13.0
33.4
48.3
31.0
32.0
61.6
70.0
16.7
30.9
41.7
32.1
71.4
30.7
26.5
23.2
21.8
29.6
31.4
16.7
32.5
32.8
20.7
37.2
54.7
24.9
26.3
Range
for x
Ug/U
60.1-132.3
53.5-126.0
7.2-152.2
43.4-118.0
41.8-133.0
42.0-140.4
25.2-145.7
31.7-148.0
D-195.0
D-139.9
41.5-130.6
D-100.0
42.9-126.0
49.2-164.7
62.8-138.6
28.9-136.8
64.9-114.4
64.5-113.5
38.4-144.7
44.1-139.1
D-134.5
19.2-119.7
D-170.6
D-199.7
8.4-111.0
48.6-112.0
16.7-153.9
37.3-105.7
8.2-212.5
44.3-119.3
D-100.0
D-100.0
47.5-126.9
68.1-136.7
18.6-131.8
D-103.5
D-188.8
42.9-121.3
71.6-108.4
D-172.2
70.9-109.4
7.8-141.5
37.8-102.2
Range
P',Ps
47-145
33-145
D-166
27-133
33-143
24-159
11-162
17-163
D-219
D-152
24-149
D-110
12-158
33-184
36-166
8-158
53-127
60-118
25-158
17-168
D-145
4-136
D-203
D-227
1-118
32-129
D-172
20-124
D-262
29-136
D-114
D-112
39-139
50-158
4-146
D-107
D-209
26-137
59-121
D-192
26.155
D-152
24-116
   8270B - 40
    Revision 2
September 1994

-------
                                   TABLE 6.
                                  (Continued)
Compound
                                    Test
                                    cone.
Limit
for s
Range
for x
Range
P» Ps
Hexachloroethane
Indeno(l,2,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Nitrosodi -n-propyl amine
PCB-1260
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
4- Chloro -3 -methyl phenol
2-Chlorophenol
2,4-Chlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl -4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachl orophenol
Phenol
2,4,6-Trichlorophenol
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
24.5
44.6
63.3
30.1
39.3
55.4
54.2
20.6
25.2
28.1
37.2
28.7
26.4
26.1
49.8
93.2
35.2
47.2
48.9
22.6
31.7
55.2-100.0
D-150.9
46.6-180.2
35.6-119.6
54.3-157.6
13.6-197.9
19.3-121.0
65.2-108.7
69.6-100.0
57.3-129,2
40.8-127.9
36.2-120.4
52.5-121.7
41,8-109,0
D-172.9
53.0-100.0
45.0-166.7
13.0-106.5
38.1-151.8
16.6-100.0
52.4-129.2
40-113
D-171
21-196
21-133
35-180
D-230
D-164
54-120
52-115
44-142
22-147
23-134
39-135
32-119
D-191
D-181
29-182
D-132
14-176
5-112
37-144
s     =     Standard deviation of four recovery measurements, in /ig/L.

x     =     Average recovery for four recovery measurements, in ^g/L.

p, ps  =     Percent recovery measured.

D     =     Detected; result must be greater than zero.

a     Criteria from 40 CFR  Part  136  for  Method  625.   These criteria are based
      directly on the method performance  data  in Table  7.  Where necessary, the
      limits for  recovery  have  been broadened to assure  applicability  of the
      limits to concentrations below those used to develop Table 7.
                                  8270B - 41
                    Revision 2
                September 1994

-------
                         TABLE  7.
METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Compound
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benz(a)anthracene
Chloroethane
Benzo (b) f 1 uoranthene
Benzo(k)fl uoranthene
Benzo(a)pyrene
Benzo(ghi )perylene
Benzyl butyl phthalate
IS-BHC
6-BHC
Bis(2-chloroethyl) ether
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl )
ether
Bis(2-ethylhexyl)
phthalate
4-Bromophenyl phenyl
ether
2-Chloronaphthalene
4-Chlorophenyl phenyl
ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4' -DDT
Di benzo{ a, h) anthracene
Di-n-butyl phthalate
1 ,2-Dichlorobenzene
1 ,3-Dichlorobenzene
1 ,4-Dichlorobenzene
353'-Dich1orobenzid1ne
Dieldrin
Di ethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfan sulfate
Endrin aldehyde
Fl uoranthene
Accuracy, as
recovery, x'
Ug/D
0.96C4-0.19
0.89C4-0.74
0.78C+1.66
0.80C+0.68
0.88C-0.60
0.99C-1.53
0.93C-1.80
0.87C-1.56
0.90C-0.13
Q.98C-0.86
0.66C-1.68
0.87C-0.94
0.29C-1.09
0.86C-1.54
1.12C-5.04
1.03C-2.31

0.84C-1.18

0.91C-1.34

Q.89C+0.01
0.91C+0.53

0.93C-1.00
0.56C-0.40
0.70C-0.54
0.79C-3.28
0.88C+4.72
0.59C+0.71
0.80C+Q.28
0.86C-0.70
0.73C-1.47
1.23C-12.65
0.82C-0.16
0.43C+1.00
0.20C+1.03
0.92C-4.81
1.06C-3.60
0.76C-0.79
0.39C+0.41
0.76C-3.86
0.81C+1.10
Single analyst
precision, s/
(M9/L)
0.15x-0.12
0.24x-1.06
0.27x-1.28
0.21X-0.32
0.15x+0.93
0.14x-0.13
0.22X+Q.43
0.19x+1.03
0.22X+0.48
0.29X+2.40
O.lSx+0.94
0.20X-0.58
0.34X+0.86
0.35X-0.99
O.lSx+1.34
0.24x+0,28

0.26x+0.73

0,13x+0.66

0.07X+0.52
0.20x-0.94

0,28x+0.13
0.29x-0.32
0.26X-1.17
0.42X+0.19
O.SOx+8.51
0.13x+1.16
0.20x+0.47
0.25X+0.68
0.24x+0.23
0.28x+7.33
0.20x-0.16
0.28x+1.44
0.54X+0.19
0.12x4-1.06
0.14X+1.26
0.21x4-1.19
0.12x4-2.47
0.18x4-3.91
0.22X-0.73
Overall
precision,
S' (M9/D
0.21X-0.67
0.26X-0.54
0.43x4-1.13
0.27X-0.64
0.26X-0.21
0.17X-0.28
0.29x4-0.96
0.35x4-0.40
0.32x4-1.35
O.Slx-0.44
0.53x4-0.92
0.30X+1.94
0.93X-0.17
0.35X+0.10
0.26x4-2.01
0.25X+1.04

0.36X+0.67

0.16X+0.66

0.13x4-0,34
O.SOx-0.46

0.33X-0.09
0.66X-0.96
0.39X-1.04
0.65X-0.58
0.59X+0.25
0.39x4-0.60
0.24x4-0.39
0.41x^0.11
0.29x4-0.36
Q,47x+3.45
0.26x-0.07
0.52x4-0.22
l.OSx-0.92
0.21X+1.50
0.19X+0.35
0.37x+1.19
0.63X-1.03
0.73x-0.62
0.28X-0.60
                        8270B - 42
    Revision 2
September 1994

-------




Compound
Fluorene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachl orobutadi ene
Hexachloroethane
I ndeno ( 1 , 2 , 3 - cd } pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Nitrosodi -n-propylamine
PCB-1260
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
4 - Chi oro- 3 -methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2 , 4-Dimethyl phenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
TABLE 7.
(Continued)
Accuracy, as
recovery, x'
Ug/L)
Q.90C-0.00
0.87C^2.97
0.9ZC-1.87
0.74C+0.66
0.71C-1.01
0.73C-Q.83
0.78C-3.10
1.1ZC+1.41
0.76C+1.58
1.09C-3.05
1.12C-6.22
0.81C-10.86
0.87C+0.06
0.84C-0.16
0.94C-0.79
0.84C+0.35
0.78C+0.29
0.87C-0.13
0.71C+4.41
0.81C-18.04
1.04C-28.04
0.07C-1.15
0.61C-1.2Z
0.93C+1.99
0.43C+1.26
0.91C-0.18


Single analyst
precision, s/
(M9/L)
0.12X+0.26
0.24x^0,56
0. 33x^0,46
O.lBx-0.10
0.19X+0.92
0.17x+0,67
0.29x+1.46
0.27x+0.77
O.Zlx-0.41
O.!9x+0.92
0.27X+0.68
0.35x+3.61
O.lZx+0.57
0.16X+0.06
0.15X+0.85
0.23X+0.75
0.18X+1.46
0. 15X+1. Z5
0.16x4-1.21
0.38X+2.36
O.lOx+42.29
0.16x4-1.94
0.38X+2.57
0.24X+3.03
0.26X+0.73
0.16x4-2.22


Overall
precision.
S' Ug/L)
0.13X+0.61
O.BOx-0.23
0.28X+0.64
0.43X-0.52
0.26X+0.49
0.17X+0.80
0.50x-0.44 .
0.33x+0.26
O.SOx-0.68
0.27X+0.21
0.44X+0.47
0. 43X4-1. 8Z
0.15X+0.25
0.15x+0,31
0.21X+0.39
0.29X+1.31
0.28X+0.97
0.21X+1.28
O.ZZX4-1.31
0.42X+26.29
0.26X+23.10
0.27x42.60
0.44X+3.24
0.30x44.33
0.35X+0.58
0.22X41.81
             Expected  recovery  for  one  or  more  measurements  of  a  sample
             containing  a  concentration  of C,  in  M9/L-

             Expected  single analyst standard deviation of  measurements  at an
             average concentration  of x,  in
S'


c

x
Expected interlaboratory standard deviation of measurements at an
average concentration found- of x, in

True value for the concentration, in

Average recovery  found  for measurements  of  samples containing a
concentration of C, in
                                  82708 - 43
                                                       Revision 2
                                                   September  1994

-------
                                   TABLE 8.
      SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES

Surrogate Compound
Nitrobenzene-d5
2-Fluorobiphenyl
Terphenyl-d14
Phenol -de
2-Fluorophenol
2 , 4 , 6-Tri bromophenol
Low/High
Water
35-114
43-116
33-141
10-94
21-100
10-123
Low/High
Soil/ Sediment
23-120
30-115
18-137
24-113
25-121
19-122
                                   TABLE 9,
              EXTRACTION  EFFICIENCY  AND  AQUEOUS  STABILITY  RESULTS
COMPOUND
PERCENT RECOVERY
   ON DAY 0
AVG.       RSD
PERCENT RECOVERY
  ON DAY 7
AVG.    RSD
3-Amino-9-ethylcarbazole                  80
4-Ch1oro-l,2-phenylenediamine             91
4-Ch1oro-l,3-phenylenedianrine             84
l,2-Dibromo-3-ehloropropane               97
2-sec-Butyl-4,6-dinitrophenol             99
Ethyl parathion                          100
4,4'-Methylenebis(N,N-dimethylaniline)   108
2-Methy1-5-nitroaniline                   99
2-Methylpyridine                          80
Tetraethyl dithiopyrophosphate            32
           8
           1
           3
           2
           3
           2
           4
           10
           4
 73
108
 70
 i8
 97
103
 90
 93
 83
3
4
3
5
6
4
4
4
4
Data from Reference 8.
                                  8270B - 44
                           Revision  2
                       September  1994

-------
                              TABLE  10.
AVERAGE PERCENT RECOVERIES AND PERCENT RSDs FOR THE TARGET COMPOUNDS
  FROM  SPIKED  CLAY  SOIL  AND TOPSOIL  BY AUTOMATED  SOXHLET  EXTRACTION
                     WITH  HEXANE-ACETONE (l:l}a
                                   Clay Soil
 Topsoil
Compound name
1,3-Dichlorobenzene
1,2-Dichlorobenzene
Nitrobenzene
Benzal chloride
Benzotrichloride
4-Chloro-2-nitrotoluene
Hexachlorocyclopentadiene
2s4-Dichloronitrobenzene
3,4-Dichloronitrobenzene
Pentachl orobenzene
2,3,4, 5 -Tetrachl oron i trobenzene
Benefin
alpha-BHC
Hexachl orobenzene
delta-BHC
Heptachlor
Aldrin
Isopropalin
Heptachlor epoxide
trans-Chlordane
Endosulfan I
Dieldrin
2,5-Dichlorophenyl-
4-nitrophenyl ether
Endrin
Endosulfan II
p,p'-DDT
2,3,6-Trichlorophenyl -
4' -nitrophenyl ether
2,3,4-Trichlorophenyl -
4' -nitrophenyl ether
Mi rex
Average
percent
recovery
0
0
0
0
0
0
4.1
35.2
34.9
13.7
55.9
62.6
58.2
26.9
95.8
46.9
97.7
102
90.4
90.1
96.3
129
110

102
104
134
110

112

104
Percent
RSD
..
--
--
__
__
_.
15
7.6
15
7.3
6.7
4.8
7.3
13
4.6
9.2
12
4.3
4.4
4.5
4.4
4.7
4.1

4.5
4.1
2.1
4.8

4.4

5.3
Average
percent
recovery
0
0
0
0
0
0
7.8
21.2
20.4
14.8
50.4
62.7
54.8
25.1
99.2
49.1
102
105
93.6
95.0
101
104
112

106
105
tit
no

112

108
Percent
RSD
..
,
,.
--
--
--
23
15
11
13
6.0
2.9
4.8
5.7
1.3
6.3
7.4
2.3
2.4
2.3
2.2
1.9
2.1

3.7
0.4
2.C
2.8

3'.3

2.2
 The  operating  conditions  for  the  Soxtec  apparatus were  as  follows:
 immersion time 45 min; extraction time 45 min;  the sample size was 10 g;
 the spiking concentration was 500 ng/g, except for the surrogate compounds
 at 1000.ng/g, compounds 23, 27,  and 28  at  1500  ng/g,  compound 3 at 2000
 ng/g, and compounds 1 and 2 at 5000 ng/g.
                             8270B -  45
    Revision 2
September 1994

-------
                           TABLE 11.
SINGLE LABORATORY ACCURACY AND PRECISION DATA FOR THE EXTRACTION
          OF SEMIVOLATILE ORGANICS  FROM SPIKED CLAY  BY
                METHOD 3541 (AUTOMATED SOXHLET)3
Compound name
Phenol
Bis(2-chloroethyl )ether
2-Chlorophenol
Benzyl alcohol
2-Methyl phenol
Bis(2-chloroisopropyl )ether
4-Methyl phenol
N-Nitroso-di-n-propyl amine
Nitrobenzene
Isophorone
2-Nitrophenol
2,4-Dimethylphenol
Benzole acid
Bis(2-ch1oroethoxy)methane
2,4-Dichlorophenol
1,2,4-Trichlorobenzene
Naphthalene
4-Chloroanil ine
4- Chi oro -3 -methyl phenol
2-Methyl naphtha! ene
Hexachl orocycl opentadi ene
2,4,6-Trichlorophenol
2,4,5-TrichlorophenOl
2-Chloronaphthalene
2-Nitroaniline
Dimethyl phthalate
Acenaphthylene
3-Nitroanil ine
Acenaphthene
2,4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di ethyl phthalate
4-Chlorophenyl-phenyl ether
Fluorene
4-Nitroam'line
4, 6-Dinitro-2 -methyl phenol
N-Ni trosodi phenyl ami ne
4-Bromophenyl-phenyl ether
Average
percent
recovery
47.8
25.4
42.7
55.9
17.6
15.0
23.4
41.4
28.2
56.1
36.0
50.1
40.6
44.1
55.6
18.1
26.2
55.7
65.1
47.0
19.3
70.2
26.8
61.2
73.8
74.6
71.6
77.6
7S.2
91,9
62.9
82.1
84.2
68.3
74.9
67.2
82.1
79.0
63.4
77.0
62.4
Percent
RSD
5.6
13
4.3
7.2
6.6
15
6.7
6.2
7.7
• 4.2
6.5
5.7
7.7
3.0
4.6
31
15
12
5.1
8.6
19
6.3
2.9
6.0
6.0
5.2
5.7
5.3
£• C
8.9
16
5.9
5.4
5.8
5.4
3.2
3.4
7.9
6.8
3.4
3.0
                          8270B  - 46
    Revision 2
September 1994

-------
                             Table  11.  (Continued)
                                                Average
                                                percent           Percent
Compound name                                   recovery            RSD
Hexachlorobenzene                                  72.6              3.7
Pentachlorophenol                                  62.7              6.1
Phenanthrene                                       83.9              5.4
Anthracene                                         96.3              3.9
Di-n-butyl phthalate                               78.3             40
Fluoranthene                                       87.7              6.9
Pyrene                                            102                0.8
Butyl benzyl phthalate                             66.3              5.2
3,3'-Dichlorobenzid1ne                             25.2             11
Benzo(a)anthracene                                 73.4              3.8
B1s(2-ethylhexyl) phthalate                        77.2              4.8
Chrysene                                           76.2              4.4
Di-n-octyl phthalate                               83.1              4.8
Benzo(b)fluoranthene                               82.7              5.0
Benzo(k)fluoranthene                               71.7              4.1
Benzo(a)pyrene                                     71.7              4.1
!ndeno(l,2,3-cd)pyrene                             72.2              4.3
Dibenzo{a,h)anthracene                             66.7              6.3
BenzoCgjhJjperylene                               63.9              8.0
1,2-Dichlorobenzene                                0
1,3-Dichlorobenzene                                0  •
1,4-Dichlorobenzene                                0
Hexachloroethane                                   0
Hexachlorobutadiene                                0
a     Number  of  determinations was three.   The operating  conditions  for the
      Soxtec apparatus were as follows:   immersion time 45 min; extraction time
      45 min; the sample size  was  10  g  clay soil;  the spike concentration was
      6 mg/kg per compound.  The sample  was  allowed to equilibrate 1 hour after
      spiking.

Data taken from Reference 9.
                                  8270B - 47                        Revision 2
                                                                September 1994

-------
                                          FIGURE 1.
            GAS  CHROMATOGRAM OF BASE/NEUTRAL AND ACID CALIBRATION  STANDARD
ftlC

S**>L£: BftsTftClO STD,2UL'2UNC UL

(MGE:*C   1,2780 Ut£l: H 6. 4.8
                                                 li
                                                 13
                                                 SPINS  2u6 TO 27W
                                          u, l.a J  6  fc*6£: U 20-  3
SIC
                                                                                            Till
                                        8270B - 48
                                                                        Revision 2
                                                                    September 1994

-------
                                  METHOD  8Z70B
SEMIVOLATILE ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY
                    (GC/MS):   CAPILLARY COLUMN TECHNIQUE
    7.1 Prepare sample
    uemg Method 3540,
      3541, or 3650.
7.1 Prepare «*mpia
using Method 3510
    or 3520.
                                  7.1 Prepare sample
                                  using Method 3540,
                                 3541, 3550, or 3580.
                                     7.2 Cleanup
                                      extract.
                                   7.3 Sat GC/MS
                                 operating condition*;
                                   pafforrr, initie:
                                     calibration.
                                   7.4 Perform daily
                                 calibration with SPCCs
                                   and CCCs prior to
                                  analysis of samples.
                                   8270B  - 49
            Revision 2
       September 1114

-------
                                    METHOD  8270B
                                     (Continued)
                             7.5.1 Screen extract
                           on GC/FID or GC/PID to
                            eliminate sample* that
                            are too concentrated.
                             7,5.3 Analyze extract
                               by GC/MS, using
                            appropriate fusad-silica
                               capillary column.
7.5.4 Dilute
  Extract.
    7.5.4
Does response
 exceed initial
  calibration
   curve?
7.6.1 Identify
analyte by comparing
the sample and standard
mas* spectra.
>
r
7.6.2 Calculate
concentration of each
individual analyte;
report results.
^
r
                                C  Stop    J
                                     8270B  -  50
                                                 Revision 2
                                            September  1994

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                      ERRATA FOR METHOD 8280


In Section 1.1, delete the following text:
      "reactor residues" with no replacement.
In Section 1.5, replace the following text:
      "the analyst must take necessary precautions  to prevent exposure to
himself, or to others, of"
with:
      "the  analyst must  take  necessary  precautions  to  prevent  human
exposure from" and
delete the following text:
      "to be  reviewed  and approved by EPA's  Dioxin  Task Force (Contact
Conrad Kleveno, WH 548A,  U.S.  EPA, 401 M  Street  S.W.,  Washington, D.C.
20450)."

In Section 6.3, replace the following text:
      "x = measured as in Figure 2"
with:
      "x =  height of the valley between  2,3,7,8-TCDD  and 1,2,3,4-TCDD,
using the column performance check mixture."

In Section 6.9.2,  replace "a 2-hr period" with "a  12 hr period".
In Section 7.4, replace "24" with "20".
                          8280 ERRATA - 1                       July  1992

-------
                                 METHOD 8280

              THE ANALYSIS OF POLYCHLORINATED DIBENZO-P-DIOXINS
                      AND POLYCHLORINATED DIBENZOFURANS
1.0  SCOPE AND APPLICATION

     1,1  This method 1s appropriate for  the determination of tetra-,  penta-,
hexa-, hepta-,  and  octachlorlnated  dibenzo-p-dioxins  (PCDD's)  and dibenzo-
furans  (PCDF's)  In  chemical  wastes  Including  still   bottoms,  fuel  oils,
sludges, fly ash, reactor residues,  soil and water.

     1.2  The sensitivity  of  this   method  1s  dependent  upon  the level  of
Interferents within a given matrix.   Proposed quantification levels for target
analytes were 2 ppb in soil samples, up to 10 ppb in other solid wastes and
10 ppt in water.  Actual values  have  been shown to vary by homologous series
and, to a lesser degree, by Individual  Isomer.  The total detection limit for
each CDD/CDF homologous  series  Is   determined  by  multiplying the detection
limit of a given Isomer within that  series by the number of peaks which can  be
resolved under the gas chromatographic conditions.

     1.3  Certain   2,3,7,8-substituted   congeners   are   used   to  provide
calibration and method  recovery  information.    Proper  column selection and
access to reference Isomer  standards,  may  in  certain cases, provide isomer
specific data.    Special  Instructions  are  included  which measure 2,3,7,8-
substituted congeners.

     1.4  This method is recommended for use only by analysts experienced with
residue analysis and skilled in mass spectral analytical  techniques.

     1.5  Because of the extreme toxicity of these compounds, the analyst must
take necessary precautions to prevent  exposure  to  himself, or to others,  of
materials known or believed to  contain  PCDD's or PCDF's.  Typical infectious
waste incinerators  are  probably  not  satisfactory  devices  for disposal  of
materials highly contaminated with PCDD's or PCDF's.  A laboratory planning to
use these compounds should prepare a disposal plan to be reviewed and approved
by EPA's Dioxin Task Force (Contact  Conrad  Kleveno, WH-548A, U.S. EPA, 401 M
Street S.W., Washington,  D.C.  20450).    Additional  safety Instructions are
outlined in Appendix B.


2.0  SUMMARY OF THE METHOD

     2.1  This procedure uses  a  matrix-specific extraction, analyte-specific
cleanup,  and   high-resolution   capillary   column   gas  chromatography/low
resolution mass spectrometry  (HRGC/LRMS) techniques.

     2.2  If   interferents  are  encountered,  the  method  provides  selected
cleanup procedures to aid  the analyst  in their elimination.  The  analysis flow
chart 1s shown  in  Figure 1.
                                  8280 - 1
                                                         Revision      0
                                                         Date  September 1986

-------
                      Complex
                       Waste
                      Sample
                            (1)  Add Internal  Standards:  13C12-PCDOfs
                                 and I3C12-PCDF's.

                            (2)  Perform matrix-specific extraction.
                      Sample
                      Extract
                            (I)
                            (2)
                  60%
                     Fraction
Wash with 20% KOH
Wash with 5* NaCl
                             3)  Wash with cone. H2S04
                            (4)  Wash with 5% NaCl
                            (5)  Dry extract
                            (6)  Solvent exchange
                                 Alumina column
                            (1)  Concentrate eluate
                            (2)  Perform carbon column cleanup
                            (3)  Add recovery standard(s)-13C12-l,2,3,4-TCDD
                  Analyze by GC/MS
Figure 1.  Method 8280 flow chart for sample extraction and cleanup as
 used for the analysis of PCDD's and PCOF's in complex waste samples.
                           8280 - 2
                                                  Revision      o
                                                  Date  September 1986

-------
3.0  INTERFERENCES

     3.1  Solvents, reagents,  glassware,  and  other sample processing hardware
may  yield  discrete  artifacts  and/or  elevated  baselines  which  may cause
misinterpretation of chromatographic data.     All  of  these materials must be
demonstrated to be free from interferents  under the conditions of analysis by
running laboratory method blanks.

     3.2  The use of  high  purity  reagents  and  solvents  helps to minimize
interference problems.  Purification of  solvents by distillation in all glass
systems may be required.

     3.3  Interferents co-extracted  from  the  sample  will vary considerably
from source to source,  depending  upon  the Industrial process being sampled.
PCDD's and PCDF's  are  often  associated  with  other Interfering chlorinated
compounds such as PCB's and polychlorinated dlphenyl ethers which may be found
at concentrations several orders of magnitude higher than that of the analytes
of interest.   Retention  times  of  target  analytes  must  be verified using
reference standards.   These  values  must  correspond  to  the retention time
windows established in  Section  6-3.    While  certain cleanup techniques are
provided as part of this method, unique samples may require additional cleanup
techniques to achieve  the  method  detection  limit   (Section 11.6) stated in
Table 8.

     3.4  High resolution capillary columns are  used  to resolve as many PCDD
and PCDF isomers as possible;  however,  no  single column  Is known to resolve
all of the isomers.

     3.5  Aqueous  samples cannot  be  allquoted  from  sample containers.  The
entire sample must be used and the sample container washed/rinsed out with the
extracting solvent.


4.0  APPARATUS AND MATERIALS

     4.1  Sampl1ng equipment  for discrete or composite sampling:

          4.1.1  Grab sample  bottle—amber  glass,  1-liter or 1-quart volume.
     French or Boston Round design 1s recommended.  The container must be acid
     washed and  solvent  rinsed before use to minimize  Interferences.

          4.1.2  Bottle  caps—threaded to screw  onto the  sample bottles.  Caps
     must be lined with  Teflon.  Solvent washed  foil,  used  with the shiny side
     toward the  sample,  may be   substituted  for  Teflon  if the sample  is not
     corrosive.  Apply tape around cap to completely seal cap to bottom.

          4.1.3  Compositing   equipment—automatic    or    manual  compositing
     system.  No tygon   or  rubber  tubing  may  be  used,  and the system must
     incorporate glass  sample containers  for  the collection of a minimum of
     250 ml.  Sample  containers  must be  kept refrigerated after sampling.

     4.2  Water  bath—heated,   with   concentric   ring    cover,  capable  of
temperature control  (+2*C).   The bath  should be  used in a hood.

                                  8280 - 3
                                                          Revision       0
                                                          Date  September 1986

-------
4.3  Gas chromatograph/mass spectrometer data system;

     4.3.1  Gas chromatograph:  An  analytical system with a temperature-
programmable gas  chromatograph  and  all  required accessories Including
syringes, analytical columns, and gases.

     4.3.2  Fused silica capillary  columns  are  required.   As shown 1n
Table 1, three columns  were  evaluated  using a column performance check
mixture   containing   1,2,3,4-TCDD,   2,3,7,8-TCDD,   1,2,3,4,7   PeCDD,
1,2,3,4,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDD, OCDD, and 2,3,7,8-TCDF.

The columns Include the  following:     (a) 50-m CP-S11-88 programmed 60*-
190* at 20*/m1nute, then 190*-240* at 5*/minute; (b) DB-5 (30-m x 0.25-mm
I.D.; 0.25-um film thickness) programmed  170* for 10 minutes, then 170*-
320* at  8*/m1nute,  hold  at  320*C  for  20  minutes;   (c) 30-m SP-2250
programmed 70*-320* at  10*/minute.     Column/conditions  (a) provide good
separation of 2,3,7,8-TCDD from the other TCDD's at  the expense of longer
retention times for higher homologs.    Column/conditions  (b) and  (c) can
also  provide  acceptable  separation   of  2,3,7,8-TCDD.    Resolution of
2,3,7,8-TCDD from the other  TCDD's  1s  better  on column  (c), but column
 (b)  1s  more  rugged,  and   may  provide  better  separation from certain
classes of Interferents.  Data presented  in  Figure 2 and  Tables 1 to 8 of
this  Method    were  obtained  using   a  DB-5  column  with  temperature
programming described 1n  (b)  above.   However, any capillary column which
provides  separation  of  2,3,7,8-TCDD    from  all  other  TCDD   isomers
equivalent to that  specified In Section  6.3 may be  used;  this  separation
must be  demonstrated and  documented  using   the performance test mixture
described 1n Paragraph 6.3.

     4.3.3  Mass  spectrometer:  A  low  resolution instrument 1s  specified,
 utilizing 70  volts  (nominal)  electron  energy   in  the electron  impact
 ionizatlon mode.   The system  must be  capable of  selected 1on  monitoring
 (SIM)  for at least  11 ions  simultaneously,   with a  cycle  time  of 1  sec or
 less.   Minimum  integration  time  for SIM  1s 50  ms per  m/z.   The use of
 systems  not capable of monitoring  11 ions simultaneously  will  require the
 analyst to make multiple  injections.

     4.3.4  6C/MS  Interface:    Any  GC-to-MS   interface  that gives an
 acceptable calibration   response   for   each   analyte  of   Interest at the
 concentration   required   and  achieves   the   required   tuning  performance
 criteria (see  Paragraphs   6.1.-6.3)  may be used.    GC-to-MS  Interfaces
 constructed of  all  glass  or  glass-lined materials are  required.  Glass
 can be deactivated by   s1lan1z1ng  with  dichlorodimethylsllane.   Inserting
 a fused silica  column directly  into   the MS source 1s recommended;  care
 must be taken  not to  expose the  end of  the column  to the  electron  beam.

     4.3.5  Data  system:  A  computer   system must be interfaced to the
 mass spectrometer.  The  system  must allow for  the  continuous  acquisition
 and storage on  machine-readable  media  of all data  obtained throughout the
 duration of the  chromatographic  program.   The computer must have software
 that can search  any GC/MS data file for  Ions  of  a specific mass  and can
 plot such  1on  abundances  versus  time   or  scan  number. This  type  of  plot


                              8280 - 4
                                                     Revision       0
                                                     Date  September 1986

-------
     1s defined as an Selected Ion Current Profile (SICP).  Software must also
     be able to Integrate the  abundance,  1n any SICP,  between specified time
     or scan number limits.

     4.4  P1pets-D1sposable,  Pasteur,  150-mm   long   x  5-mm  I.D.  (Fisher
Scientific Company, No. 13-678-6A, or equivalent).

          4.4.1  P1pet,  disposable,  serological  10-mL  (American Scientific
     Products No.  P4644-10,  or  equivalent)  for  preparation  of the carbon
     column specified 1n Paragraph 4.19.

     4.5  Amber glass bottle (SOO-mL, Teflon-lined screw-cap).

     4.6  React1-v1al 2-mL,  amber  glass  (Pierce  Chemical  Company).  These
should be sllanlzed prior to use.

     4.7  500-mL Erlenmeyer flask (American Scientific Products Cat. No. f4295
SOOfO) fitted with Teflon stoppers  (ASP No. S9058-8, or equivalent).

     4.8  Wrist Action Shaker (VWR No. 57040-049, or equivalent).

     4.9  125-mL  and  2-L  Separatory  Funnels   (Fisher  Scientific  Company,
No. 10-437-5b, or equivalent).

     4.10  500-mL Kuderna-Danlsh  fitted with a 10-mL concentrator tube and
3-ball Snyder column  (Ace Glass No.  6707-02, 6707-12, 6575-02, or equivalent).

     4.11  Teflon boiling chips  (Berghof/American Inc., Main St., Raymond, New
Hampshire 03077, No.  15021-450,   or  equivalent).    Wash with hexane prior to
use.

     4.12  300-mm x  10.5-mm glass   chromatographlc  column fitted with  Teflon
stopcock.

     4.13  15-mL  conical   concentrator   tubes   (Kontes   No.  K-288250,  or
equivalent).

     4.14  Adaptors  for  concentrator tubes   (14/20  to   19/22)  (Ace Glass No.
9092-20, or  equivalent).

     4.15  Nitrogen  blowdown  apparatus  (N-Evap (reg.   trademark)  Analytical
Evaporator   Model    111,    Organomatlon    Associates    Inc.,   Northborough,
Massachusetts or  equivalent).    Teflon   tubing connection   to  trap  and gas
regulator  1s required.

     4.16  Mlcroflex conical vials  2.0-mL  (Kontes K-749000, or equivalent).

     4.17  Filter paper  (Whatman  No. 54,   or equivalent).   Glass fiber  filters
or glass wool plugs  are  also recommended.

     4.18  Sol vent reseryoi r  (125-mL)   Kontes;    (special  order Item)  12.5-cm
diameter, compatible with  gravity carbon column.


                                  8280 - 5
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     4.19  Carbon column (gravity  flow);    Prepare carbon/si11ca gel packing
material bymixing5percent  (byweight)  active  carbon  AX-21  (Anderson
Development Co., Adraln,  Michigan),  pre-washed  with  methanol  and dried |ri
vacuo at 110*C and 95 percent (by  weight)  Silica gel (Type 60, EM reagent 70
to 230 mesh, CMS No. 393-066)  followed  by  activation of the mixture at 130*
for 6 hr.  Prepare a  10-mL  disposable  serologlcal plpet by cutting off each
end to achieve a  4-in.  column.    F1re  polish  both ends; flare 1f desired.
Insert a glass-wool plug at one end and pack with 1 g of the carbon/silica gel
mixture.  Cap the packing with a glass-wool plug.  (Attach reservoir to column
for addition of solvents).

     Option;  Carbon column  (HPLC):  A  sllanlzed glass HPLC column (10 mm x 7
cm), or equivalent, which  contains  1  g  of  a  packing prepared by mixing 5
percent (by weight) active  carbon  AX-21,   (Anderson Development Co., Adrian,
Michigan), washed with methanol and  dried  jn  vacuo at 110*C, and 95 percent
(by weight)  10  urn  silica  (Spherlsorb  S10W  from  Phase Separations, Inc.,
Norwalk, Connecticut).  The mixture must  then be stirred and sieved through a
38-um screen (U.S. Sieve  Designation  400-mesh, American Scientific Products,
No. S1212-400, or equivalent) to remove any clumps.1

     4.20  HPLC pump with loop  valve  (1.0  ml)  Injector  to  be used 1n the
optional carbon column cleanup procedure.

     4.21  Dean-Stark trap,  5-  or  10-mL  with  T  joints, (Fisher Scientific
Company, No. 09-146-5, or equivalent) condenser and 125-mL flask.

     4.22  Continuous liquid-liquid extractor (Hershberg-Wolfe type,  Lab Glass
No. LG-6915; or equivalent.).

     4.23  Roto-evaporator,  R-110.   Buch1/Br1nkman   - American Scientific No.
E5045-10; or equivalent.


5.0  REAGENTS

     5.1  Potassium hydroxide  (ASC):  20  percent  (w/v) 1n distilled water.

     5.2  Sulfurlc  add  (ACS),  concentrated.

     5.3  Methylene  chloride,  hexane,   benzene,   petroleum   ether,  methanol,
trldecane,  Isooctane,  toluene,  cyclohexane.    Distilled   1n glass or  highest
available purity.

     5.4   Prepare  stock  standards   1n  a   glovebox   from concentrates  or  neat
materials.   The stock solutions (50 ppm)   are   stored 1n the dark at 4*C,  and
checked frequently  for signs  of   degradation   or evaporation,  especially  just
prior  to  the preparation of working standards.
 1     The carbon column preparation and  use  1s adapted from W.  A.  Korfmacher,
  L.  G.  Rushing, D.  M.  Nestorlck,  H.  C. Thompson,  Jr.,  R.  K.  Mltchum,  and J.  R.
  Kominsky,   Journal  of  High  Resolution  Chromatography  and  Chromatography
  Communications,  8,  12-19 (1985).

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     5.5  Alumina, neutral, Super 1,  Woelm,   80/200  mesh.    Store 1n a sealed
container at room temperature 1n a desiccator over self-Indicating silica gel.

     5.6  PrepuHfled nitrogen gas.

     5.7  Anhydrous sod1 urn  su1fate  (reagent  grade):    Extracted  by manual
shaking with several portions of hexane and dried at 100'C.

     5.8  Sodium chloride - (analytical reagent), 5 percent (w/v) In distilled
water.
6.0  CALIBRATION

     6.1  Two types of calibration procedures are required.  One type, Initial
calibration, 1s required  before  any  samples  are  analyzed  and 1s required
Intermittently throughout sample analyses  as  dictated  by results of routine
calibration procedures described below.   The other type, routine calibration,
consists  of  analyzing   the   column   performance   check  solution  and  a
concentration calibration solution of 500  ng/mL  (Paragraph 6.2).  No samples
are to be analyzed until acceptable calibration as described In Paragraphs 6.3
and 6.6 Is demonstrated and documented.

     6.2  Initial calibration:

          6.2.1     Prepare multi-level calibration  standards2 keeping one of
the recovery standards and the  Internal standard at fixed concentrations (500
ng/mL).    Additional   Internal   standards   (13Cj2-OCDD  1,000  ng/mL)  are
recommended when quantification of  the  hepta-  and octa-lsomers Is required.
The use of separate  Internal  standards  for  the PCDF's 1s also recommended.
Each calibration standard should contain the following compounds:

2,3,7,8-TCDD,
1,2,3,7,8-PeCDD      or any available   2,3,7,8,X-PeCDD isomer,
1,2,3,4,7,8-HxCDD    or any available   2,3,7,8,X,Y-HxCDD Isomer,
1,2,3,4,6,7,8-HpCDD  or any available   2,3,7,8,X,Y,Z-HpCDD isomer,

2,3,7,8-TCDF
l,2,3,7,8,PeCDF      or any available   2,3,7,8,X-PeCDF Isomer,
1,2,3,4,7,8-HxCDF    or any available   2,3,7,8,X,Y,HxCDF isomer,
1,2,3,4,6,7,8-HpCDF  or any available   2,3,7,8,X,Y,Z-HpCDF isomer,

     OCDD, OCDF, 13Ci2-2,3,7,8-TCDD, 13C12-1,2,3,4-TCDD and i3C12-OCDD.
 2     13Cj2-labeled  analytes  are   available   from Cambridge  Isotope  Laboratory,
 Woburn,  Massachusetts.   Proper  quantification  requires  the  use of a  specific
 labeled  Isomer for each  congener to   be  determined.  When labeled PCDD's and
 PCDF's of each homolog are   available,   their  use will be  required consistent
 with the technique of isotopic  dilution.
                                   8280 - 7
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Recommended concentration levels for  standard  analytes  are 200,  500,  1,000,
2,000, and 5,000 ng/ml_.  These values  may be adjusted in order to insure that
the  analyte  concentration  falls  within  the  calibration  range.    Two uL
Injections of calibration  standards  should  be  made.    However, some GC/MS
Instruments may require the use of  a 1-uL injection volume,- if this injection
volume 1s used then  all  injections  of  standards, sample extracts and blank
extracts must also be made at  this injection volume.  Calculation of relative
response factors is described in Paragraph 11.1.2.  Standards must be analyzed
using the  same  solvent  as  used  1n  the  final  sample  extract.   A wider
calibration range is  useful  for  higher  level  samples  provided  it can be
described within  the   linear  range  of  the  method,  and the Identification
criteria defined In Paragraph 10.4 are  met.   All standards must be stored in
an Isolated  refrigerator  at  4*C  and  protected  from  light.   Calibration
standard solutions must be replaced routinely after six months.

     6.3  Establish operating parameters for  the GC/MS system,- the instrument
should be tuned to meet  the  Isotopic  ratio  criteria  listed in Table 3 for
PCDD's and PCDF's.   Once  tuning  and  mass  calibration procedures have been
completed, a column performance  check  mixture3 containing the isomers listed
below should be injected Into the GC/MS system:

TCDD      1,3,6,8; 1,2,8,9; 2,3,7,8; 1,2,3,4; 1,2,3,7;  1,2,3,9
PeCDD     1,2,4,6,8; 1,2,3,8,9
HxCDD     1,2,3,4,6,9;  1,2,3,4,6,7
HpCDD     1,2,3,4,6,7,8; 1,2,3,4,6,7,9
OCDD      1,2,3,4,6,7,8,9

TCDF      1,3,6,8; 1,2,8,9
PeCDF     1,3,4,6,8; 1,2,3,8,9
HxCDF     1,2,3,4,6,8;  1,2,3,4,8,9
HpCDF     1,2,3,4,6,7,8; 1,2,3,4,7,8,9
OCDF      1,2,3,4,6,7,8,9

      Because of the known  overlap  between the late-elutlng tetra-isomers and
the early-eluting penta-isomers  under  certain  column  conditions, 1t may be
necessary to perform two   Injections  to  define the TCDD/TCDF and  PeCDD/PeCDF
elutlon windows, respectively.   Use  of  this  performance check mixture will
enable the following parameters to be  checked:   (a) the retention windows for
each  of the homologues,   (b)  the  GC  resolution of 2,3,7,8-TCDD  and 1,2,3,4-
TCDD, and  (c)  the relative  Ion  abundance criteria listed for PCDD's and  PCDF's
1n Table 3.  GC column  performance   should be checked  dally for resolution and
peak  shape using this  check mixture.

      The chromatographic peak separation between  2,3,7,8-TCDD  and  1,2,3,4-TCDD
must  be resolved with  a valley  of ^25 percent, where

           Valley Percent  = (x/y)  (100)

      x  = measured as  in Figure  2
      y  - the peak height of 2,3,7,8-TCDD
 3    Performance check mixtures  are  available  from Brehm Laboratory,  Wright
  State University,  Dayton,  Ohio.

                                   8280 - 8
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                                                          Date  September 1986

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     It 1s the  responsibility  of  the  laboratory  to  verify the conditions
suitable for maximum resolution of  2,3,7,8-TCDD  from all  other TCDD Isomers.
The peak representing 2,3,7,8-TCDD should be labeled and Identified as such on
all chromatograms.

     6,4  Acceptable  SIM  sensitivity  1s  verified  by  achieving  a minimum
signal-to-no1se ratio of 50:1  for  the  m/z  320 ion of 2,3,7,8-TCDD obtained
from injection of the 200 ng/mL calibration standard.

     6.5  From  Injections  of  the  5  calibration  standards,  calculate the
relative response factors  (RRF's)  of  analytes  vs. the appropriate internal
standards, as described in  Paragraph  11.1.2.   Relative response factors for
the hepta- and octa-chlorlnated CDD's and CDF's are to be calculated using the
corresponding l^c^-oetachlorinated standards.

     6.6  For each analyte calculate the  mean relative response factor (RRF),
the standard  deviation,  and  the  percent  relative  standard deviation from
triplicate determinations of  relative  response  factors for each calibration
standard solution.

     6.7  The  percent  relative  standard  deviations  (based  on  triplicate
analysis) of  the  relative  response  factors  for  each calibration standard
solution should not  exceed 15  percent.    If this condition is not satisfied,
remedial action should be taken.

     6.8  The Laboratory must  not  proceed  with  analysis  of samples before
determining and documenting acceptable calibration with the criteria specified
1n Paragraphs 6.3 and 6.7.

     6.9  Routine calibration;

          6.9.1   Inject  a  2-uL  aliquot  of  the  column  performance  check
     mixture.  Acquire at least five data  points for each GC peak and use the
      same data acquisition time for each of the ions being monitored.
          NOTE:   The same  data  acquisition  parameters  previously  used to
                  analyze concentration  calibration  solutions  during initial
                  calibration must be used  for the performance check solution.
                  The column performance  check  solution  must  be  run at the
                  beginning and end  of  a  12  hr  period.   If the contractor
                  laboratory   operates   during   consecutive   12-hr  periods
                  (shifts), analysis of the  performance  check solution at the
                  beginning of each 12-hr period and at the end of the final
                  12-hr period is  sufficient.
      Determine  and   document
      Paragraph  6.3.
acceptable  column  performance  as described in
           6.9.2   Inject  a  2-uL  aliquot of  the calibration standard solution at
      500 ng/mL at the beginning   of  a  2-hr  period.  Determine and document
      acceptable   calibration  as   specified   in    Paragraph  6.3,   I.e.,  SIM
      sensitivity and relative ion  abundance  criteria.   The measured RRF's of
                                   8280 - 9
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     all  analytes must be within +30 percent of the  mean  values  established  by
     initial  analyses of the calibration standard solutions.


7.0  QUALITY CONTROL

     7.1  Before processing any samples,  the analyst must demonstrate through
the  analysis  of  a  method  blank   that  all  glassware  and   reagents  are
1nterferent-free at the  method  detection  limit  of  the matrix of Interest.
Each time a set of samples 1s  extracted,  or there 1s a change  in reagents, a
method  blank  must   be   processed   as   a   safeguard  against  laboratory
contamination.

     7.2  A laboratory "method blank" must  be  run along with each analytical
batch (20 or fewer samples).  A  method blank 1s performed by executing all  of
the specified extraction and cleanup  steps,  except for the Introduction of a
sample.  The method blank  1s  also  dosed  with  the Internal standards.  For
water samples, one liter of delonlzed and/or distilled water should be used as
the method blank.  Mineral  oil  may  be  used  as  the method blank for other
matrices.

     7.3  The laboratory will  be  expected  to analyze performance evaluation
samples as provided by the EPA on  a periodic basis throughout the course of a
given project.   Additional  sample  analyses  will  not  be  permitted 1f the
performance criteria  are not achieved.    Corrective  action must be taken and
acceptable performance must be demonstrated before  sample analyses can resume.

     7.4  Samples may be split  with  other  participating  labs on a periodic
basis to ensure  Interlaboratory consistency.   At   least one sample per set of
24 must be run  1n duplicate to determine  Intralaboratory precision.

     7.5  Field  duplicates  (Individual  samples taken from the same location at
the  same  time)  should  be  analyzed  periodically  to  determine  the total
precision  (field and  lab).

     7.6  Where  appropriate, "field blanks"  will   be  provided to monitor  for
possible cross-contamination of  samples  in   the   field.   The typical  "field
blank" will consist  of  uncontaminated soil  (background soil taken off-site).

     7.7  GC  column  performance  must   be  demonstrated  Initially and verified
prior to analyzing any  sample In   a   12-hr  period.  The GC column performance
check solution   must be  analyzed under  the   same  chromatographic and mass
spectrometric conditions used for  other samples  and standards.

     7.8  Before using   any  cleanup  procedure,  the  analyst  must process a
series of  calibration   standards   (Paragraph  6.2)  through  the procedure to
validate elutlon patterns and the  absence of interferents from  reagents.  Both
alumina column  and carbon column performance must be checked.   Routinely check
the  8 percent CHgC^/hexane eluate of  environmental extracts from the alumina
column  for presence  of  target analytes.
     NOTE:   This fraction  is Intended to  contain a high  level  of interferents
             and analysis  near the  method  detection  limit may  not be possible.


                                   8280  - 10
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8.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     8.1  Grab and composite samples  must  be  collected 1n glass containers.
Conventional sampling practices must  be  followed.    The  bottle must not be
prewashed  with  sample  before  collection.    Composite  samples  should  be
collected 1n glass containers.    Sampling  equipment  must  be free of tygon,
rubber tubing, other potential sources  of  contamination which may absorb the
target analytes.

     8.2  All samples must be  stored  at  4*C,   extracted  within 30 days and
completely analyzed within 45 days of collection.


9.0  EXTRACTION AND CLEANUP PROCEDURES

     9.1  Internal standard addition.  Use a sample aliquot of 1 g to 1,000 mL
(typical sample size requirements  for  each  type  of  matrix are provided 1n
Paragraph 9.2) of the chemical  waste  or  soil   to be analyzed.  Transfer the
sample to a tared  flask  and  determine  the  weight  of  the sample.  Add an
appropriate quantity of 13Ci2-2,3,7,8-TCDD, and any other material which is to
be used as an  Internal  standard,   (Paragraph  6.2).    All samples should be
spiked with at least  one  internal  standard, for example, 13Ci2-2,3,7,8-TCDD,
to give a concentration of 500 ng/mL 1n the final concentrated extract.  As an
example, a 10 g sample concentrated  to  a  final volume of 100 uL requires the
addition of 50 ng of 13Ci2-2,3,7,8-TCDD,  assuming 100% recovery.  Adoption of
different  calibration  solution   sets   (as   needed  to  achieve  different
quantification limits for different  congeners)  will  require a change in the
fortification level.    Individual   concentration  levels  for each homologous
series must be specified.

     9.2  Extraction

          9.2.1  Sludge/fuel  oil.  Extract aqueous sludge samples by refluxlng
     a sample  (e.g. 2 g) with 50  mL  of  toluene (benzene) in a 125-mL flask
     fitted with a Dean-Stark water  separator.  Continue refluxing the sample
     until all the  water  has  been  removed.    Cool  the sample, filter the
     toluene  extract through  a  fiber  filter,  or  equivalent, Into a 100-mL
     round bottom flask.  Rinse the  filter  with 10 mL of toluene, combine the
     extract  and rinsate.  Concentrate  the  combined solution to near dryness
     using a  rotary evaporator at  50*C.    Use  of an inert gas to concentrate
     the extract is also permitted.  Proceed with Step 9.2.4.

          9.2.2  Still bottom.     Extract  still  bottom  samples  by mixing  a
     sample  (e.g., 1.0 g) with 10  mL  of  toluene (benzene) in a small beaker
     and filtering the solution through  a  glass fiber filter  (or equivalent)
     Into a 50-mL round bottom flask.   Rinse the beaker and filter with 10 mL
     of toluene.  Concentrate the  combined  toluene solution to near dryness
     using a  rotary evaporator at  50*C  while connected to a water aspirator.
     Proceed with Step 9.2.4.
                                  8280 - 11
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     9.2.3  Fly ash.  Extract fly  ash  samples by placing a sample (e.g.
10 g) and an equivalent amount  of  anhydrous sodium Sulfate 1n a Soxhlet
extraction apparatus charged with 100 ml of toluene (benzene) and extract
for 16 hr using a three cycle/hour schedule.  Cool and filter the toluene
extract through a glass  fiber  filter  paper  Into a 500-mL round bottom
flask.  Rinse the filter with 5  ml of toluene.  Concentrate the combined
toluene solution to  near  dryness  using  a  rotary  evaporator at 50*C.
Proceed with Step 9.2.4.

     9.2.4  Transfer the  residue  to  a  125-mL  separatory funnel using
15 ml of hexane.  Rinse  the  flask  with two 5-mL allquots of hexane and
add the rinses to  the  funnel.    Shake  2  m1n  with  50  ml of 5% NaCl
solution, discard the aqueous layer and proceed with Step 9.3.

     9.2.5  Soil.  Extract soil samples by placing the sample (e.g. 10 g)
and  an  equivalent  amount  of  anhydrous  sodium  sulfate  1n  a 500-mL
Erlenmeyer flask fitted with a Teflon stopper.  Add 20 ml of methanol and
80 ml of petroleum ether, 1n that order, to the flask.  Shake on a wrist-
action shaker for two hr.  The solid portion of sample should mix freely.
If a smaller soil  aliquot  1s  used,  scale  down the amount of methanol
proportionally.

          9.2.5.1  Filter the  extract  from  Paragraph  9.2.5  through a
     glass funnel  fitted  with  a  glass   fiber  filter  and filled with
     anhydrous   sodium  sulfate   Into   a   500-mL  Kuderna-Danlsh  (KD)
     concentrator fitted with a  10-mL  concentrator  tube.   Add 50 mL of
     petroleum  ether to  the  Erlenmeyer  flask,  restopper  the flask and
     swirl the  sample gently, remove the stopper  carefully and decant the
     solvent through the funnel  as above.   Repeat this procedure with two
     additional  50-mL  allquots  of  petroleum  ether.    Wash the sodium
     sulfate 1n the funnel with  two additional  5-mL  portions of petroleum
     ether.

          9.2.5.2   Add  a Teflon  or   PFTE   boiling   chip  and a three-ball
      Snyder  column  to  the  KD flask.    Concentrate 1n a 70*C  water  bath to
      an  apparent volume  of 10 mL.     Remove  the  apparatus  from  the  water
      bath and  allow 1t  to  cool  for 5  m1n.

          9.2.5.3   Add 50  mL of hexane and   a  new boiling  chip  to the KD
      flask.  Concentrate  1n  a water  bath   to  an apparent  volume  of 10 mL.
      Remove  the apparatus  from the   water   bath  and allow to  cool  for 5
      m1n.

          9.2.5.4   Remove  and Invert the Snyder  column  and rinse 1t down
      Into the  KD with  two  1-mL  portions   of hexane. Decant the contents
      of the  KD and  concentrator  tube  Into  a 125-mL separatory funnel.
      Rinse  the KD  with two  additional  5-mL portions of hexane,  combine.
      Proceed with  Step 9.3.

      9.2.6   Aqueous samples:  Mark the water  meniscus on the side of the
 1-L sample  bottle  for  later  determination  of  the exact  sample volume.
                              8280 - 12
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                                                     Date  September 1986

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    Pour the entire sample  (approximately  1-L) into a 2-L separatory funnel.
    Proceed with Step 9.2.6.1.
         NOTE:  A continuous liquid-liquid extractor may  be used in place of
                a separatory funnel  when  experience  with  a  sample from a
                given source Indicates that  a  serious emulsion problem will
                result or   an  emulsion  is  encountered  using  a separatory
                funnel.   Add  60  ml  of  methylene  chloride  to the sample
                bottle, seal,  and  shake  for  30  sec  to  rinse  the inner
                surface.  Transfer the solvent  to the extractor.  Repeat the
                sample bottle rinse with an  additional 50- to 100-mL portion
                of methylene chloride  and  add  the  rinse to the extractor.
                Add 200 to  500  ml  of  methylene  chloride to the distilling
                flask;  add sufficient   reagent   water  to  ensure  proper
                operation,  and extract for 24 hr.  Allow to cool, then detach
                the distilling flask.    Dry  and  concentrate the extract as
                described in Paragraphs  9.2.6.1  and  9.2.6.2.  Proceed with
                Paragraph 9.2.6.3.

               9.2.6.1  Add  60 ml  methylene  chloride  to  the sample bottle,
         seal  and shake 30  sec  to  rinse  the  inner surface.  Transfer the
         solvent to the separatory funnel  and  extract the sample by shaking
         the funnel for 2 min with periodic venting.  Allow the organic layer
         to separate from the water phase  for  a  minimum of 10 m1n.  If the
         emulsion interface between layers is  more than one-third the volume
         of the solvent layer, the  analyst must employ mechanical techniques
         to complete the phase separation.  Collect the methylene chloride
          (3 x  60  ml)  directly  into  a  500-mL Kuderna-Danlsh concentrator
          (mounted with  a   10-mL  concentrator  tube)  by  passing the sample
         extracts through a filter funnel packed with a glass wool plug and
         5 g of anhydrous sodium sulfate.   After the third extraction, rinse
         the sodium sulfate with an additional 30 ml of methylene chloride to
         ensure quantitative transfer.

               9.2.6.2  Attach  a Snyder column  and concentrate the extract on
         a water bath  until the apparent  volume  of the  liquid  reaches 5 ml.
         Remove the  K-D apparatus and allow  it to drain and cool  for  at least
          10 min.   Remove  the Snyder  column,   add 50 ml hexane,  re-attach the
         Snyder column and  concentrate  to   approximately 5  ml.   Add a new
         boiling chip  to  the  K-D  apparatus  before proceeding with the  second
          concentration step.

          Rinse the  flask  and  the  lower joint with 2  x  5 ml hexane  and combine
          rinses with  extract  to  give a  final volume  of  about  15  ml.

               9.2.6.3  Determine the original  sample  volume  by  refilling the
          sample bottle to the mark  and   transferring the  liquid  to  a  1,000-mL
          graduated cylinder.   Record  the   sample   volume  to  the  nearest 5 ml.
          Proceed  with  Paragraph  9.3.

     9.3  In  a  250-mL Separatory  funnel,   partition  the solvent  (15 ml hexane)
against 40 ml of  20  percent   (w/v)   potassium  hydroxide.   Shake  for 2 m1n.
                                  8280 - 13
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                                                         Date  September 1986

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Remove and discard the aqueous layer  (bottom).   Repeat  the  base washing  until
no color 1s visible 1n the  bottom  layer  (perform base washings  a maximum of
four times).   Strong  base  (KOH)  1s  known  to degrade certain  PCDD/PCDF's,
contact time must be minimized.

     9.4  Partition the solvent (15  ml  hexane)   against  40  ml  of 5 percent
(w/v) sodium chloride.  Shake  for  2  m1n.   Remove and discard aqueous  layer
(bottom).
     NOTE:  Care  should  be  taken  due  to  the  heat  of neutralization and
     hydratlon.

     9.5  Partition the solvent (15 ml  hexane)  against 40 mL of  concentrated
sulfurlc add.   Shake  for  2  mln.    Remove  and  discard the aqueous  layer
(bottom).   Repeat the add  washings  until  no  color  1s visible 1n the add
layer.  (Perform add washings a maximum of four times.)

     9.6  Partition the  extract  against  40  ml  of  5  percent  (w/v) sodium
chloride.   Shake for 2 m1n.    Remove  and discard the aqueous layer (bottom).
Dry  the organic layer by pouring  through a funnel containing anhydrous sodium
sulfate Into a 50-mL round bottom  flask,  wash the separatery funnel with two
15-mL portions of hexane,  pour  through  the  funnel,  and combine the hexane
extracts.   Concentrate  the  hexane  solution  to  near  dryness  with a rotary
evaporator  (35*C water bath), making  sure  all traces of toluene  are removed.
(Use of  blowdown  with  an  Inert  gas  to  concentrate  the  extract 1s also
permitted).

     9.7  Pack a gravity column (glass 300-mm x 10.5-mm), fitted with a Teflon
stopcock, 1n the following manner:

     Insert a glass-wool plug  Into the bottom  of the column.  Add a 4-g layer
of sodium sulfate.  Add a 4-g  layer of Woelm super 1 neutral alumina.  Tap the
top  of the  column gently.  Woelm  super 1 neutral alumina need not be activated
or cleaned  prior to use but should be stored 1n a sealed desiccator.  Add a 4-
g layer of  sodium sulfate to cover  the  alumina,   Elute with 10 ml of hexane
and  close the  stopcock just prior to  the  exposure of the sodium sulfate layer
to air.   Discard the  eluant.   Check the column for channeling.  If channeling
is present  discard  the column.  Do not tap a wetted column.

      9.8  Dissolve  the residue from Step 9.6   1n  2 ml  of hexane and apply the
hexane  solution  to  the top  of  the column.   Elute with  enough hexane  (3-4 ml)
to complete the  transfer  of the sample   cleanly to the  surface of  the  alumina.
Discard  the eluant.

           9.8.1   Elute with 10 ml  of 8  percent   (v/v) methylene chloride in
      hexane.   Check by GC/MS  analysis that  no  PCDD's  or  PCDF's are  eluted 1n
      this fraction.   See  Paragraph  9.9.1.

           9.8.2  Elute  the PCDD's and PCDF's from  the  column  with 15 ml of 60
      percent (v/v)  methylene chloride in hexane  and  collect this  fraction  in a
      conical  shaped (15-mL) concentrator tube.
                                   8280 - 14
                                                          Revision
                                                          Date  September 1986

-------
    9.9  Carbon column cleanup;

         Prepare a carbon column as described In Paragraph 4.18.

         9.9.1  Using a  carefully  regulated  stream  of nitrogen  (Paragraph
    4.15),  concentrate  the  8  percent  fraction  from  the  alumina column
    (Paragraph 9.8.1) to about 1 ml.  Wash the sides of the tube with a small
    volume of hexane  (1 to 2 ml) and  reconcentrate to about 1 ml.  Save this
    8 percent concentrate for  GC/MS  analysis  to  check for breakthrough of
    PCDD's and PCDF's.  Concentrate the 60 percent fraction (Paragraph 9.8.2)
    to about 2 to 3  ml.    Rinse  the carbon with 5 ml cyclohexane/methylene
    chloride  (50:50 v/v) 1n the  forward  direction  of  flow and then 1n the
    reverse direction of flow.  While still  1n the reverse direction of flow,
    transfer the sample concentrate to  the  column  and  elute with 10 ml of
    cyclohexane/methylene  chloride   (50;50  v/v)   and  5  ml  of  methylene
    chlon'de/methanol/benzene  (75:20:5, v/v).    Save  all  above eluates and
    combine  (this fraction may be  used as a  check on column efficiency).  Now
    turn the column over  and  1n  the  direction  of  forward flow elute the
    PCDD/PCDF fraction with 20 ml  toluene.
         NOTE:  Be sure no carbon  fines are  present 1n the eluant.

         9.9.2  Alternate carbon column cleanup.  Proceed as 1n Section 9.9.1
    to obtain the 60  percent  fraction  re-concentrated  to  400 uL which 1s
    transferred to an  HPLC   Injector loop   (1  ml).    The Injector  loop 1s
    connected to the  optional  column  described   1n Paragraph 4.18.  Rinse the
    centrifuge tube with  500  uL  of hexane  and  add  this  rlnsate to the
    Injector  loop.    Load  the  combined  concentrate  and  rlnsate onto the
    column.   Elute the column  at 2 ml_/m1n, ambient temperature, with 30 ml of
    cyclohexane/methylene chloride 1:1  (v/v).  Discard the eluant.  Backflush
    the  column with 40  ml  toluene   to  elute   and collect PCDD's  and PCDF's
     (entire   fraction).    The column  1s   then  discarded  and   30  ml  of
    cyclohexane/methylene chloride 1:1  (v/v) 1s  pumped through a  new column
    to prepare  it  for the next sample.

         9.9.3   Evaporate the  toluene fraction  to  about  1  ml on a rotary
    evaporator using  a water  bath  at  50*C.  Transfer to a 2.0-mL Reaeti-v1al
    using a  toluene   rinse  and  concentrate to  the  desired volume  using  a
    stream of N2«  The final  volume  should be 100 uL for soil samples  and
    500  uL for sludge, still   bottom,  and   fly  ash samples; this 1s provided
    for  guidance,  the correct  volume  will   depend on the relative  concentra-
    tion of  target analytes.   Extracts which are determined to be outside the
    calibration  range for  Individual  analytes   must  be diluted or a  smaller
    portion  of  the sample must be  re-extracted.  Gently swirl the  solvent on
    the  lower portion of   the  vessel   to  ensure complete dissolution of the
     PCDD's  and  PCDF's.

    9.10  Approximately  1  hr before   HRGC/LRMS   analysis,  transfer  an  aliquot
of the extract to   a   m1cro-v1al   (Paragraph   4.16).    Add to  this  sufficient
recovery standard (13Ci2l|2,3,4-TCDD)  to   give   a  concentration  of  500 ng/mL.
(Example:  36 uL aliquot  of  extract   and   4  uL  of  recovery  standard solution.
Remember to  adjust the final  result  to   correct for  this dilution.   Inject  an
appropriate  aliquot (1 or 2 uL) of the sample Into  the  GC/MS  Instrument.


                                  8280 - 15
                                                         Revision      0
                                                         Date   September 1986

-------
10.0  GC/MS ANALYSIS

     10.1  When toluene 1s employed as the final  solvent use of a bonded phase
column from Paragraph 4.3.2 1s  recommended.   Solvent exchange Into trldecane
Is required for other liquid phases or nonbonded columns (CP-S11-88).
     NOTE:  Chromatographlc conditions must be adjusted to account for solvent
            boiling points.

     10.2  Calculate response factors for  standards  relative to the Internal
standards, 13Ci2-2,3.7,8-TCDD  and  13Ci2-OCDD  (see  Section  11).    Add the
recovery standard  (13Ci2-l|2,3,4-TCDD) to the samples prior to Injection.  The
concentration of the recovery standard 1n  the sample extract must be the same
as that 1n the calibration standards used to measure the response factors.

     10.3  Analyze samples with selected 1on monitoring, using all of the Ions
listed In Table 2.  It 1s recommended  that the GC/MS run be divided Into five
selected 1on monitoring sections, namely:   (1) 243, 257,, 304, 306, 320, 322,
332, 334, 340, 356, 376   (TCDD's,  TCDF's, 13Cj2-labeled Internal and recovery
standards, PeCDD's, PeCDF's,  HxCDE);  (2)  277,  293,  306, 332, 338, 340, 342,
354, 356, 358, 410  (peCDD's,  PeCDF's,  HpCDE);   (3)  311, 327, 340, 356, 372,
374, 376, 388, 390, 392,  446,   (HxCDD's,  HxCDF's,  OCDE);  (4) 345, 361, 374,
390, 406, 408, 410, 422,  424,  426,  480  (HpCDD's,  HpCDF's, NCDE) and (5) 379,
395, 408, 424, 442,  444,  458,  460,  470,  472, 514  (OCDD, OCDF,  13Ci2-OCDD,
DCDE).  Cycle  time  not  to   exceed   1  sec/descriptor.   It Is  recommended that
selected  1on monitoring section  1   should  be  applied during   the GC  run to
encompass the  retention window  (determined  1n Paragraph 6.3) of the  first- and
Iast-elut1ng tetra-chlorlnated Isomers.   If a  response 1s observed  at m/z 340
or  356,  then the   GC/MS   analysis  must   be  repeated;  selected 1on  monitoring
section  2 should  then  be applied   to  encompass   the  retention  window  of the
first- and last-eluting penta-chlorinated Isomers.   HxCDE,  HpCDE,  OCDE, NCDE,
DCDE, are abbreviations for   hexa-,   hepta-, octa-,  nona-, and decachlorlnated
dlphenyl  ether,  respectively.

      10.4   Identification criteria for PCDD's and PCDF's;

           10.4.1   All  of the   characteristic  ions,   I.e.  quantltation 1on,
      confirmation Ions, listed  in  Table   2  for   each   class of PCDD and PCDF,
      must be present  in the   reconstructed  Ion chromatogram.  It is desirable
      that the  M  -   COC1   ion   be   monitored  as   an   additional  requirement.
      Detection limits will be based   on quantltation Ions within  the molecules
      in  cluster.

           10.4.2   The maximum  Intensity   of  each   of   the  specified charac-
      teristic  Ions must coincide within 2 scans or  2 sec.

           10.4.3   The  relative  Intensity  of the selected, isotoplc  Ions  within
      the molecular ion cluster of  a  homologous  series  of PCDD's of  PCDF's must
      He within  the range specified  in Table 3.

           10.4.4  The  SC  peaks  assigned to a given  homologous  series must have
      retention times  within   the  window   established   for   that  series  by the
      column  performance  solution.


                                   8280 -  16
                                                          Revision      0
                                                          Date  September 1986

-------
     10.5  Quantltate the PCDD and  PCDF  peaks  from the response relative to
the appropriate Internal  standard.    Recovery  of each Internal  standard)  vs.
the recovery standard must be greater than 40 percent.  It Is recommended that
samples with recoveries of less than 40 percent or greater than 120 percent be
re-extracted and re-analyzed.
     NOTE:  These  criteria  are  used  to  assess  method  performance;   when
            properly applied, Isotope  dilution  techniques are Independent of
            Internal standard recovery.

In those  circumstances  where  these  procedures  do  not  yield a definitive
conclusion, the use  of  high  resolution  mass  spectrometry or HRGC/MS/MS 1s
suggested.


11.0  CALCULATIONS

      NOTE:  The relative response  factors  of  a  given  congener within any
             homologous series  are  known  to  be  different.    However, for
             purposes of these  calculations,  1t  will  be assumed that every
             congener within a  given  series  has  the same relative response
             factor.  In order to  minimize  the  effect of this assumption on
             risk   assessment,   a   2,3,7,8-substltuted   Isomer   that   Is
             commercially  available  was  chosen  as  representative  of each
             series.  All relative  response  factor  calculations for a given
             homologous series are based on that compound.

     11.1  Determine the concentration of Individual  Isomers of tetra-, penta,
and hexa-CDD/CDF according to the equation:

                                    Q1<5 x A
           Concentration, ng/g  -  G x ^ x m

where:

     Qls   =  n9 °f  Internal  standard   13Ci2-2,3,7,8-TCDD,  added to the sample
             before extraction.

        G   =  g of sample extracted.

       As   =  area of quantltatlon 1on  of  the compound of  Interest.

     A^s   =  area of quantltatlon   1on   (m/z   334)  of  the  Internal standard,
             13C12-2,3,7,8-TCDD.

     RRF   =  response  factor of  the  quantltatlon   Ion   of   the  compound of
             Interest  relative to m/z  334 of  l3Ci2-2,3,7,8-TCDD.

     NOTE:  Any dilution  factor  Introduced   by   following  the  procedure In
             Paragraph  9.10 should be applied to this  calculation.
                                   8280 -  17
                                                         Revision      0	
                                                         Date  September 1986

-------
          11.1.1  Determine the concentration of  individual  Isomers of hepta-
     CDD/CDF and the concentration of OCDD and OCDF according to the equation:

                                    Q1s x A
          Concentration, ng/g  =  G x ^—x RRp


where:

     Q^s  «•  ng of internal standard  13Ci2-OCDD,  added  to the sample before
             extraction.

       6  =  g of sample extracted,

      AS  =  area of quantltatlon ion of the compound of Interest.

     A-|s  =  area of quantitation  1on  (m/z  472)  of  the Internal standard,
             13C12-OCDD.

     RRF  =  response factor  of  the  quantitation  ion  of  the  compound of
             Interest relative to m/z 472 of 13Ci2-OCDD.

     NOTE:  Any dilution  factor  introduced  by  following  the  procedure in
            Paragraph 9.10 should be applied to this calculation.

          11.1.2  Relative response factors are calculated using data obtained
     from the analysis  of  multi-level  calibration standards according to the
     equation;


          RRF -   s  x  1s
                 A1sx  Cs
where:

      As   =   area  of  quantltatlon  ion of the compound of Interest.

      A-|S   =   area  of  quantitation   ion  of  the  appropriate  internal  standard
              (m/z  334 for 13C12-2,3,7,8-TCDD,- m/z 472 for  13C12-OCDD).

      C^s   -   concentration  of the  appropriate internal  standard,
              13Ci2-2,3,7,8-TCDD or 13Gi2-OCDD)

      Cs   =   concentration  of the  compound  of interest.

           11.1.3   The concentrations  of  unknown   isomers of  TCDD   shall be
      calculated using the mean RRF determined for 2,3,7,8-TCDD.

           The concentrations of unknown  Isomers  of PeCDD shall  be calculated
      using the  mean  RRF  determined  for  1,2,3,7,8-PeCDD  or   any  available
      2,3,7,8,X-PeCDD  Isomer.
                                   8280 - 18
                                                          Revision
                                                          Date  September  1986

-------
     The concentrations of unknown  Isomers  of HxCDD shall  be calculated
using the mean  RRF  determined  for  1,2,3,4,7,8-HxCDD  or any available
2,3,7,8,-X,Y-HXCDD isomer.

     The concentrations of unknown  Isomers  of HpCDD shall  be calculated
using the mean RRF  determined  for  1,2,3,4,6,7,8-HpCDD or any available
2,3,7,8lX,Y,Z-HpCDD Isomer.

     The concentrations of unknown  Isomers  of  TCDF shall  be calculated
using the mean RRF determined for 2,3,7,8-TCDF.

     The concentrations of unknown  Isomers  of PeCDF shall  be calculated
using the  mean  RRF  determined  for  1,2,3,7,8-PeCDF  or  any available
2,3,7,8,X-PeCDF Isomer.

     The concentrations of unknown  Isomers  of HxCDF shall  be calculated
using the  mean  RRF  determined  for  1,2,4,7,8-HxCDF  or  any available
2,3,7,8-X,Y-HxCDF Isomer.

     The concentrations of unknown  Isomers  of HpCDF shall  be calculated
using the mean RRF  determined  for  1,2,3,4,6,7,8-HpCDF or any available
2,3,7,8(X,Y,Z-HpCDF Isomer.

     The concentration of the  octa-CDD  and octa-CDF shall  be calculated
using the mean RRF determined for each.

     Mean relative response factors  for  selected  PCDD's and PCDF's are
given 1n Table 4,

     11.1.4  Calculate  the  percent  recovery,  R^s,  for  each Internal
standard 1n the sample extract, using the equation:

              A.     Q
               is  x  rs
                x RFf x Q1
where:

     Ars  *  Area of quantltatlon 1on (m/z 334} of the recovery standard,
     Qrs  =  n9  °f  recovery   standard,  13Ci2-l,2,3,4-TCDD,  added  to
             extract .

The  response factor  for  determination  of  recovery is calculated using
data obtained from the analysis  of the multi-level calibration standards
according to the equation:


     RF  _  Ais  x   Crs

         "
                             8280 - 19
                                                    Revision      0
                                                    Date  September 1986

-------
     where:

          Crs  -  Concentration of the recovery  standard,  13r.12-l,2,3,4-TCDD.

          11.1.5  Calculation of  total   concentration  of  all  Isomers  within
     each homologous series of PCDD's and PCDF's.

     Total concentration  „  Sum of the concentrations of the Individual
     of PCDD's or PCDF's     PCDD or PCDF Isomers

     11.4  Report results 1n  nanograms  per  gram;   when duplicate and  spiked
samples are reanalyzed, all data obtained should be  reported.

     11.5  Accuracy and Precision.    Table  5  gives  the  precision data for
revised Method 8280 for  selected  analytes  1n  the  matrices shown.  Table 6
lists recovery data for the same analyses.  Table  2  shows the linear range and
variation of  response  factors  for  selected  analyte  standards.    Table 8
provides the method detection limits as measured 1n  specific sample matrices.

     11.6  Method Detection  Limit.    The  Method  Detection  Limit  (MDL) 1s
defined as the minimum concentration of  a  substance that can be measured and
reported with 99  percent  confidence  that  the  value  1s  above  zero.  The
procedure used to determine the  MDL  values  reported 1n Table 8 was obtained
from Appendix  A  of  EPA  Test  Methods  manual,   EPA-600/4-82-057 July 1982,
"Methods  for  Organic   Chemical   Analysis   of    Municipal  and  Industrial
Wastewater."

     11.7  Maximum Holding Time  (MHT),   Is  that   time  at which a 10 percent
change 1n the analyte  concentration  (Ctio)  occurs  and the precision of the
method of  measurement  allows  the  10  percent  change  to  be statistically
different from the 0 percent change  (Cto) at the  90 percent confidence level.
When  the  precision  of  the   method  Is  not  sufficient  to  statistically
discriminate a 10 percent change  1n  the concentration from 0 percent change,
then the maximum holding time   1s  that  time  where the percent change 1n the
analyte concentration  (Ctn)  1s   statistically different than the concentration
at 0 percent change  (C^ol and greater than 10 percent change at the 90 percent
confidence level.
                                   8280 - 20
                                                          Revision
                                                                September  1986

-------
TABLE 1.  REPRESENTATIVE GAS CHROMATOGRAPH RETENTION TIMES* OF ANALYTES
Analyte
2,3,7,8-TCDF
2,3,7, 8-TCDD
1,2,3,4-TCDD
1,2,3,4,7-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
50-m
CP-S11-88
25.2
23.6
24.1
30.0
39.5
57.0
NM
30-m
DB-5
17.8
17.4
17.3
20.1
22.1
24.1
25.6
3~m
SP-2250
26.7
26.7
26.5
28.1
30.6
33.7
NM
*Retent1on time in m1n, using temperature programs shown below.
NM  =  not measured.
Temperature Programs:
          CP-Sil-88           60*C-190*C at 20*/min; 190°-240« at 5*/m1n.
          DB-5                170% 10 min,* then at 8'/min to 320'C, hold
          30 m x 0.25 mm      at 320*C 20 mln  (until OCDD elutes).
          Thin film  (0.25 urn)
          SP-2250             70'-320* at 10*/minute.
                            Column Manufacturers
CP-S11-88            Chrompack,  Incorporated, Bridgewater, New Jersey
DB-5,                J  and   W   Scientific,   Incorporated,  Rancho  Cordova,
                     California
SP-2250              Supelco,     Incorporated,     Bellefonte,    Pennsylvania
                                   8280 - 21
                                                          Revision
                                                          Date   September 1986

-------
                    TABLE 2.   IONS SPECIFIED3 FOR SELECTED ION MONITORING
                            FOR PCDD'S AND PCDF'S
                        Quantitatlon
                            1on
                  Confirmation
                      Ions
        M-COC1
PCDD's
13c12-Tetra
Tetra
Penta
Hexa
Hepta
Octa
13Ci2~Octa
PCDF's
Tetra
Penta
Hexa
Hepta
Octa
334
322
356
390
424
460
472

306
340
374
408
444
332
320
354; 358
388; 392
422 ,-426
458
470

304
338; 342
372;376
406; 410
442
___
257
293
327
361
395


243
277
311
345
379
alons at m/z 376  (HxCDE), 410  (HpCDE), 446  (OCDE), 480  (NCDE) and  514  (DCDE)
 are also  Included  1n the scan monitoring sections  (1)  to  (5),  respectively.
 See Paragraph  10.3.
  TABLE 3.   CRITERIA  FOR  ISOTOPIC  RATIO  MEASUREMENTS  FOR  PCDD'S  AND PCDF'S
                         Selected  Ions  (m/z)
                               Relative Intensity
 PCDD's

 Tetra
 Penta
 Hexa
 Hepta
 Octa

 PCDF's

 Tetra
 Penta
 Hexa
 Hepta
 Octa
320/322
358/356
392/390
426/424
458/460
304/306
342/340
376/374
410/408
442/444
0.65-0.89
0.55-0.75
0.69-0.93
0.83-1.12
0.75-1.01
0.65-0.89
0.55-0.75
0.69-0.93
0.83-1.12
0.75-1.01
                                   8280 - 22
                                                          Revision      0
                                                          Date  September 1986

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     TABLE 4.  MEAN RELATIVE RESPONSE FACTORS OF CALIBRATION STANDARDS
Analyte
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
l,2,3,4,6,7,8-HpCDDb
OCDDb
2,3,7,8-TCDF
1,2,3,7, 8-PeCDF
1,2,3,4,7,8-HxCDF
l,2,3,4»6,7,8-HpCDFb
OCDFb
13C12-2,3,7,8-TCDD
13Ci2-l,2,3,4-TCDD
13Ci2-OCDD
RRFa
1.13
0.70
0.51
1.08
1.30
1.70
1.25
0.84
1.19
1.57
1.00
0.75
1.00
RSD%
(n - 5)
3.9
10.1
6.6
6.6
7.2
8.0
8.7
9.4
3.8
8.6
-
4.6
-
Quantltation 1on
(m/z)
322
356
390
424
460
306
340
374
444
408
334
334
472
aThe RRF value 1s the mean of the five determinations made.  Nominal weights
 injected were 0.2, 0.5, 1.0, 2,0 and 5.0 ng.

bRRF values for these analytes were determined relative to l3Ci2~OCDD.  All
 other RRF's were determined relative to 13Ci2-2,3,7,8-TCDD.

Instrument Conditions/Tune - GC/MS system was tuned as specified in
                             Paragraph 6.3.  RRF data was acquired under
                             SIM control, as specified in Paragraph 10.3.

GC Program - The GC column temperature was programmed as specified in
             Paragraph 4.3.2(b).
                                  8280 - 23
                                                         Revision
                                                         Date  September 1986

-------
TABLE 5.  PRECISION DATA FOR REVISED METHOD 8280
Compound
2,3,7,8-TCDD




1,2,3,4-TCDD




1,3,6,8-TCDD




1,3,7,9-TCDD




1,3,7,8-TCDD




1,2,7,8-TCDD




1,2,8,9-TCDD




Analyte
Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
son
sludge
fly ash
stm bottom
clay
soil
sludge
fly ash
still bottom
clay
son
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
level (ng/g)
Native
NDb
378
ND
ND
487
ND
ND
ND
38.5
ND
ND
ND
ND
19.1
227
ND
ND
ND
58.4
ND
ND
ND
ND
16.0
422
ND
ND
ND
2.6
ND
ND
ND
ND
ND
ND
Native
+ spike
5.0
378
125
46
487
5.0
25.0
125
38.5
2500
2.5
25.0
125
19.1
2727
2.5
25.0
125.0
58.4
2500
5.0
25.0
125
16.0
2920
5.0
25.0
125
2.6
2500
5.0
25.0
125
46
2500
N
4
4
4
2
4
3
4
4
4
4
4
4
4
2
2
4
4
4
2
2
4
4
4
4
2
4
4
4
3
2
4
4
4
2
2
Percent
RSD
4.4
2.8
4.8
-
24
1.7
1.1
9.0
7.9
-
7.0
5.1
3.1
-
-
19
2.3
6.5
_
-
7.3
1.3
5.8
3.5
_
7.7
9.0
7.7
23
-
10
0.6
1.9
_
_
                    8280 -  24
                                           Revision      0
                                           Dflte  September  1986

-------
TABLE 5  (Continued)
Compound
1,2,3,4,7-PeCDD




1,2,3,7,8-PeCDD




1,2,3,4,7,8-HxCDD




1,2,3,4,6,7,8-HpCDD




1,2,7,8-TCDF




1,2,3,7,8-PeCDF




1,2,3,4, 7, 8-HxCDF




Analyte
Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
stm bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge0
fly ash
still bottom
clay
soil
sludge
fly ash
stm bottom
clay
soil
sludge
fly ash
still bottom3
clay
soil
sludge
fly ash
still bottom
level (ng/g)
Native
ND
ND
ND
25.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8760
ND
ND
ND
ND
ND
7.4
ND
ND
ND
ND
ND
25600
ND
ND
13.6
24.2
ND
Native
+ spike
5.0
25.0
125
25.8
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
8780
-
-
5.0
25.0
125
7.4
2500
5.0
25.0
125
46
28100
5.0
25.0
139
24.2
2500
N
4
4
4
2
2
4
4
4
2
2
4
4
4
2
2
4
4
4
-
-
4
4
4
3
2
4
4
4
2
2
4
4
4
4
2
Percent
RSD
10
2.8
4.6
6.9
-
25
20
4.7
-
-
38
8.8
3.4
-
_
_
_
-
-
-
3.9
1.0
7.2
7.6
-
6.1
5.0
4.8
m
-
26
6.8
5.6
13.5

8280 - 25
Revision
0
                              Date   September 1986

-------
                            TABLE 5.   (Continued)


Compound
OCDF




Analyte

Matrix3
clay
soil
sludge
fly ash
still bottom
level (ng/g)
Native Percent
Native + spike N RSD
ND -
ND -
192 317 4 3.3
ND -
ND -
amatr1x types:
 clay:  pottery clay.
 soil:  Times Beach,  Missouri,  soil  blended  to  form a homogeneous sample.
This sample was analyzed as  a  performance evaluation sample for the Contract
Laboratory Program  (CLP)  in  April  1983.    The  results  from EMSL-LV and 8
contract laboratories using  the  CLP  protocol  were  305.8 ng/g 2,3,7,8-TCDD
with a standard deviation of 81.0.
 fly ash:  ash from a municipal Incinerator; resource recovery ash No. 1.
 still bottom:  distillation bottoms (tar) from 2,4-d1chlorophenol production.
sludge:    sludge   from  cooling   tower  which  received  both  creosote  and
pentachlorophenollc wastewaters.
Cleanup of clay, soil and fly ash samples was through alumina column only.
(Carbon column not  used.)
bND - not detected  at concentration  Injected (final volume 0.1 mL or greater).
GEst1mated concentration out of calibration range of standards.
                                  8280 - 26
                                                         Revision
                                                         Date  September  1986

-------
TABLE 6.  RECOVERY DATA FOR REVISED METHOD 8280
Compound
2,3,7,8-TCDD




1,2,3,4-TCDD




1,3,6,8-TCDD




1,3,7,9-TCDD




1,3,7,8-TCDD




1,2,7,8-TCDD




1,2,8,9-TCDD




Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
si udge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
Nat1veb
(ng/g)
ND
378
ND
ND
487
ND
ND
ND
38.5
ND
ND
ND
ND
19.1
227
ND
ND
ND
58.4
ND
ND
ND
ND
16.0
615
ND
ND
ND
2.6
ND
ND
ND
ND
ND
ND
Sp1kedc
level
(ng/g)
5.0
-
125
46
-
5.0
25.0
125
46
2500
2.5
25.0
125
46
2500
2.5
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
Mean
percent
recovery
61.7
_
90.0
90.0
-
67.0
60.3
73.1
105.6
93.8
39.4
64.0
64.5
127.5
80.2
68.5
61.3
78.4
85.0
91.7
68.0
79.3
78.9
80.2
90.5
68.0
75.3
80.4
90.4
88.4
59.7
60.3
72.8
114.3
81.2
                    8280 - 27
                                           Revision      0
                                           Date  September 1986

-------
TABLE 6.  (Continued)
Compound
1,2,3,4,7-PeCDD




1,2,3,7,8-PeCDD




1,2,3,4,7,8-HxCDD




1, 2,3,4,6, 7,8-HpCDD




2,3,7, 8-TCDD
(C-13)



1,2,7,8-TCDF




1,2,3, 7,8-PeCDF




Matrix3
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
stm bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge"
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
clay
soil
si udge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
Nat1veb
(ng/g)
ND
NO
ND
25.8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
8780
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
7.4
ND
ND
ND
ND
ND
25600
Sp1kedc
level
(ng/g)
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
-
-
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
5.0
25.0
125
46
2500
Mean
percent
recovery
58.4
62.2
79.2
102.4
81.8
61.7
68.4
81.5
104.9
84.0
46.8
65.0
81.9
125.4
89.1
ND
ND

_
-
64.9
78.8
78.6
88.6
69.7
65.4
71.1
80.4
90.4
104.5
57.4
64.4
84.8
105.8
-
       8280 - 28
                              Revision      0
                              Date  September 1986

-------
                            TABLE  6.   (Continued)

Compound
1,2,3,4,7,8-HxCDF




OCDF





Matrix9
clay
soil
sludge
fly ash
still bottom
clay
soil
sludge
fly ash
still bottom
Nat1veb
(ng/g)
ND
ND
13.6
24.2
ND
ND
ND
192
ND
ND
Sp1kedc
level
(ng/g)
5.0
25.0
125
46
2500
_
-
125
-
-
Mean
percent
recovery
54.2
68.5
82.2
91.0
92.9
_
-
86.8
-
-
amatrix types:

clay:  pottery clay.

soil:  Times Beach, Missouri soil blended  to form a homogeneous sample.  This
sample was  analyzed  as  a  performance  evaluation  sample  for the Contract
Laboratory Program (CLP)  1n  April  1983.    The  results  from EMSL-LV and 8
contract laboratories using  the  CLP  protocol  were  305.8 ng/g 2,3,7,8-TCDD
with a standard deviation of 81.0.

fly ash:  ash from a municipal Incinerator:  resource recovery ash No. 1.

still bottom:  distillation bottoms (tar) from 2,4-d1chlorophenol production.

sludge:    sludge  from  cooling   tower  which  received  both  creosote  and
pentachlorophenol wastewaters.

The clay, soil and fly ash  samples  were subjected to alumina column cleanup,
no carbon column was used.
       volume of concentrate 0.1 ml  or greater, ND means below quantification
limit, 2 or more samples analyzed.

cAmount of analyte added to sample, 2 or more samples analyzed.

^Estimated concentration out of calibration range of standards.
                                  8280 - 29
Revision
                                                                       0
                                                                        _
                                                               September 1986

-------
          TABLE 7.   LINEAR RANGE AND VARIATIOIN  OF  RESPONSE  FACTORS
Analyte Linear range tested (pg) n&
l,2,7,8-TCDFa
2,3,7,8-TCDDa
2,3,7,8-TCDF
50-6000
50-7000
300-4000
8
7
5
Mean RF
1.634
0.721
2.208
XRSD
12.0
11.9
7.9
aResponse factors for these analytes were calculated using 2,3,7,8-TCDF as  the
Internal standard.  The response  factors for 2,3,7,8-TCDF were calculated  vs.
13Ci2-l,2,3,4-TCDD.

^Each value of n represents a different concentration level.
                                  8280 - 30
                                                         Revision
                                                         Date  September 1986

-------
   TABLE 8.  METHOD DETECTION LIMITS OF   C12 - LABELED FOOD'S and PCDF'S

             IN REAGENT WATER (PPT) AND ENVIRONMENTAL SAMPLES (PPB)
13C --Labeled
Amlyte
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
l,2,3,6»7»8-H*Q»
l,2»3,4,6»7,8H3pCDD
ODD
2,3,7,8-TCDF
1,2,3,7,8-BeCDF
1,2,3,4,7,8-ftcGDF
Reagent
Water3
0.44
1.27
2.21
2.77
3.93
0.63
1.64
2.53
Missouri
Sol?
0.17
0.70
1.25
1.87
2.35
O.U
0.33
0.83
f?
Ash
0.07
0.25
0.55
1.41
2.27
0.06
0.16
0.30
Industrial
Sludge
0.82
1.34
2.30
4.65
6.44
0.46
0.92
2.17
Still-d
Bottom
1.81
2.46
6.21
4.59
10.1
0.26
1.61
2.27
Fuel
Oil5
0.75
2.09
5.02
8.14
23.2
0.48
0.80
2.09
Fuel
Saudi
0.1
0.1
0.2
0.5
1.4
0.4
0.4
2.2
a
, Sample size 1 ,000 mL.
 Sample size 10 g.
.Sample size 2 g*
 Sample size 1 g.
Note:  The final sample-extract volume was 100 uL for all samples.

Matrix types used in MDL Study:

     - Reagent water:  distilled, deionized laboratory water.
     - Missouri soil:  soil blended to form a homogeneous sample.
     - Ply-ash:  alkaline ash recovered from the electrostatic precipitator of
       a coal-burning power plant.
     - Industrial sludge:  sludge from  cooling tower which received creosotic
       and pentachlorophenolic wastewaters.  Sample  was ca_. 70 percent water,
       mixed with oil and sludge*
     - Still-bottom:    distillation  bottoms  (tar)  from  2,4-dichlorophenol
       production.
     - Fuel oil:  wood-preservative solution from the modified Thermal Process
       tanks.  Sample  was  an  oily  liquid  (>90  percent oil) containing no
       water.
     - Fuel oil/Sawdust:  sawdust was obtained  as a very fine powder from the
       local lumber yard.   Fuel  oil  (described  above)  was  mixed at the 4
       percent (w/w) level.

Procedure used for the Determination  of  Method Detection Limits was obtained
from "Methods  for  Organic  Chemical  Analysis  of  Municipal  and Industrial
Wastewater" Appendix A, EPA-600/4-82-057,  July  1982.   Using this procedure,
the method detection  limit  is  defined  as  the  minimum  concentration of a
substance that can be measured  and  reported  with 99 percent confidence that
the value is above zero.
                                  8280 - 31
                                                         Revision      0	
                                                         Date  September 1986

-------
 I

O
 aaoi-8'£'rz
  dQ01-8'£'rZ
                                                      co

                                                      V

                                                      V

                                                      ?
                                                      O
                                                      U

                                                      u.
                                                      Q
and
matogram of Selected
Mass Ch
          CM




          1
          O)
o£
                     8280 - 32
                                      Revision    0

                                      Date September 1986

-------
                             METHOD B280

POLYCHUORINATEO OIBCNZQ-P-OIOXIINS AND POLYCHLOHINATEO DXBENZONFUBANS
f     Start      J
  6. 1
 Perform Initial
 calibration on
  GC/MS system
  S.9
                                                      10. Z
     Calculate
     response
   factors for
    standards
   Do routine
   calibrotion
                                                      10.3
      Analyze
   samples with
   selected ion
    monitoring
  9.2 i
      I  Extract
    • article using
    appropriate
  method for the
   waste matrix
  9.9
       Prepare
  carbon column;
     do carbon
  column cleanup
                                                      10.5
Quantitate PGOO
 and PCDF peaks
                                                Yes
    Q
    Determine
 concentrations
   and report.
    result*
                                                   f     Stop       J
                                   8280 - 33
                                                             Revision       Q
                                                             Date  September 1986

-------

-------
                                 APPENDIX A

                    SIGNAL-TO-NOISE DETERMINATION METHODS
MANUAL DETERMINATION

     This method corresponds to a manual determination of the S/N from a GC/MS
signal, based on the measurement of  Its  peak height relative to the baseline
noise.  The procedure Is composed of  four steps as outlined below.  (Refer to
Figure 1 for the following discussion).

     1.   Estimate the peak-to-peak noise (N) by tracing the two lines (Ei and
          £3) defining the noise envelope.   The lines should pass through the
          estimated statistical mean  of  the  positive  and the negative peak
          excursions as shown In Figure 1.  In addition, the signal offset (0)
          should be set high enough such that negative-going noise (except for
          spurious negative spikes) 1s recorded.

     2.   Draw the  line   (C)  corresponding  to  the  mean  noise between the
          segments defining the noise envelope.

     3.   Measure the height of the GC/MS  signal  (S) at the apex of the peak
          relative to the mean noise C.   For noisy GC/MS signals, the average
          peak height should be measured from the estimated mean apex signal D
          between £3 and £4.

     4.   Compute the S/N.

     This method of  S/N  measurement   1s  a  conventional, accepted method of
noise  measurement 1n analytical chemistry.


INTERACTIVE  COMPUTER GRAPHICAL METHOD

     This method calls for  the  measurement  of  the GC/MS peak area using the
computer data system and Eq. 1;
                                    A/t
                         S/N = Aj/2t +  Ar/2t
where  t  is the elutlon time window   (time  interval, t£-t2, at the base of the
peak used to measure  the peak area A).   (Refer to Figure 2, for the following
discussion).

     AI  and Ar correspond to the areas  of  the noise level in a region to the
left (Ai) and to the  right (Ar) of the GC peak of interest.
                                8280 - A -  1
                                                         Rev 1 s1on      0
                                                         Date  September 1986

-------
     The  procedure to  determine  the  S/N  1s  as  follows:

     1.    Estimate the average negative   peak   excursions  of the noise  (I.e.,
          the low segment-E2~of   the  noise envelope).    Line  £2  should pass
          through the  estimated  statistical  mean  of the  negative-going noise
          excursions.   As  stated earlier,   1t   1s  Important  to have the  signal
          offset  (0)   set  high  enough such  that  negative-going  noise  Is
          recorded.

     2.    Using the cross-hairs   of   the video display terminal,  measure the
          peak area (A)  above a  baseline   corresponding  to the mean  negative
          noise value  (£2) and between the  time tj and  t2  where  the GC/MS peak
          Intersects the baseline, £2-  Make note  of the time width t-t2-tj.

     3.    Following a  similar procedure   as described  above, measure  the area
          of the noise In  a region to the   left (Aj) and  to the right (Ar)  of
          the GC/MS signal using a time  window twice the size of t, that Is,
          2 x t.

     The analyst must  sound  Judgement  1n   regard  to  the proper  selection  of
Interference-free regions   1n  the  measurement  of  Aj and Ar.     It  1s not
recommended to perform these noise measurements  (Aj and Ar) 1n  remote regions
exceeding ten time widths  (lOt),

     4.    Compute the S/N  using Eq.  1.

     NOTE:  If the noise does not occupy  at  least  10  percent  of  the vertical
            axis  (I.e., the noise envelope cannot be defined accurately),  then
            1t 1s necessary to  amplify  the  vertical   axis so that the noise
            occupies 20 percent of the terminal display (see Figure 3).
                                8280 - A - 2
                                                         Revision
                                                         Date  September 1986

-------
                               FIGURE CAPTIONS

Figure 1,  Manual  determination of S/N.
           The peak height (S)  Is measured between the mean noise (lines C and
           D).  These mean  signal  values  are  obtained  by tracing the line
           between the baseline average  noise extremes, Ej and £2,  and between
           the apex average noise  extremes,  £3  and  £4,  at the  apex of the
           signal.  Note,  1t  Is  Imperative  that the Instrument's Interface
           amplifier electronlc's zero  offset  be  set  high enough such that
           negative-going baseline noise 1s recorded.

Figure 2.  Interactive determination of  S/N.
           The peak area (A) 1s  measured  above the baseline average negative
           noise E£ and between times t\  and  t£.  The noise Is obtained from
           the areas Aj and Ar measured   to  the  left and to the right of the
           peak of Interest using time windows Tj and Tr (Ti=Tr=2t).

Figure 3.  Interactive determination of  S/N.
           A) Area measurements  without  amplification  of the vertical axis.
           Note that  the  noise  cannot  be  determined  accurately by visual
           means.    B)  Area  measurements  after  amplification  (10X) of the
           vertical axis so  that  the  noise  level occupies approximately 20
           percent of the display, thus  enabling a better visual estimation of
           the baseline noise,  E\, £2, and C.
                                8280 - A
                                                         Revision      0
                                                         Date  September 1986

-------
     00
     f\>
     00
     o

     I

     >

     I
O SO


r+ <
 I O
» 3
CT
n>
                   20:00
22:00
24:00
26:00
28:00
30:00
«o
00
                                                    1.  Manual Determination of S/N.

-------
          = 558.10
                               t = t2
                                 = Tr = 2T
                                     14.7
                    Ar = 88.55
26:30 26:00  26:30
27:00   27:30 28:00
              17 sec.
  Figure 2.  Interactive Determination of S/N.
             8280 - A - 5
                                 Revision    p
                                 Date  September 1986

-------
100-n
90-
80-
70-
60-
§0-
40-
30-
20-
10-

(* = 686.41
®




Ar= 13.32
*-Ar
r
• iMwh Ml
T • I 1 i «
  25:30  26:00  36:30  27:00  27:30  28:00
                       = 706.59
  26:30  26:00  26:30  27:00  27:30  28:00
Figure  3.  Interactive Determination of S/N.
              8280 - A - 6
                                     Revision      0
                                     Date  September 1986

-------
                                 APPENDIX B

        RECOMMENDED SAFETY AND HANDLING PROCEDURES FOR PCDD'S/PCDF'S


     1.  The human toxicology  of  PCDD/PCDF  1s  not well  defined at present,
although the 2,3,7,8-TCDD Isomer has been found to be acnegenlc,  carcinogenic,
and teratogenlc In the course of  laboratory animal studies.  The 2,3,7,8-TCDD
1s a solid at room temperature, and  has a relatively low vapor pressure.   The
solubility of this compound 1n water Is only about 200 parts-per-tr1H1on,  but
the solubility 1n various organic  solvents  ranges from about 0.001 perent to
0.14 percent.  The physical properties  of  the 135 other tetra- through octa-
chlorlnated PCDD/PCDF have not been  well established, although 1t 1s presumed
that the physical properties of these congeners are generally similar to those
of the 2,3,7,8-TCDD Isomer.  On  the  basis of the available toxlcologlcal  and
physical property data for TCDD, this compound,  as well as the other PCDD and
PCDF, should be handled only  by  highly  trained personnel who are thoroughly
versed 1n the appropriate procedures, and who understand the associated risks.

     2.  PCDD/PCDF and samples  containing these are handled using essentially
the same techniques as  those  employed  In handling radioactive or Infectious
materials.  Well-ventHated, controlled-access  laboratories are required,  and
laboratory personel entering these laboratories should wear appropriate safety
clothing, Including disposable coveralls,  shoe  covers,  gloves, and face and
head masks.  During analytical operations  which  may give rise to aerosols or
dusts,  personnel  should  wear  respirators  equipped  with  activated carbon
filters.  Eye protection equipment (preferably full face shields) must be warn
at all  times  while  working  1n  the  analytical  laboratory with PCDD/PCDF.
Various  types  of  gloves  can  be  used  by  personnel,  depending  upon the
analytical operation being accomplished.  Latex gloves are generally utilized,
and when handling samples thought  to be particularly hazardous, an additional
set of gloves are also  worn  beneath  the  latex gloves (for example, Playtex
gloves supplied by American Scientific  Products, Cat. No. 67216).  Bench-tops
and other work surfaces  1n  the  laboratory  should  be covered with plastic-
backed absorbent paper during all  analytical processing.  When finely divided
samples  (dusts, soils, dry  chemicals)  are  processed,  removal of these from
sample  contaners,  as   well   as   other   operations,   Including  weighing,
transferring, and mixing with  solvents,  should  all be accomplished within a
glove box.  Glove boxes, hoods  and the effluents from mechanical vacuum pumps
and gas chromatographs  on  the  mass  spectrometers  should  be vented to the
atmosphere preferably only after passing  through HEPA particulate filters and
vapor-sorblng charcoal.

     3.  All laboratory  ware,  safety  clothing,   and other  Items potentially
contaminated with  PCDD/PCDF   In  the  course   of   analyses   must be carefully
secured and  subjected to proper  disposal.    When  feasible,  liquid wastes are
concentrated, and  the residues  are  placed  1n approved steel hazardous waste
drums  fitted with  heavy   gauge  polyethylene   liners.   Glass and combustible
Items  are  compacted  using  a dedicated  trash compactor  used only  for hazardous
waste  materials  and  then placed 1n   the   same  type  of disposal drum.  Disposal
of  accumulated  wastes  1s   periodically accomplished  by   high  temperature
Incineration at  EPA-aproved facilities.


                                8280 - B - 1
                                                         Revision      0
                                                         Date September 1986

-------
     4.  Surfaces of laboratory benches,  apparatus and other appropriate areas
should be periodically subjected  to  surface  wipe tests using solvent-wetted
filter paper which 1s then  analyzed  to  check for PCDD/PCDF contamination 1n
the laboratory.  Typically, 1f the detectable  level  of TCDD or TCDF from such
a test Is greater than 50  ng/m2,  this Indicates the need for decontamination
of the laboratory.  A typical  action  limit 1n terms of surface contamination
of the other PCDD/PCDF (summed) 1s 500 ng/m2.   In the event of a spill  within
the laboratory, absorbent paper 1s  used  to  wipe up the spilled material and
this is then placed into a hazardous  waste drum.  The contaminated surface is
subsequently  cleaned  thoroughly   by   washing   with  appropriate  solvents
(methylene chloride followed by methanol)  and laboratory detergents.  This 1s
repeated until wipe tests  Indicate  that  the levels of surface contamination
are below the limits cited.

     5.  In  the  unlikely  event  that  analytical  personnel experience skin
contact with PCDD/PCDF   or  samples  containing  these, the contaminated skin
area should Immediately  be  thoroughly  scurbbed  using  mild soap and water.
Personnel involved 1n any such  accident  should  subsequently be taken to the
nearest medical facility, preferably  a  facility whose staff is knowledgeable
in  the  toxicology  of   chlorinated   hydrocarbons.     Again,  disposal  of
contaminated clothing 1s accomplished by placing 1t 1n hazardous waste drums.

     6.    It  1s  desirable  that  personnel  working  in  laboratories where
PCDD/PCDF are  handled  be  given  periodic  physical  examinations  (at least
yearly).  Such examinations  should  Include  specialized tests, such as those
for urinary porphyrins  and  for  certain  blood  parameters which, based upon
published clinical  observations,  are  appropriate  for  persons  who  may be
exposed to PCDD/PCDF.  Periodic  facial  photographs  to document the onset of
deriatologlc problems are also advisable.
                                 8280 - B - 2
                                                          Revision
                                                         Date  September  1986

-------
                                                                   Page 1 of 2



                   DIOXIN SAMPLE DATA SUMMARY FORM 8280-1



LAB NAME 	     CONTRACT No.	


CASE No, 	

                                          QUANTITY FOUND (ng/g)


SAMPLE NO.     FILE NAME       TCDD      PeCDD      HxCDD      HpCDD      OCDD
DATA  RELEASE AUTHORIZED  BY
                                8280 -  B -  3
                                                          Revision       0
                                                          Date   September  1986

-------
                                                                   Page  2  of  2



                   DIOXIN SAMPLE DATA SUMMARY FORM 8280-1



LAB NAME 	      CONTRACT No.  	


CASE No. 	

                                          QUANTITY FOUND (ng/g)


SAMPLE NO.     FILE NAME       TCDF      PeCDF      HxCDF      HpCDF      OCDF
                                 8280 - B - 4
                                                          Revision
                                                          Date   September 1986

-------
                                                                   Page 1 of 2
                  DIOXIN SAMPLE DATA SUMMARY FORM 8280-1-W
LAB NAME
CONTRACT No.
CASE No.
                                          QUANTITY FOUND (ug/L)
SAMPLE NO.     FILE NAME       TCDD      PeCDD      HxCDD      HpCDD      OCDD
 DATA  RELEASE AUTHORIZED  BY
                                 8280 -  B -  5
                                                          Revision       0
                                                          Date   September  1986

-------
                                                                   Page  2 of 2



                  DIOXIN SAMPLE DATA SUMMARY FORM 8280-1-W



LAB NAME 	      CONTRACT No.  	


CASE No. 	

                                          QUANTITY FOUND (ug/L)


SAMPLE NO.     FILE NAME       TCDF      PeCDF      HxCDF      HpCDF      OCDF
                                 8280 - B - 6
                                                          Revision
                                                          Date   September  1986

-------
                     DIOXIN RAW SAMPLE DATA FORM 8280-2
LAB NAME  	  ANALYST(s) 	  CASE No.
SAMPLE No.	  TYPE OF SAMPLE 	CONTRACT No,


SAMPLE SIZE           % MOISTURE 	  FINAL EXTRACT VOLUME
EXTRACTION METHOD 	ALIQUOT USED FOR ANALYSIS


CLEAN UP OPTION 	
CONCENTRATION FACTOR	 DILUTION FACTOR


DATE EXTRACTED              	     DATA ANALYZED
VOLUME 13Ci2-l»2,3,4-TCDD ADDED 	 TO SAMPLE VOLUME
VOLUME INJECTED 	Vlt 13Ci2-l,2,3,4-TCDD ADDED
Wt l3Ci2-2,3,7,8-TCDD ADDED 	 13Ci2-2,3,7,8-TCDD % RECOVERY


Wt 13Ci2-2,3,7,8-OCDD ADDED 	 13C12-OCDD % RECOVERY 	
 13C12-2,3,7,8-TCDD  RRF 	   13Ci2-OCDD RRF 	

                              13Ci2-2,3,7(8-TCDD

 AREA  332 	AREA  334	 RATIO 332/334 _


 !3Ci2-OCDD AREA 470 	 AREA 472 	   RATIO 470/472


 RT 2,3,7,8-TCDD (Standard) 	 RT 2,3,7,8-TCDD  (Sample) 	


 13Ci2-2,3,7,8-TCDD  -  13Ci2-l,2»3,4-TCDD Percent  Valley 	
                                 8280 -  B -  7
                                                          Revision
                                                         Date  September  1986

-------
              DIOXIN INITIAL CALIBRATION STANDARD DATA SUMMARY

                                 FORM 8280-3

                                          CASE No.
Lab Name
Date of Initial Calibration

Relative to 13Ci2-2,3,7,8-
                        Contract No.

                        Analyst(s)	
CALIBRATION
STANDARD
                                              or 13C12-1,2,3,4-TCDD_
RRF
 1
                           RRF
                            2
RRF   RRF
 3     4
RRF
 5
MEAN    %RSD
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
 PeCDF
 HxCDF
 HpCDF
 OCDF
                                 8280 - B - 8
                                                          Revision      0
                                                          Date  September 1986

-------
                           FORM 8280-3 (Continued)


                           CONCENTRATIONS IN PG/UL

                  1        2345
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
PeCOF
HxCDF
HpCDF
OCDF
                                 8280 - B - 9
                                                          Revision
                                                          Date  September 1986

-------
                    DIOXIN CONTINUING CALIBRATION  SUMMARY

                                 FORM 8280-4


                                         CASE No.
Lab Name 	     Contract No.

Date of Initial Calibration 	     Analyst(s)	

Relative to 13Ci2-2,3(7,8-TCDD	     or
COMPOUND             RRF             RRF               %D
TCDD
PeCDD
HxCDD
HpCDD
OCDD
TCDF
 PeCDF
 HxCDF
 HpCDF
 OCDF
                                 8280 - B - 10
                                                          Revision
                                                         Date   September  1986

-------
                    DIOXIN RAW SAMPLE DATA FORM 8280-5-A
LAB NAME
ANALYST(s)
           CASE No.
CONTRACT No.
                 SAMPLE No.
TCDD REQUIRED 320/322 RATIO WINDOW IS 0.65 - 0.89
QUANTITATED FROM 2,3,7,8-TCDD

SCAN I  RRT   AREA       AREA
              322        320
         AREA
         257
1,2,3,4-TCDD

     320/
     322
                                      RRF
CONFIRM
AS TCDD
  Y/N      CONG.
                                             TOTAL  TCDD
 TCDF  REQUIRED 304/306  RATIO WINDOW IS  0.65  -  0.89

 QUANTITATED FROM  2,3,7,8-TCDD 	 1,2,3,4-TCDD
                                        RRF
 SCAN  I   RRT   AREA       AREA       AREA       304/
               306        304        243         306
                               CONFIRM
                               AS TCDD
                                 Y/N      CONC.
                                             TOTAL TCDD
                                 8280 - B - 11
                                                          Revision      0
                                                          Date   September 1986

-------
                    DIOXIN RAW SAMPLE DATA FORM 8280-5-B
LAB NAME
            ANALYST(s)
                            CASE No.
CONTRACT No.
                             SAMPLE No.
PeCDD REQUIRED 320/322 RATIO WINDOW IS 0.55 - 0.75
QUANTITATED FROM 2,3,7,8-TCDD

SCAN #  RRT   AREA      AREA
              356       358
                    AREA
                    354
                            1,2,3,4-TCDD
                    AREA
                    293
                  3587
                  356
                                         RRF
                  CONFIRM
                  AS  PeCDD
                   Y/N
                                                                         CONC.
                                           TOTAL  PeCDD
 PeCDF  REQUIRED  342/340  RATIO WINDOW  IS  0.55  - 0.75

 QUANTITATED  FROM 2,3,7,8-TCDD  	  1,2,3,4-TCDD

 SCAN #  RRT
AREA
340
AREA
342
AREA
338
AREA
277
3427
340
                                                    RRF
CONFIRM
AS PeCDF
  Y/N
                                                                          CONC.
                                            TOTAL PeCDF
                                 8280 - B - 12
                                                          Revision       0
                                                          Date   September  1986

-------
                    DIOXIN RAW SAMPLE DATA FORM 8280-5-C
LAB NAME
ANALYST(s)
         CASE No.
CONTRACT No.
                  SAMPLE No.
HxCDD REQUIRED 392/390 RATIO WINDOW IS 0.69 - 0.93
QUANTITATED FROM 2,3,7,8-TCDD

SCAN I  RRT   AREA      AREA
              390       392
                1,2,3,4-TCDD
       AREA
       388
AREA
327
3927
390
                     RRF
CONFIRM
AS HxCDD
  Y/N
                                                                         CONC.
                                           TOTAL HxCDD

HxCDF REQUIRED 376/374
QUANTITATED FROM 2,3,7,
SCAN # RRT AREA
376
RATIO WINDOW IS
8-TCDD
AREA
374
0.69 - 0.93

1,2,3,4-TCDD
AREA
372
AREA
311
3767
374

RRF
CONFIRM
AS HxCDF
Y/N CONC.
                                           TOTAL  HxCDF
                                 8280 - B - 13
                                                          Revision       0
                                                          Date   September  1986

-------
                    DIOXIN RAW SAMPLE DATA FORM 8280-5-D
LAB NAME
ANALYST(s)
         CASE No.
CONTRACT No.
                  SAMPLE No.
HpCDD REQUIRED 426/444 RATIO WINDOW IS 0.83 -1.12
QUANTITATED FROM 2,3,7,8-TCDD

SCAN I  RRT   AREA      AREA
              424       426
                1,2,3,4-TCDD
       AREA
       422
AREA
361
426/
424
                     RRF
CONFIRM
AS HpCDD
  Y/N
                                                                         CONC.
                                           TOTAL HpCDD

HpCDF REQUIRED 410/408
QUANTITATED FROM 2,3,7
SCAN I RRT AREA
408
RATIO WINDOW IS
,8-TCDD
AREA
410
AREA
406
0.83 - 1.12
1,2, 3, 4-TCDD
AREA
345
4107
408
RRF
CONFIRM
AS HpCDF
Y/N CONC.
                                           TOTAL HpCDF
                                 8280 - B - 14
                                                          Revision      0
                                                          Date  September 1986

-------
                    DIOXIN RAW SAMPLE DATA FORM 8280-5-E
LAB NAME
 ANALYST(s)
                 CASE No.
CONTRACT No.
                    SAMPLE No.
OCDD REQUIRED 458/460 RATIO WINDOW IS 0.75 - 1.01
QUANTITATED FROM 2,3,7,8-TCDD
SCAN I  RRT   AREA
              460
AREA
458
AREA
395
1,2,3,4-TCDD

    458/
    460
                                       RRF
CONFIRM
AS OCDD
  Y/N      CONC.
                                           TOTAL OCDD
OCDF REQUIRED 442/444 RATIO WINDOW IS 0.75 - 1.01

QUANTITATED FROM 2,3,7,8-TCDD	  1,2,3,4-TCDD
                                        RRF
SCAN I  RRT   AREA
              444
AREA
442
AREA
379
    442/
    444
CONFIRM
AS OCDF
  Y/N      CONC,
                                           TOTAL OCDF
                                 8280 - B - 15
                                                          Revision       0
                                                          Date   September  1986

-------
            DIOXIN SYSTEM PERFORMANCE CHECK ANALYSIS FORM 8280-6
LAB NAME
                   CASE No.
BEGINNING DATE

ENDING DATE
       TIME

       TIME
                   CONTRACT No..

                    ANALYST(s)  .
PC SOLUTION IDENTIFIER
PCDD's
                       ISOTOPIC RATIO CRITERIA MEASUREMENT
  IONS
RATIOED
RATIO AT
BEGINNING OF
12 HOUR PERIOD
RATIO AT
END OF 12   ACCEPTABLE
HOUR PERIOD   WINDOW
Tetra
320/322
                               0.65-0.89
Penta
358/356
                               0.55-0.75
Hexa
392/390
                               0.69-0.93
Hepta
426/424
                               0.83-1.12
Octa
458/460
                               0.75-1.01
 PCDF's

 Tetra
304/306
                               0.65-0.89
 Penta
342-340
                               0.55-0.75
 Hexa
376-374
                               0.69-0.93
 Hepta
410/408
                               0.83-1.12
 Octa
442/444
                               0.75-1.01
 Ratios  out of criteria
 PCDD

 PCDF
      Beginning

      _ out of

       out of
                            End

                           out of

                           out of
 NOTE:  One form 1s required for each 12 hour period samples are analyzed.
                                 8280 - B - 16
                                                          Revision      0
                                                          Date  September 1986

-------
                                  METHOD 8290

    POLYCHLORINATED DIBENZODIOXINS  fPCDDs) AND POLYCHLORINATED DIBENZOFURANS
          (PCDFs)BY HIGH-RESOLUTION GAS CHROHATOGRAPHY/HIGH-RESOLUTIQN
                         MASS SPECTROHETRY (HRGC/HRHS)
 1.0   SCOPE AND APPLICATION

      1.1   This method provides procedures for the detection and quantitative
 measurement of polychlorinated dibenzo-p-dioxins (tetra-  through octachlorinated
 homologues;   PCDDs),   and   polychlorinated  dibenzofurans   (tetra-  through
 octachlorinated homologues; PCDFs)  in a variety of environmental matrices  and at
 part-per-trillion  (ppt)  to  part-per-quadrillion  (ppq)  concentrations.   The
 following compounds can be determined by this method:
                        Compound Name
CAS No*
2,3,7,8-Tetrachlorodibenzo-p-dioxfn (TCDD)
1,2,3,7,8-Pentachlorodibenzo-p-dioxin (PeCDD)
1,2, 3, 6, 7, 8-Hexachl orodi benzo-p~dioxin (HxCDD)
1,2, 3, 4, 7, 8-Hexachl orodi benzo-p-di oxi n (HxCDD)
1,2, 3, 7, 8, 9-Hexachl orodi benzo-p-di oxi n (HxCDD)
1,2,3,4,6,7,8-Heptachlorodibenzo-p-dioxin (HpCDD)
1,2,3,4,6,7,8,9-Octachlorodibenzo-p-dioxin (OCDD)
2,3,7, 8-Tetrachl orodi benzof uran (TCDF)
1,2,3,7,8-Pentachlorodibenzofuran (PeCDF)
2,3,4,7 , 8- Pentachl orodi benzof uran ( PeCDF )
1,2,3,6, 7 ,8-Hexachl orodi benzof uran (HxCDF)
1,2,3, 7 ,8,9-Hexachl orodi benzof uran (HxCDF)
1,2,3,4,7, 8-Hexachl orodi benzof uran (HxCDF)
2,3,4,6,7, 8-Hexachl orodi benzof uran (HxCDF )
1 , 2, 3, 4, 6, 7 ,8-Heptachlorodi benzofuran (HpCDF)
1,2,3,4,7,8, 9 -Heptachl orodi benzofuran (HpCDF)
1,2,3,4,6,7,8,9-Qctachlorodibenzofuran (OCDF)
1746-01-6
40321-76-4
57653-85-7
39227-28-6
19408-74-3
35822-39-4
3268-87-9
51207-31-9
57117-41-6
57117-31-4
57117-44-9
72918-21-9
70648-26-9
60851-34-5
67562-39-4
55673-89-7
39001-02-0
      3     Chemical Abstract Service Registry Number

      1.2   The  analytical  method calls  for the  use  of  high-resolution gas
chromatography and  high-resolution  mass spectrometry  (HRGC/HRMS)  on purified
sample  extracts.    Table  1  lists  the  various  sample types  covered  by this
analytical protocol, the 2,3,7,8-TCDD-based method cal ibration limits (MCLs), and
other  pertinent  information.   Samples  containing concentrations  of specific
congeneric analytes (PCDDs and PCDFs) considered within the  scope of this method
that are greater than ten times the  upper MCLs  must  be analyzed  by a protocol
designed for such concentration levels,  e.g., Method 8280.   An optional method
for reporting the analytical results using a 2,3,7,8-TCDD toxicity equivalency
factor (TEF) is described.
                                   8290 - 1
       Revision 0
   September 1994

-------
       1.3   The sensitivity of this method  is dependent upon the level  of  inter-
ferences within a given matrix.  The calibration range of the method  for all
water  sample is 10 to 2000 ppq  for TCDD/TCDF and PeCDD/PeCDF, and 1.0 to 200 ppt
for  a  10 g soil,  sediment,  fly ash,  or  tissue sample for  the same analytes
(Table 1).  Analysis of a one-tenth aliquot of the sample permits measurement of
concentrations up to 10 times the upper MCL,  The actual limits  of detection and
quantitation will differ from the lower MCL,  depending on the complexity  of the
matrix.

       1.4   This method is designed for use by analysts who  are experienced with
residue analysis and skilled in HRGC/HRMS.

       1.5   Because  of the  extreme  toxicity  of many of these  compounds,  the
analyst must  take  the necessary precautions to  prevent  exposure  to materials
known  or believed to contain PCDDs or  PCDFs.   It is the  responsibility of the
laboratory personnel to ensure  that safe handling procedures are employed.  Sec.
11 of this method discusses safety procedures.


2.0   SUMMARY OF METHOD

      2.1   This procedure  uses matrix specific extraction,  analyte  specific
cleanup,  and HRGC/HRMS analysis techniques.

      2.2   If  interferences   are  encountered,  the  method  provides  selected
cleanup  procedures  to  aid  the analyst  in their  elimination.   A simplified
analysis flow chart is presented at the end of this method.

      2.3   A specified amount  (see Table  1)  of soil, sediment,  fly  ash, water,
.sludge (including paper pulp),  still bottom, fuel oil, chemical reactor residue,
fish tissue,  or human adipose tissue  is spiked  with  a  solution containing
specified amounts of each of the nine  isotopically (13C12)  labeled  PCDDs/PCDFs
listed in Column  1  of Table 2,  The sample is  then extracted  according to a
matrix specific extraction procedure. Aqueous samples that are judged to contain
1  percent or  more  solids,  and  solid samples  that  show an  aqueous phase,  are
filtered, the  solid  phase (including the filter) and the aqueous  phase extracted
separately,  and the extracts combined  before  extract  cleanup.   The extraction
procedures are:

      a)     Toluene:  Soxhlet extraction  for  soil,  seaiment, fly asn, ana paper
            pulp samples;

      b)     Methylene chloride:  liquid-liquid extraction for water samples;

      c)     Toluene:   Dean-Stark extraction  for fuel oil,  and  aqueous sludge
            samples;

      d)     Toluene extraction for still bottom samples;

      e)     Hexane/methylene   chloride:     Soxhlet  extraction  or  methylene
            chloride:  Soxhlet extraction for fish tissue samples;  and

      f)     Methylene chloride extraction for human adipose tissue  samples.
                                   8290 - 2
    Revision 0
September 1994

-------
      g)    As an option, all solid  samples  (wet or dry) may be extracted with
            toluene using a Soxhlet/Dean Stark extraction system.

      The decision  for the  selection of an  extraction  procedure for chemical
reactor residue samples is based on  the appearance (consistency, viscosity) of
the samples.  Generally, they can be  handled according to the procedure used for
still bottom  (or chemical sludge) samples.

      2.4   The extracts  are  submitted to an  acid-base washing treatment and
dried.  Following  a  solvent exchange  step, the extracts are cleaned  up by column
chromatography on alumina, silica gel, and activated carbon.

            2.4.1 The  extracts  from  adipose  tissue  samples are  treated  with
      silica gel  impregnated with sulfuric  acid before chromatography on acidic
      silica gel,  neutral  alumina, and activated carbon.

            2.4.2 Fish tissue and paper pulp extracts are subjected to an acid
      wash  treatment  only,  prior to chromatography  on  alumina and activated
      carbon.

      2.5   The preparation  of  the  final  extract  for  HRGC/HRMS  analysis  is
accomplished  by  adding  10  to  50 pL (depending  on  the  matrix)  of  a  nonane
solution containing 50 pg/juL  of the  recovery  standards 13C12-1,2,3,4-TCDD and
13C12-l,2,3,7,8,9-HxCDD (Table 2).  The former is used to determine the percent
recoveries of tetra- and pentachlorinated PCDD/PCDF congeners, while the latter
is  used  to  determine  the  percent  recoveries  of  the   hexa-,  hepta-  and
octachlorinated PCDD/PCDF congeners.

      2.6   Two pi  of  the concentrated  extract are  injected into an HRGC/HRMS
system capable of performing selected ion monitoring at resolving powers of at
least 10,000  (10 percent valley definition).

      2.7   The  identification   of   OCDD  and  nine  of  the fifteen  2,3,7,8-
substituted congeners   (Table 3), for which a  13C-labeled standard is available
in the sample fortification  and  recovery standard  solutions  (Table  2), is based
on their elution at their exact retention time (within 0.005 retention time units
measured in the routine calibration)  and the simultaneous detection of the two
most abundant  ions  in the molecular ion  region.   The  remaining  six 2,3,7,8-
substituted congeners  (i.e.,  2,3,4,7,8-PeCDF;  1,2,3,4,7,8-HxCDD; 1,2,3,6,7,8-
HxCDF; 1,2,3,7,8,9-HxCDF; 2,3,4,6,7,8-HxCDF, and 1,2,3,4,7,8,9-HpCDF), for which
no carbon-labeled internal standards  are available in the sample fortification
solution,  and all  other PCDD/PCDF congeners are identified when their relative
retention times fall within their respective PCDD/PCDF retention time windows,
as established from  the routine calibration data,  and the simultaneous detection
of the two most abundant ions in the molecular ion region.  The identification
of OCDF  is based on its retention time relative to 13C12-OCDD and the simultaneous
detection  of  the  two most  abundant  ions   in  the  molecular   ion  region.
Identification also  is based on  a comparison of the ratios of the integrated ion
abundance of the molecular ion species to their theoretical  abundance ratios.

      2.8   Quantisation of the individual  congeners, total PCDDs and total PCDFs
is achieved in conjunction with  the  establishment  of a multipoint (five points)
                                   8290 - 3                         Revision 0
                                                                September 1994

-------
 calibration curve for each homologue, during which each calibration solution is
 analyzed  once.


 3.0    INTERFERENCES

       3,1   Solvents, reagents, glassware and other sample processing hardware
 may  yield discrete artifacts  or  elevated  baselines that may  cause  misinter-
 pretation of  the  chromatographic  data  (see  references  1  and  2.)   All  of these
 materials must be demonstrated to  be free from interferants under the conditions
 of analysis by performing laboratory method blanks.   Analysts  should avoid using
 PVC  gloves.

       3.2   The  use  of  high purity  reagents  and solvents  helps  minimize
 interference  problems.   Purification  of  solvents by distillation  in  all-glass
 systems may be necessary.

       3.3   Interferants coextracted from the sample will  vary considerably from
 matrix to matrix.  PCDDs and  PCDFs are often associated with other interfering
 chlorinated substances such as polychlorinated biphenyls (PCBs), polychlorinated
 diphenyl  ethers   (PCDPEs),  polychlorinated  naphthalenes, and  polychlorinated
 alkyldibenzofurans,  that may  be  found  at   concentrations  several  orders  of
 magnitude  higher  than the  analytes  of  interest.   Retention times of  target
 analytes  must be verified  using  reference  standards.    These  values  must
 correspond to  the retention  time  windows established in Sec. 8.1.1.3.   While
 cleanup techniques  are  provided  as  part of  this  method,  unique samples  may
 require additional cleanup steps to achieve lower detection  limits.

      3.4   A  high-resolution  capillary  column  (60  m DB-5,  J&W  Scientific,  or
equivalent) is  used  in  this  method.   However, no  single  column  is  known  to
 resolve all isomers.   The 60  m DB-5 GC column  is capable of 2,3,7,8-TCDD isomer
 specificity  (Sec.  8.1.1).   In order  to determine  the  concentration  of  the
 2,3,7,8-TCDF  (if  detected on the DB-5  column),  the  sample extract  must  be
 reanalyzed on a column capable of 2,3,7,8-TCDF isotner specificity (e.g., D8-225,
SP-2330, SP-2331, or equivalent).


4.0   APPARATUS AND MATERIALS

      4.1    High-Resolution    Gas    Chromatograph/High-Resc"ution    Mass
Spectrometer/Data System (HRGC/HRMS/DS) - The GC must be equipped for temperature
programming, and all  required accessories must be available,  such  as  syringes,
gases, and capillary columns.

            4.1.1 GC Injection Port  - The GC injection port must be designed for
      capillary  columns.    The   use  of splitless  injection  techniques  is
      recommended.   On  column 1  ^L  injections can be used  on  the 60  m  DB-5
      column.   The use  of a moving needle  injection port is also acceptable.
      When using the  method  described  in  this protocol,  a 2 jitL injection volume
      is  used consistently  (i.e.,  the  injection   volumes  for  all  extracts,
      blanks,  calibration solutions and the performance  check  samples are 2  ^L).
      One   juL  injections  are  allowed;  however,   laboratories  must  remain
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consistent throughout the analyses by using the same injection volume at
all times.

      4,1.2 Gas Chromatograph/Mass Spectrometer  (GC/MS)  Interface - The
GC/MS interface components should withstand 350°C.  the interface must be
designed  so  that  the  separation  of  2,3,7,8-TCDD  from  the  other  TCDD
isomers  achieved  in  the  gas  chromatographic  column is  not appreciably
degraded.  Cold spots or active surfaces {adsorption sites)  in the GC/MS
interface can cause peak tailing and peak broadening.   It is recommended
that the GC  column  be  fitted directly  into  the mass spectrometer ion
source without  being exposed to  the  ionizing electron beam.   Graphite
ferrules should be avoided in the injection port because  they may adsorb
the PCDDs and PCDFs.   Vespel™,  or equivalent,  ferrules are  recommended.

      4.1.3 Mass  Spectrometer  -  The   static  resolving  power  of  the
instrument must be maintained  at a minimum of 10,000  (10 percent valley).

      4.1.4 Data System - A dedicated data system is employed to control
the  rapid multiple-ion  monitoring process  and  to acquire  the  data.
Quantitation  data (peak areas  or peak heights)  and SIM traces (displays of
intensities of each ion signal being monitored  including the lock-mass ion
as a function of  time) must  be  acquired  during  the  analyses and stored.
Quantitations may be  reported based upon computer generated peak areas or
upon measured peak heights  (chart recording).   The data  system  must be
capable of acquiring  data at  a minimum of  10 ions  in a single scan. It is
also recommended to have a data system capable of switching  to different
sets  of  ions   (descriptors)  at  specified times during  an  HRGC/HRMS
acquisition.   The  data  system should  be able  to  provide  hard copies of
individual  ion  chromatograms  for  selected  gas  chromatographic  time
intervals.  It should also be able to acquire mass spectral peak profiles
(Sec. 8.1.2.3)  and provide hard copies of peak profiles to demonstrate the
required resolving power.  The data system should permit  the measurement
of noise on the base  line.

      NOTE: The detector  ADC zero setting must allow peak-to-peak measure-
            ment of the  noise on  the base line of every monitored channel
            and allow for good  estimation  of the  instrument resolving
            power.  In Figure 2,  the effect of different zero settings on
            the measured resolving power is shown.

4.2   GC Columns

      4.2,1 In order  to have an isomer  specific determination for 2,3,7,8-
TCDD and  to  allow the detection  of  OCDD/OCDF within a  reasonable  time
interval   in  one HRGC/HRMS analysis,  use  of the  60  m DB-5  fused silica
capillary column  is  recommended.  Minimum acceptance  criteria  must be
demonstrated  and  documented  (Sec,  8.2.2).   At the  beginning  of  each IE
hour period  (after mass  resolution and GC  resolution  are demonstrated)
during which  sample extracts or concentration  calibration solutions will
be analyzed,  column operating  conditions must be  attained for the required
separation on the  column to  be used for  samples.   Operating  conditions
known to produce acceptable  results with the recommended column are shown
in Sec. 7.6.
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            4.2.2 Isomer specificity  for  all  2,3,7,8-substituted  PCDDs/PCDFs
      cannot  be  achieved on  the 60  m DB-5  GC column  alone.    In order  to
      determine the proper concentrations of the individual 2,3,7,8-substituted
      congeners,  the sample extract must be reanalyzed on another GC column that
      resolves the isomers.

            4.2.3 30 m DB-225 fused silica capillary column, (J&W Scientific) or
      equivalent.

      4.3   Miscellaneous Equipment  and Materials - The following list of items
does not  necessarily constitute an exhaustive compendium of the equipment needed
for this  analytical  method.

            4.3.1 Nitrogen  evaporation apparatus with variable flow rate.

            4.3.2 Balances  capable  of accurately  weighing  to  0.01   g  and
      0.0001 g.

            4.3,3 Centrifuge.

            4,3,4 Water  bath,  equipped with concentric ring  covers  and  capable
      of  being temperature  controlled  within ± 2°C.

            4.3.5 Stainless  steel  or   glass container  large enough  to  hold
      contents of one pint  sample containers.

            4.3.6 Glove  box.

            4.3.7 Drying oven.

            4.3.8 Stainless steel  spoons  and spatulas.

            4.3.9 Laboratory hoods.

            4.3.10      Pipets,  disposable,  Pasteur,  150 mm  long  x  5 mm ID.

            4.3.11      Pipets,   disposable,  serological,  10  ml,  for  the
      preparation of the carbon  columns specified  in Sec.  7.5.3.

            4.3.12      Reaction vial, 2ml, silanized  amber glass (Reacti-vial,
      or  equivalent).

            4.3.13      Stainless steel meat grinder with  a 3 to 5 mm hole size
      inner plate.

            4.3,14      Separatory funnels,  125 ml  and 2000  ml.

            4.3.15      Kuderna-Danish concentrator,  500 ml,  fitted with  10  ml
      concentrator tube  and three ball  Snyder  column.

            4.3.16      Teflon™ or carborundum  (silicon carbide)  boiling  chips
      {or equivalent), washed  with hexane  before use.
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      NOTE: Teflon™ boiling chips may  float  in  methylene chloride,  may
            not work  in the  presence  of  any water  phase,  and may  be
            penetrated by nonpolar organic compounds.

      4.3.17      Chromatographic columns,  glass, 300 mm x 10.5 mm, fitted
with Teflon™ stopcock.

      4.3.18      Adapters for concentrator tubes.

      4.3.19      Glass   fiber   filters,   0.70  pm,  Whatman   GFF,   or
equivalent,

      4.3.20      Dean-Stark trap, 5  or 10 ml, with T-joints,  condenser
and 125 ml flask.

      4.3.21      Continuous liquid-liquid extractor.

      4.3.22      All  glass Soxhlet apparatus, 500  ml flask.

      4.3.23      Soxhlet/Dean Stark  extractor (optional), all glass,  500
ml flask.

      4.3.24      Glass  funnels,  sized to hold 170  ml of liquid.

      4.3.25      Desiccator.

      4.3.26      Solvent reservoir  (125 ml),  Kontes;  12.35  cm diameter
(special  order item),  compatible with gravity carbon column.

      4.3.27      Rotary evaporator with a temperature  controlled  water
bath.

      4.3.28      High speed  tissue  homogenizer,  equipped with  an  EN-8
probe, or equivalent.

      4.3.29      Glass  wool, extracted with methylene chloride, dried and
stored in a clean  glass  jar.

      4.3.30      Extract:or ja^s,  glass, 25C  r.L, with taflor. "Mnsd screw
cap.

      4.3.31      Volumetric flasks,  Class A  - 10 ml to 1000  ml.

      4.3.32      Glass  vials, 1  dram (or metric  equivalent).

      NOTE: Reuse  of glassware should be minimized  to  avoid  the risk  of
            contamination.     All  glassware   that   is  reused  must   be'
            scrupulously cleaned  as soon'as possible after use,  according
            to the following  procedure:  Rinse glassware with  the  last
            solvent used in it.  Wash  with hot  detergent water, then rinse
            with copious amounts of   tap water and several  portions  of
            organic-free reagent water.  Rinse with  high purity acetone
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                  and hexane and store it inverted or capped with solvent rinsed
                  aluminum foil in a clean environment.
5.0   REAGENTS AND STANDARD SOLUTIONS

      5.1   Organic-free reagent water  - All references to water in this method
refer to organic-free reagent water,  as defined in Chapter One.

      5.2   Column Chromatography Reagents

            5.2.1 Alumina,   neutral,   80/200   mesh   (Super   1,   Woelm®,   or
      equivalent).   Store  in  a sealed container at room  temperature,  in  a
      desiccator, over self-indicating  silica  gel.

            5.2.2 Alumina,  acidic AG4,  (Bio Rad. Laboratories catalog #132-1240,
      or equivalent).   Soxhlet extract  with  methylene chloride for 24  hours if
      blanks show contamination,  and activate by heating in a foil covered glass
      container for 24 hours at  190°C.   Store  in  a glass  bottle  sealed with  a
      Teflon™ lined screw  cap.

            5.2.3 Silica gel,  high  purity  grade,  type 60,  70-230 mesh;  Soxhlet
      extract with methylene chloride for 24  hours if blanks show contamination,
      and activate by  heating  in  a foil  covered glass container for 24  hours at
      190°C.   Store  in  a  glass  bottle sealed with  a Teflon™ lined screw cap.

            5.2.4 Silica gel  impregnated with  sodium hydroxide.   Add  one  part
      (by weight) of  1 M NaOH  solution  to  two  parts  (by weight)  silica  gel
      (extracted and activated)  in  a  screw cap bottle and  mix  with a glass  rod
      until  free of  lumps.  Store in a glass  bottle sealed with a Teflon™ lined
      screw cap.

            5.2.5 Silica gel  impregnated with  40  percent  (by  weight)  sulfuric
      acid.   Add two parts (by weight) concentrated sulfuric acid to three parts
      (by weight) silica gel  (extracted and activated),  mix with a glass  rod
      until  free of lumps,  and store  in a  screw capped glass bottle.   Store in
      a glass bottle sealed with a  Teflon™  lined screw cap.

            5.2.6 Cellte 545® (Supelcc),  or  SQi;4.v&len*.

            5.2.7 Active carbon AX-21 (Anderson Development Co., Adrian, MI), or
      equivalent, prewashed with  methanol and dried in vacuo  at 110°C.  Store in
      a glass bottle sealed with a  Teflon™  lined screw cap.

      5.3   Reagents

            5.3.1 Sulfuric acid, H2S04, concentrated, ACS grade, specific gravity
            5,3.2 Potassium hydroxide,  KOH,  ACS  grade,  20  percent  (w/v)  in
      organic-free reagent water.
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             5.3.3  Sodium chloride, NaCl, analytical reagent,  5 percent (w/v)  in
       organic-free reagent water.

             5.3.4  Potassium  carbonate, K2C03, anhydrous, analytical reagent.

       5,4    Desiccating agent

             5.4.1  Sodium sulfate (powder, anhydrous), Na2S04.  Purify by  heating
       at  400°C  for 4 hours  in a shallow  tray,  or  by  precleaning the  sodium
       sulfate with methylene chloride.   If the sodium sulfate  is precleaned with
       methylene  chloride,  a  method  blank must be analyzed, demonstrating that
       there  is no  interference from the  sodium sulfate.

       5.5    Solvents

             5.5.1  Methylene  chloride,  CH2C12.  High purity, distilled in glass
       or highest available purity.

             5.5.2  Hexane,  C6H14.   High purity,  distilled  in  glass or  highest
       available purity,

             5.5.3  Methanol,  CH3OH.   High purity, distilled in glass or  highest
       available purity.

             5.5.4  Nonane,  C9H20.   High purity,  distilled  in  glass or  highest
       available purity.

             5.5.5  Toluene, CeH5CH3.  High purity, distilled in glass or  highest
       available purity.

             5.5.6  Cyclohexane, C6H12-  High  purity, distilled in glass or  highest
       available purity.

             5.5.7  Acetone, CH3COCH3.  High purity, distilled in glass or  highest
       available purity.

       5.6   High-Resolution Concentration Calibration Solutions (Table 5) - Five
nonane solutions containing unlabeled (totaling 17)  and carbon-labeled  (totaling
II) PCDDs and PCDFs at known concentrations  are -sec to calibrate the instrument.
The concentration ranges  are  homologue  dependent, with the lowest values  for the
tetrachlorinated dioxin and  furan  (1.0 pg/^L) and  the  highest values for the
octachlorinated congeners  (1000 pg/^L).

            5.6.1  Depending  on  the  availability  of materials,  these high-
       resolution concentration calibration  solutions may be  obtained from the
       Environmental Monitoring Systems Laboratory,  U.S.   EPA,  Cincinnati, Ohio.
       However,  additional secondary standards must be obtained from commercial
       sources,  and solutions should be  prepared in the analyst's laboratory.   It
       is the responsibility of the laboratory to  ascertain  that the calibration
       solutions  received   (or  prepared)   are  indeed   at   the  appropriate
       concentrations before  they are used to analyze samples.
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            5.6.2 Store  the  concentration  calibration  solutions  in  1  mL
      mini vials at room temperature in the dark.

      5.7   GC Column Performance Check  Solution  -  This solution contains the
first and last eluting  isomers  for  each  homologous  series from tetra- through
heptachlorinated congeners.  The solution also contains a series of other TCDD
isomers  for  the  purpose of  documenting  the chromatographic  resolution.   The
13C12-2,3,7,8~TCDD is also present.   The laboratory is required to use nonane as
the solvent and adjust the volume so  that the final  concentration does not exceed
100 pg/ML pei" congener.  Table 7 summarizes the qualitative composition (minimum
requirement) of this performance evaluation solution.

      5.8   Sample Fortification Solution  - This  nonane solution contains the
nine internal  standards at the nominal concentrations that are listed in Table 2.
The solution contains at least one carbon-labeled standard for each homologous
series, and it is used to measure the concentrations of the native substances.
(Note that 13C12-OCDF is not present in the solution.)

      5.9   Recovery Standard  Solution  -  This nonane  solution contains  two
recovery standards,  13C12-1,2,3,4-TCDD and 13C12-l,2,3,7,8,9-HxCDD, at a nominal
concentration of 50 pg//iL  per compound.   10 to  50 ^L  of this solution will be
spiked into each sample extract before the final  concentration step and HRGC/HRMS
analysis.

      5.10  Matrix Spike Fortification Solution -  Solution used to prepare the
MS and MSD samples.  It contains  all  unlabeled analytes listed in Table 5 at con-
centrations corresponding to the HRCC 3.


6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1   See the  introductory material  to this  chapter,  Organic  Analytes,
Sec. 4.1.

      6.2   Sample Collection

            6.2.1 Sample collection personnel should, to  the extent  possible,
      homogenize  samples  in  the field before  filling  the  sample  containers.
      This should minimize or eliminate the necessity for sample homogenization
      in the  laboratory.   The  analyst  should  make a  judgment, based  on  the
      appearance  of the sample,  regarding the necessity for additional  mixing.
      If the sample is clearly  not  homogeneous, the entire  contents  should be
      transferred to a  glass  or  stainless  steel pan  for mixing with a stainless
      steel  spoon or spatula before removal of a sample portion for analysis.

            6.2.2 Grab  and  composite  samples  must  be  collected  in  glass
      containers. Conventional  sampling practices must be  followed.  The bottle
      must not be prewashed with sample before  collection.  Sampling equipment
      must be free of potential  sources of contamination.

      6.3   Grinding or Blending of  Fish Samples -  If not otherwise specified by
the U.S. EPA,  the whole fish (frozen)  should be blended or ground to provide a
homogeneous sample.   The use  of  a stainless  steel  meat grinder with a 3 to 5 mm


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hole size inner plate is  recommended.  In some circumstances, analysis of fillet
or specific organs of fish may be requested by the U.S. EPA.  If so requested,
the above whole fish requirement is superseded.

      6.4   Storage  and  Holding  Times - All  samples,  except  fish  and adipose
tissue samples, must be stored at 4°C  in the dark, extracted within 30 days and
completely  analyzed  within 45 days  of extraction.    Fish and  adipose  tissue
samples  must  be  stored  at -20°C  in  the dark,  extracted within  30  days  and
completely analyzed within 45  days of collection.   Whenever samples are analyzed
after the holding time expiration date, the results  should be considered to be
minimum concentrations and should be identified as such.

      NOTE: The holding times  listed in Sec. 6.4 are  recommendations.  PCDDs and
            PCDFs are very stable  in  a  variety of matrices,  and holding times
            under the conditions  listed  in Sec. 6.4 may be as high as a year for
            certain  matrices.   Sample extracts,  however,   should always  be
            analyzed within 45 days of extraction.

      6.5   Phase Separation  - This is a guideline for phase separation for very
wet (>25 percent  water)  soil,  sediment  and paper pulp samples.  Place  a  50 g
portion  in a  suitable  centrifuge  bottle  and  centrifuge  for 30 minutes  at
2,000 rpm.   Remove  the  bottle  and mark  the interface  level  on  the  bottle.
Estimate the relative volume of each phase.  With a  disposable pipet,  transfer
the liquid  layer  into  a clean bottle.   Mix the  solid with a  stainless steel
spatula and remove  a portion to be  weighed and  analyzed (percent  dry  weight
determination, extraction).  Return the  remaining  solid portion to the original
sample bottle  (empty) or to a  clean sample bottle that  is properly labeled,  and
store  it  as appropriate.   Analyze the  solid phase  by  using  only the soil,
sediment and paper pulp method.   Take  note of, and report, the estimated volume
of liquid before disposing of the liquid as a liquid waste.

      6.6   Soil,  Sediment,   or   Paper  Sludge   (Pulp)   Percent   Dry  Weight
Determination  - the percent dry weight of soil,  sediment  or  paper pulp samples
showing detectable levels (see note below)  of at  least one 2,3,7,8-substituted
PCDD/PCDF congener is determined  according  to  the following procedure.   Weigh a
10 g  portion  of the soil  or  sediment sample  (+  0.5 g)   to three  significant
figures.  Dry it to constant weight at 110°C in an adequately ventilated oven.
Allow the  sample to cool  in  a  desiccator.   Weigh   the  dried  solid  to three
significant figures.  Calculate and report the percent dry weight.   Do not  use
this solid portion of the  sample for  extraction,  but  instead dispose  of it as
hazardous waste.

      NOTE: Until detection limits have been established  (Sec.  1.3),  the lower
            MCLs  (Table  1) may  be used  to  estimate  the minimum  detectable
            levels.

      % dry weight = gofdry sample x 100
                       g of sample

      CAUTION:    Finely  divided   soils   and  sediments   contaminated  with
                  PCDDs/PCDFs  are   hazardous  because  of  the  potential   for
                  inhalation  or  ingestion of  particles containing  PCDDs/PCDFs
                                  8290  -  11                         Revision 0
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                  (including 2,3,7,8-TCDD).   Such samples should be handled in
                  a confined environment (i.e.,  a closed hood or a glove box).

      6.7   Lipid Content Determination

            6.7.1 Fish Tissue - To determine the lipid content of fish tissue,
      concentrate 125 ml  of the fish tissue extract (Sec.  7.2.2),  in a tared 200
      ml round bottom flask,  on  a  rotary evaporator until a constant weight (W)
      is achieved.
                             100 (H)
            Percent lipid = 	
                               10

            Dispose of the lipid residue as  a hazardous waste if the results of
      the analysis  indicate the presence of PCDDs or PCDFs.

            6.7.2 Adipose Tissue - Details for the determination of the adipose
      tissue lipid  content are provided in Sec.  7.3.3.


7.0   PROCEDURE

      7.1   Internal  standard addition

            7.1.1 Use a portion  of 1 g  to 1000 g  (± 5 percent) of the sample to
      be analyzed.  Typical sample  size requirements for different matrices are
      given in Sec.  7.4 and  in Table 1.  Transfer the sample portion to a tared
      flask and determine its weight.

            7.1.2 Except  for adipose tissue, add  an appropriate quantity of the
      sample fortification mixture  (Sec. 5.8) to the sample.  All samples should
      be spiked with  100 pi of the sample fortification mixture to give internal
      standard concentrations as indicated in Table 1.  As an example, for 13C12-
      2,3,7,8-TCDD,  a 10 g soil sample  requires the  addition of 1000 pg of 13C12-
      2,3,7,8-TCDD  to give the required 100  ppt  fortification level.   The fish
      tissue sample (20 g) must  be spiked  with 200  pi of the  internal  standard
      solution, because half  of  the extract will be used to determine the lipid
      content (Sec.  6.7.1).

                  7.1.2.1     For the fortification of soil, sediment, fly ash,
            water,  fish  tissue,  paper pulp  and wet  sludge  samples, mix  the
            sample  fortification solution  with  1.0 ml acetone.

                 7.1.2.2     Do not dilute the nonane  solution  for  the other
            matrices.

                 7.1.2.3     The fortification of adipose tissue  is carried out
            at the  time of homogenization  (Sec.  7.3.2.3).

      7.2   Extraction and Purification of Fish  and Paper Pulp Samples

            7.2.1 Add 60  g  anhydrous   sodium sulfate  to a 20  g portion  of  a
      homogeneous fish sample  (Sec. 6.3)  and mix thoroughly with  a  stainless


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steel spatula.  After breaking up any lumps,  place the fish/sodium sulfate
mixture in the Soxhlet apparatus on top of a glass wool plug.  Add 250 ml
methylene  chloride or  hexane/methylene chloride  (1:1)  to  the  Soxhlet
apparatus  and  reflux for 16 hours.   The solvent must  cycle completely
through the system five times per hour.  Follow the same procedure for the
partially  dewatered  paper  pulp  sample  (using  a  10 g  sample,  30  g  of
anhydrous sodium sulfate and 200 ml of toluene).

      NOTE: As  an  option,  a Soxhlet/Dean Stark extractor  system  may be
            used, with toluene as the solvent.  No sodium sulfate is added
            when using this option.

      7.2.2 Transfer  the fish  extract  from  Sec.  7.2.1  to  a  250  ml
volumetric flask and fill  to the mark with methylene chloride.  Mix well,
then  remove  125 ml  for the determination  of  the  lipid  content  (Sec.
6.7,1),   Transfer  the remaining 125 ml  of  the extract, plus  two  15 ml
hexane/methylene  chloride  rinses  of  the  volumetric  flask,  to  a  KD
apparatus equipped with a Snyder column.  Quantitatively transfer all of
the paper pulp extract to a KD  apparatus equipped with a Snyder column.

      NOTE: As an option,  a  rotary  evaporator  may be used in place of the
            KD apparatus for the concentration of the extracts.

      7.2.3 Add a Teflon™,  or equivalent, boiling chip.  Concentrate the
extract in  a  water  bath  to an apparent volume of  10  ml.   Remove  the
apparatus from the water bath and allow to cool for 5 minutes.

      7.2.4 Add  50  ml  hexane and  a  new  boiling chip  to  the  KD  flask.
Concentrate in  a water bath to  an  apparent  volume of 5 mL.   Remove the
apparatus from the water bath and allow to cool for 5 minutes.

      NOTE: The  methylene  chloride must have  been  completely  removed
            before proceeding with  the next  step.

      7.2.5 Remove and invert the Snyder column and rinse it into the KD
apparatus with two  1  ml portions of hexane.  Decant the contents of the KD
apparatus and concentrator tube into a  125  ml separatory  funnel.   Rinse
the KD apparatus with two additional  5 ml portions  of hexane and add the
rinses  to the  funnel.    Proceed  with  the  cleanup according  to  the
instructions starting  in Sec. 7.5.1.1,  but omit the procedures described
in Sees. 7.5.1.2 and 7.5.1,3.

7.3   Extraction and Purification of Human Adipose  Tissue

      7.3.1 Human adipose tissue samples must be stored at a temperature
of -20°C or lower from  the time of collection until  the time of analysis.
The use of chlorinated  materials during the collection of the samples must
be avoided.  Samples are handled with  stainless steel  forceps, spatulas,
or scissors.   All sample bottles (glass) are cleaned as specified in the
note at the end 'of Sec. 4.3.  Teflon™ lined caps  should be used.
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NOTE: The  specified storage  temperature  of -20DC is  the maximum
      storage  temperature  permissible  for adipose tissue samples.
      Lower storage temperatures are recommended.

7.3.2 Adipose Tissue Extraction

      7.3.2.1     Weigh, to the nearest 0.01 g,  a 10 g portion of a
frozen adipose tissue sample  into a culture tube  (2.2 x 15 cm).

      NOTE: The   sample  size  may   be  smaller,   depending   on
            availability.  In  such  a  situation,  the   analyst  is
            required to adjust the volume of the  internal standard
            solution added to the sample to meet  the fortification
            level stipulated  in Table 1.

      7,3.2.2     Allow the  adipose tissue  specimen  to reach room
temperature (up to 2 hours).

      7.3.2.3     Add 10 ml  methylene  chloride and 100 juL  of the
sample  fortification   solution.    Homogenize  the   mixture  for
approximately 1 minute with a tissue homogenizer.

      7.3.2.4     Allow the  mixture  to separate,  then  remove the
methylene chloride extract from the residual solid material  with a
disposable pipet. Percolate the methylene  chloride through a filter
funnel containing a clean glass wool plug  and 10 g anhydrous sodium
sulfate.  Collect the dried extract in  a graduated 100 ml volumetric
flask.

      7.3.2.5     Add a second 10 ml portion of methylene chloride
to the sample and homogenize for  1 minute.   Decant the solvent, dry
it, and transfer  it to the 100 ml volumetric flask (Sec. 7.3.2-,4).

      7.3.2.6     Rinse  the   culture   tube with  at   least  two
additional portions of methylene chloride (10 ml each), and transfer
the entire contents to  the  filter  funnel  containing  the anhydrous
sodium sulfate.   Rinse  the  filter  funnel  and the anhydrous  sodium
sulfate contents  with additional methylene  chloride  (20 to  40 ml)
into the 100 ml flask.   Discard the sodium sulfate.

      7.3,2.7     Adjust  the  volume   to  the   100 ml  mark  with
methylene chloride.

7.3.3 Adipose Tissue Lipid Content Determination

      7.3.3.1     Preweigh a  clean  1  dram  (or  metric  equivalent)
glass vial to  the nearest 0.0001 g on an analytical balance tared to
zero.

      7.3,3.2     Accurately  transfer  1.0 ml of the  final extract
(100 ml) from Sec.  7.3.2.7 to the  vial.   Reduce the  volume  of the
extract on a  water bath (50-60°C)  by a gentle  stream  of purified
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nitrogen  until   an  oily  residue  remains.   Nitrogen  blowdown  is
continued until  a constant weight is achieved.

      NOTE: When the  sample  size  of the adipose tissue is  smaller
            than 10 g, then the analyst may use a larger portion (up
            to  10 percent) of  the extract defined in Sec.  7.3.2.7
            for  the lipid determination.

      7.3.3.3     Accurately weigh the vial  with the  residue to the
nearest 0.0001  g and  calculate  the  weight of the lipid present  in
the vial based on the difference of the weights.

      7.3.3.4     Calculate  the  percent  lipid  content   of   the
original sample  to the nearest 0.1 percent as shown  below;

                               W,  x  Vext
      Lipid content,  LC (%)  - 	     x  100
                               w*  x val
where:

      W|r    =     weight of the lipid residue to the  nearest 0.0001
                  g calculated from Sec. 7.3.3.3,

      Vext   =     total volume  (100  ml) of  the  extract in ml  from
                  Sec. 7.3.2.7,

      Wat    =     weight of  the  original  adipose tissue sample  to
                  the nearest 0.01 g from Sec. 7.3.2.1, and

      Val    =     volume of the aliquot of the final extract in  ml
                  used  for  the  quantitative measure of the lipid
                  residue (1.0 ml) from Sec. 7.3.3.2.

      7.3.3.5     Record the lipid residue measured  in  Sec.  7.3.3.3
and the percent  lipid content from Sec. 7.3.3.4.

7.3.4 Adipose Tissue  Extract Concentration

      7.3.4.1     Quantitatively transfer the remaining extract  from
Sec.  7.3.3.2  (99.0  ml)  to a 500  ml Erlenmeyer  flask.   Rinse  the
volumetric flask with 20 to 30 ml of additional methylene chloride
to ensure quantitative transfer.

      7.3.4.2     Concentrate the extract on a rotary evaporator and
a water bath at  40°C until  an oily residue remains.

7.3.5 Adipose Tissue  Extract Cleanup

      7.3.5.1     Add 200 ml hexane to the lipid  residue in  the 500
ml Erlenmeyer flask and swirl the flask to dissolve  the residue.
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            7.3.5.2     Slowly add, with  stirring,  100 g  of  40 percent
      (w/w) sulfuric acid-impregnated silica gel.   Stir with  a magnetic
      stirrer for two hours at room temperature.

            7.3.5.3     Allow the solid phase  to  settle,  and  decant the
      liquid through  a  filter funnel containing  10 g  anhydrous sodium
      sulfate on a glass  wool  plug,  into another 500 ml Erlenmeyer flask.

            7.3.5.4     Rinse the solid  phase with two 50 ml portions of
      hexane.   Stir  each  rinse  for 15  minutes,  decant,  and dry  as
      described under Sec.  7.3.5.3.  Combine the hexane extracts  from Sec.
      7.3.5.3 with the rinses.

            7.3.5.5     Rinse the  sodium sulfate in the filter funnel with
      an additional 25 ml hexane  and combine this  rinse with  the hexane
      extracts from Sec.  7.3.5.4.

            7.3.5.6     Prepare an acidic  silica column  as follows:  Pack
      a 2 cm x 10  cm chromatographic column with  a  glass  wool  plug, add
      approximately 20 ml hexane,  add 1 g  silica gel and allow to settle,
      then add 4 g of 40  percent  (w/w) sulfuric acid-impregnated silica
      gel and allow to settle.  Elute the excess  hexane from  the column
      until the  solvent   level  reaches  the top  of the chromatographic
      packing.   Verify that the column does  not have any air bubbles and
      channels.

            7.3.5.7     Quantitatively  transfer the hexane  extract from
      the Erlenmeyer flask (Sees.  7.3.5.3  through  7.3.5.5) to  the silica
      gel column reservoir.  Allow the hexane extract to percolate through
      the column and collect the eluate  in a 500 ml KD apparatus.

            7.3.5.8     Complete the elution by percolating 50 ml hexane
      through the  column  into the KD apparatus.   Concentrate the  eluate on
      a steam bath to  approximately  5 ml.  Use nitrogen blowdown to bring
      the final  volume to about 100 /iL.

            NOTE:  If the  silica gel  impregnated with 40  percent sulfuric
                  acid is highly discolored  throughout the length of the
                  adsorbent bed,  the cleaning  procedure  must be repeated
                  beginning with Sec.  7.3.5.1.

            7.3.5.9     The extract  is  ready  for  the  column  cleanups
      described in Sees.  7.5.2 through 7.5.3.6.

7.4   Extraction and Purification  of Environmental  and Waste Samples

      7.4.1 Sludge/Wet Fuel  Oil

            7.4.1.1     Extract aqueous sludge  or wet fuel oil  samples by
      refluxing a  sample  (e.g.,  2  g) with  50 ml toluene  in a 125 ml flask
      fitted with a Dean-Stark water separator.   Continue refluxing the
      sample until all  the water is removed.
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      NOTE: If the sludge or fuel  oil  sample dissolves in toluene,
            treat it  according  to the  instructions  in  Sec. 7.4.2
            below.   If  the  labeled sludge  sample  originates  from
            pulp  (paper  mills},   treat   it   according   to   the
            instructions  starting in  Sec. 7,2,  but without  the
            addition of sodium sulfate.

      7.4.1,2     Cool  the   sample,  filter the  toluene  extract
through a  glass  fiber filter,  or  equivalent, into a 100  ml round
bottom flask.

      7.4.1.3     Rinse the filter with  10 ml  toluene and combine
the extract with the rinse.

      7.4.1.4     Concentrate the  combined solutions to near dryness
on a rotary evaporator at 50°C.  Use of an  inert gas to concentrate
the extract is also permitted.  Proceed with Sec.  7.4.4.

7.4.2 Still Bottom/Oil

      7.4.2.1     Extract still  bottom or  oil  samples by  mixing a
sample portion (e.g., 1.0 g) with  10 ml  toluene in a small  beaker
and  filtering the   solution  through  a glass  fiber filter  (or
equivalent}" into a 50 ml round bottom flask.  Rinse the beaker and
filter with 10 ml toluene,

      7.4.2.2     Concentrate the  combined toluene solutions  to near
dryness on a rotary evaporator at  50°C.   Proceed with Sec.  7,4.4.
7.4.3 Fly Ash

NOTE: Because of the  tendency of  fly ash  to "fly",   all  handling
      steps  should  be performed  in  a hood in order to  minimize
      contamination.

      7.4.3.1     Weigh about 10 g fly ash to two decimal places and
transfer to  an  extraction jar.   Add 100 /jL  sample  fortification
solution (Sec, 5.8), diluted to 1 ml with  acetone, to the sample.
Add 150 ml of 1  M HC1  to  the  fly ash sample.  Seal the jar with the
Teflon™ lined screw cap  and  shake for 3 hours at room temperature,

      7.4.3,2     Rinse  a  glass  fiber filter  with   toluene,  and
filter the  sample  through the filter  paper,  placed   in  a Buchner
funnel, into all flask.  Wash the fly ash  cake with  approximately
500 ml organic-free  reagent water  and dry the filter cake overnight
at room temperature in a desiccator.

      7.4.3.3     Add 10 g anhydrous powdered  sodium sulfate,  mix
thoroughly, let sit in a closed container for one hour,  mix again,
let sit for another hour, and mix  again.

      7.4.3.4     Place  the  sample and  the filter  paper  into  an
extraction thimble,   and  extract in  a  Soxhlet extraction apparatus
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      charged with  200  ml  toluene for 16 hours using  a  five cycle/hour
      schedule.

            NOTE; As an option,  a Soxhlet/Dean Stark extractor system may
                  be used,  with  toluene as the solvent.  No sodium sulfate
                  is added when using this option.

            7.4.3.5     Cool  and  filter the  toluene  extract  through  a
      glass fiber  filter  into a  500  ml  round  bottom flask.   Rinse the
      filter  with   10 ml  toluene.   Add  the  rinse to  the  extract  and
      concentrate  the  combined  toluene  solutions  to  near dryness  on  a
      rotary evaporator at 50°C.   Proceed with Sec.  7.4.4.

      7.4.4 Transfer the concentrate to a 125 ml separatory funnel  using
15 ml hexane.  Rinse the flask with  two  5 ml  portions  of hexane and add
the rinses to the funnel.   Shake  the combined solutions in the separatory
funnel  for two minutes with 50 ml of 5 percent sodium chloride solution,
discard the aqueous layer,  and proceed with  Sec. 7.5.

      7.4.5 Aqueous samples

            7.4.5.1     Allow the sample to  come to ambient temperature,
      then mark the water  meniscus on the side  of the  1  L sample bottle
      for  later  determination  of the  exact sample  volume.   Add  the
      required acetone diluted sample fortification solution (Sec.  5.8).

            7.4.5.2     When the sample  is judged  to contain 1 percent or
      more solids,  the sample  must  be  filtered  through a  glass  fiber
      filter that has been rinsed with toluene.   If the suspended solids
      content  is  too   great  to  filter  through  the  0.45 jtm  filter,
      centrifuge the sample,  decant,  and  then filter the aqueous phase.

            NOTE: Paper mill  effluent  samples normally contain 0.02%-0.2%
                  solids,  and would not require  filtration.  However, for
                  optimum  analytical  results,   all  paper mill  effluent
                  samples  should  be  filtered,  the  isolated  solids  and
                  filtrate  extracted   separately,   and  the   extracts
                  recombined.

            7.4.5.3     Combine the solids from the centrifuge bottle(s)
      with the particulates on the filter and with the filter itself and
      proceed with  the  Soxhlet extraction as  specified  in Sees. 7.4.6.1
      through 7.4.6.4.   Remove and invert the Snyder column and rinse it
      down into the KD apparatus with two 1  ml portions of hexane.

            7.4.5.4     Pour the  aqueous filtrate  into a  2  L separatory
      funnel.  Add  60 ml methylene chloride to the  sample bottle, seal and
      shake for  30 seconds to  rinse  the inner  surface.    Transfer the
      solvent to the separatory funnel and extract the sample by shaking
      the funnel  for two minutes with periodic venting.

            7.4.5.5     Allow the organic layer to separate from  the water
      phase  for  a  minimum of  10 minutes.    If the emulsion  interface


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between  layers  is more than  one  third the volume  of  the solvent
layer, the analyst must employ mechanical techniques  to complete the
phase separation  (e.g., glass stirring rod).

      7.4.5.6     Collect the methylene chloride into a KD apparatus
(mounted  with  a  10  ml concentrator  tube)  by passing  the sample
extracts  through  a filter funnel packed with a glass wool plug and
5 g anhydrous sodium sulfate,

      NOTE: As an option, a rotary evaporator may be used in place
            of  the  KD  apparatus  for  the concentration  of  the
            extracts.

      7.4.5.7     Repeat  the extraction  twice with  fresh 60  ml
portions  of methylene chloride.  After the third extraction, rinse
the sodium sulfate with  an  additional  30 ml methylene  chloride to
ensure quantitative transfer.  Combine all extracts and the rinse in
the KD apparatus.

      NOTE: A continuous  liquid-liquid extractor may  be  used  in
            place  of a separatory  funnel  when experience  with  a
            sample from  a given  source  indicates that  a  serious
            emulsion  problem  will   result   or   an  emulsion  is
            encountered when using a separatory funnel.   Add 60 ml
            methylene chloride to the sample bottle,  seal, and shake
            for 30 seconds to rinse the inner surface.  Transfer the
            solvent  to  the  extractor.   Repeat  the rinse  of  the
            sample bottle with an additional 50 to 100 ml portion of
            methylene chloride and add the rinse to  the extractor.
            Add 200 to 500 ml methylene chloride to  the distilling
            flask, add sufficient organic-free reagent  water (Sec.
            5.1}  to  ensure  proper  operation,  and  extract  for
            24 hours.  Allow to cool, then detach  the  distilling
            flask.  Dry and  concentrate the extract as described in
            Sees. 7.4.5,6 and  7,4,5,8 through 7.4.5.10.   Proceed
            with Sec. 7.4.5.11.

      7.4.5.8     Attach a Snyder column and concentrate the extract
on a water bath  until  the apparent volume of  the liquid  is 5 ml.
Remove the KD apparatus and  allow  it to drain and cool for at leasi
10 minutes.

      7.4.5.9     Remove the  Snyder column, add  50  ml  hexane,  add
the  concentrate  obtained  from  the   Soxhlet  extraction  of  the
suspended solids  (Sec. 7.4.5.3}, if applicable,  re-attach the Snyder
column,  and concentrate to  approximately  5 ml.   Add a  new boiling
chip  to  the  KD  apparatus  before  proceeding  with  the  second
concentration step.

      7.4.5.10    Rinse the  flask and  the  lower joint with two 5 ml
portions  of hexane and combine the rinses with the extract to give
a final  volume of about 15 ml.
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            7,4.5.11    Determine the original sample volume  by filling
      the sample bottle to  the mark with water and transferring the water
      to a 1000 ml graduated cylinder.  Record the  sample  volume to the
      nearest 5 ml.   Proceed with Sec.  7.5,

      7.4.6 Soil/Sediment

            7.4.6.1      Add 10 g  anhydrous powdered sodium sulfate to the
      sample portion  (e.g.,  10  g)  and mix  thoroughly with a  stainless
      steel spatula.   After breaking  up any  lumps,  place the  soil/sodium
      sulfate mixture in  the Soxhlet apparatus on  top of  a glass wool plug
      (the use of an extraction  thimble is optional).

            NOTE:  As an option, a Soxhlet/Dean Stark extractor system may
                  be used,  with toluene as the solvent.  No sodium sulfate
                  is added  when  using this option.

            7.4,6.2      Add 200 to 250 ml toluene  to the Soxhlet apparatus
      and reflux for 16 hours.  The solvent  must cycle completely through
      the system five times per  hour.

            NOTE;  If the dried sample is not of free flowing consistency,
                  more sodium sulfate must be added.

            7.4.6.3      Cool  and  filter the extract through a glass fiber
      filter into a  500 ml  round  bottom flask  for  evaporation  of the
      toluene.   Rinse the  filter with 10 ml  of toluene,  and  concentrate
      the combined fractions to  near dryness on  a rotary  evaporator at
      50°C.   Remove  the flask from the water bath and allow to cool for
      5 minutes.

            7.4.6.4      Transfer the residue  to  a   125  ml  separatory
      funnel, using  15 ml of  hexane.  Rinse the flask with two  additional
      portions of hexane, and add the rinses to the funnel.  Proceed with
      Sec. 7.5.

7.5   Cleanup

      7.5.1 Partition

            7.5.1.1      Partition the  hexane extract  against  40 ml  of
      concentrated sulfuric  acid.    Shake for  two  minutes.   Remove and
      discard the sulfuric  acid  layer (bottom).   Repeat  the acid washing
      until no color  is  visible  in the acid  layer  (perform a  maximum of
      four acid washings).

            7.5.1.2      Omit this  step  for  the fish  sample  extract.
      Partition the  extract against 40 ml  of 5 percent  (w/v)  aqueous
      sodium chloride.   Shake for  two minutes.   Remove  and discard the
      aqueous layer (bottom).

            7.5.1.3      Omit this  step  for  the fish  sample  extract.
      Partition the  extract  against  40 ml of  20 percent  (w/v)  aqueous
                            8290 - 20                         Revision 0
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potassium  hydroxide  (KQH),   Shake for  two minutes.    Remove and
discard the aqueous layer  (bottom).  Repeat the base washing until
no color is visible in the bottom layer (perform a maximum of four
base  washings).   Strong  base (KOH) is  known to  degrade certain
PCDDs/PCDFs, so contact time must be minimized.

      7.5.1.4     Partition the extract against 40 ml of 5 percent
(w/v) aqueous sodium chloride.  Shake for two minutes.  Remove and
discard the aqueous layer  (bottom).  Dry the extract by pouring it
through a  filter  funnel  containing anhydrous  sodium  sulfate  on a
glass wool  plug,  and  collect  it  in a  50 ml  round  bottom flask.
Rinse the funnel  with  the  sodium  sulfate with  two 15 ml portions of
hexane, add  the  rinses to the 50  ml  flask,  and  concentrate the
hexane solution to near dryness on a rotary evaporator  (35°C water
bath), making  sure all  traces of  toluene  (when  applicable)  are
removed.    (Use  of blowdown with  an inert gas to  concentrate the
extract is also permitted.)

7.5.2 Silica/Alumina Column Cleanup

      7.5.2.1     Pack a gravity  column  (glass,  30 cm x 10.5 mm),
fitted with a Teflon™  stopcock, with silica  gel as  follows:  Insert
a glass wool plug into the bottom of the column.   Place 1 g silica
gel 1n the  Column  and  tap the column gently  to  settle the silica
gel.   Add  2 g sodium hydroxide-impregnated silica gel, 4 g sulfuric
acid-impregnated silica gel,  and  Z g  silica gel.   Tap the column
gently after each addition.   A small positive pressure (5 psi) of
clean nitrogen may be used if needed.   Elute with 10 ml hexane and
close the stopcock just before exposure of the top layer of silica
gel to air.  Discard the eluate.   Check the  column for channeling.
If channeling  is  observed, discard  the  column.    Do not  tap the
wetted column.

      7.5.2.2     Pack a gravity  column (glass, 300 mm x 10.5 mm),
fitted with a Teflon™  stopcock, with alumina  as follows:  Insert a
glass wool  plug into the bottom of the  column.  Add a 4 g layer of
sodium sulfate.   Add a  4 g  layer of Woelm® Super 1 neutral alumina.
Tap the top of the column  gently.   Woelm® Super  1  neutral alumina
need  not be activated or cleaned before  use,  but it  should be stored
in a  sealed desiccator.  Add a 4 g layer of anhydrous sodium sulfate
to cover  the  alumina.    Elute with 10  ml  hexane  and  close  the
stopcock just before exposure  of  the sodium sulfate layer to air.
Discard the eluate.  Check the column for channeling.  If channeling
is observed, discard the column.   Do not tap a wetted column.

      NOTE: Optionally, acidic alumina  (Sec, 5.2.2) can be used in
            place of neutral  alumina.

      7.5.2.3     Dissolve the residue  from  Sec.  7.5.1.4  in  2 ml
hexane and apply the hexane solution to the top  of the silica gel
column.  Rinse the flask with enough hexane (3-4 ml) to complete the
quantitative transfer  of  the  sample to the surface of the silica
gel.
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      7.5.2.4     Elute the silica gel  column with  90 ml of hexane,
concentrate the eluate on  a rotary  evaporator (35°C water bath) to
approximately  1  ml,  and apply  the  concentrate to the  top  of the
alumina  column  (Sec.  7.5.2.2).   Rinse  the rotary evaporator flask
twice with  2  ml of hexane, and add the rinses to the  top  of the
alumina  column.

      7.5.2.5     Add 20 ml hexane  to the alumina column and elute
until the hexane level is just below the top  of the sodium sulfate.
Do not discard the eluted hexane, but collect it in  a separate flask
and store it for later use, as it may be useful in determining where
the  labeled  analytes  are  being  lost  if   recoveries  are  not
satisfactory.

      7.5.2.6     Add  15 ml  of  60  percent methylene  chloride in
hexane  (v/v)  to the  alumina  column and  collect  the eluate  in  a
conical  shaped  (15 ml)  concentration  tube.   With  a  carefully
regulated stream of nitrogen,  concentrate the  60 percent methylene
chloride/hexane fraction to about 2 ml.

7,5.3 Carbon Column Cleanup

      7.5.3.1     Prepare  an AX-21/Celite  545® column  as follows:
Thoroughly mix 5,40  g  active carbon  AX-21  and  62.0 g Celite 545® to
produce  an 8 percent  (w/w) mixture.  Activate the mixture at  130°C
for 6 hours and store it in a desiccator.

      7,5.3.2     Cut  off  both  ends   of  a  10   ml   disposable
serological pi pet to  give  a  10 cm  long  column.   Fire  polish both
ends and flare, if desired.   Insert a  glass  wool  plug  at one end,
then pack the column  with  enough Celite  545® to  form a 1 cm plug,
add 1 g of the AX-21/Celite 545® mixture, top  with additional Celite
545®  (enough  for a 1 cm  plug), and cap  the  packing with  another
glass wool  plug.

      NOTE: Each new batch of AX-21/Celite 545® must be checked as
            follows:    Add 50 /xL  of  the continuing  calibration
            solution to 950 jiL  hexane.  Take  this solution through
            the carbon column  cleanup  step,   concentrate to  50 ^L
            and analyze.   If the recovery of  any of the analytes is
            <80 percent,  discard this batch of AX-21/Celite 545®.

      7.5.3.3     Rinse the AX-21/Celite  545® column with  5 ml of
toluene, followed  by 2 ml of  75:20:5  (v/v)  methylene  chloride/
methanol/toluene, 1  ml of 1:1  (v/v)  cyclohexane/methylene chloride,
and 5 ml hexane.   The flow rate should be  less  than  0.5 mL/min.
Discard the rinses.  While  the column is  still  wet with hexane, add
the sample  concentrate  (Sec.  7.5.2.6)  to the top of  the  column.
Rinse the concentrator tube {which contained the sample concentrate)
twice with  1  ml hexane, and add the rinses to  the top of the column.

      7.5.3.4     Elute  the   column sequentially  with  two   2  ml
portions of  hexane,   2 ml  cyclohexane/methylene chloride  (50:50,


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            v/v), and 2 ml methylene chloride/methanol/toluene (75:20:5, v/v).
            Combine these eluates; this  combined fraction may be used as  a check.
            on column efficiency.

                  7.5.3.5     Turn  the  column  upside  down  and  elute  the
            PCDD/PCDF fraction with 20 ml toluene.   Verify that no carbon fines
            are  present  in the  eluate.   If  carbon  fines  are present  in the
            eluate, filter the eluate through a glass fiber filter (0.45 ^tm) and
            rinse the filter with 2 ml toluene.  Add the rinse to the eluate.

                  7.5.3.6     Concentrate the toluene fraction to about  1 ml on
            a  rotary  evaporator  by using  a  water  bath  at  5Q°C.    Carefully
            transfer the concentrate into a  1 ml minivial  and,  again  at elevated
            temperature (5Q°C),  reduce the volume to about 100  /xL using a stream
            of nitrogen  and  a  sand bath.   Rinse the  rotary  evaporator flask
            three  times  with  300 jiL  of  a  solution  of  1  percent  toluene  in
            methylene chloride,  and add the  rinses  to the concentrate.   Add
            10 fj,L of the nonane recovery standard solution (Sec. 5.9) for soil,
            sediment,  water,  fish, paper pulp  and adipose tissue samples, or 50
            #L of the recovery  standard solution for sludge,  still  bottom and
            fly ash samples.   Store the  sample  at room  temperature in the dark.

      7.6   Chromatographic/Mass Spectrometric Conditions and Data Acquisition
Parameters

            7.6.1 Gas Chromatograph

            Column coating:         DB-5
            Film thickness:         0.25 /urn
            Column dimension:       60 m x 0.32 mm
            Injector temperature:   270°C
            Splitless valve time:   45 s
            Interface temperature:  Function of the final  temperature
            Temperature program:

            Stage     Init.    Init.        Temp.        Final        Final
                      Temp.    Hold Time    Ramp         Temp.        Hold
                      (°C)     (min)         (°C/min)     (°C)         Time (m1n)


             1        200       2           5            220          16
             2                             5            235          7
             3                             5            330          5

            Total time:   60 min

            7.6.2 Mass  Spectrometer

                   7.6.2.1     The  mass   spectrometer  must  be operated  in  a
            selected  ion  monitoring   (SIM)   mode  with  a  total  cycle  time
            (including the  voltage reset time)  of one  second or  less (Sec.
            7.6.3.1).   At a minimum, the ions  listed  in Table  6 for each of the
            five  SIM  descriptors  must  be  monitored.   Note that with  the


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      exception  of the  last  descriptor  (OCDD/OCDF),  all  descriptors
      contain 10 ions.  The selection (Table 6} of the  molecular  ions M
      and M+2  for  13C-HxCDF and  13C-HpCDF rather  than  M+2 and M+4  (for
      consistency)  was made to  eliminate, even under high-resolution mass
      spectrometrie conditions, interferences  occurring  in these  two ion
      channels for samples containing high  levels of native HxCDDs and
      HpCDDs.  It is important  to maintain the same  set  of ions for both
      calibration and  sample extract analyses.   The selection of the lock-
      mass ion is left to the performing laboratory.

             NOTE:       At the  option   of the analyst,  the  tetra-  and
                        pentachlorinated  dioxins   and  furans  can  be
                        combined into a  single descriptor.

             7.6.2,2     The   recommended    mass    spectrometer   tuning
      conditions are based on the groups of monitored ions shown in Table
      6.  By using a PFK molecular leak,  tune the  instrument  to meet the
      minimum required resolving power of 10,000  (10 percent valley)  at
      m/z 304.9824  (PFK)  or any other  reference  signal  close  to  m/z
      303.9016 (from TCDF).   By  using peak  matching conditions and the
      aforementioned PFK reference peak,  verify that the exact mass of m/z
      380.9760 (PFK) is within 5 ppm of the required value.  Note that the
      selection of the  low-  and high-mass  ions must  be  such  that  they
      provide the largest voltage jump performed in any  of the  five  mass
      descriptors (Table 6).

      7.6.3   Data Acquisition

             7.6.3,1     The total  cycle  time for data acquisition must be
      <  I second.   The total cycle time includes the sum of all  the dwell
      times  and voltage reset times.

             7.6.3.2     Acquire SIM data for all  the ions  listed  in the
      five descriptors of Table 6.

7.7   Calibration

      7.7.1   Initial Calibration - Initial  calibration  is required  before
any samples  are analyzed for PCDDs and PCDFs.  Initial  calibration is also
required  if any routine calibration  (Sec. 7.7.3}  does  not  meet  the
required criteria listed in  Sec.  7.7.2,

             7.7.1.1     All five high-resolution concentration calibration
      solutions  listed  in  Table  5 must  be used   for the  initial
      calibration.

             7.7.1.2     Tune  the  instrument with  PFK  as described  in
      Sec. 7.6.2.2.

             7.7.1.3     Inject  2 pi  of  the  GC column performance  check
      solution (Sec. 5.7)  and acquire SIH mass spectral  data as  described
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earlier in Sec.  7.6.2. The total cycle time must  be < 1 second.  The
laboratory must  not perform  any further analysis until  it is demon-
strated and documented that  the criterion listed in  Sec. 8.2.1 was
met.

       7.7.1.4     By  using   the  same  GC  (Sec.   7.6.1)  and  MS
(Sec. 7.6.2} conditions that produced acceptable results with the
column performance check solution, analyze a 2 /zL portion of each
of  the five  concentration  calibration  solutions   once with  the
following mass spectrometer  operating parameters.

            7.7.1.4.1    The  ratio  of  integrated ion current for the
       ions  appearing  in Table  8  (homologous series  quantitation
       ions)  must  be within  the indicated control limits (set for
       each   homologous   series)   for all   unlabeled   calibration
       standards in  Table 5.

            7.7.1.4.2    The  ratio  of  integrated ion current for the
       ions  belonging  to the carbon-labeled internal  and recovery
       standards   (Table  5)   must  be within  the  control  limits
       stipulated  in Table 8.

            NOTE:  Sees.  7.7.1.4.1  and 7.7.1.4.2 require that 17 ion
                  ratios from Sec. 7.7.1.4.1 and 11  ion ratios from
                  Sec.  7.7.1.4.2  be  within  the specified  control
                  limits simultaneously  in  one  run.    It  is  the
                  laboratory's  responsibility  to  take  corrective
                  action if the ion  abundance ratios are  outside
                  the  1iraits.

            7.7,1.4.3    For  each selected ion current profile (SICP)
       and  for each GC  signal  corresponding to  the elution  of  a
       target  analyte and of its labeled  standards,  the  signal-to-
       noise  ratio  (S/N)  must   be better than  or  equal to  2.5.
       Measurement  of S/N  is required for any GC peak that  has an
       apparent S/N of less than 5:1.  The result of the calculation
       must  appear  on the SICP above  the GC peak in question.

            7.7.1.4.4    Referring  to Table  9,  calculate  the  17
       relative response factors (RFJ  for unlabeled  target ana^ytes
       [RF(n); n =  1 to  17]  relative  to  their  appropriate internal
       standards  (Table  5)  and  the nine  RFs for the  labeled  13C12
       internal standards [RF(m); m =  18 to 26)] relative to the two
       recovery  standards (Table  5)   according  to  the  following
       formulae:
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             Ax x Qis                       Ata x Q
  RFn    =  -            RFm    =
             Qx * Ajs                       Qis x A,
where:
     Ax     =      sum of the integrated ion abundances of the
                  quantisation   ions  (Tables  6  and  9)  for
                  unlabeled  PCDDs/PCDFs,

     Ais     =      sum of the integrated ion abundances of the
                  quantitation  ions (Tables  6 and  9)  for the
                  labeled  internal  standards,

     Ars     =      sum of the integrated ion abundances of the
                  quantitation  ions (Tables  6 and  9}  for the
                  labeled  recovery  standards,

     Qis     =      quantity of the  internal standard  injected
                  (pg),

     Qrs     =      quantity of the  recovery standard  injected
                  (pg),
     Qx     =      quantity of the unlabeled PCDD/PCDF analyte
                  injected  (pg).

     The RFn and RFm are dimensionless quantities;  the units
used to express Qis, Qre and Qx must  be the same.
     7.7.1.4.5    Calculate   the   RF  and  their  respective
percent  relative  standard  deviations (%RSD)  for the  five
calibration solutions:
                    5
     RFn   = 1/5  I RFn
     Where  n represents  a  particular  PCDD/PCDF  (2,3,7,8-
substituted) congener  (n  =  1 to 17; Table 9), and j  is  the
injection number  (or  calibration  solution number; j  =  1  to
5).

     7.7.1.4.6    The relative response factors to  be used for
the determination of the concentration of total isomers  in a
homologous series (Table 9}  are calculated as  follows:
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       7.7.1.4.6.1  For   congeners   that  belong  to   a
homologous series containing only one isomer (e.g., OCDD
and  OCDF}  or  only  one  2,3,7,8-substituted   isomer
(Table 4; TCDD,  PeCDD,  HpCDD,  and_JCDF),  the mean  RF
used will be the same as the mean  RF determined  in Sec.
7.7.1.4.5.

       NOTE: The  calibration  solutions  do  not  contain
            13C12-OCDF as an internal  standard.  This  is
            because a minimum resolving power of 12,000
            is  required to resolve the  [M+6]+  ion  of
            "C12-OCDF from the [M+2]+  ion  of OCDD  (and
            [M+4]+  from 13C12lpCDF with [H]+  of  OCDD).
            Therefore,  the  RF for  OCDF is  calculated
            relative to  13C12-OCDD.

       7.7.1.4.6.2  For   congeners   that  belong  to   a
homologous    series    containing    more    than_  one
2,3,7,8-substituted isomer (Table  4), the mean  RF used
for those homologous series will be the mean  of  the RFs
calculated  for   all   individual   2,3,7,8-substituted
congeners using the equation  below:

                   1       t

       RFk   -      -      I RFn
                   t      n=1

where:

       k  =  27 to  30  (Table 9), with 27 = PeCDF; 28  =
            HxCDF; 29 =  HxCDD; and 30  = HpCDF,

       t  =  total number of 2,3,7,8-substituted  isomers
            present in the calibration  solutions  (Table
            5)  for each homologous  series  (e.g.,  two
            for PeCDF, four for HxCDF,  three  for  HxCDD,
            two for HpCDF},

       NOTE: Presumably,  the HRGC/HRMS  response  factors
            of  different isomers  within  a  homologous
            series   are   different.     However,  this
            analytical    protocol    will    make   the
            assumption that the HRGC/HRMS  responses  of
            all  isomers  in a homologous series  that  do
            not  have  the 2,3,7,8-substitution  pattern
            are  the  same as  the  responses  of  one  or
            more  of  the 2,3,7,8-substituted  isomer(s}
            in that homologous series.
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                  7.7.1,4.7   Relative response factors [RFm] to be used
             for  the determination  of  the percent recoveries for the nine
             internal  standards  are calculated  as  follows:

                             Aism  x  Qrs
                                       5
                        RFm  = 1/5    I  RFmU,
                                       j-l
            where:
                  m     =     18 to  26 (congener type)  and  j =  1  to 5
                              (injection number),

                  Aism    =     sum of the integrated  ion abundances of the
                              quantitation ions  (Tables  6 and 9}  for a
                              given internal  standard (m = 18 to 26),

                  Ars    =     sum of the integrated  ion abundances of the
                              quantitation ions (Tables 6 and 9)  for the
                              appropriate recovery standard  (see Table 5,
                              footnotes),

                  Qrs»  Qis"1 =    quantities of,  respectively,  the recovery
                              standard  (rs)  and  a  particular  internal
                              standard  (is = m) injected (pg),

                  RFm  =       relative  response  factor of  a particular
                              internal  standard   (m)   relative   to  an
                              appropriate    recovery    standard,    as
                              determined from one injection, and

                  RFm  =       calculated mean relative response factor of
                              a particular internal  standard  (m) relative
                              to  an  appropriate  recovery standard,  as
                              determined from  the  five  initial  calibra-
                              tion injections  (j).

      7.7.2 Criteria  for Acceptable  Calibration  -  The  criteria  listed
below for acceptable  calibration must  be  met before sample analyses are
performed.

            7.7.2.1     The percent relative standard deviations for the
      mean  response factors  [RFn and RFmj from  the 17 unlabeled standards
      must  not  exceed  + 20  percent,   and  those for  the nine  labeled
      reference compounds must not exceed + 30 percent.
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             7.7.2.2     The S/N for the 6C signals present in every SICP
      (including the ones for the labeled standards) must be > 10.

             7.7.2.3     The ion abundance ratios  (Table 8) must be within
      the specified control limits.

             NOTE:       If  the  criterion  for  acceptable  calibration
                        listed  in  Sec,  7,7.2.1   is  met,  the  analyte-
                        specific RF can then be considered independent of
                        the analyte quantity for the calibration concen-
                        tration range.  The mean  RFs will be used for all
                        calculations   until   the   routine   calibration
                        criteria (Sec.  7.7.4)  are no longer met.  At such
                        time, new mean RFs will  be calculated from a new
                        set of injections of the calibration solutions.

      7.7.3  Routine Calibration  (Continuing Calibration Check) - Routine
calibrations must be performed at the beginning of a 12-hour period after
successful  mass resolution  and GC  resolution   performance  checks.   A
routine calibration is also required at the end of a 12-hour shift.

             7.7.3.1     Inject  2 ML  of  the  concentration  calibration
      solution HRCC-3 standard  (Table  5).   By using the  same HRGC/HRMS
      conditions as used  in Sees,  7.6.1 and 7.6.2, determine and document
      an acceptable calibration as provided in Sec.  7.7.4.

      7.7.4  Criteria  for  Acceptable Routine  Calibration  -  The following
criteria must be met before further analysis is performed.

             7.7.4.1     The measured RFs  [RFn for  the unlabeled standards]
      obtained during the  routine  calibration runs  must be  within  + 20
      percent  of  the  mean   values   established   during   the  initial
      calibration (Sec.  7.7.1.4.5).

             7.7.4.2     The measured RFs  [RFm for the labeled standards]
      obtained  during the  routine calibration  runs  must  be  within
      + 30 percent of  the mean  values  established  during  the  initial
      calibration (Sec,  7.7.1.4.7).

             7.7,4.3     The ".or. abundance rat:cs  CTab'-s 8] must be w4th4-
      the allowed control  limits.

             7.7.4.4     If either one of the criteria in Sees. 7.7.4.1 and
      7.7A.2 is not satisfied, repeat one more time.   If these criteria
      are still  not  satisfied,  the  entire routine  calibration  process
      (Sec.  7.7.1) must  be reviewed.    It is realized  that it  may not
      always be possible  to achieve all RF criteria.  For example, it has
      occurred that the RF criteria for 13C12-HpCDD and 13C12-OCDD were not
      met,  however,   the   RF  values   for  the  corresponding  unlabeled
      compounds were  routinely within the  criteria established  in the
      method.  In  these cases, 24 of the  26 RF parameters have met the QC
      criteria, and the  data quality  for  the unlabeled HpCDD  and  OCDD
      values were not compromised  as a result of the calibration event,


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      In these situations,  the analyst  must  assess  the  effect  on  overall
      data quality  as  required for the data quality  objectives  and decide
      on appropriate action.  Corrective  action  would  be in  order,  for
      example, if the compounds for which  the  RF criteria were  not  met
      included both  the unlabeled and the corresponding  internal  standard
      compounds.   If the  ion abundance  ratio criterion  (Sec. 7.7.4.3)  is
      not satisfied, refer  to the  note  in  Sec,  7.7.1,4.2  for resolution.

            NOT£:      An   initial  calibration  must  be  carried   out
                       whenever the HRCC-3, the sample  fortification,  or
                       the recovery  standard solution  is replaced by a
                       new solution from  a  different lot.

7.8   Analysis

      7.8.1  Remove  the sample or blank  extract (from Sec, 7.5.3.6)  from
storage.  With  a stream of  dry,  purified  nitrogen,  reduce the  extract
volume to 10 jLtL to  50 fj,L.
      NOTE:
            A  final  volume of  20 til  or more  should  be used  whenever
            possible.  A  10 y,L  final  volume  is  difficult  to  handle,  and
            injection  of  2 y.1  out of  10 pi leaves  little sample  for
            confirmations and repeat injections, and for archiving.

      7.8.2 Inject a  2  jxL aliquot of the extract into the GC,  operated
under the  conditions  that have  been  established to produce  acceptable
results with the performance check solution  (Sees.  7.6.1  and  7.6.2).

      7.8.3 Acquire SIM data according to Sees.  7.6.2 and 7.6.3.  Use  the
same acquisition  and  mass spectrometer operating conditions  previously
used to determine the relative response factors  (Sees.  7.7.1.4.4 through
7.7.1.4.7).  Ions characteristic of polychlorinated  diphenyl   ethers  are
included in the descriptors listed in Table  6.

      NOTE: The acquisition period must at least encompass the  PCDD/PCDF
            overall  retention time window  previously  determined  (Sec.
            8.2.1.3). Selected ion current profiles  (SICP) for the  lock-
            mass  ions (one per mass descriptor) must also be recorded  and
            included  in  the  data package.    These  SICPs  must  be true
            representations  of  the   evol-tior:   of  the  lock-mass  ions
            amplitudes during the  HRGC/HRMS  run  (see Sec. 8.2.2 for  the
            proper level of reference compound to be metered into the  ion
            chamber.)  The analyst may be required  to monitor a PFK ion,
            not as a  lock-mass,  but  as a regular ion,  in order to meet
            this  requirement.   It is recommended to examine the lock-mass
            ion SICP for obvious basic sensitivity  and  stability changes
            of the instrument during the GC/MS run  that could affect  the
            measurements  [Tondeur et  a!.,  1984,   1987].    Report  any
            discrepancies in  the  case narrative.
                            8290 - 30                         Revision 0
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      7.8.4  Identification Criteria - For  a  gas  chromatographic peak to
be  identified  as a  PCDD or  PCDF,  it must  meet all  of the  following
criteria:

             7.8.4.1     Retention  Times

                 7,8.4.1.1    For  2,3,7,8-substituted  congeners,  which
             have an  isotopically  labeled internal or  recovery standard
             present in the sample extract (this represents a total  of 10
             congeners including OCDD;  Tables  2 and 3), the retention time
             (RRT; at maximum  peak  height) of the sample components (i.e.,
             the two ions used for quantitation purposes  listed in  Table
             6)  must  be  within  -1  to -t-3  seconds of  the  isotopically
             labeled standard.

                 7.8.4.1.2    For  2,3,7,8-substituted compounds  that  do
             not have an  isotopically labeled internal  standard present in
             the sample extract (this represents a total of six congeners;
             Table 3), the retention time must fall within 0.005 retention
             time units  of  the relative  retention times measured  in the
             routine calibration.  Identification of OCDF is  based on its
             retention time relative to 13C12-OCDD  as  determined from the
             daily routine calibration results.

                 7.8,4,1.3    For non-2,3,7,8-substituted compounds (tetra
             through octa;  totaling  119  congeners),  the  retention  time
             must be within the  corresponding homologous  retention  time
             windows established  by analyzing the column performance check
             solution (Sec. 8.1.3).

                 7.8.4.1.4    The  ion current responses  for both ions used
             for quantitative  purposes  (e.g.,  for TCDDs:  m/z  319.8965 and
             321.8936) must reach maximum simultaneously (+ 2 seconds).

                 7.8.4.1.5    The  ion current responses  for both ions used
             for the labeled standards  (e.g.,  for  13C12-TCDD:  m/z 331.9368
             and m/z  333.9339)  must  reach  maximum simultaneously  (+  2
             seconds),

                 NOTE:  The analyst is required to verify the presence of
                        1,2,8,9-TCDD and  1,3,4,6,8-PeCDF  (Sec.  8.1.3)  in
                        the   SICPs  of the   daily performance  checks.
                        Should  either one   compound  be  missing,   the
                        analyst  is required to  take corrective  action  as
                        it  may  indicate  a  potential  problem  with  the
                        ability  to detect all the  PCDDs/PCDFs.

             7.8.4.2     Ion Abundance  Ratios

                 7.8.4.2.1    The  integrated ion currents for the two ions
             used for quantitation purposes  must have  a  ratio between the
             lower and upper limits established  for the  homologous series
                            8290 - 33                         Revision  0
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            to  which  the  peak  is  assigned.  See  Sees.  7,7.1.4,1  and
            7.7,1.4,2  and Table  8  for  details.

            7.8.4.3     Signal-to-Noise Ratio

                  7.8.4.3.1    All ion  current intensities must  be  > 2.5
            times noise level for positive identification of a PCDD/PCDF
            compound or a group of coeluting  isomers.  Figure 6 describes
            the  procedure  to be  followed  for the  determination of the
            S/N.

            7.8.4.4     Polychlorinated Diphenyl  Ether Interferences

                  7.8.4.4.1    In  addition  to  the  above  criteria,  the
            identification of a GC peak as a PCDF can only be made  if no
            signal having a  S/N  >  2.5  is detected at the  same retention
            time  {+  2 seconds)  in the  corresponding  polychlorinated
            diphenyl ether (PCDPE, Table 6)  channel.

7.9   Calculations

      7.9.1  For  gas  chromatographic peaks  that  have  met the  criteria
outlined in  Sees. 7.8.4.1.1 through 7.8.4.3.1,  calculate the concentration
of the PCDD or PCDF compounds using the formula:

              Ax  x  Qis
            Ais x W x RFn

where:

      Cx     =    concentration of unlabeled PCDD/PCDF congeners (or group
                 of  coeluting isomers  within  an homologous  series)  in
                 pg/g»

      Ax     =    sum of the integrated ion abundances of the quantitation
                 ions  (Table  6)  for  unlabeled  PCDDs/PCDFs,

      Ais     =    sum of the integrated '.or: abundances of the quant:tat?of
                 ions  (Table  6)  for  the labeled  internal  standards,

      Q1S     =    quantity,  in pg,  of the internal  standard added to the
                 sample before extraction,

      W     =    weight,  in g, of the sample (solid or organic liquid),
                 or volume  in ml of  an  aqueous sample,  and

      RFn    =    calculated mean relative response factor  for the analyte
                 [RFn with n  = 1 to  17;  Sec. 7.7.1.4.5].

      If the analyte is identified as  one of the 2,3,7,8-substituted PCDDs
or PCDFs, RFn is the value calculated using the equation in Sec.  7.7.1.4.5.
However,  if it is a non-2,3,7,8-substituted congener, the RF(k) value Is

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the one calculated using  the  equation  in Sec.  7.7.1.4.6.2,   [RFk  k = 27
to 30].

      7.9.2  Calculate the percent recovery of the nine  internal standards
measured in  the sample extract, using  the formula:

                                              A*  *  Qre
      Internal standard percent recovery  =  ——	——   x  100
                                            Qis x Are x RFm

where:

      Ajs     =    sum of the integrated ion abundances of the quantitation
                  ions (Table  6)  for the labeled internal  standard,

      Ars     =    sum of the integrated ion abundances of the quantitation
                  ions (Table  6)  for the labeled recovery standard; the
                  selection  of the recovery standard depends on the type
                  of  congeners (see  Table  5,  footnotes),

      Qis     =    quantity,  in pg,  of the internal standard added to the
                  sample  before extraction,

      Qrs     =    quantity,  in pg,  of the  recovery standard added to the
                  cleaned-up sample residue before HRGC/HRMS analysis, and

      RFm =       calculated mean relative response factor  for the labeled
                  internal standard relative to the appropriate  (see Table
                  5,  footnotes) recovery standard.	This  represents the
                  mean obtained in Sec. 7.7.1.4.7 [RFm with m =  18 to 26].

      NOTE:  For  human adipose tissue,  adjust  the percent recoveries by
             adding  1 percent  to  the calculated  value  to  compensate for
             the   1 percent  of  the  extract  diverted  for  the  lipid
             determination.

      7.9.3  If  the  concentration  in  the  final  extract  of  any of the
fifteen 2,3,7,8-substituted  PCDD/PCDF  compounds (Table  3)  exceeds the
upper method calibrator lirrnts (MCL) l:sted :r: Table I (e.g.,  200  pg/ul
for TCDD in soil), the linear range of response versus  concentration may
have been exceeded, and a  second analysis of the sample  (using a one tenth
aliquot) should be undertaken.  The volumes of the internal  and recovery
standard solutions should remain the  same  as described  for  the sample
preparation  (Sees. 7.1  to 7.9.3).   For the other  congeners  (including
OCDD), however, report the measured  concentration and  indicate that the
value exceeds the MCL.

             7.9.3.1     If  a  smaller   sample  size  would   not   be
      representative  of the entire sample, one of the  following options is
      recommended:

      (1)     Re-extract an additional aliquot of sufficient size to insure
      that  it is  representative of  the entire sample.   Spike  it with  a

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      higher concentration of internal standard.  Prior to GC/MS analysis,
      dilute  the  sample  so that  it has  a concentration  of  internal
      standard equivalent to that  present  in the calibration  standard.
      Then, analyze the diluted extract.

      (2)    Re-extract an additional  aliquot of sufficient size to insure
      that it is representative of the  entire  sample.   Spike  it  with  a
      higher concentration of  internal standard.   Immediately  following
      extraction, transfer the  sample to a volumetric flask and dilute to
      known  volume.    Remove  an appropriate  aliquot and  proceed  with
      cleanup and  analysis.

      (3)    Use the original   analysis data to  quantitate the  internal
      standard recoveries.   Respike  the  original  extract (note that no
      additional cleanup is  necessary) with  100  times the usual  quantity
      of internal standards.  Dilute the re-spiked extract by a factor of
      100.   Reanalyze  the  diluted  sample   using  the  internal  standard
      recoveries  calculated from  the initial  analysis  to  correct  the
      results for  losses during isolation and cleanup.

      7.9.4  The total concentration for each homologous series of PCDD and
PCDF  is  calculated  by  summing up the concentrations  of all  positively
identified isomers  of each homologous  series. Therefore, the total  should
also include the 2,3,7,8-substituted  congeners.   The total number of GC
signals  included  in the homologous  total   concentration  value must be
specified in the report.  If an isomer is not detected,  use zero  (0) in
this calculation.

      7.9.5  Sample  Specific  Estimated  Detection   Limit  -  The  sample
specific estimated detection limit  (EDL)  is  the  concentration  of a given
analyte required to produce a  signal  with a peak height  of at  least 2.5
times  the background  signal   level.    An   EDL  is   calculated  for  each
2,3,7,8-substituted congener that is not identified, regardless of whether
or not other non-2,3,7,8-substituted  isomers are present.  Two  methods of
calculation can be  used, as follows,  depending  on the type of  response
produced during the analysis of a  particular sample.

             7.9.5.1     Samples giving a response for both quantisation
      ions (Tables  6 and 9) that  is  less  than  2.5 times the  background
      level.

                 7.9,5.1.1    Use   the  expression  for  EDL   (specific
             2,3,7,8-substituted PCDD/PCDF)  below to calculate  an EDL for
             each absent 2,3,7,8-substituted PCDD/PCDF (i.e.,  S/N < 2.5).
             The background level is determined  by  measuring  the range of
             the noise (peak to peak)  for the two quantitation ions (Table
             6)  of  a particular  2,3,7,8-substituted  isomer  within an
             homologous   series,   in   the   region   of  the  SICP   trace
             corresponding to the elution of  the internal  standard (if the
             congener possesses an internal  standard) or  in the region of
             the  SICP  where  the  congener  is  expected  to   elute by
             comparison  with  the  routine  calibration  data  (for  those
             congeners   that   do  not  have  a   13C-labeled   standard).
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             multiplying  that  noise  height  by  2.5,  and  relating  the
             product  to an estimated concentration that  would produce that
             peak height.

                  Use the formula;

                                                      2.5  x  Hx   x  QiE
             EDL  (specific  2,3,7,8-subst.  PCDD/PCDF)  =  	—	
                                                       Hta x W  x RFn

             where:

                  EDL =  estimated   detection   limit   for   homologous
                        2,3,7,8-substituted PCDDs/PCDFs.

                  Hx  =  sum of  the  height of  the noise   level for  each
                        quantitation  ion   (Table  6}   for  the  unlabeled
                        PCDDs/PCDFs, measured as shown in Figure  6.

                  His  =   sum of  the  height of  the noise   level for  each
                        quantitation  ion   (Table  6}  for  the  labeled
                        internal standard, measured as  shown in Figure 6.

                  W,  RFn,  and  QiE retain the same  meanings as  defined  in
             Sec.  7.9.1.

             7,9.5.2     Samples characterized  by a  response   above  the
      background level  with a S/N of  at least  2.5 for  both quantitation
      ions (Tables 6  and  9).

                  7.9.5.2.1    When  the response  of  a  signal  having  the
             same retention time as  a  2,3,7,8-substituted congener has a
             S/N  in excess of  2.5  and does  not  meet  any of  the other
             qualitative  identification criteria  listed   in Sec.  7.8.4,
             calculate  the  "Estimated Maximum Possible  Concentration"
             (EHPC)  according  to  the  expression shown   in  Sec. 7.9.1,
             except that A,, in Sec.  7.9.1  should represent the  sum of the
             area under  the  smaller  peak and  of the other   peak  area
             calculated using the theoretical chlorine  isotope  ratio.

      7.9.6  The  relative percent difference (RPD)  of any duplicate sample
results are calculated as follows:
      RPD  «  	    x  100
             (S, + S2 ) / 2
      S,  and  S2 represent sample and duplicate sample results.

      7.9.7  The 2,3,7,8-TCDD toxicity equivalents (TE) of PCDDs and PCDFs
present  in  the  sample  are  calculated,  if  requested  by the  data user,
according to the method recommended by the Chlorinated Dioxins Workgroup

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(CDWG) of the EPA and the Center for Disease Control  (CDC).   This method
assigns a 2,3,7,8-TCDD toxicity equivalency factor (TEF)  to  each of the
fifteen 2,3,7,8-substituted  PCDDs  and PCDFs  (Table  3)  and to OCDD and
OCDF, as shown in Table  10.   The 2,3,7,8-TCDD equivalent of the PCDDs and
PCDFs present in the sample is calculated by summing  the TEF  times their
concentration for each of the compounds or groups of  compounds listed in
Table 10.  The exclusion of  other  homologous  series  such  as  mono-,  di-s
and tri- chlorinated dibenzodioxins and dibenzofurans does not mean that
they are non-toxic.  However, their toxicity, as  known  at this time, is
much lower than  the toxicity of the  compounds  listed in Table  10.  The
above procedure for calculating the 2,3,7,8-TCDD toxicity equivalents is
not claimed by the CDldG to be based  on  a thoroughly established scientific
foundation.   The procedure, rather,  represents a "consensus recommendation
on science policy".   Since  the  procedure may be  changed  in  the  future,
reporting requirements  for  PCDD and  PCDF  data  would still  include the
reporting of  the analyte  concentrations  of the  PCDD/PCDF congener  as
calculated in Sees. 7.9.1 and 7.9.4.

            7,9.7,1     Two  GC Column  TEF  Determination

                  7.9.7.1.1    The concentration of 2,3,7,8-TCDD (see note
            below), is calculated from the analysis of the sample extract
            on  the  60   m  DB-5  fused  silica  capillary  column.    The
            experimental  conditions  remain the  same as  the  conditions
            described previously in  Sec.  7.8,  and the  calculations are
            performed  as outlined  in  Sec.  7.9.   The  chromatographic
            separation  between  the 2,3,7,8-TCDD  and its close  eluters
             (1,2,3,7/1,2,3,8-TCDD and 1,2,3,9-TCDD) must be equal or less
            than 25 percent  valley.

                 7.9.7.1.2    The  concentration  of the  2,3,7,8-TCDF  is
            obtained from the analysis of the sample  extract  on the 30 m
            DB-225  fused silica capillary  column.   However,  the  GC/MS
            conditions must be altered so  that:   (1) only the  first three
            descriptors  (i.e.,  tetra-,   penta-,  and   hexachlorinated
            congeners) of Table 6  are used; and  (2)  the  switching  time
            between  descriptor  2   (pentachlorinated  congeners)   and
            descriptor   3    (hexachlorinated   congeners)   takes   place
            following   the   elution   of   13C12-l,2,3,7,8-PeCDD.    The
            concentration calculations are performed  as  outlined  In Sec.
            7.9.  The chromatographic  separation between  the 2,3,7,8-TCDF
            and its close eluters (2,3,4,7-TCDF and 1,2,3,9-TCDF)  must be
            equal or less than 25 percent valley.

                 NOTE:  The confirmation and quantisation of 2,3,7,8-TCDD
                        (Sec. 7.9.7.1.1)  may be accomplished  on  the SP-
                        2330   GC  column   instead  of   the  DB-5  column,
                        provided  the  criteria  listed in  Sec.  8.2.1  are
                        met   and  the   requirements   described   in   Sec.
                        8.3.2 are followed.
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                        7.9,7.1.3   For  a  gas  chromatographic  peak  to  be
                   identified as a  2,3,7,8-substituted  PCDD/PCDF congener, it
                   must  meet  the   ion   abundance  and  signal-to-noise  ratio
                   criteria listed  in Sees, 7.8.4.2 and 7.8.4.3, respectively.
                   In  addition,  the  retention  time  identification  criterion
                   described in Sec.  7.8.4.1,1  applies  here  for congeners for
                   which a carbon-labeled  analogue is  available in  the sample
                   extract.  However,  the relative retention time (RRT) of the
                   2,3,7,8-substituted congeners  for  which  no  carbon-labeled
                   analogues are available  must fall  within 0.006 units of the
                   carbon-labeled  standard  RRT.     Experimentally,   this  is
                   accomplished by  using  the attributions described in Table 11
                   and the  results from the  routine  calibration  run  on  the
                   SP-2330 column.
8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control (QC) procedures.
Quality control to  validate  sample extraction is covered in Method  3500.   If
extract cleanup was performed,  follow the QC  in Method 3600 and in the specific
cleanup method.

      8.2   System  Performance  Criteria -  System  performance  criteria  are
presented below.  The laboratory may use  the  recommended GC column described in
Sec. 4.2.   It must be documented that all  applicable  system performance criteria
(specified in Sees. 8.2.1 and 8.2.2) were met before analysis of any sample is
performed.  Sec. 7.6.1 provides  recommended  GC conditions that  can  be used to
satisfy the required  criteria.   Figure  3 provides  a  typical  12-hour analysis
sequence,  whereby the  response factors  and  mass  spectrometer  resolving power
checks must be performed  at  the beginning and the  end of each 12-hour period of
operation.  A GC column performance check is only required at the beginning of
each 12-hour period during which samples are analyzed.  An HRGC/HRMS method blank
run is required between a calibration  run and the first  sample  run.   The same
method blank extract may thus be analyzed  more than once if the number of samples
within a batch requires more than 12 hours of analyses.

            8.2.1  GC  Column  Performance

                   8.2.1.1     Inject 2 pi (Sec. 4.1.1) of the column performance
            check solution (Sec. 5.7)  and acquire  selected ion monitoring (SIM)
            data as described  in  Sec.  7.6.2  within a total  cycle time  of  < 1
            second (Sec.  7.6.3.1).

                   8.2.1.2     The chromatographic  separation  between 2,3,7,8-
            TCDD and the  peaks representing  any  other unlabeled  TCDD isomers
            must be resolved with a valley of < 25 percent (Figure 4), where:

                   Valley  percent    =   (x/y)  (100)

                   x  =  measured as in Figure 4  from  the  2,3,7,8-closest TCDD
                       eluting isomer, and
                  y  =  the  peak height of 2,3,7,8-TCDD.


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       It is  the  responsibility of  the  laboratory to  verify the
conditions suitable for the appropriate resolution of 2,3,7,8-TCDD
from  all other  TCDD  isomers.   The  GC  column  performance  check
solution also  contains  the  known  first  and last PCDD/PCDF eluters
under the conditions  specified  in  this  protocol.  Their retention
times  are  used to  determine the  eight  homologue  retention  time
windows  that  are   used   for   qualitative   (Sec. 7.8.4.1}   and
quantitative purposes.  All  peaks (that includes 13C12-2,3,7,8-TCDD)
should be labeled  and  identified on the chromatograms.  Furthermore,
all first eluters of a homologous series should  be labeled with the
letter  F,  and all last eluters of a homologous  series  should  be
labeled  with   the  letter  L  (Figure  4  shows an  example of  peak
labeling for  TCDD isomers).  Any  individual  selected  ion current
profile  (SICP) (for the tetras,  this would be the SICP for m/z 322
and m/z  304)  or  the reconstructed homologue  ion  current (for the
tetras, this would correspond to m/z 320 + m/z 322 + m/z 304 -f m/z
306) constitutes an acceptable form of data presentation.  An SICP
for the labeled compounds (e.g., m/z 334 for labeled TCDD) is also
required.

       8.2.1.3    The retention  times for the  switching of SIM ions
characteristic  of  one  homologous  series  to  the  next  higher
homologous  series must be indicated in the SICP.  Accurate switching
at  the   appropriate  times   is  absolutely  necessary for  accurate
monitoring  of  these  compounds.   Allowable tolerance on  the  daily
verification with  the  GC performance check solution should be better
than  10 seconds  for  the   absolute  retention  times   of all  the
components  of  the mixture.   Particular caution should  be exercised
for the  switching time  between  the last tetrachlorinated congener
(i.e., 1,2,8,9-TCDD)  and the first  pentachlorinated congener (i.e.,
1,3,4,6,8-PeCDF),  as these two compounds elute within 15 seconds of
each other  on the 60 m DB-5 column.  A  laboratory with a  GC/HS
system that  is not capable of detecting both congeners (1,2,8,9-TCDD
and  1,3,4,6,8-PeCDF)  within  one  analysis  must take  corrective
action.  If the recommended  column is not  used,  then the first and
last  eluting  isomer  of   each   homologue   must   be   determined
experimentally on  the column which  is  used, and the  appropriate
isomers must then  be used for window definition and switching times.

8.2.2 Mass  Spectrometer Performance

      8.2.2.1    The mass  spectrometer  must  be operated in  the
electron ionization mode.   A static  resolving  power of  at  least
10,000  (10  percent  valley  definition)  must  be demonstrated  at
appropriate masses  before  any  analysis is performed  (Sec.  7.8).
Static resolving power checks must be performed at the beginning and
at the  end  of each 12  hour  period of operation.   However,  it  is
recommended that  a check  of the  static   resolution  be made  and
documented  before and after  each analysis.   Corrective  action must
be  implemented whenever the  resolving power  does not meet  the
requirement.
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             8.2.2.2     Chromatography time for PCDDs and  PCDFs  exceeds
      the long term mass  stability of the mass spectrometer.  Because the
      instrument is operated in the  high-resolution  mode,  mass  drifts of
      a few ppm (e.g.,  5  ppm in mass) can have serious adverse effects on
      instrument  performance.  Therefore,  a  mass  drift  correction  is
      mandatory.  To that effect, it is recommended to select a lock-mass
      ion from the  reference compound (PFK is recommended) used for tuning
      the mass  spectrometer.   The  selection  of  the lock-mass   ion  is
      dependent  on  the   masses  of  the  ions monitored  within  each
      descriptor.  Table  6 offers some  suggestions for the lock-mass ions.
      However,  an  acceptable  lock-mass   ion  at  any mass  between  the
      lightest and heaviest  ion  in each descriptor can be used to  monitor
      and correct mass  drifts.  The level  of the reference compound (PFK)
      metered into the ion  chamber  during HRGC/HRMS analyses  should  be
      adjusted so that the amplitude of  the most  intense  selected lock-
      mass  ion  signal  (regardless  of  the descriptor number)  does  not
      exceed 10 percent of the full  scale deflection for  a  given  set of
      detector parameters.  Under those  conditions,  sensitivity  changes
      that  might occur  during the  analysis  can  be more  effectively
      monitored.

      NOTE:   Excessive  PFK (or  any other  reference substance)  may cause
             noise  problems and contamination of the  ion  source  resulting
             in  an  increase  in downtime for source cleaning.

             8.2.2.3    Documentation  of  the  instrument  resolving power
      must then  be  accomplished by recording the peak profile of the high-
      mass reference signal  (m/z 380.9760) obtained during the above peak
      matching experiment by using the  low-mass PFK ion at m/z 304.9824 as
      a  reference.    The minimum  resolving  power   of  10,000  must  be
      demonstrated on the high-mass ion while  it is transmitted at a lower
      accelerating voltage  than the  low-mass reference  ion,  which  is
      transmitted at full sensitivity.   The  format  of the  peak  profile
      representation (Figure 5) must  allow  manual  determination  of  the
      resolution, i.e.,  the  horizontal  axis  must be a  calibrated  mass
      scale   (amu or  ppm  per division).   The  result of  the peak width
      measurement  (performed  at  5  percent  of  the  maximum,   which
      corresponds to the  10 percent valley definition) must appear on the
      hard copy and cannot exceed 100 ppm  at m/z 380.9760 (or 0.038 amu at
      that particular mass).

8.3   Quality Control Samples

      8.3.1   Performance  Evaluation  Samples -  Included among the  samples
in all batches  may be  samples  (blind  or  double blind) containing known
amounts of  unlabeled 2,3,7,8-substituted  PCDDs/PCDFs or  other  PCDD/PCDF
congeners.

      8.3.2   Performance  Check Solutions

             8,3.2.1    At the beginning  of  each  12-hour period  during
      which  samples are  to  be  analyzed,  an  aliquot  of the  1)  GC  column
      performance  check  solution  and  2) high-resolution  concentration
      calibration solution No.  3 (HRCC-3; see  Table  5) shall  be analyzed

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to  demonstrate adequate GC  resolution and  sensitivity,  response
factor reproducibility,  and mass range calibration,  and to establish
the PCDD/PCDF retention  time windows.  A mass  resolution check shall
also be performed to demonstrate adequate mass resolution using an
appropriate  reference  compound  (PFK  is  recommended).     If  the
required criteria are not met,  remedial  action must be  taken before
any samples are analyzed.

       8.3.2.2    To validate positive sample data, the routine or
continuing calibration  (HRCC-3;  Table 5)  and the  mass resolution
check must  be performed also  at the  end  of each  12-hour period
during which  samples  are analyzed.  Furthermore, an HRGC/HRMS method
blank run must be recorded following a calibration run  and the first
sample run.

           8.3.2.2.1   If the laboratory operates  only during one
       period   (shift)   each  day of  12  hours  or  less,  the  GC
       performance check solution must be analyzed only once  (at the
       beginning of the period) to validate the data acquired during
       the period.    However,  the  mass resolution  and continuing
       calibration checks must be performed at the beginning  as well
       as  at  the end  of  the period.

           8.3.2.2.2   If   the    laboratory    operates   during
       consecutive  12-hour periods  (shifts), analysis of  the  GC
       performance check solution must be performed  at the beginning
       of  each 12-hour period.   The mass resolution and continuing
       calibration checks from  the  previous  period  can be used for
       the beginning  of  the next  period.

       8.3.2.3    Results of  at least one analysis of the GC column
performance check  solution and of two mass resolution and continuing
calibration checks must be  reported with the sample data collected
during a 12 hour period.

       8.3.2.4    Deviations  from  criteria  specified  for  the  GC
performance check or  for the mass  resolution check invalidate all
positive sample data collected between analyses  of  the performance
check solution, and  the extracts from those oositive samples shall
be reanalyzed.

       If  the  routine calibration run fails  at the beginning  of a 12
hour shift, the instructions  in Sec. 7,7.4.4 must be followed.  If
the continuing calibration  check performed at the end of a 12 hour
period fails  by no more than  25 percent RPD for the  17  unlabeled
compounds and 35 percent RPD for  the 9 labeled reference compounds,
use the mean  RFs  from  the two daily routine calibration  runs  to
compute the analyte concentrations, instead of the RFs obtained from
the initial calibration.  A  new initial calibration  (new  RFs)  is
required immediately  (within two hours)  following  the analysis  of
the  samples,   whenever   the  RPD  from  the  end-of-shift  routine
calibration exceeds 25 percent or 35 percent,  respectively.  Failure
to  perform a  new  initial  calibration  immediately following  the
analysis of the samples will  automatically require reanalysis of all

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      positive sample extracts  analyzed before the  failed  end-of-shift
      continuing calibration check,

      8.3.3 The  GC  column  performance  check, mixture,  high-resolution
concentration calibration   solutions,   and  the   sample   fortification
solutions may be obtained from  the  EMSL-CIN.   However,  if not available
from the  EMSL-CIN,   standards can  be obtained  from other  sources,  and
solutions  can  be prepared  in  the  laboratory.   Concentrations of  all
solutions  containing 2,3,7,8-substituted  PCDDs/PCDFs,  which  are  not
obtained from the EMSL-CIN, must be  verified  by comparison  with the  EPA
standard solutions that  are available from the EMSL-CIN.

      8.3.4 Field Blanks - Each  batch of samples usually contains a field
blank sample  of uncontaminated  soil,  sediment or water  that is  to  be
fortified before analysis according  to Sec. 8.3.4.1.  In addition to this
field blank,  a batch  of  samples  may  include a rinsate, which is a portion
of the solvent  (usually trichloroethylene) that was  used to rinse sampling
equipment.  The rinsate  is  analyzed  to  assure  that the  samples  were  not
contaminated by the sampling equipment,

            8.3.4.1     Fortified  Field  Blank

                 8.3.4.1.1    Weigh  a 10 g portion  or use 1 L (for aqueous
            samples) of  the specified field blank  sample  and  add  100  p,L
            of  the  solution  containing  the  nine  internal   standards
            (Table 2) diluted with  1.0 mL  acetone  (Sec. 7.1).

                 8.3.4.1.2    Extract by using the procedures beginning
            in  Sees.  7.4.5 or  7.4.6, as applicable, add  10  ^L of  the
            recovery standard solution (Sec.  7.5.3.6) and  analyze  a 2  ^L
            aliquot  of the concentrated extract.

                 8,3.4.1.3    Calculate  the concentration (Sec. 7.9.1) of
            2,3,7,8-substituted PCDDs/PCDFs and the  percent recovery of
            the internal standards  (Sec. 7.9.2).

                 8.3.4.1.4    Extract  and  analyze   a  new   simulated
            fortified  field  blank   whenever  new   lots  of  solvents  or
            reagents  are  used  for  sample  extraction  or  for  column
            chromatographic procedures.

            8.3.4.2     Rinsate  Sample

                 8.3,4.2.1    The  rinsate sample must be  fortified like
            a regular sample.

                 8.3,4.2.2    Take  a  100 ml  (± 0.5  mL)  portion of  the
            sampling equipment rinse solvent (rinsate sample), filter,  if
            necessary, and add 100 IJ.L of the solution containing the nine
            internal standards  (Table 2).

                 8.3.4.2.3    Using   a  KD  apparatus,  concentrate   to
            approximately 5 mL.


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            NOTE: As an option, a rotary evaporator may be used in
                  place of the  KD  apparatus  for the concentration
                  of the rinsate.

            8.3.4.2.4   Transfer the  5  ml  concentrate  from the KD
       concentrator tube  in   1  ml  portions  to  a  1 ml  minivial,
       reducing  the  volume  in  the minivial   as necessary  with  a
       gentle stream of dry nitrogen.

            8.3.4.2.5   Rinse  the  KD concentrator  tube  with  two
       0.5 ml portions  of hexane and transfer  the rinses to the 1 ml
       minivial.   Blow  down with dry nitrogen  as necessary.

            8,3.4.2.6   Just  before  analysis,  add 10 nl  recovery
       standard  solution  (Table 2) and  reduce  the volume  to  its
       final   volume,   as   necessary  (Sec.  7.8.1).     No  column
       chromatography is required.

            8.3.4.2.7    Analyze  an  aliquot  following  the  same
       procedures used  to  analyze  samples.

            8.3.4.2.8   Report  percent  recovery  of the  internal
       standard and  the presence of any PCDD/PCDF compounds in /ug/L
       of rinsate solvent.

8.3.5  Duplicate Analyses

       8.3.5.1    In each batch  of  samples,   locate  the  sample
specified for duplicate analysis,  and  analyze a  second 10 g soil or
sediment  sample  portion or  1 L water  sample,  or  an  appropriate
amount of the type of matrix under consideration.

            8.3.5.1.1    The results  of  the  laboratory  duplicates
       (percent recovery and  concentrations of 2,3,7,8-substituted
       PCDD/PCDF compounds) should  agree within 25 percent relative
       difference (difference  expressed  as  percentage of the mean).
       Report all results.

            8.3.5.1.2    Recommended actions to he! p 1 ocate problems:

                  8.3.5.1,2.1 Verify    satisfactory    instrument
            performance (Sees. 8.2  and 8.3).

                  8.3.5.1.2.2 If possible,  verify that no error was
            made while  weighing  the sample  portions.

                  8.3.5.1.2.3 Review the analytical procedures with
            the performing laboratory  personnel.

8.3.6  Matrix Spike  and Matrix Spike Duplicate

       8.3.6.1    Locate the  sample for the MS and MSD analyses (the
sample may be labeled  "double volume").
                       8290  -  42                         Revision 0
                                                    September 1994

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                   8.3,6.2     Add  an  appropriate volume  of the  matrix  spike
            fortification solution (Sec. 5.10) and of the sample fortification
            solution (Sec.  5.8),  adjusting  the fortification level as specified
            in Table 1 under IS Spiking Levels.

                   8.3.6.3     Analyze the  MS  and MSD samples  as  described in
            Sec. 7.

                   8.3.6.4     The results obtained from the MS and MSD samples
            (concentrations of  2,3,7,8-substituted  PCDDs/PCDFs)  should  agree
            within 20 percent relative difference.

      8.4   Percent Recovery of the Internal Standards -  For each sample, method
blank and rinsate,  calculate  the percent recovery (Sec.  7.9.2).   The percent
recovery should be between 40 percent and 135 percent for  all 2,3,7,8-substituted
internal standards.

      NOTE:        A low  or  high  percent  recovery for a  blank does not require
                   discarding  the  analytical  data  but  it  may  indicate  a
                   potential problem with future  analytical  data.

      8.5   Identification Criteria

            8.5.1  If either one of  the  identification criteria  appearing in
      Sees. 7.8.4.1.1 through  7.8.4.1.4 is  not met for an homologous series, it
      is reported that the sample does not contain unlabeled 2,3,7,8-substituted
      PCDD/PCDF isomers for that homologous series at the calculated detection
      limit (Sec. 7.9,5)

            8.5.2  If the first initial identification criteria (Sees. 7.8.4,1.1
      through 7.8.4.1.4) are met,  but  the criteria appearing in Sees, 7.8.4.1.5
      and 7.8.4.2,1 are not  met,  that  sample is presumed to contain interfering
      contaminants.  This must be noted on the analytical  report form, and the
      sample should be rerun or the extract reanalyzed.

      8.6   Unused portions  of samples and  sample extracts should be preserved
for six months after sample  receipt to allow further  analyses.

      8.7   Reuse  of glassware  is  to  be minimized  to  avoid  the  risk  of
contamination.
9.0   METHOD PERFORMANCE

      9.1   Data are currently not available.


10,0  REFERENCES

1.     "Control  of  Interferences  in the  Analysis  of Human Adipose  Tissue for
      2,3,7,8-Tetrachlorodibenzo-p-dioxin".  D.  G.  Patterson, J.S. Holler, D.F.
      Grote,  L.R.   Alexander,  C.R.  Lapeza,  R.C.  O'Connor  and  J.A.  Liddle.
      Environ. Toxicol. Chem. 5, 355-360 (1986).


                                   8290  - 43                         Revision 0
                                                                September 1994

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2.     "Method 8290: Analytical Procedures and Quality Assurance for Multimedia
       Analysis of  Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans by High-
       Resolution  Gas  Chromatography/High-Resolution  Mass  Spectrometry".   Y.
       Tondeur  and  W.F.  Beckert.    U.S.  Environmental  Protection  Agency,
       Environmental Monitoring Systems  Laboratory, Las Vegas, NV.

3,     "Carcinogens - Working with Carcinogens", Department of Health, Education,
       and Welfare, Public Health Service,  Center for Disease Control.  National
       Institute  for  Occupational  Safety  and  Health.  Publication  No.  77-206,
       August 1977,

4.     "OSHA  Safety and  Health  Standards, General  Industry",  (29  CFR  1910),
       Occupational Safety and Health Administration, OSHA 2206 (revised January
       1976).

5.     "Safety  in  Academic Chemistry  Laboratories", American  Chemical  Society
       Publication, Committee on Chemical Safety  (3rd Edition, 1979.)

6.     "Hybrid  HR6C/MS/MS Method for  the  Characterization  of Tetrachlorinated
       Dibenzo-p-dioxins  in Environmental Samples." Y. Tondeur, W.J. Niederhut,
       S.R. Missler, and  J.E. Campana, Mass Spectrom. 14, 449-456 (1987).

7.     USEPA National  Dioxin Study -  Phase II,  "Analytical Procedures  and Quality
       Assurance Plan  for the Determination  of PCDD/PCDF in Fish",  EPA-Duluth,
       October 26,  1987.


11.0   SAFETY

       11.1  The following  safety  practices  are excerpts from EPA  Method 613,
Sec. 4 (July 1982 version) and amended for use  in  conjunction with this method.
The  2,3,7,8-TCDD  isomer  has been  found  to  be acnegenic, carcinogenic,  and
teratogenic in  laboratory animal  studies.   Other PCDDs and  PCDFs  containing
chlorine atoms in positions 2,3,7,8 are known to have toxicities comparable to
that of 2,3,7,8-TCDD.   The analyst  should note  that finely divided dry soils
contaminated with  PCDDs and PCDFs  are  particularly  hazardous because  of the
potential  for inhalation and ingestion.   It is  recommended  that such samples be
processed in a confined environment, such  as a  hood or a glove box.   Laboratory
personnel  handling these types of samples should wear masks  fitted with charcoal
filters to prevent inhalation of dust.

       11.2  The toxicity or carcinogenicity of each reagent used in this method
is not precisely defined; however, each chemical compound should be treated as
a potential  health  hazard.  From this viewpoint, exposure to  these chemicals must
be kept to a minimum.   The laboratory is responsible for maintaining a current
awareness file of OSHA regulations regarding the safe handling of the chemicals
specified in this method.  A reference  file of material  safety data sheets should
be made available to all  personnel involved in  the chemical  analysis of samples
suspected to contain  PCDDs  and/or PCDFs.  Additional  references  to laboratory
safety are given in references 3,  4 and 5.

       11.3  Each laboratory must develop a strict safety program for the handling
of PCDDs and PCDFs.  The laboratory practices listed below  are recommended.


                                  8290  -  44                         Revision 0
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            11.3.1      Contamination  of the laboratory  will  be minimized  by
      conducting most of the manipulations in a hood.

            11.3.2      The   effluents  of   sample   splitters   for  the   gas
      chromatograph  and roughing pumps  on  the HRGC/HRMS  system should  pass
      through either a column of activated charcoal  or be  bubbled through a trap
      containing oil or high boiling alcohols.

            11.3.3      Liquid waste should be dissolved in methanol  or  ethanol
      and irradiated with ultraviolet light at a wavelength  less than 290 nm for
      several days  (use F 40 BL  lamps,  or equivalent).   Using this  analytical
      method, analyze the  irradiated liquid wastes and dispose of the solutions
      when 2,3,7,8-TCDD and -TCDF congeners  can no  longer be detected.

      11.4  The following precautions were issued by  Dow Chemical U.S.A. (revised
11/78)  for safe handling of 2,3,7,8-TCDD in  the laboratory  and amended  for use
in conjunction with this method.

            11.4.1      The following statements on safe handling are as complete
      as possible  on the  basis of  available toxicological information.   The
      precautions for safe handling and use  are necessarily general  in nature
      since  detailed,   specific  recommendations can  be  made  only  for  the
      particular exposure  and circumstances of each  individual  use.   Assistance
      in evaluating  the health  hazards  of particular plant conditions  may  be
      obtained from certain consulting laboratories and from State  Departments
      of Health or  of Labor, many of which have an  industrial health service.
      The 2,3,7,8-TCDD isomer is  extremely toxic to  certain kinds of laboratory
      animals.   However,   it  has been  handled for  years  without   injury  in
      analytical and biological  laboratories.  Many  techniques used  in handling
      radioactive and infectious materials  are  applicable to 2,3,7,8-TCDD.

                   11.4.1.1   Protective Equipment:  Throw away plastic  gloves,
            apron or lab coat,  safety  glasses and laboratory hood adequate for
            radioactive  work.   However,  PVC gloves  should not  be  used.

                   11.4.1.2   Training:   Workers must be  trained  in  the proper
            method  of  removing  contaminated  gloves   and clothing  without
            contacting the  exterior  surfaces.

                   II.4.I.3   Personal  Hygiene:  Thorough washing of hands and
            forearms after  each  manipulation  and before  breaks (coffee,  lunch,
            and shift).

                   11.4.1.4   Confinement:    Isolated  work  area,  posted  with
            signs,  segregated glassware and tools,  plastic backed  absorbent
            paper on benchtops.

                   11.4.1.5   Waste:     Good  technique   includes   minimizing
            contaminated waste.   Plastic bag liners should  be  used in  waste
            cans.

                   11.4.1.6   Disposal   of  Hazardous  Wastes:    Refer  to  the
            November 7,  1986 issue of  the Federal Register  on  Land  Ban  Rulings
            for details  concerning the handling of  dioxin containing wastes.

                                  8290  - 45                         Revision  0
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       11.4.1.7   Decontamination:  Personnel  -  apply a mild soap
with plenty of scrubbing  action.   Glassware,  tools and surfaces -
Chlorothene NU  Solvent  (Trademark  of  the  Dow Chemical Company) is
the  least toxic  solvent  shown to  be  effective.   Satisfactory
cleaning  may   be  accomplished  by  rinsing with  Chlorothene,  then
washing with a .detergent and water.  Dish water may be disposed to
the sewer after percolation through a  charcoal  bed filter.   It is
prudent to  minimize solvent wastes  because they  require special
disposal through commercial services that are expensive.

       11.4.1.8   Laundry; Clothing known to be contaminated should
be  disposed  with  the  precautions  described  under  "Disposal  of
Hazardous Wastes",  Laboratory  coats   or  other  clothing worn  in
2,3,7,8-TCDD work  area  may be laundered.    Clothing  should  be
collected in plastic bags.   Persons who convey the  bags and launder
the clothing should be advised of the  hazard and trained in proper
handling.   The  clothing may be put  into a washer without contact if
the launderer knows the problem.  The  washer should be run through
one full cycle  before being used again for other clothing.

       11.4.1.9   Wipe  Tests:    A  useful  method  for determining
cleanliness of work surfaces and tools is to wipe the surface with
a piece of filter paper,  extract the  filter paper and analyze the
extract.

       NOTE;       A  procedure   for    the   collection,   handling,
                  analysis,  and reporting  requirements  of  wipe
                  tests   performed   within   the   laboratory   is
                  described  in  Attachment  A.    The   results  and
                  decision  making  processes  are  based  on  the
                  presence of 2,3,7,8-substituted PCDDs/PCDFs.

       11.4.1.10  Inhalation:    Any  procedure  that  may  generate
airborne contamination must be  carried out  with  good ventilation.
Gross losses  to a  ventilation system must  not be allowed.  Handling
of the  dilute solutions normally used in analytical and animal work
presents no  significant inhalation hazards  except in case  of an
accident.

       11.4.1.11  Accidents:       Remove    contaminated   clothing
immediately,  taking precautions  not  to contaminate  skin  or  other
articles.  Wash exposed skin vigorously and repeatedly  until medical
attention  is  obtained.
                      8290  - 46                         Revision 0
                                                    September 1994

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                                 Attachment A

            PROCEDURES  FOR  THE  COLLECTION,  HANDLING, ANALYSIS, AND
            REPORTING OF  WIPE TESTS  PERFORMED WITHIN THE  LABORATORY

      This  procedure is designed for the periodic evaluation of potential con-
tamination by 2,3,7,8-substituted PCDD/PCDF congeners of the working areas inside
the laboratory.

      A.I   Perform the wipe tests  on surface areas of two inches  by one foot
with glass fiber paper  saturated with distilled in glass acetone using a pair of
clean stainless steel forceps.  Use  one wiper for each of the designated areas.
Combine the wipers to one composite sample in an extraction jar containing 200
mL distilled in glass acetone.  Place an equal  number of unused wipers in 200 ml
acetone and  use this as a  control.  Add  100 ML of the  sample  fortification
solution to each jar containing used or unused wipers  (Sec. 5.8).

            A. 1.1  Close  the jar  containing the  wipers   and  the acetone  and
      extract for 20 minutes using a wrist  action shaker.  Transfer the extract
      into  a  KD apparatus  fitted with  a  concentration  tube and a  three ball
      Snyder  column.    Add two  Teflon™  or Carborundum™ boiling   chips  and
      concentrate the extract to an apparent volume of 1.0 mL on a  steam bath.
      Rinse the  Snyder column  and  the KD  assembly  with  two 1 mL  portions of
      hexane  into the  concentrator  tube,  and  concentrate its  contents to near
      dryness  with  a gentle stream of nitrogen.   Add  1.0  mL  hexane  to  the
      concentrator tube and swirl the solvent on the walls.

            A.1.2  Prepare a neutral alumina column as described in Sec. 7.5.2.2
      and follow the steps outlined in Sees. 7.5.2.3 through 7.5.2.5.
            A.1.3 Add  10 ML of the recovery standard  solution  as  described in
      Sec. 7.5.3.6.

      A.2   Concentrate the contents  of  the vial to a final  volume of  10 ML
(either in  a  minivial  or in a  capillary tube).   Inject  2 pi of each extract
(wipe and control)  onto a capillary column and analyze  for 2,3,7,8-substituted
PCDDs/PCDFs  as  specified  in  the  analytical  method  in  Sec. 7.8.    Perform
calculations according  to Sec.  7.9.

      A.3   Report the presence  of 2,3,7,8-substituted  PCDDs  and  PCDFs as  a
quantity (pg or ng)  per wipe test experiment (WTE^.   Under the  conditions out-
lined in this  analytical  protocol, a lower limit of calibration of 10 pg/WTE is
expected for  2,3,7,8-TCDD.   A  positive  response for  the blank (control)  is
defined as  a  signal  in the TCDD  retention time window  at any of  the  masses
monitored which  is equivalent to  or above 3 pg of 2,3,7,8-TCDD per  WTE.   For
other congeners, use  the  multiplication factors listed in Table 1,  footnote (a)
(e.g.,  for OCDD, the lower  MCL  is 10 x 5 = 50 pg/WTE  and  the positive response
for the blank would  be 3 x 5  =  15 pg).   Also,  report  the recoveries  of  the
internal standards during the simplified cleanup procedure.

      A.4   At a minimum, wipe  tests should  be performed when there is evidence
of contamination in the method  blanks.
                                  8290 - 47                         Revision 0
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      A.5   An upper limit of 25 pg per TCDD isomer and per wipe test experiment
is allowed (use multiplication factors listed in footnote (a) from Table 1 for
other congeners).  This value corresponds to 2| times the  lower calibration limit
of the  analytical  method.   Steps  to  correct the contamination must  be taken
whenever these levels are  exceeded.   To  that effect,  first  vacuum the working
places  (hoods,  benches,  sink)  using  a  vacuum cleaner  equipped  with  a  high
efficiency partlculate absorbent (HEPA)  filter and then  wash with a detergent.
A new set of wipes should  be analyzed before anyone  is  allowed  to work in the
dioxin area of the laboratory after corrective action has been taken.
                                  8290  - 48                         Revision 0
                                                                September 1994

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                   Figure 1,
  8
              Dibenzodioxin
  8
               Dibenzof urar.
General  structures of dibenzo-p-dioxin and dibenzofuran.
                   8290 - 49
   Revision 0
September Iii4

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                                  Figure 2.
                                                 M/AM
                                                 5,600
                                                 5,600
                                                 8,550
                                 400 ppm
  Peak profile displays demonstrating  the effect of the detector zero  on  the
measured resolving power.  In this example, the true resolving power is 5,600.

      A)    The  zero  was  set  too  high;  no  effect  is  observed  upon  the
      measurement  of the  resolving power.

      B)    The zero was adjusted properly,

      C)    The zero was set too  low; this results  in overestimating the actual
      resolving  power  because   the  peak-to-peak   noise  cannot  be  measured
      accurately.
                                 8290 - 50
    Revision  0
September 1994

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                             Figure 3.
   8:00 AM
Mass Resolution
 Mass Accuracy
                    Analytical Procedure
                       Thaw Sample Extract
                       Concentrate to 10 uL
 9:00 AM
 Initial or
 Routine
Calibration
              GC Column
              Performance
11:00 AM
        Method
         Blank
8:00 PM
                   Mass
                 Resolution
         Routine
        Calibration
              Typical 12 hour analysis sequence of events.
                            8290 - 51
                              Revision 0
                           September 1994

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                                      Figure 4.
10On
                     I
                   22:30
  I
24:00

    Time
  I
25:30
  T
27:00
     Selected ion current profile for m/z 322 (TCDDs)  produced  by  MS  analysis of
    the GC  performance  check  solution  on  a 60 m DB-5 fused silica capillary column
    under the  conditions  listed  in Sec. 7.6.
                                      8290 - 52
                                  Revision 0
                              September 1994

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                                 Figure 5.
       8CH
       60-
       40-
       20-
                                         Ref. mass 304.9824 Peak top
                                         Span. 200 ppm
System file name

Data file name

Resolution

Group number

lonization mode

Switching

Ref. masses
YVES150

A:852567

   10000

        1

      El-t-

VOLTAGE

304,9824

380.9260
                                             M/AM—10.500
                                          Channel B 380.9260 Lock mass
                                          Span 200 ppm
 Peak profiles representing two PFK reference ions  at m/z 305 and 381.   The
resolution of  the high-mass signal  is  95 ppm  at 5 percent of the  peak height;
  this corresponds  to a  resolving power M/£)M of  10,500  (10 percent valley
                               definition).
                                 8290  -  53
                        Revision 0
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                                   Figure 6.
100-,


 90-


 80-


 70-


 60-


 50-


 40-


 30-

 20-


 10
  20:00
22:00
                            30:00
                         Manual  determination  of  S/N.

      The peak height (S) is measured between the mean noise (lines C and  0).
      These mean  signal  values  are obtained  by  tracing  the  line between  the
      baseline average noise extremes,  El  and  E2,  and  between the  apex average
      noise extremes, E3 and E4, at the apex of the  signal.
      NOTE:
    It  is  imperative  that
    electronic  zero offset
    going  baseline  noise
   the instrument  interface amplifier
  be  set  high  enough  so that negative
is recorded.
                                  8290 - 54
                                                     Revision 0
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                                   Table 1.

            Types of Matrices,  Sample Sizes  and 2,3,7,8-TCDD-Based
                Method Calibration Limits (Parts per Trillion)
                      Soil                         Human
                      Sediment    Fly     Fish    Adipose   Sludges,   Still-
              Water   Paper Pulpb  Ash     Tissue0  Tissue    Fuel  Oil   Bottom
Lower MCLa        0.01    1.0

Upper MCL3        2     ZOO

Weight (g)     1000      10
IS Spiking
Levels (ppt)
1    100
Final Extr.
Vol. (ML)d   10-50   10-50
                    1.0     1.0     1.0

                 200     200     200

                   10      20      10
100    100
100
                  50   10-50   10-50
                            5.0       10

                         1000       2000

                            2          I
500
                           50
1000
                      50
a     For other congeners multiply  the values by 1 for TCDF/PeCDD/PeCDF, by 2.5
      for HxCDD/HxCDF/HpCDD/HpCDF,  and by 5 for OCDD/OCOF.

b     Sample dewatered according to Sec. 6.5.

c     One half of the extract  from  the 20 g sample is used for determination of
      lipid content (Sec. 7.2.2),

d     See Sec. 7.8.1, Note.


NOTE:  Chemical  reactor  residues  are  treated  as  still  bottoms  if  their
      appearances so suggest.
                                  8290 - 55
                                                   Revision 0
                                               September 1994

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                                   Table 2.

                    Composition of the  Sample Fortification
                        and  Recovery Standard Solutions8
                         Sample  Fortification     Recovery Standard
                         Solution                  Solution
Analyte                  Concentration            Concentration
                         (pg/^tL; Solvent:         (pg/jiL; Solvent;
                         Nonane)                  Nonane}
13C12-2,3,7,8-TCDD              10
13C12-2,3,7,8-TCDF              10
13C12-1,2,3,4-TCDD              --                      50

13C12-l,2,3,7,8-PeCDD           10
13C12-l,2,3,7,8-PeCDF           10

13C12-l,2,3»6,7,8~HxCDD         25
13C12-l,2,3,4,7,8-HxCDF    ,     25
13C12-l,2,3,7,8,9-HxCDD         --                      50

13C12-l,2,3,4,6,7,8-HpCDD       25
13Cl2-l,2,3,4,6,7,8-HpCDF       25
13C12-OCDD                      50
(a)  These solutions  should be made freshly every day because of the possibility
of adsorptive losses to glassware.   If  these  solutions  are to be kept for more
than one day, then the  sample fortification  solution concentrations  should be
increased ten fold,  and the recovery standard solution concentrations should be
doubled.  Corresponding adjustments  of  the spiking  volumes must then be made.
                                   8290 - 56                         Revision 0
                                                                 September 1994

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                                   Table 3.

           The  Fifteen  2,3,7,8-Substituted  PCDD  and  PCDF  Congeners


      PCDD                             PCDF


   253,7,8-TCDD(*)                   2,3,7,8-TCDF(*)

   l,2,3,7,8-PeCDD(*)                l,2,3,7,8-PeCDF(*)

   l,2,3,6,7,8-HxCDD(*)              2,3,4,7,8-PeCDF

   1,2,3,4,7,8-HxCDD                 1,2,3,6,7,8-HxCDF

   l,2,3,7,8,9-HxCDD(+)              1,2,3,7,8,9-HxCDF

   l,2,3,4,6,7,8-HpCDD(*)            l,2,3,4,7,8-HxCDF{*)

                                    2,3,4,6,7,8-HxCDF

                                    l,2,3,4,6,7,8-HpCDF(*)

                                    1,2,3,4,7,8,9-HpCDF



(*) The  130-labeled analogue is used as an internal  standard.

(+} The  13C-labeled analogue is used as a recovery standard.
                                   8290  -  57                         Revision 0
                                                                September 1994

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                   Table 4.

Isomers of Chlorinated  Dioxins  and  Furans  as  a
   Function of the  Number of  Chlorine Atoms
Number of
Chlorine
Atoms
1
2
3
4
5
6
7
8
Total
Number of
Dloxin
Isomers
2
10
14
22
14
10
2
1
75
Number of
2,3,7,8
Isomers
—
—
—
1
1
3
1
1
7
Number of
Furan
Isomers
4
16
28
38
28
16
4
1
135
Number of
2,3,7,8
Isomers
—
—
—
1
2
4
2
1
10
                  8290 - 58
    Revision 0
September 1994

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                                   Table 5.

              High-Resolution Concentration Calibration Solutions
                                          Concentration (pg/^L, inj^onanej
Compound
HRCC
2
1
Unlabeled Analytes
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
Internal Standards
13C12-2,3,7,8-TCDD
13C12-2,3,7,8-TCDF
13C12-l,2,3,7,8-PeCDD
13C12-l,2,3,7,8-PeCDF
13C12-l,2,3,6,7,8-HxCDD
13C12-l,2,3,4,7,8-HxCDF
13C,2-1,2,3,4,6,7,8-HDCDD
™C12-l,2,3,4,6,7,8-HpCDF
13C12-OCDD
Recovery Standards
13C12-l,2,3,4-TCDD(a>
13C12-l,2,3,758,9-HxCDD(bl
200
200
500
500
500
500
500
500
500
500
500
500
500
500
500
1,000
1,000

50
50
50
50
125
125
125
125
250

50
125
50
50
125
125
125
125
125
125
125
125
125
125
125
125
125
250
250

50
50
50
50
125
125
125
125
250

50
125
10
10
25
25
25
25
25
25
25
25
25
25
25
25
25
50
50

50
50
50
50
125
125
125
125
250

50
125
2.5
2.5
6.25
6.25
6.25
6.25
6.25
6.25
6.25
6.25
6.25
6.25
6.25
6.25
6.25
12.5
12.5

50
50
50
50
125
125
125
125
250

50
125
1
1
2.5
2.5
2.5
2,5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
5
5

50
50
50
50
125
125
125
125
250

50
125
la)   Used for recovery  determinations of TCDD, TCDF,  PeCDD  and PeCDF internal
    standards.
iw   Used for recovery  determinations of  HxCDD,  HxCDF, HpCDD,  HpCDF  and OCDD
    internal  standards.
                                   8290 -  59
                                           • Revision 0
                                        September 1994

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                      Table S.
Ions Monitored for HRGC/HRMS Analysis  of  PCDDs/PCDFs
Descriptor
1









2









3










Accurate'"1
Mass
303.9016
305,8987
315.9419
317.9389
319.8965
321.8936
331.9368
333.9338
375.8364
[354.9792]
339.8597
341.8567
351.9000
353.8970
355,8546
357.8516
367.8949
369.8919
409.7974
[354.9792]
373.8208
375,8178
383.8639
385.8610
389.8156
391.8127
401.8559
403.8529
445.7555
[430.9728]

Ion
ID
M
M+2
M
M+2
M
M+2
M
M+2
M+2
LOCK
M+2
M+4
M+2
M+4
M+2
M+4
M+2
M+4
M+2
LOCK
M+2
M+4
M
M+2
M+2
M+4
M+2
M+4
M+4
LOCK

Elemental
Composition
C12H435C140
C12H435C1337C10
13C12H435C140
13C12H435C1337C1Q
C12H435C1402
C12H435C1337C102
13C12H435C1402
13C12H435C1337C102
C12H43SC1537C1Q
^9' 13
C12H335C1437C10
C12H335C1337C12Q
13C12H335C1437C10
13C12H335C1337C120
C12H335C1437C102
C12H336C1337C1202
13C12H335C1437C1Q2
Ci2'"3 Cl3 C 1 202
C12H335C1637C10
Cg' 13
C12H235C1537C1Q
C,2H235C1437C12Q
%2H235C160
13C12H235C1537C10
C12H235C1537C102
C^2H2 C14 Ci202
13C12H235C1537C102
13C12H235C1437C1202
C12H235C1637C120
C9r17
8290 - 60
Analyte
TCDF
TCDF
TCDF (S)
TCDF (S)
TCDD
TCDD
TCDD (S)
TCDD (S)
HxCDPE
PFK
PeCDF
PeCDF
PeCDF (S)
PeCDF (S)
PeCDD
PeCDD
PeCDD (S)
PeCDD (S)
HpCDPE
PFK
HxCDF
HxCDF
HxCDF (S)
HxCDF (S)
HxCDD
HxCDD
HxCDD (S)
HxCDD (S)
OCDPE
PFK
Revision 0
                                                   September 1994

-------

Table 6.

Continued
Descriptor Accurate'81 Ion
Mass ID
4 407.7818 M+2
409.7788 M+4
417.8250 M
419.8220 M+2
423.7767 M+2
425.7737 M+4
435.8169 M+2
437.8140 M+4
479.7165 M+4
[430.9728] LOCK
5 441.7428 M+2
443.7399 M+4
457.7377 M+2
459.7348 M+4
469.7780 M+2
471.7750 M+4
513.6775 M+4
[442.9728] LOCK
Elemental
Composition
C12H35C1637C10
C12H35C1537C120
13C12H35C170
13C12H35C1637C10
C12H35C1637C102
CT2H35C1537C12Q2
13C12H35C1637C102
13C12H35C1537C1202
C12H35C1737C120
Cg' 17
Ct235C1737C10
C1235C1637C120
C123SC1737C102
C1235C1637C1202
13C1235C1737C102
13C 35C1 37C1 0
C1235C1837C120
C10F17
Analyte

HpCDF
HpCDF
HpCDF (S)
HpCDF
HpCDD
HpCDD
HpCDD (S)
HpCDD (S)
NCDPE
PFK
OCDF
OCDF
OCDD
OCDD
OCDD (S)
OCDD (S)
DCDPE
PFK
(a! The following nuclidic masses were used:
H = 1.007825 0
C = 12.000000 35C1
13C = 13,003355 37C1
F = 18.9984
15.994915
34.968853
36.965903





S = internal/recovery standard
                                  8290 - 61
    Revision 0
September 1994

-------
                                         Table 7.

                   PCDD  and  PCDF  Congeners  Present in the GC Performance
                      Evaluation Solution  and  Used for Defining the
                        Homologous GC Retention Time Windows on a
                                     60 m DB-5 Column
No. of
Chlorine
Atoms
41-!
5
6
7
8

PCDD Positional
First
Eluter
1,3,6,8
1,2,4,6,8/
1,2,4,7,9
1,2,4,6,7,9/
1,2,4,6,8,9
1,2,3,4,6,7,9


Isomer
Last
Eluter
1,2,8,9
1,2,3,8,9
1,2,3,4,6,7
1,2,3,4,6,7,8
1,2,3,4,6,7,8,

PCDF Positional
First
Eluter
1,3,6,8
1,3,4,6,8
1,2,3,4,6,8
1,2,3,4,6,7,8
,9

Isomer
Last
Eluter
1,2,8,9
1,2,3,8,9
1,2,3,4,8,9
1,2,3,4,7,8,9
1,2,3,4,6,7,8,9

!ai     In addition to these  two TCDD isomers, the  1,2,3,4-,  1,2,3,7-, 1,2,3,8-, 2,3,7,8-,
      13C12-2,3,7,8-,  and  1,2,3,9-TCDD  isomers must also  be  present  as  a  check of column
      resolution.
                                         8290  -  62                         Revision 0
                                                                      September  1994

-------
                              Table 8.

     Theoretical  Ion Abundance Ratios and Their Control  Limits
                        for PCDDs  and PCDFs
Number
Chlori
Atoms
4
5
6
6w
jib)
7
8
of
ne Ion
Type
M/M+2
M+2/M+4
M+2/M+4
M/M+2
M/M+2 "
M+2/M+4
M+2/M+4
Theoretical
Ratio
0.77
1,55
1.24
0.51
0.44
1.04
0.89
Control
lower
0.65
1.32
1.05
0,43
0.37
0.88
0.76
Limits
upper
0.89
1.78
1.43
0.59
0.51
1.20
1.02
ia)      Used  only for 13C-HxCDF  (IS).

|bi      Used  only for 13C-HpCDF  (IS).
                             8290 - 63
    Revision 0
September 1994

-------
                               Table 9.

         Relative Response Factor [RF (number)] Attributions
Number                        Specific Congener Name
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
2,3,7,8-TCDD (and total
2,3,7,8-TCDF (and total
TCDDs)
TCDFs)
1,2,3,7,8-PeCDD (and total PeCDDs)
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1, 2,3,4,7, 8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD (and
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
13C12-2,3,7,8-TCDD
13C12-2,3,7,8-TCDF
13C12-l,2,3,7,8-PeCDD
13C12-1, 2,3,7, 8-PeCDF
13C12-l,2,3,6,7,8-HxCDD
13C12-l,2,3,4,7,8-HxCDF
13C12-l,2,3,4,6,7,8-HpCDD
13C12-l,2,3,4,6,7,8-HpCDF
13C12-OCDD
Total PeCDFs
Total HxCDFs
Total HxCDDs
Total HpCDFs









total HpCDDs)

















                              8290 - 64                         Revision 0
                                                            September 1994

-------
                                Table 10.

         2j3,7,8-TCDD  Toxicity  Equivalency  Factors  (TEFs)  for  the
             Polychlorinated  Dibenzodioxins  and  Dibenzofurans
Number           Compound(s)                          TEF"
1
I
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDD
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8,9-OCDD
2,3,758-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,6,7,8-HxCDF
1,2,3,7, 8, 9-HxCDF
1,2,3,4,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDF
1.00
0.50
0.10
0.10
0.10
0.01
0.001
0.1
0.05
0.5
0.1
0.1
0.1
0.1
0.01
0.01
0.001
Taken from "Interim Procedures for Estimating Risks Associated with  Exposures
to Mixtures of Chlorinated Dibenzo-p-Dioxin and -Dibenzofurans (CDDs and CDFs)
and 1989 Update", (EPA/625/3-89/016, March 1989).
                                8290 -  65                        Revision  0
                                                             September  1994

-------
                                   Table 11.

            Analyte Relative Retention Time Reference Attributions
            Analyte                     Analyte  RRT  Reference
                                                              (a)
            1,2,3,4,7,8-HxCDD            "C12-l,2,3,6,7,8-HxCDD

            1,2,3,6,7,8-HxCDF            13C12-l,2,3,4,7,8-HxCDF

            1,2,3,7,8,9-HxCDF            13C12-l,2,3,4,7,8-HxCDF

            2,3,4,6,7,8-HxCDF             13C12-l,2,3,4,758-HxCDF
{a}  The retention time of 2,3,4,7,8-PeCDF on the DB-5 column is measured relative
   to 13C12-l,2,3,7,8-PeCDF and the retention time of 1,2,3,4,7,8,9-HpCDF relative
   to 13C12-l,2,3,4,6,7,8-HpCDF.
                                   8290  -  66                         Revision  0
                                                                September  1994

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                                                                   METHOD  8290
                POLYCHLORINATED DIBENZODIOXINS  (PCDDs)  AND POLYCHLORINATED  DIBENZOFURANS   (PCDFs)
                       BY  HIGH-RESOLUTION  GAS  CHROMATOGRAPHY/HIGH-RESOLUTION  MASS SPECTROMETRY
                                                                   (HRGC/HRMS)
              1
  7.1 Internal Standard Addition
 7.1.1 Sample size of 1 to 1000
 grams, see Section 7.4 & Table 1.
 Determine wl  on tared flask
7.1.2 Spike samples w/100 uL
fortification mixture yielding internal
standard cones, of Table 1, except
for adipose tissue
 7.1.2.1 For soil, sediment, fly ash,
 water, and fish tissue, mix 1 ml
 acetone with 100 uL mixture
  7.1.2.2 Do not dilute for other
  sample matrices
                                                         L
                                                7.2 Fish and Paper Pulp
                                                        I
  7.2.1 Mix 60 gr sodium sulfate
  and 20 gr sample; place
  mix in Soxhlet; add 200 ml
  1:1 hexane/MeCI; reflux
  12 hours
  7.2.2 Transfer extract to a
  KD apparatus with a Snyder
  column
                                                        I
I  7.2.3 Add Teflon boiling
  chip; concentrate to 10 ml
I  in water bath; cool for 5 mins.
                                                        I
  7.2 4 Add new chip, 50 ml
  hexane to flask; concentrate
  to !> ml; cool for 5 mlns.;
  assure MeCI out before next
  step
                                               7.2.5 Rinse apparatus with
                                               hexane; transfer contents
                                               to a separately runnel; do
                                               cleanup procedure
                                                                                7.2 Sample Extraction and Purification
                                                                                     7.3 Human Adipose Tissue
                                                  I
7.3.1 Store samples at or
below -20 C, care taken
in handling
                                                                                    7.3.2 Extraction
  .1 Weigh out sample
  .2 Let stand to room Temp
  .3 Add MeCI, fortification
    soln., homogenize
  .4 Separate MeCI layer,
    filter, dry, transfer to
    vol. flask
  .5 Redo step 3, add to
    vol. flask
  .6 Rinse sample train,
    add to vol. flask
  .7 Adjust to mark w/MeCI
                                                                                   7.3.3 Determine Lipid Content
                                           .1 Preweighl gram
                                             glass vial
                                           .2 Transfer and reduce 1
                                             ml extract to vial until
                                             weight constant
                                           .3 Calculate weight dried
                                             extract
                                           .4 Calculate % lipid
                                             content from eqn.
                                           .5 Record lipid extract wl
                                             and % lipid content
                                                                                                 L
                                                                    8290  -  67
                                                                              7.4 Environmental and Waste
                                                           •0
  7.3.4 Extract Concentration
                                      .1 Transfer and rinse vol.
                                        flask contents of 7.32.7
                                        to round bottom
                                      .2 Concentrate on rotovap
                                        at40C
                                                                                                                        7.3.5 Extract Cleanup
.1 Dissolve Section 4 extract
  with hexane
.2 Add acid impregnated
  silica, stir for 2 hours
.3 Decant and dry liquid
  with sodium sulfate
.4 Rinse silica 2x w/hexane,
  dry w/sodium sulfate,
 combine rinses w/step 3
.5 Rinse sodium sulfate,
  combine rinse w/step 4
.6 Prepare acidic silica
  column
.7 Pass hexane extract
  through column, collect
  eluate in 500 ml KD assembly
.8 Rinse column w/hexane,
  combine eluate w/step 7,
  concentrate total eluate
  tolOOuL
Note: If column discolored repeat
      cleanup (7.3.5.1)
.9 Extract ready for column
  cleanup
                                                                                              Revision  0
                                                                                        September  1994

-------
                                                                        METHOD  8290
                                                                          continued
                                                    I  7.4 Environmental and Waste Samples  |
                                                                       i
           7.4.1 Sludge/Wei Fuel Oil
             .1 Extract sample with toluene
               using Dean-Stark water
               separator
             .2 Cool sample, filter through
               glass fiber filter
             .3 Rinse filter w/toluene,
               combine w/extract
             .4 Concentrate to near dryness
               uslna rotovap
             Note: Sample dissolves in toluene,
                   treat as In Section 7.4.2;
                   sample from pulp, treat as
                  in Section 7.2
                                                          7.4.2 Still Bottom/Oil
                           .1 Extract sample w/toluene,
                             filter through glass fiber
                             filter into round bottom
                           .2 Concentrate on rotovap
                             atSOC
                        7.4.4 Transfer concentrate to sep.
                            funnel using hexane; rinse
                            container, add to funnel;
                            add 5% NaCI sola, shake
                            2 minutes; discard aqueous
                            layer
                            1
 7.4.5 Aqueous
.1 Let sample stand to room Temp;
  mark meniscus on bottle; add
  fortification soln.
.2 Filter sample: centrifuge first
  if needed
.3 Combine flltered/centrlfuged
  solids along w/filter; do Soxhlet
  extraction of Section 7.4.6.1;
  rinse assembly & combine
.4 Transfer aqueous phase to sep
  funnel; rinse sample bottles
  w/MeCI & transfer to funnel;
  shake and extract water
.5 Let phases separate, use
  mechanical means if needed
.6 Pass MeCI layer through drying
  agent, collect in KD assembly
  w/concentrator tube
 .7 Repeat step 4-6  2x, rinse
   drying agent, combine all
   in KD assembly	
Note: Continuous liquid-liquid
     extractor may be used if
     emulsion problems occur
.8 Attach Snyder column,
  concentrate on water bath
  til 5 mL left; remove KD
  assembly, allow to drain & cool
.9 Remove column; add hexane,
  extraction concentrate of solids,
  & new boiling chip; attach column,
  concentrate to 5 mL
.to Rinse flask and assembly to final
   volume 15 mL
.11 Determine original sample volume
   by transferring meniscus volume
   to graduated cylinder
7.4.3 Fly Ash
 .1 Weigh sample; add
   fortification soln. in acetone,
    1 M HCI; shake in extraction
    jar for 3 hours
 .2 Filter mix in Buchner funnel;
   rinse filter cake w/water; dry
   filter cake at room Temp.
 .3 Add sodium sulfate to cake,
   mix and let stand for t hr.,
   mix again and let stand
.4 Place sample In extraction
  thimble; extract in Soxhlet
  for 16 hours w/toluene
.5 Cool and filter extract; rinse
  containers & combine;
  rotovap to near dryness
  at50C
  7.4.6 Soil
     .1 Add sodium sulfate, mix; transfer mixture to
       Soxhlet assembly atop glass wool plug
     .2 Add toluene, reflux for 24 hours
     Note: Add more sodium sulfate if sample does not
           flow freely
     .3 Transfer extract to round bottom
     .4 Concentrate to 10 mL on rotovap, allow to cool
     .5 Transfer concentrate and hexane rinses to KD
       assembly; concentrate to 10 mL, allow to cool
     .6 Rinse Snydor column into KD; transfer KD
       & concentrator tube liquids to sep funnel;
       rinse KD assembly w/hexane & add to funnel
                                                                                                                                                   8290A.UP2
                                                                          8290  -  68
                                                                                                                   Revision  0
                                                                                                             September  1994

-------
                                                                     METHOD 8290
                                                                       continued
               7.5 Cleanup    [

              ~
7.5.1 Partition
    .1 Partition extract w/concentrated
     sulfuric add; shake, discard
     acid layer; repeat add wash till
     no color present or done 4x
  .2 OMIT FOR FISH SAMPLES. Partition
      extract w/NaCI sola; shake,
     discard aqueous layer
  .3 OMIT FOR FISH SAMPLES. Partition
     extract w/KOH soln.; shake,
     discard base layer; repeat base
     wash till no color obtained In wash
     or done 4x
  .4 Partition extract w/NaCI soln.;
     shake, discard aqueous layer.
     Dry extract w/sodlum sutfate
     Into round bottom flask; rinse
     sodium sulfate w/hexane;
     concentrate hexane soln. In
     rotovap
                                                       7.5.2 Silica/Alumina Column
                                                         .1 Pack a gravity column w/slltea gel; fill
                                                           w/hexane, elute to top of bed;
                                                           check for channeling
                                                         .2 Pack a gravity column w/alumlna; fill
                                                           w/hexane, elute to top of bed, check
                                                           for channeling
                                                         Note: Acidic alumina may be used Instead of
                                                               neutral alumina.
                                                          .3 Dissolve residue of Section 7.5.1.4
                                                            in hexane; transfer soln. to top of
                                                            silica column
                                                          .4 Elute silica column w/hexane
                                                            directly onto alumina column
                                                          .5 Add hexane to alumina column;
                                                            elute to top of sodium sulfate in
                                                            collect and save eluted hexane
                                                          .6 Add MeCI/hexane soln. to alumina
                                                            column; collect eluate In concentrator
                                                            tube
                                                                                                                     7.5.3 Carbon Column
.1 Prepare AX-21/Celite 545 column;
  activate mixture at 130 C for 6 hours;
   store in desslcator
.2 Pack a 10 mL serologlcal plpet
   w/prepared AX-21/Celite 545 mix
Note: Each batch of AX-21/Celite 545
     must be checked for % recovery
     of analytes.
.3 Concentrate MeCI/hexane fraction
   of Section 7.5.2.6 to 2 mL
   w/nitrogen; rinse column
   w/several solns.; add sample
   concentrate and rinses to top
   of column
.4 Elute column sequentially
   w/cydohexane/MeCI; MeCI/
   methanol/toluene; combine eluates
.5 Turn column upside down, elute
   PCDD/PCDF fraction w/toluene;
   filter If carbon fines present
.6 Concentrate toluene fraction on
   rotovap; further concentrate to
   100 uL in minivial using nitrogen
   at 50 C; rinse flask 3x w/1%
   toluene in MeCI; add tridecane
   recovery std.; store room temp.
   In the dark
                                                                        8290  -  69
                           Revision  0
                     September 1994

-------
                                                                     METHOD  8290
                                                                      continued
7.6 Chromatographlc, Mass Spectrometrlc, and
   Data Acquisition Parameters	
7.6.1 Gas Chromatograph
   Select correct dimensions and parameters
   of column, and set-up chromatographic
   conditions.
7.6.2 Mass Spectrometer
   .1 Operate mass spectrometer In selected
      ion monitoring (SIM) mode; monitor ions
     of five SIM descriptors
   .2 Tune mass spectrometer based on Ions
     of SIM descriptors
7.6.3 Data Aquteltion
    . 1 Total cycle time of < or - 1 second
    .2 Acquire SIM data for ions of 5
      descriptors
                                                                                                       1
                          |  7.7 Calibration   [
                                   r
                                                                  7.7.1 Initial Calibration
Required before any sample analysis,
and If routine calibration does not
meet criteria
.1 All 5 calibration solns. must be
  used for initial calibration
.2 Tune mass spectrometer w/PFK as
  described In Section 7.7.3
.3 Inject 2 uL of GC column performance
  check soln. and acquire SIM data;
  assure Section 8.1.2 criteria are'met
.4 Analyze each of 5 calibration standards
  using the same conditions, with the
  following MS  operating parameters:
  .1 Ratio of integrated ion current for
   Table 8 ions within control limits
  .2 Ratio of integrated ion current for
    carbon labeled internal and recovery
   standards within control limits
Note: Control limits must be achieved in
     one run for all ions.
.3 Signal to noise (S/N)  ratio for each
  target analyte and labeled std. selected
  ion current profiles (SICP) and
   GC signals > 2.5
7.7.1.4
 .4 Calculate relative response factors (RRF)
    for unlabeled and labeled target analytes
    relative to internal stds. (Table 5)
 .5 Calculate average and relative standard
    deviation for the 5 calibration solutions
 .6 RRF's for concentration determination of
    total isomers in a homologous series
    are calculated as:
    .1  Congeners in a homologous series w/one
      isomer, mean RRF used is same as
      Section 7.7.1.4.5
 Note: Calibration solns. do not contain
       labeled OCDF; therefore, RRF OCDF
       relative to labeled OCDD
    .2 Calculation for mean RRF for congeners
      in a homologous series w/more than one
      isomer
  Note: Isomers in homologous series w/o
       2,3,7,8 substitution pattern alloted
       same response factor as other 2,3,
       7, 8 isomers in series
  .7 Calculation of RRF's used to determine
    % recoveries of nine internal standards
t
7.7.2 Criteria for Acceptable Calibration
Criteria listed must be met before analysis
.1 The % RSD for unlabeled stds. must
be within +/- 20%; for labeled, +/- 30%
.2 S/N ratio for GC signals > = 2.5
.3 Table 8 isotopic ratios within limits
Note: When criteria for acceptable calibration
are met, mean RRF's used for calculations
until routine calibration criteria are not met
1

                                                            7.7.3 Routine Calibration
                                                              Performed at 12 hour periods after
                                                              successful resolution checks
                                                            .1 Inject 2 UL calibration soln. HRCC-3;
                                                              use same HRGC/HRMS conditions of
                                                              Sections 7.6.1  and 7.6.2; document
                                                              an acceptable  calibration
                                                                                L
                                                                                                                7.7.4 Criteria for Acceptable Routine Calibration
                                            .1 Measured unlabeled RRFs must be w/in
                                               +/• 20% of initial calibration values
                                            .2 Measured labeled RRFs must be w/in
                                              +/- 30% of initial calibration values
                                            .3 Table 8 ion abundance ratios must be
                                              w/in limits
                                            .4 Review routine calibration process if
                                              criteria of steps 1  and 2 are not satisfied
                                           Note: An initial calibration must be done when
                                                new HRCC-3, sample fortification, or
                                                recovery std. soln. from another lot is used
                                                                      8290  -  70
                                                                            Revision  0
                                                                      September  1994

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                                                                    METHOD  8290
                                                                     continued
                    JL
                 7.8 Analysis ]
         7.8.1 Reduce extract or blank
            volume to 10 or 50 uL
         7.8.2 Inject 2 ul aliquot of the
             sample into the QC
       7.8.3 Acquire SIM data according
          to Section 7.6.2 and 7.6.3
        Note: Acquisition period must at
        least encompass PCDD/PCDF
         overall retention time window
                                                7.8.4 GC Identification Criteria
           .1 Relative Retention Times
              .1 2,3,7,8 sub: Sample components
                relative retention time (RRT) w/in
                •1 to 3 seconds of retention      Note:
                time of labeled internal or
                recovery std.
              .2 2,3,7,8 sub: Sample RRTs
                w/in homologous retention
                time windows if w/o labeled
                internal std.
              .3 non 2,3,7,8 sub: Retention
                time w/in homologous
                retention time window
              .4 Ion current responses for
                quantitation must reach maximum
                w/in 2 seconds
.5  Ion current responses for labeled
  stds. must reach maximum w/in
  2 seconds
 Verify presence of 1,2,8,9-TCDD and
  1,3,4,6,8-PeCDFinSICPs
.2 Ion Abundance Ratios
 .1 Ratio of integrated ion current for
   two ions used for quantification
   w/in limits of homologous series
.3 Signal-to-Noise Ratio
  .1 All ion current intensities > =2.5
.4 Polychlorinated Diphenyl Ether
   Interferences
   .1 Corresponding PCDPE channel
     clear of signal > = S/N 2.5 at
     same retention time
             JL
      17.9 Calculations |
             JL
 7.9.1 Calculate concentration of
    PCDD or PCDF compounds
           w/formula
7.9.2 Calculate % recovery of nine
   internal stds. using formula
Note:  Add 1% recovery for human
      adipose tissue samples
 7.9.3 Use smaller sample amt. if
    calculated concentration
 exceeds method calibration limits
7.9.4 Sum of isomer concentration
    is total concentration for a
      homologous series
7.9.5 Samplo-Specific-Estimated Detection
     Limit (EDL)	
   EDL: Analyte concentration yielding
   peak ht 2.5x noise level. EDLs calculated
   for non-identified 2,3,7,8-sub congeners
   Two methods of calculation:
     . t Samples w/resppnse <2.5x noise for
       both quantification ions
       .1 Use EDL expression to
         calculate for absent
         2,3,7,8 substituted PCDD/PCDF
    .2 Samples w/response >2.5x noise for
       at least  1 quantification ion
       .1  Calculate "Estimated Maximum Possible
         Concentration" (EMPC) when signal >
         2. fix noise and retention time the same
                  I
                                       7.9.6 Relative percent difference (RPD) formula I
                                                                     8290  -  71
             7.9.7 Calculation of 2,3,7,8-TCDD toxicity
                 equivalent factors (TEF) of PCDDs and PCDFs
                 .t Two GC Column TEF Determination:
                    Reanalyze sample extract on 60 meter
                    SP-2330 column
                     .1 Concentrations of specified congeners
                       calculated from analysis done on DBS
                       column
                     .2 Concentrations of specified congeners
                       calculated from analysis done on
                       SP-2330 column w/different GC/MS
                       conditions
                    Confirmation and quantification of 2,3,7,8-
                    TCDD done on either column as long as
                    Section 8.1.2 criteria met
                    .3 GC peak must meet criteria of Sections
                       7.8.4.2, 7.8.4.3, and/or 7.8.4.1.)  RRTs
                       of 2,3,7,8-sub congeners w/no carbon-
                       labeled analogues referred to w/in 0.006
                       RRT units of carbon-labeled std.
Note:
                                                                                                       Revision 0
                                                                                                 September  1994

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                                  METHOD 8275

             THERMAL CHROMATOGRAPHY/MASS SPECTROMETRY (TC/HS1 FOR
                   SCREENING SEMIVOLATILE ORGANIC COMPOUNDS
1.0   SCOPE AND APPLICATION

      1.1   Method  8275 is  a  screening technique  that may  be  used  for  the
gualjlatiye identification of semi volatile organic compounds in extracts prepared
from nonaqueous solid wastes  and soils.  It  is not intended for use as a rigorous
quantitative  method.    Direct  injection of a  sample may  be used  in  limited
applications.  The  following analytes  can  be  qualitatively determined  by this
method:
      Compound Name                                   CAS No.a


      2-Chlorophenol                                   95-57-8
      4-Methylphenol                                  106-44-5
      2,4-Dichlorophenol                              120-83-2
      Naphthalene                                      91-20-3
      4-Chloro-3-methylphenol                          59-50-7
      1-Chloronaphthalene                              90-13-1
      2,4-Dinitrotoluene                              121-14-2
      Fluorene                                         86-73-7
      Diphenylamine                                   122-39-4
      Hexachlorobenzene                               118-74-1
      Dibenzothiophene                                132-65-0
      Phenanthrene                                     85-01-8
      Carbazole                                        86-74-8
      Aldrin                                          309-00-2
      Pyrene                                          129-00-0
      Benzo(k)fluoranthene                            207-08-9
      Benzo(a)pyrene                                   50-32-8


      3   Chemical  Abstract Services  Registry Number.

      1.2   Method  8275  can be  used  to qualitatively identify  most  neutral,
acidic,  and basic  organic compounds that can  be thermally desorbed  from a sample,
and are  capable of being eluted without derivatization as  sharp peaks from a gas
chromatographic fused-silica capillary  column  coated with  a slightly  polar
silicone.

      1.3   This  method  is  restricted to use by  or under the supervision of
analysts experienced  in the use of gas chromatograph/mass  spectrometers  and
skilled in  the interpretation of mass spectra.  Each analyst must demonstrate the
ability to  generate acceptable results with this method.
                                   8275 - 1                         Revision 0
                                                                September 1994

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2.0   SUMMARY OF METHOD

      2.1   A portion of  the  sample  (0.010-0.100  g) is weighed  into  a  sample
crucible.   The  crucible  is placed  in  a pyrocell  and  heated.    The  compounds
desorbed from the sample are detected using a flame ionization  detector  (FID),
The FID response is used  to calculate the  optimal  amount  of  sample  needed for
mass spectrometry.   A  second sample is desorbed and the compounds are condensed
on the head of a fused  silica capillary column.   The column  is  heated using a
temperature program, and the effluent  from the column is  introduced into the mass
spectrometer.


3.0   INTERFERENCES

      3.1   Contamination by carryover can  occur whenever low-level  samples are
analyzed after high-level  samples.  Whenever an unusually concentrated sample is
encountered, it  should be followed by the analysis of an empty (clean)  crucible
to check for cross  contamination.
4.0   APPARATUS AND MATERIALS

      4.1   Thermal Chromatograph (TC)  System

            4.1.1 Thermal  chrornatograph™,  Ruska  Laboratories,  or  equivalent.

            4.1.2 Column  -  30 m  x 0.25  mm .ID  (or 0.32  mm   ID),  1  fj,m  film
      thickness, sil icone-coated,  fused-silica capillary column (J&W Scientific
      DB-5 or equivalent).

            4.1.3 Flame Ionization detector (FID).

      4.2   Mass Spectrometer (MS) system

            4.2.1 Mass Spectrometer -  Capable of scanning from 35  to  500 arnu
      every one second or  less, using 70 volts (nominal) electron energy in the
      electron impact ionization  mode.

            4.2.2 TC/MS interface - Any GC-to-MS interface producing acceptable
      calibration data in  the concentration range of interest  may  be
            4.2.3 Data System  -  A  computer must  be interfaced  to the  mass
      spectrometer.   The  data system must allow the continuous  acquisition and
      storage on machine-readable media of all mass spectra obtained throughout
      the duration  of the chromatographic  program.   The  computer must  have
      software that  can search  any  GC/MS  data file for ions of  a specific mass
      (or group of masses)  and  that  can plot such ion abundances versus time or
      scan  number.     This  type  of  plot  is   defined  as  an  extracted  ion
      chromatogram  (EIC).   Software must  also be  available  that  allows  for
      integration of the abundances  in, and EIC  between, specified time or scan-
      number 1 imits.
                                   8275 - 2                         Revision 0
                                                                September 1994

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      4.3   Tools and equipment
            4.3.1 Fused quartz spatula.
            4.3.2 Fused quartz incinerator ladle.
            4.3.3 Metal forceps for sample crucible.
            4,3.4 Sample crucible storage dishes.
            4.3.5 Porous fused quartz sample crucibles with lids.
            4.3.6 Sample crucible cleaning incinerator.
            4.3.7 Cooling rack.
            4.3.8 Microbalance, 1 g capacity, 0.000001  g  sensitivity,  Hettler
      Model M-3 or equivalent.
      4.4   Vials -  10 ml, glass with Teflon lined screw-caps or crimp tops.
      4.5   Volumetric flasks, Class A - 10 ml to  1000 ml.

5.0   REAGENTS
      5.1   Reagent grade inorganic chemicals shall  be used in all  tests.  Unless
otherwise  indicated,  it is  intended  that all reagents  shall conform  to  the
specifications of the Committee on Analytical  Reagents of the American Chemical
Society, where such specifications are available.
      5.2   Solvents
            5.2.1 Methanol, CH3OH -  Pesticide grade or equivalent.
            5.2.2 Acetone, CH3COCH3  -  Pesticide grade or equivalent.
            5.2.3 Toluene, C6HSCH3 - Pesticide grade or equivalent.
            5.2.4 Methylene chloride,  CK2C~2  - Pest'c-de grace or equivalent.
            5.2.5 Carbon disulfide,  CS2  -  Pesticide grade  or equivalent.
            5,2.6 Hexane, C6H14  - Pesticide grade or equivalent.
            5.2.7 Other suitable solvents - Pesticide  grade or equivalent.
      5.3   Stock Standard solutions - Standard solutions  may be prepared from
pure standard materials or purchased as  certified  solutions.
            5.3.1 Prepare stock standard solutions by  weighing about 0.01 g of
      pure material.   Dissolve the  material   in pesticide  quality  acetone,  or
                                   8275 - 3                         Revision 0
                                                                September 1994

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      other suitable solvent,  and dilute to 10 ml in a volumetric flask.  Larger
      volumes may be used at the convenience of the analyst.

            5.3.2 Transfer the  stock  standard  solutions  into glass vials with
      Teflon lined screw-caps or crimp tops.   Store at -10"C to -20°C or less
      and  protect  from  light.   Stock  standard  solutions  should  be checked
      frequently for signs of degradation  or  evaporation,  especially prior to
      use in preparation of calibration standards.

            5.3.3 Stock  standard solutions  must be replaced  after 1  year,  or
      sooner  if  comparison with  quality  control  check  samples   indicates  a
      problem.

      5.4   Internal Standard  solutions - The internal  standards recommended are
l,4-dichlorobenzene-d4,   naphthalene-da,    acenaphthene-d10,   phenanthrene-d,0,
chrysene-d12, and perylene-d12.  Other compounds may be used as internal standards
as long as the requirements  given in  Sec. 7  are  met.  Dissolve about 0.200 g of
each compound with  a small  volume of carbon  disulfide.   Transfer  to  a  50 ml
volumetric flask and  dilute to volume with methylene chloride,  so that the final
solvent is approximately 20/80  (V/V)  carbon disulfide/methylene chloride.  Most
of the  compounds  are also soluble in  small  volumes of methanol,  acetone,  or
toluene, except for perylene-d12.   Prior  to each analysis,  deposit about  10 /*L
of the  internal  standard onto  the  sample  in  the  crucible.    Store  internal
standard solutions at 4°C or less before,  and  between,  use.

      5.5   Calibration  standards  -  Prepare calibration standards within  the
working range of  the  TC/MS system.  Each standard should contain each analyte or
interest (e.g.  some or all  of  the compounds listed in Sec.  1,1 may be included).
Each aliquot of calibration standard  should be  spiked with internal standards
prior to analysis.  Stock solutions should be stored at  -10°C to -20°C and should
be freshly prepared once  a year,  or sooner if check standards  indicate a problem.
The daily calibration standard should be  prepared weekly, and stored at 4°C.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory material  to  this  Chapter,  Organic Analytes,
Sec.  4.1.
7.0   PROCEDURE

      7.1   Crucible Preparation

            7.1.1 Turn on  the  incinerator  and let  it heat  for at  least  10
      minutes.   The bore of the incinerator should be glowing red.

            7.1.2 Load the sample crucible  and  lid  into  the incinerator ladle
      and insert  into  the  incinerator bore.   Leave in the  incinerator  for 5
      minutes,  then remove and place on the cooling rack.

            7.1.3 Allow the crucibles and lids to cool for five minutes before
      placing them in the storage dishes.


                                   8275 - 4                         Revision 0
                                                                September 1994

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      CAUTION:    Do not touch the crucibles with your fingers.  This can
                  result  in  a  serious  burn,  as well  as contamination of
                  the  crucible.   Always handle the sample crucibles and
                  lids with  forceps and tools  specified,

      7.1.4 All  sample crucibles  and  lids  required  for the  number of
analyses planned should be cleaned and  placed in  the storage dishes ready
for use.

7.2   Sample Preparation and Loading

      7.2.1 The  analyst  should  take  care  in selecting  a sample  for
analysis, since the sample size is generally limited to 0.100 g or less.
This  implies that  the  sample should be mixed  as thoroughly as possible
before taking an aliquot.  Because the sample size is limited, the analyst
may wish to analyze several  aliquots for determination.

      7.2.2 The  sample  should  be mixed or ground such that a  0.010 to
0.100 g  aliquot  can be  removed.   Remove  one  sample  crucible  from  the
storage dish and place  it on  the microbalance.  Establish the tare weight.
Remove the sample crucible from the balance with  the forceps and place it
on a clean surface.

      7.2.3 Load an amount of  sample into  the  sample  crucible  using the
fused  quartz  spatula.    Place  the  assembly  on  the  microbalance  and
determine the weight of  the  sample.   For  severely contaminated samples,
less  than 0.010  g will suffice,  while 0.050-0.100 g  is  needed  for  low
concentrations of contaminants.  Place the crucible lid on the crucible;
the sample is now ready for  analysis.

7.3   FID Analysis

      7.3.1  Load the sample  into  the TC.   Hold the sample at 30°C for 2
minutes  followed  by linear  temperature programmed heating  to  260°C at
30°C/minute.   Follow the temperature program with an  isothermal  heating
period of 10  minutes at 260°C, followed  by cooling  back to 30°C.  The total
analysis cycle time is 24.2 minutes

      7.3.2  Monitor the  FID  response in real  time during analysis,  and
note  the  highest response in  millivolts  (mV). Use this  information to
determine the   proper  weight  of  sample  needed  for  combined  thermal
extraction/gas chromatography/mass spectrometry.

7.4   Thermal Extraction/GC/MS

      7.4.1  Prepare a calibration curve using a clean  crucible and lid by
spiking the compounds of interest at five concentrations into the crucible
and applying the internal standards to the crucible  lid.   Analyze these
standards and establish response factors at different concentrations.

      7.4.2  Weigh  out  the  amount  of   fresh  sample  that will  provide
approximately 1000 to 3000 mv response.  For example,  if 0.010 g of sample
gives an FID response of 500 mv,  then  0.020  to 0.060  g (0.040  g i 50 %)


                             8275 - 5                         Revision 0
                                                          September 19i4

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should be used.  If 0.100 g gives 8000 mv,  then 0.025 g ± 50 % should be
used.

      7.4.3 After weighing out the sample into the crucible, deposit the
internal standards (10 fj,L) onto  the  sample.   Load the crucible into the
pyrocell, using  the  same temperature program  in  Sec. 7.3.1.   Hold the
capillary at 5°C during this time to focus the released semivolatiles (the
intermediate trap is  held at 330°C to  pass all compounds onto the column).
Maintain the splitter zone at 3IQ°C,  and the  GC/MS  transfer line at 285°C.
After the isothermal  heating period  is complete,  temperature program the
column from 5°C to 285°C  at 10°C/minute  and  hold  at 285°C  for 5 minutes.
Acquire data during the entire run time.

      7.4.4 If the response for any  quantitation  ion exceeds the initial
calibration curve range of the TC/MS  system, a smaller  sample should be
analyzed.

7.5   Data Interpretation

      7.5.1 Qualitative Analysis

            7.5.1.1     The  qualitative  identification  of  compounds
      determined  by  this  method is  based  on  retention time,  and  on
      comparison of the sample mass spectrum, after background correction,
      with  characteristic ions  in  a  reference   mass  spectrum.    The
      reference mass spectrum must be generated by the  laboratory  using
      the conditions of  this  method.   The characteristic ions  from the
      reference mass  spectrum are defined to  be  the three ions of greatest
      relative intensity,  or any  ions  over 30% relative intensity if less
      than three such  ions occur in  the reference  spectrum.   Compounds
      should be identified as  present when the  criteria below are met.

                  7.5.1.1.1   The intensities  of  the characteristic ions
            of a compound maximize in  the same scan or within one scan of
            each other.   Selection  of  a  peak by  a data system target
            compound search routine  where  the  search  is  based on  the
            presence of  a target chromatographic  peak containing  ions
            specific  for the  target  compound at  a  compound-specific
            retention time will  be accepted  as  meeting this  criterion.

                  7.5.1.1.2   The RRT of the sample  component is within
            ±0.06 RRT units of the  RRT of the  standard component.

                  7.5.1.1.3   The    relative    intensities    of    the
            characteristic  ions  agree  within   30%  of  the  relative
            intensities  of  these  ions  in   the   reference  spectrum.
            (Example:   For an   ion  with an  abundance  of   50%  in  the
            reference spectrum,  the corresponding  abundance  in  a sample
            spectrum can  range between 20% and  80%.}

                  7.5.1.1.4   Structural isomers that produce very similar
            mass spectra  should  be  identified  as  individual  isomers  if
            they  have   sufficiently   different   GC  retention  times.


                            8275 -  6                         Revision  0
                                                          September 1994

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      Sufficient  GC  resolution is  achieved  if the  height  of the
      valley between two isomer peaks is less than 25% of the sum of
      the  two peak  heights.    Otherwise,  structural  isomers are
      identified  as  isomeric pairs.

            7.5.1.1.5   Identification  is  hampered  when  sample
      components  are not  resolved chromatographically and produce
      mass  spectra  containing  ions contributing by  more  than one
      analyte.  When gas chromatographic peaks obviously represent
      more  than one  sample  component  (i.e.,  a broadened peak with
      shoulder(s)  or  a  valley  between  two  or  more  maxima),
      appropriate  selection  of  analyte   spectra  and  background
      spectra  is  important.   Examination  of extracted ion current
      profiles  of appropriate  ions can aid  in  the  selection  of
      spectra, and in qualitative  identification of compounds.  When
      analytes  coelute (i.e.,  only one  chromatographic peak  is
      apparent),  the  identification criteria  can  be  met,  but each
      analyte  spectrum will contain extraneous ions contributed by
      the coeluting compound.

      7.5.1.2     For samples containing components not associated
with the calibration standards,  a  library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification will be determined by the purpose  of the
analyses  being  conducted.     Computer  generated  library  search
routines  should   not  use  normalization  routines   that   would
misrepresent the  library or unknown spectra  when  compared to each
other.  For  example,  the RCRA permit or waste delisting requirements
may require the reporting of non-target analytes.  Only after visual
comparison of sample spectra with  the nearest  library  searches will
the  mass spectral  interpretation  specialist  assign a  tentative
identification. Guidelines  for making tentative identification are:

      (1)   Relative  intensities  of major ions  in  the reference
spectrum (ions > 10% of the  most abundant ion)  should  be present in
the sample spectrum.

      (2)   The relative intensities of  the major ions should agree
within + 20%.   (Example:  For an ion with an abundance of 50% in the
standard spectrum, the  corresponding sample  :or.  abundance must  be
within 30 and  70%).

      (3)   Molecular ions present in the reference spectrum should
be present in  the sample spectrum.

      (4)   Ions  present  in the  sample spectrum  but not  in the
reference  spectrum  should  be  reviewed  for   possible  background
contamination  or presence of coeluting compounds.

      (5)   Ions  present in the reference  spectrum but  not  in the
sample spectrum should be reviewed for possible subtraction from the
sample  spectrum because of  background  contamination  or coeluting.
Data system library  reduction  programs  can sometimes create these
discrepancies.

                       8275 - 7                         Revision 0
                                                    September 1994

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8.0   QUALITY CONTROL

      8.1   Refer to Chapter One and Method 8000  for  specific  quality control
procedures.


9.0   METHOD PERFORMANCE

      9.1   Table 1 presents method  performance data, generated using spiked soil
samples.   Method performance data in an aqueous matrix are not  available.


10.0  REFERENCES

1.    Zumberge,  J.E., C. Sutton,  R.D.  Worden,  1.  Junk, T.R,  Irvin,  C.B. Henry,
      V.  Shirley,  and  E.B. Overton,  "Determination of Semi-Volatile Organic
      Pollutants in Soils by Thermal Chromatography-Mass Spectrometry (TC/MS):
      an  Assessment for Field Analysis,"  in preparation.
                                   8275 -  8                         Revision 0
                                                                September 1994

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                                TABLE 1
                    METHOD PERFORMANCE, SOIL MATRIX
Analyte
2-Chlorophenol
4-Methyl phenol
2,4-Dichlorophenol
Naphthalene
4-Chloro-3-methyl -phenol
1-Chloronaphthalene
2,4-Dinitrotoluene
Fluorene
Diphenylaraine
Hexachl orobenzene
Dibenzothiophene
Phenanthrene
Carbazole
Aldrin
Pyrene
Benzo(k)fluoranthene
Benzo(a)pyrene
Averaqe
Clay
30
10
23
77
9
96
7
9
5
68
20
11
4
3
7
4
4
% Recovery"
Silt
22
77
20
120
12
103
10
25
6
64
35
31
8
19
19
9
8

Subsoil
2
7
26
63
9
70
10
19
6
80
50
40
9
15
20
11
11
Mean
Recovery
18
31
23
87
10
90
9
18
6
71
35
24
7
12
15
8
8
Percent theoretical  recovery based upon linearity of injections deposited on
the crucible lid (slope and y-intercept).  Average of 9 replicates  (-10 mg
soil spiked with 50 ppm of analyte);  3  different  instruments  at 3 different
laboratories.
                               8275  -  9                          Revision  0
                                                             September  1994

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                                    TABLE 2
                CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS
Compound
Primary
Ion
Secondary
Ion(s)
2-Chlorophenol
4-Methylphenol
2,4-Dichlorophenol
Naphthalene
4-Chloro-3-methyl-phenol
1-Chloronaphthalene
2,4-Dinitrotoluene
Fluorene
Diphenylamine
Hexachlorobenzene
Phenanthrene
Aldrin
Pyrene
Benzo(k)fluoranthene
Benzo(a)pyrene
  128
  107
  162
  128
  107
  162
  165
  166
  169
  284
  178
   66
  202
  252
  252
  64,130
 107,108,77,79,90
 164,98
 129,127
 144,142
 127,164
  63,89
 165,167
 168,167
 142,249
 179,176
 263,220
 200,203
 253,125
 253,125
                                   8275 - 10
                                Revision 0
                            September 1994

-------
                               METHOD  8275
      THERMAL  CHROMATOGRAPHY/HASS SPECTROMETRY (TC/MS)  FOR
             SCREENING  SEHIVOLATILE ORGANIC COMPOUNDS
     Start
  7.1 Prepare
   crucible
     7,2.2
   Establish
  tare weight
  of crucible.
   7.2.3 Place
    sample in
crucible; establish
    weight.
    7.3.1 RD
  Analysis using
   linear temp.
   programmed
    heating.
   7.3.2 Using
  FID response,
    determine
  sarnpie weigh:
  for TE/GC/MS.
7.4.1 Prepare
 calibration
   eurva.
7.4.2 Prepare
  amount of
  sample for
 appropriate
F!D response.
 7.4.3 Weigh
 sample into
 crucible; use
t«rnp. program
in Sec. 7.3.1.
                            7.4.4 Use
                             smaller
                             sample.
                                8275 -  11
                                       Revision  0
                                  September  1994

-------

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                                 METHOD 8310

                      POLYNUCLEAR AROMATIC HYDROCARBONS


1.0  SCOPE AND APPLICATION

     1.1  Method 8310 1s used to  determine the concentration of certain poly-
nuclear aromatic hydrocarbons (PAH)  in ground water and wastes.   Specifically,
Method 8310 is used to detect the following substances:

          Acenaphthene                     Chrysene
          Acenaphthy1ene                   Di benzo(a, h)anthracene
          Anthracene                       Fluoranthene
          Benzo(a)anthracene               Fluorene
          Benzo(a)pyrene                   Indeno(1,2,3-cd)pyrene
          Benzo(b)f1uoranthene             Naphthalene
          Benzo(ghi)perylene               Phenanthrene
          Benzo(k)fluoranthene             Pyrene

     1.2  Use of Method 8310  presupposes  a  high  expectation of finding the
specific compounds of interest.  If  the  user 1s attempting to screen samples
for any or all  of  the  compounds  listed  above, he must develop independent
protocols for the verification of identity.

     1.3  The method detection limits  for  each  compound 1n reagent water are
listed  1n Table 1.  Table  2  lists the practical quantitatlon limit (PQL) for
other matrices.  The sensitivity of  this  method usually depends on the level
of  Interferences  rather  than  instrumental  limitations.    The  limits  of
detection listed in Table 1  for the liquid chromatographic approach represent
sensitivities that can be  achieved  in  the  absence  of Interferences.  When
Interferences are present, the level of sensitivity will be lower.

     1.4  This method  1s  recommended  for  use  only  by experienced residue
analysts or under the close supervision of such qualified persons.


2.0  SUMMARY OF METHOD

     2.1  Method 8310 provides high  performance liquid chromatographic  (HPLC)
conditions for the detection  of  ppb   levels  of certain polynuclear aromatic
hydrocarbons.  Prior  to  use  of  this  method, appropriate sample extraction
techniques must be used.  A  5-  to  25-uL  aliquot of the extract is injected
Into an HPLC, and compounds in  the  effluent are detected by ultraviolet (UV)
and fluorescence detectors.

     2.2   If  interferences  prevent   proper  detection  of  the  analytes  of
interest, the method may  also  be  performed  on extracts that have undergone
cleanup using silica gel column cleanup  (Method 3630).
                                  8310 -  1
                                                          Revision
                                                         Date   September  1986

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TABLE 1.  HIGH PERFORMANCE LIQUID CHROMATOGRAPHY OF PAHsa
Compound
Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthrene
Pyrene
Benzo (a) anthracene
Chrysene
Benzo(b)f1uoranthene
Benzo (k) f 1 uoranthene
Benzo(a)pyrene
D1 benzo (a r h) anthracene
Benzo (ghl)perylene
Indeno(l,2,3-cd)pyrene
Retention
time (m1n)
16.6
18.5
20.5
21.2
22.1
23.4
24.5
25.4
28.5
29.3
31.6
32.9
33.9
35.7
36.3
37.4
Col umn
capad ty
factor (k1)
12.2
13.7
15.2
15.8
16.6
17.6
18.5
19.1
21.6
22.2
24.0
25.1
25.9
27.4
27.8
28.7
Method Detection
limit (ug/L)
UV Fluorescence
1.8
2.3
1.8
0.21
0.64
0.66
0.21
0.27
0.013
0.15
0.018
0.017
0.023
0.030
0.076
0.043
 In
  a HPLC conditions:  Reverse  phase  HC-ODS S11-X, 5 micron particle size,
a 250-mm x 2.6-mm I.D. stainless steel column.  Isocratlc elutlon for 5 mln
 using  aceton1tr1le/water  (4:6)(v/v),   then   linear  gradient   elutlon  to  100%
 acetonltrlle  over 25  m1n at   0.5   mL/m1n   flow   rate.   If  columns  having other
 Internal  diameters are  used,  the   flow rate  should be adjusted to maintain a
 linear velocity of 2  mm/sec.
 TABLE 2.   DETERMINATION OF PRACTICAL QUANTITATION LIMITS  (PQL)  FOR VARIOUS
           MATRICES3
     Matrix
                                                           Factorb
 Ground water
 Low-level  soil  by sontcatlon with GPC cleanup
 High-level  soil  and sludges by sonlcation
 Non-water mlsclble waste
                                                              10
                                                             670
                                                          10,000
                                                         100,000
      aSample PQLs are highly  matrix-dependent.     The  PQLs  listed herein  are
      provided for guidance and may not always be achievable.

      bPQL - [Method Detection Limit (Table 1) X [Factor (Table 2)].  For non-
      aqueous samples, the factor 1s on a wet-weight basis.
                                   8310 - 2
                                                          Revision      0
                                                          Date  September 1986

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3.0  INTERFERENCES

     3.1  Solvents, reagents, glassware,  and  other sample processing hardware
may yield discrete artifacts and/or elevated baselines,  causing misinterpreta-
tion of the chromatograms.  All of  these materials must be demonstrated to be
free from Interferences,  under  the  conditions  of  the analysis,  by running
method blanks.  Specific selection of reagents and purification of solvents by
distillation 1n all-glass systems may be required.

     3.2  Interferences coextracted from  the  samples  will vary considerably
from source to source.   Although  a  general cleanup technique 1s provided as
part  of  this  method,  individual  samples  may  require  additional cleanup
approaches to achieve the sensitivities stated 1n Table 1.

     3.3  The  chromatograpMc  conditions   described   allow  for  a  unique
resolution of the specific PAH  compounds  covered  by this method.   Other PAH
compounds, 1n addition to matrix artifacts, may Interfere.


4.0  APPARATUS AND MATERIALS

     4.1  Kuderna-Danish  (K-D) apparatus:

          4.1.1  Concentrator tube:  10-mL, graduated (Kontes K-570050-1025 or
     equivalent).  Ground-glass  stopper  is  used  to  prevent evaporation of
     extracts.

          4.1.2  Evaporation   flask:      500-mL   (Kontes   K-570001-500  or
     equivalent).  Attach to concentrator tube with springs.

          4.1.3  Snyder column:    Three-ball  macro  (Kontes K-503000-0121 or
     equivalent).

          4.1.4  Snyder  column:    Two-ball  micro   (Kontes  K-569001-0219 or
     equivalent).

     4.2  Boiling  chips;  Solvent  extracted,  approximately  10/40 mesh  (silicon
carbide or equivalent).

     4.3  Water  bath;    Heated,  with  concentric   ring   cover,  capable  of
temperature  control  (+5'C).  The bath  should  be  used  in a hood.

     4.4  Syri nge;   5-mL.

     4.5  High pressure syringes.

     4.6  HPLC apparatus;

          4.6.1  Gradient pumping  system:  Constant flow.

          4.6.2  Reverse  phase column:   HC-ODS   Sil-X, 5-micron particle size
     diameter, in  a  250-mm  x 2.6-mm  I.D.  stainless steel column  (Perkin Elmer
     No.  089-0716  or equivalent).

                                   8310 - 3
                                                         Revision      0
                                                         Date  September 1986

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          4.6.3   Detectors:   Fluorescence  and/or UV detectors may be  used.

              4.6.3.1   Fluorescence  detector:   For  excitation at 280-nm and
          emission greater than   389-nm cutoff  (Corning  3-75 or equivalent).
          Fluorometers  should have  dispersive  optics   for excitation and can
          utilize either filter  or  dispersive optics  at  the emission  detector.

              4.6.3.2   UV detector:     254-nm,  coupled  to  the fluorescence
          detector.

          4.6.4   Strip-chart recorder:   compatible  with  detectors.     A data
     system for  measuring peak areas  and retention  times 1s recommended.

     4.7  Volumetric flasks:  10-,  50-, and 100-mL.


5.0  REAGENTS

     5.1  Reagent water;   Reagent  water  1s  defined   as water   1n which  an
interferent 1s not observed at the  method detection  limit of the compounds  of
interest.

     5-2  Aceton1tr1le;  HPLC quality,  distilled 1n glass.

     5.3  Stock  standard solutions;

          5.3.1   Prepare stock standard solutions   at  a concentration  of  1.00
     ug/uL by dissolving  0.0100  g  of  assayed   reference material  1n aeeto-
     nltrlle and diluting  to  volume  1n  a  10-mL  volumetric flask.   Larger
     volumes can be used at  the  convenience  of   the analyst.   When compound
     purity is assayed to be 96%  or  greater,   the weight can  be used  without
     correction  to  calculate  the   concentration  of  the   stock  standard.
     Commercially prepared stock standards can be  used at any concentration 1f
     they are certified by the manufacturer or by  an Independent source.

          5.3.2  Transfer  the  stock  standard  solutions  Into Teflon-sealed
     screw-cap bottles.  Store at 4'C and protect  from light.  Stock standards
     should be checked  frequently   for  signs  of degradation or evaporation,
     especially  just prior to preparing calibration standards from them.

          5.3.3  Stock  standard solutions must be  replaced after one year, or
     sooner  1f comparison with check standards Indicates a problem.

     5.4 Calibration  standards;  Calibration  standards  at a minimum of five
concentrationlevelsshouldbe  prepared  through  dilution  of   the  stock
standards with acetonitrlle.  One of  the  concentration  levels should be at a
concentration near, but  above,  the  method  detection   limit.  The remaining
concentration levels should  correspond  to the expected  range of concentrations
found  In real samples  or  should define  the  working range of the HPLC.  Cali-
bration standards  must  be  replaced   after  six months,  or sooner 1f  comparison
with check standards Indicates a problem.
                                  8310 - 4
                                                         Revision      0
                                                         Date  September 1986

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     5.5  Internal standards (1f Internal   standard  calibration 1s used);   To
use this approach, the analyst must select one or more Internal  standards that
are similar 1n analytical behavior to  the compounds of Interest.  The analyst
must further demonstrate that the measurement  of the Internal  standard 1s not
affected by method or matrix Interferences.   Because of these limitations, no
Internal standard can be suggested that 1s applicable to all samples.

          5.5.1  Prepare  calibration   standards   at   a   minimum  of  five
     concentration levels for each analyte as described 1n Paragraph 5.4.

          5.5.2  To each calibration standard, add  a known constant amount of
     one or more Internal standards, and dilute to volume with acetonltrlle.

          5.5.3  Analyze each calibration standard according to Section 7.0.

     5.6  Surrogate standards;  The analyst  should monitor the performance of
the  extraction^cleanup(Tf  necessary),  and  analytical  system  and  the
effectiveness of the method 1n dealing with each sample matrix by spiking each
sample, standard, and reagent water  blank  with  one or two surrogates (e.g.,
decafluoroblphenyl or other PAHs  not  expected  to  be present in the sample)
recommended to encompass the  range  of  the  temperature program used 1n this
method.  Deuterated analogs of analytes  should  not be used as surrogates for
HPLC analysis due to coelutlon problems.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1  See the Introductory  material  to  this  chapter, Organic Analytes,
Section 4.1.  Extracts must be stored under refrigeration and must be analyzed
within 40 days of extraction.


7.0  PROCEDURE

     7.1  Extraction;

          7.1.1   Refer to Chapter Two for guidance on choosing the appropriate
     extraction procedure.   In  general,  water  samples  are  extracted at a
     neutral pH with methylene  chloride,  using  either  Method 3510 or 3520.
     Solid samples are extracted using either Method 3540 or 3550.  To achieve
     maximum sensitivity with this method, the extract must be concentrated to
     1 mL.

          7.1.2   Prior   to  HPLC  analysis,  the  extraction  solvent  must be
     exchanged to acetonltrlle.    The  exchange  is  performed during the  K-D
     procedures  listed in all  of  the  extraction  methods.   The exchange is
     performed as follows.

               7.1.2.1   Following K-D of  the methylene chloride extract to
          1 mL using  the macro-Snyder column,  allow the apparatus to cool  and
          drain  for at least  10 min.
                                   8310 - 5
                                                          Revision      0
                                                          Date  September 1986

-------
         7.1.2.2  Increase the temperature of the  hot water bath to 95-
    100'C.    Momentarily  remove  the   Snyder  column,  add  4  ml  of
    acetonltrlle, a new boiling chip, and attach a two-ball mlcro-Snyder
    column.  Concentrate  the  extract  using  1  ml  of acetonltrlle to
    prewet the Snyder column.  Place the K-D apparatus on the water bath
    so  that  the  concentrator  tube  1s  partially  Immersed  1n the hot
    water.   Adjust the vertical position  of the apparatus and the water
    temperature, as required,  to  complete  concentration 1n 15-20 m1n.
    At  the proper rate  of  distillation  the  balls  of the column will
    actively chatter,  but  the  chambers  will  not  flood.    When the
    apparent volume of liquid  reaches  0.5  ml, remove the K-D apparatus
    and allow  1t to drain and  cool for at least 10 m1n.

          7.1.2.3  When the apparatus  Is  cool,  remove the mlcro-Snyder
    column and rinse  Its  lower  joint  Into  the concentrator tube with
    about 0.2  ml of   acetonltrlle.    A  5-mL syringe 1s recommended for
    this operation.   Adjust the extract  volume  to 1.0 ml.  Stopper the
    concentrator   tube   and   store    refrigerated  at  4*C,  1f   further
    processing will  not  be performed  Immediately.    If the extract will
    be stored  longer  than  two  days,  1t   should  be  transferred to  a
    Teflon-sealed  screw-cap vial.   Proceed with HPLC  analysis  1f  further
    cleanup  1s not required.

7.2 HPLC conditions  (Recommended);

     7.2.1  Using  the column   described  1n   Paragraph  4.6.2:   Isocratlc
elutlon  for  5 m1n   using  aceton1tr1le/water   (4:6)(v/v),  then linear
gradient elutlon to 100%   acetonltrlle over   25  m1n  at 0.5 ml_/m1n flow
rate.   If columns  having  other Internal diameters are  used, the  flow rate
should be adjusted  to maintain a  linear velocity of 2  mm/sec.

7.3  Calibration;

     7.3.1  Refer  to  Method  8000  for  proper  calibration procedures.  The
procedure of Internal  or  external  standard  calibration may be  used.  Use
Table  1 and especially Table 2 for guidance on selecting the  lowest point
on the calibration  curve.

     7.3.2  Assemble the  necessary HPLC  apparatus  and  establish  operating
parameters equivalent to  those Indicated   1n  Section  7.2.1.  By Injecting
calibration standards, establish  the  sensitivity   limit of the  detectors
and the linear range of the  analytical systems for each  compound.

     7.3.3  Before  using  any  cleanup   procedure,   the  analyst  should
process a  series  of  calibration  standards  through  the  procedure  to
confirm elutlon  patterns  and  the  absence  of  Interferences  from the
reagents.

7.4  HPLC analysis;

     7.4.1  Table 1  summarizes  the  estimate  retention   times  of PAHs
determinate by this method.   Figure  1  1s an example of the separation
achievable using the conditions given 1n Paragraph 7.2.1.

                             8310 - 6
                                                    Revision      0
                                                    Date  September 1986

-------
                                        00
                                       IO
       00
       OJ
       l-»
       o

       I
 O 73
 fu O>
 r+ <
 fl> -4.
loo o
|fl> 3

 r+
1 0>|
c
5.'
o

3

at
S
IO
2

O_

2

o>
3
m


O
z
H
I
m
                                  z
                                       IO
Phenanthrene
    Anthracene
                               Fluorene

                                                                             Pyrene
                                        CO
                                        IO
                                       CO
                                       en
                                       o
                                               Benzo(b)fluoranthene
. Naphthalene

. Acenaphthylene

 Acenaphthene




i Fluoranthene




  Benzo (a) anthracene




 Benzo(k )f luoranthene
                                                                                                              f
         rc
                    Benzo(a)pyrene

                    . Dibenzo(a.h) anthracene
                                        Benzo(g,h,i) pery lene

                                                                                      lndeno(1,2,3-cd)pyrene
vo
00

-------
         7.4.2  If Internal standard calibration Is to be performed, add
    10 uL of Internal standard to the sample prior to injection.  Inject
    2-5 uL of  the  sample  extract  with  a  high-pressure syringe or sample
    Injection loop.  Record the  volume  injected  to the nearest 0.1 uL, and
    the resulting peak size, in  area  units or peak heights.  Re-equilibrate
    the HPLC column at the  initial  gradient  conditions for at least 10 min
    between Injections.

         7.4.3  Using either the  internal  or external calibration procedure
     (Method 8000), determine the identity and quantity of each component peak
     in the sample chromatogram  which  corresponds  to the compounds used for
     calibration purposes.  See  Section  7.8  of  Method 8000 for calculation
     equations.

         7.4.4   If the peak  area   exceeds  the  linear  range of the system,
     dilute the  extract and  .:analyze.

         7.4.5   If the peak area measurement  1s prevented by the presence of
     interferences, further  cleanup  1s  required.

     7.5  Cleanup;

         7.5.1   Cleanup  of  the  acetonltrile   extract  takes place using  Method
     3630  (Silica Gel   Cleanup).     Specific   instructions  for  cleanup  of the
     extract  for PAHs is  given  in  Section 7.1  of  Method  3630.

          7.5.2   Following  cleanup,  analyze   the    samples  using HPLC  as
     described 1n Section 7.4.
8.0  QUALITY CONTROL

     8.1  Refer  to  Chapter  One  for  specific  quality  control  procedures.
Quality control to validate sample extraction is covered 1n Method 3500 and in
the extraction method used.  If  extract  cleanup was performed,  follow the QC
in Method 3600 and in the specific cleanup method.

     8.2  Mandatory quality control to  validate  the HPLC system operation is
found in Method 8000, Section 8.6.

          8.2.1  The quality control  check  sample  concentrate  (Method 8000,
     Section 8.6) should contain each  analyte at the following concentrations
     in acetonltrile:    naphthalene,  100  ug/mL;  acenaphthylene, 100 ug/mL;
     acenaphthene, 100 ug/mL;  fluorene,  100  ug/mL; phenanthrene, 100 ug/mL;
     anthracene, 100 ug/mL; benzo(k)fluoranthene,  5  ug/mL; and  any other PAH
     at 10 ug/mL.

          8.2.2  Table 3 indicates the  calibration and QC acceptance criteria
     for this  method.    Table  4  gives  method  accuracy  and   precision as
     functions of concentration for the analytes of interest.  The contents of
     both Tables should be used to  evaluate a laboratory's ability to perform
     and generate acceptable data by this method.


                                  8310 - 8
                                                         Revision      0
                                                         Date  September 1986

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     8.3  Calculate surrogate standard  recovery  on  all  samples,  blanks,  and
spikes.  Determine if  the  recovery  is  within limits (limits established by
performing QC procedures outlined 1n Method 8000,  Section  8,10).

          8.3.1  If recovery 1s  not  within  limits,  the  following procedures
     are required.

               •  Check to  be  sure  there  are  no  errors  in calculations,
                  surrogate solutions  and  internal  standards.   Also, check
                  Instrument performance,

               »  Recalculate the data and/or reanalyze  the extract if any of
                  the above checks reveal a problem.

               •  Reextract and reanalyze the sample  if none of the above are
                  a problem or flag the data as "estimated concentration."


9.0  METHOD PERFORMANCE

     9.1  The method  was  tested  by  16  laboratories  using  reagent water,
drinking water, surface water, and  three Industrial wastewaters spiked at six
concentrations over the range  0.1  to  425  ug/L.  Single operator precision,
overall precision, and method accuracy  were  found  to be directly related to
the concentration of the  analyte  and  essentially  Independent of the sample
matrix.  Linear equations  to  describe  these  relationships are presented in
Table  4.

     9.2  This method has been  tested  for  linearity  of spike recovery  from
reagent  water  and  has   been   demonstrated   to  be  applicable  over  the
concentration range from 8 x MDL  to  800  x MDL with the following exception:
benzo(ghi)perylene recovery at 80  x  and  800  x  MDL  were low (35% and  45%,
respectively).

     9.3  The accuracy and precision obtained will be determined by the sample
matrix, sample-preparation technique, and calibration procedures used.


10.0   REFERENCES

1.   "Development  and Application of Test Procedures for Specific Organic Toxic
Substances  in Wastewaters, Category 9 -  PAHs,"  Report for EPA  Contract 68-03-
2624  (1n preparation).

2.  Sauter, A.D.,  L.D. Betowskl, T.R. Smith, V.A. Strlckler, R.G.  Beimer,  B.N.
Colby,  and  J.E.  Wilkinson,   "Fused  Silica  Capillary  Column GC/MS  for the
Analysis of Priority Pollutants," Journal of HRC&CC 4, 366-384, 1981.

3.   "Determination of  Polynuclear  Aromatic  Hydrocarbons  in  Industrial and
Municipal   Wastewaters,"   EPA-600/4-82-025,    U.S.  Environmental  Protection
Agency, Environmental  Monitoring  and  Support Laboratory,  Cincinnati,  Ohio
45268,  September  1982.


                                  8310 - 9
                                                         Revision       0
                                                         Date  September  1986

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4.  Burke, J.A.  "Gas  Chromatography  for  Pesticide  Residue  Analysis; Some
Practical  Aspects,"  Journal  of   the  Association  of  Official  Analytical
Chemists, 48, 1037, 1965.

5.  "EPA  Method  Validation  Study   20,  Method  610  (Polynuclear  Aromatic
Hydrocarbons)," Report for EPA Contract 68-03-2624 (1n preparation).

6.  U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and  Interim Final
Rule and Proposed Rule," October 26, 1984.

7.  Provost, L.P. and R.S.  Elder,  "Interpretation of Percent Recovery Data,"
American Laboratory, lj>, pp. 58-63, 1983.
                                   8310 - 10
                                                          Revision
                                                          Date  September 1986

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'TABLE 3.   QC ACCEPTANCE  CRITERIA3
Parameter
Acenaphthene
Acenaphthylene
Anthracene
Benzo a) anthracene
Benzo ajpyrene
Benzo b)fl uoranthene
Benzo (gh1 ) pery 1 ene
Benzo (k) f 1 uoranthene
Chrysene
D1benzo(a,h)anthracene
Fl uoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
Test
cone.
(ug/L)
100
100
100
10
10
10
10
5
10
10
10
100
10
100
100
10
Limit
for s
(ug/L)
40
45
28
4
4
3
2
2
4
2
3
43
3
40
37
3
.3
.1
.7
.0
.0
.1
.3
.5
.2
,0
.0
.0
.0
.7
.7
.4
Range
for X
(ug/L)
22.
11.
3
0
1



0
2
D-105
1-112
2-112
.1-11
.2-11
.8-13
D-10
D-7
D-17
.3-10
.7-11
.7
.1
.3
.6
.0
.8
.7
.0
.5
.0
.1
D-119
1
21.
8.
1
.2-10
5-100
4-133
.4-12
.0
.0
.7
.1
Range
P» Ps
(%)
0-124
D-139
D-126
12-135
D-128
6-150
D-116
D-159
D-199
D-110
14-123
D-142
D-116
D-122
D-155
D-140
      s * Standard deviation of four recovery measurements,  1n ug/L.
      X = Average recovery for four recovery measurements,  1n ug/L.
      p, ps = Percent recovery measured.
      D = Detected; result must be greater than zero.
      8Cr1ter1a from 40 CFR Part 136 for  Method 610.   These criteria are based
 directly upon the method performance  data  1n  Table 3.  Where necessary,  the
 limits for recovery have been broadened  to assure applicability of the limits
 to concentrations below those used to develop Table 3.
                                   8310 - 11
                                                          Revision
                                                          Date  September 1986

-------
TABLE 4.  METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Parameter
Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo (a) pyrene
Benzo (b) f 1 uoranthene
Benzo (gh1 )peryl ene
Benzo (k) f 1 uoranthene
Chrysene
Dlbenzo (a , h) anthracene
Fl uoranthene
Fluorene
Indeno (1 , 2, 3-cd) pyrene
Naphthalene
Phenanthrene
Pyrene
Accuracy, as
recovery, x1
(ug/L)
0.52C+0.54
0.69C-1.89
0.63C-1.26
0.73C+0.05
0.56C+0.01
0.78C+0.01
0.44C+0.30
0.59C+0.00
0.77C-0.18
0.41C-0.11
0.68C+0.07
0.56C-0.52
0.54C+0.06
0.57C-0.70
0.72C-0.95
0.69C-0.12
Single analyst
precision, sr'
(ug/L)
0.397+0.76
0.367+0.29
0.237+1.16
0.281+0.04
0.387-0.01
0.217+0.01
0.257+0.04
0.447-0.00
0.321-0.18
0.247+0.02
0.227+0.06
0.447-1.12
0.297+0.02
0.397-0.18
0.297+0.05
0.257+0.14
Overall
precision,
S' (ug/L)
0.537+1.32
0.427+0.52
0.417+0.45
0.347+0.02
0.537-0.01
0.387-0.00
0.587+0.10
0.697+0.10
0.667-0.22
0.457+0.03
0.327+0.03
0.637-0.65
0.427+0.01
0.417+0.74
0.477-0.25
0.427-0.00
     x1  *  Expected  recovery  for  one  or  more  measurements  of  a  sample
            containing a concentration of C, 1n ug/L.

     sr' *  Expected single analyst  standard  deviation  of measurements at an
            average concentration of 7, In ug/L.

     S1  *  Expected Interlaboratory standard  deviation  of measurements at an
            average concentration found of 7, 1n ug/L.

     C   =  True  value for the  concentration, 1n ug/L.

     7   *  Average recovery  found for measurements of samples containing a
            concentration of  C, 1n ug/L.
                                   8310 - 12
                                                          Revision
                                                                September 1986

-------
                                          METHOD S3 10

                               POLYNUCLEAR AROMATIC HYDROCARBONS
C
 7.1.1
    o
        Choose
     appropriate
     extraction
      procedure
 (see Chapter z)
 7.1.2
                                                     7,3.3
       Process
    • •cries  of
    eallbratIon
     standards
        Exchange
        extract-
  ion solvent to
    acetonltrile
     during K-O
     procedures
  7.2
 7.4 I  Perform
        HPLC
  analysis  (see
   Method 6000
fcr calculation
    aquations
     Set  HPLC
    conditions
  7.3
       Refer  to
     Method 8000
     for proper
     calibration
     techniques
                                                      Is peak area
                                                      measurement
                          Cleanup using
                           Method 3630
7.3.2
HPLC I
f
C
pi
Aaaemble
ipparatua;
ictabliBh
iparating
irameterc
    O
                                      8310 - 13
                                                                Revision        p
                                                                Date  September 1986

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                                 METHOD 8315

                      DETERMINATION OF  CARBONYL COMPOUNDS
               BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC)
1.0   SCOPE AND APPLICATION

      1.1   This  method  provides  procedures for  the  determination  of  free
carbonyl    compounds    in    various    matrices    by   derivatization    with
2,4-dinitrophenylhydrazine  (DNPH).   The  method utilizes high performance liquid
chromatography (HPLC) with ultraviolet/visible (UV/vis) detection to identify and
quantitate the target  analytes  using two different sets of conditions:  Option 1
and Option 2.   Option  1  has  been shown  to perform well for  one  set of target
analytes  for  aqueous samples, soil or waste samples, and stack samples collected
by Method 0011.   Option 2 has been  shown to work well  for another set of target
analytes  in indoor air  samples collected by Method 0100.  The two sets of target
analytes  overlap for some compounds.  Refer to the Analysis Option listed in the
following table  to determine which analytes may be analyzed by  which option.  The
following compounds may be  determined  by this method:
      Compound Name                       CAS No.a           Analysis Option1
Acetaldehyde
Acetone
Acrolein
Benzaldehyde
Butanal (butyraldehyde)
Crotonaldehyde
Cyclohexanone
Decanal
2,5-Dimethylbenzaldehyde
Formaldehyde
Heptanal
Hexanal (hexaldehyde)
Isovaleraldehyde
Nonanal
Octanal
Pentanal (valeraldehyde)
Propanal (propionaldehyde)
m-Tolualdehyde
o-Tolualdehyde
p-Tolualdehyde
75-07-0
67-64-1
107-02-8
100-52-7
123-72-8
123-73-9
108-94-1
112-31-2
5779-94-2
50-00-0
111-71-7
66-25-1
590-86-3
I24-IS-6
124-13-0
110-62-3
123-38-6
620-23-5
529-20-4
104-87-0
1,2
2
2
2
1,2
1,2
1
1
2
1,2
1
1,2
2
J,
1
1,2
1,2
2
2
2
            Chemical Abstract Services Registry Number.
            This  list  of  target  analytes  contains  an  overlapping  li^t  of
            compounds  that  have  been evaluated  using  modifications  of  the
                                   8315 - 1                         Revision 0
                                                                September 1994

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            analysis.  Refer to the respective option number when choosing the
            appropriate analysis technique for a particular compound.

      1.2   The Option  1 method detection limits  (MDL) are listed  in Tables 1 and
2.  The sensitivity data  for  sampling and analysis using Method 0100 (Option 2)
are given in Table 3.  The MDL for a specific sample may differ from that listed,
depending upon the nature of interferences in the sample matrix  and the amount
of sample used in the procedure.

      1.3   The  extraction  procedure  for  solid  samples is  similar  to  that
specified in Method 1311.  Thus, a single sample  may  be extracted to measure the
analytes included  in the  scope  of other  appropriate methods.   The  analyst is
allowed the flexibility to select chromatographic conditions appropriate for the
simultaneous  measurement  of combinations of these analytes.

      1.4   When this  method is used  to  analyze unfamiliar  sample matrices,
compound  identification   should  be  supported  by  at  least  one  additional
qualitative technique.  A gas  ehromatograph/mass spectrometer (GC/MS) may be used
for the qualitative confirmation of results for  the  target analytes, using the
extract produced by this  method.

      1.5   This method is restricted to use by,  or under the supervision of,
analysts experienced in the use  of chromatography and in the interpretation of
chromatograms.  Each analyst must demonstrate the ability to generate acceptable
results with  this method,  using  the procedure described  in Sec,   7,0.


2.0   SUMMARY  OF METHOD

      2.1   Liquid and  Solid  Samples (Option 1)

            2.1.1 For  wastes comprised  of  solids,  or  for  aqueous  wastes
      containing significant  amounts of solid material,  the  aqueous phase,  if
      any,  is  separated from  the solid  phase and stored for later analysis.  If
      necessary, the particle size of the  solids in  the  waste is reduced.   The
      solid  phase is extracted with an amount of  extraction  fluid  equal  to 20
      times  the weight  of the solid phase.   The  extraction fluid employed is a
      function of the alkalinity  of  the solid  phase of the waste.  A special
      extractor vessel  is used when testing  for volatiles. Following extraction,
      the aqueous  extract is  separated  from  the  solid  phase  by  filtration
      employing 0.6 to  0.8 ^m glass fiber  filter.

            2.1.2 If  compatible  (i.e.,  multiple  phases  will   not  form  on
      combination), the  initial  aqueous  phase  of the waste  is added to  the
      aqueous   extract,  and  these   liquids   are  analyzed  together.     If
      incompatible, the  liquids are analyzed separately  and the  results  are
      mathematically combined to yield  a volume-weighted average  concentration.

            2.1.3 A measured volume  of aqueous  sample (approx.  100 mL)  or an
      appropriate amount  of solids extract (approx.  25 g), is buffered to pH 3
      and derivatized with 2,4-dinitrophenylhydrazine (DNPH),  using either the
      liquid-solid or a liquid-liquid  extraction  option.   If  the liquid-solid


                                   8315 -  2                         Revision 0
                                                                September 1994

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      option  is  used,  the  derivative  is  extracted  using  solid  sorbent
      cartridges, followed by elution with ethanol.   If the liquid-liquid option
      is  used,  the derivative  is extracted  from  the  sample with  three  (3)
      portions  of  methylene chloride.   The  methylene chloride  extracts  are
      concentrated using the Kuderna-Danish  (K-D) procedure and  exchanged with
      acetonitrile  prior to HPLC analysis.   Liquid chromatographic conditions
      are described  which  permit  the separation  and measurement  of various
      carbonyl compounds in the extract by absorbance detection at 360 nm.

            2,1,4 If formaldehyde is the only analyte of interest, the aqueous
      sample or solids  extract should be buffered to pH 5.0 to minimize artifact
      formaldehyde formation,

      2,2   Stack Gas Samples  Collected by Method 0011 (Option 1) - The entire
sample returned to the laboratory is extracted with methylene chloride and the
methylene chloride extract is  brought up to a known volume.   An aliquot of the
methylene chloride extract is  solvent exchanged and concentrated or diluted as
necessary.   Liquid  chromatographic conditions  are described that  permit  the
separation and  measurement of  various  carbonyl compounds  in the  extract  by
absorbance detection at 360 nm.

      2.3   Indoor Air  Samples by Method 0100 (Option 2) - The  sample cartridges
are returned  to  the  laboratory  and backflushed with  acetonitrile  into  a 5 ml
volumetric flask.   The eluate is brought up to volume with  more acetonitrile.
Two (2) aliquots of the  acetonitrile  extract  are pipetted  into  two (2)  sample
vials having Teflon-lined septa.  Liquid chromatographic conditions are described
that permit  the separation and measurement of  the various carbonyl compounds in
the extract  by absorbance detection at 360 nm.


3.0   INTERFERENCES

      3.1   Method  interferences  may be caused  by contaminants  in solvents,
reagents, glassware, and other sample  processing  hardware that lead to discrete
artifacts and/or elevated baselines in the chromatograms.  All  of these materials
must be routinely demonstrated to be free from interferences under  the conditions
of the analysis by analyzing laboratory reagent blanks as described in Sec. 8,5,

            3.1.1 Glassware must be scrupulously cleaned.   Clean all glassware
      as soon as possible after use by rinsing with  the last solvent  used.  This
      should be  followed by detergent washing  with hot water, and rinses with
      tap water  and organic-free reagent water.   It  should  then be drained,
      dried,  and heated in a laboratory oven at 130°C for several hours before
      use.  Solvent rinses with acetonitrile   may  be substituted for the oven
      heating.  After drying and cooling, glassware should be  stored  in a clean
      environment to prevent any accumulation of dust or other contaminants.

            NOTE: Do not  use  acetone  or methanol.    These solvents react with
                  DNPH to form interfering compounds.
                                   8315 - 3                         Revision 0
                                                                September 1994

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            3.1.2 The use of high purity reagents and solvents helps to minimize
      interference  problems.   Purification  of solvents  by distillation in all
      glass systems may be required.

            3.1.3 Polyethylene gloves must be worn  when  handling the silica gel
      cartridges to reduce the possibility of contamination.

      3.2   Formaldehyde  contamination  of  the  DNPH  reagent is  a  frequently
encountered problem due to  its widespread occurrence in the environment.   The
DNPH reagent in Option 2 must be purified  by  multiple recrystallizations in UV-
grade acetonitrile.   Recrystallization  is  accomplished, at  40-60°C,  by  slow
evaporation of the solvent to maximize crystal size.  The purified DNPH crystals
are stored under UV-grade acetonitrile until use.  Impurity levels of carbonyl
compounds in the DNPH are determined  prior  to the  analysis  of the samples and
should be less than 25 mg/L.   Refer to  Appendix  A  for the recrystallization
procedure.

      3.3   Matrix  interferences  may  be  caused  by   contaminants  that  are
coextracted from  the  sample.   The extent  of matrix interferences will  vary
considerably from source to  source, depending upon the nature and diversity of
the matrix being sampled.  Although  the  HPLC conditions described allow for a
resolution  of  the  specific  compounds  covered  by this method,  other matrix
components  may interfere.    If  interferences  occur  in subsequent  samples,
modification of the mobile phase or some  additional cleanup may be necessary.

      3.4   In Option  1, acetaldehyde is generated during the  derivatization step
if ethanol is present in the sample.  This background will impair the measurement
of acetaldehyde at levels below 0.5 ppm (500 ppb).

      3.5   For Option  2, at  the  stated  two column analysis  conditions,  the
identification  and  quantitation  of  butyraldehyde may  be  difficult  due  to
coelution with isobutyraldehyde and methyl ethyl  ketone.  Precautions should be
taken and adjustment of the analysis conditions should be done, if necessary, to
avoid potential problems.


4.0   APPARATUS AND MATERIALS

      4.1   High performance liquid chromatograph  (modular)

            4.1.1  Pumping system - Gradient,  with constant flow control  capable
      of 1.50 mL/min.

            4.1.2  High pressure injection valve with 20 fj.1  loop.

            4.1.3  Column - 250 mm x 4.6  mm ID, 5 fim particle size, CIS (Zorbax
      or equivalent).

            4.1.4  Absorbance detector -  360 nm.

            4.1.5  Strip-chart recorder compatible with detector  - Use of a data
      system for measuring peak areas and retention times is recommended.


                                   8315  - 4                         Revision 0
                                                                September 1994

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      4.1.6 Helium  -  for  degassing  mobile  phase  solvents.  (Options
1 and 2)

      4.1.7 Mobile Phase Reservoirs and Suction Filtration Apparatus - For
holding and filtering HPLC mobile phase.  Filtering system should be all
glass and Teflon and use a 0.22 jim polyester membrane filter. (Option 2)

      4.1.8 Syringes - for HPLC injection loop loading,  with capacity at
least four times the loop volume.

4.2   Apparatus and Materials for Option 1

      4.2.1 Reaction vessel - 250 ml Florence flask.

      4.2.2 Separatory funnel - 250 ml,  with Teflon stopcock.

      4.2.3 Kuderna-Danish (K-D) apparatus.

            4.2.3.1     Concentrator  tube  -   10  ml  graduated  (Kontes
      K-57QQ50-1Q25 or  equivalent).   A  ground glass stopper  is  used to
      prevent evaporation of extracts.

            4.2.3.2     Evaporation flask - 500 ml  (Kontes K-5700Q1-5QQ or
      equivalent).  Attach to concentrator tube with springs, clamps, or
      equivalent.

            4.2.3.3     Snyder  column   -   Three   ball  macro   (Kontes
      K-503000-0121 or equivalent).

            4.2.3.4     Snyder   column   -   Two   ball   micro   (Kontes
      K-569001-0219 or equivalent).

            4.2.3.5     Springs   -    1/2   inch   (Kontes  K-662750   or
      equivalent).

      4.2.4 Boiling chips  -  Solvent extracted with  methylene chloride,
approximately 10/40 mesh (silicon carbide or equivalent).

      4.2.5 pH meter - Capable of measuring  to the nearest  0.01  units.

      4.2.6 Glass fiber filter paper - 1.2 jim pore size  (Fisher Grade G4
or equivalent).

      4.2.7 Solid  sorbent  cartridges  -  Packed  with 2  g C18  (Baker or
equivalent).

      4.2.8 Vacuum manifold - Capable  of simultaneous extraction of up to
12 samples (Supelco or equivalent).

      4.2.9 Sample reservoirs - 60 ml capacity (Supelco or equivalent).
                             8315 - 5                         Revision 0
                                                          September 1994

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            4,2.10      Pipet  -  Capable   of accurately  delivering  0.10  ml
      solution (Pipetman or equivalent).

            4.2.11      Water bath - Heated, with concentric  ring cover, capable
      of temperature control (+ 2°C).   The  bath  should  be  used under a hood.

            4.2.12      Sample shaker  - Controlled temperature incubator (± 2°C)
      with  orbital   shaking  (Lab-Line Orbit   Environ-Shaker Model  3527  or
      equivalent).

            4.2.13      Syringes  -  5  ml,  500  jiL,  100  pi,  (Luer-Lok  or
      equivalent).

            4.2.14      Syringe  Filters  -   0.45 p,v\  filtration disks (Gelman
      Acrodisc 4438 or equivalent).

      4.3   Apparatus and Materials for Option 2

            4.3.1 Syringes  -  10  ml,  with  Luer-Lok  type   adapter,  used  to
      backflush the sample cartridges  by gravity feed.

            4.3.2 Syringe Rack - made  of an aluminum  plate with adjustable legs
      on all four corners.   Circular  holes of a diameter  slightly larger than
      the diameter of the 10 mL syringes are drilled  through  the plate to allow
      batch processing of cartridges for cleaning, coating, and sample elution,
      A plate (0.16 x 36 x 53 cm)  with  45 holes  in a  5x9 matrix is recommended.
      See Figure 2 in Method 0100.

      4.4   Volumetric Flasks -  5 ml, 10  mL, and 250 or 500 mL.

      4,5   Vials -  10  or 25 mL,  glass with Teflon-lined screw  caps or crimp
tops.

      4.6   Balance - Analytical, capable  of accurately weighing to 0.0001 g.

      4.7   Glass Funnels

      4.8   Polyethylene Gloves - used to  handle silica gel  cartridges.


5.0   REAGENTS

      5.1   Reagent grade inorganic chemicals shall be used in all  tests.  Unless
otherwise  indicated,  it  is  intended  that   all  reagents  shall conform  to the
specifications of the Committee on Analytical Reagents of the American Chemical
Society, where such  specifications  are available.   Other grades  may be used,
provided it is  first  ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.

      5.2   Organic-free reagent water -  Water  in which an  interferant is not
observed at the method detection limit for the compounds of interest.
                                   8315 - 6                         Revision 0
                                                                September 1994

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      5.3   Formalin - Solution of formaldehyde (CH20) in organic-free reagent
water, nominally 37.6  percent (w/w).  Exact concentration will  be determined for
the stock solution in Sec. 5.7.1.1.

      5.4   Aldehydes and ketones  -  analytical grade,  used for preparation of
DNPH derivative standards of target analytes other than  formaldehyde.  Refer to
the target analyte list.

      5.5   Option 1 Reagents

            5.5.1   Methylene chloride,  CH2C12 - HPLC grade or equivalent.

            5.5.2   Acetom'trile,  CH3CN  - HPLC grade or  equivalent.

            5.5.3   Sodium hydroxide  solutions, NaOH,  1.0 N and 5  N.

            5.5.4   Sodium chloride,  NaCl,  saturated  solution  - Prepare  by
      dissolving an excess of the  reagent grade  solid in organic-free reagent
      water.

            5.5.5   Sodium sulfite  solution, Na2S03,  0.1 M.

            5.5.6   Sodium sulfate, Na2S04 -  granular, anhydrous.

            5.5.7   Citric Acid, C8H807,  1.0  M  solution.

            5.5.8   Sodium Citrate, C6H5Na307.2H20, 1.0 M trisodium salt dihydrate
      solution.

            5.5.9   Acetic acid  (glacial), CH3C02H.

            5.5.10  Sodium acetate, CH3C02Na.

            5.5.11  Hydrochloric Acid, HC1, 0.1 N.

            5.5.12  Citrate buffer, 1 M, pH 3  - Prepare  by adding 80 ml of 1 M
      citric  acid  solution  to  20 ml  of  1 M sodium  citrate solution.   Mix
      thoroughly.  Adjust pH with  NaOH or HC1  as needed.

            5.5.13  pH  5.0 Acetate buffer  (5M)  - Formaldehyde analysis only.
      Prepared  by  adding 40 ml  5M  acetic  acid  solution  to  60  ml  5M  sodium
      acetate solution.   Mix  thoroughly.  Adjust pH with  NaOH  or HC1 as needed.

            5.5.14  2,4-Dinitrophenylhydrazine, 2,4~(02N)2CeH3]NHNH2, (DNPH), 70%
      in organic-free reagent water (w/w).

                    5.5.14.1   DNPH (3.00 rag/mL) - Dissolve 428.7 mg of 70% (w/w)
            DNPH solution in 100 ml acetonitrile.

            5.5.15  Extraction fluid for Option 1 -  Dilute 64.3 ml  of  1.0 N NaOH
      and 5.7 mL glacial  acetic  acid  to  900 ml with organic-free reagent water.
                                   8315 - 7                         Revision 0
                                                                September 1994

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Dilute to 1 liter with organic-free reagent water.   The pH should be 4.93
± 0,02.

5.6   Option 2 Reagents

      5.6.1   Acetonitrile,  CH3CN  -  UV grade.

      5.6.2   2,4-Dinitrophenylhydrazine,  C6H6N404,  (DNPH) - recrystallize
at least twice with UV grade acetonitrile  using the  procedure in Appendix
A.

5.7   Stock Standard Solutions for Option  1
      5.7.1
diluting  an
formaldehyde
water.  If a
any question
 Stock formaldehyde  (approximately  1000  mg/L)  - Prepare by
  appropriate  amount  of  the  certified  or   standardized
 (approximately  265  ^.L)  to 100 ml with organic-free reagent
certified formaldehyde solution is not  available or there is
 regarding the quality of  a certified solution,  the solution
may be standardized using the procedure in Sec. 5.7.1.1.
              5.7.1.1    Standardization of formaldehyde stock solution -
      Transfer a 25 ml aliquot of a 0.1 M Na2S03 solution to a beaker and
      record  the  pH.   Add  a  25.0  ml aliquot of  the  formaldehyde stock
      solution (Sec. 5.18.1) and record the pH.  Titrate this mixture back
      to the original  pH using 0.1  N HC1.  The formaldehyde concentration
      is calculated using the following equation:
              Concentration (mg/L)  =
                               (30.03)(N HCl}(mL HC1

                                      25.0 ml
      where:
              N HC1
              ml HC1
              30.03
                 Normality  of HC1  solution used (in
                 equivalents/ml) (1 mmole  of HC1 =  1
                 equivalent of HC1)
                 ml of  standardized HC1 solution used
                 Molecular  of weight  of  formaldehyde
                 mg/mmole)
mill i -
mill i -
   (in
      5.7.2   Stock aldehyde(s)  and  ketone(s)  -  Prepare  by  adding an
appropriate  amount of the  pure material to  90 ml of  acetonitrile and
dilute to 100 ml,  to give a final concentration of 1000 mg/L.

5.8   Stock Standard Solutions  for Option 2

      5.8,1   Preparation of the DNPH Derivatives for  HPLC  analysis

              5.8.1.1     To  a portion  of the  recrystallized  DNPH,  add
      sufficient  2N  HC1  to obtain  an  approximately  saturated solution.
      Add to this solution the target analyte in molar excess  of the DNPH.
      Filter the DNPH derivative precipitate, wash it with 2N  HC1, wash it
      again with water,  and allow it to dry in air.
                             8315  - 8
                                                  Revision  0
                                              September  1994

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                    5.8.1.2    Check the purity of the DNPH derivative by melting
            point determination or HPLC analysis.   If the impurity level is not
            acceptable, recrystallize  the  derivative in  acetonitrile.   Repeat
            the purity check and recrystallization as necessary until 99% purity
            is achieved.

            5.8,2   Preparation  of DNPH  Derivative Standards and  Calibration
      Standards for HPLC analysis

                    5.8.2.1    Stock  Standard  Solutions  -  Prepare  individual
            stock  standard   solutions  for  each  of  the target  analyte  DNPH
            derivatives   by   dissolving   accurately   weighed   amounts   in
            acetonitrile.  Individual stock solutions of approximately 100 mg/L
            may be  prepared  by  dissolving 0.010 g of the  solid  derivative in
            100 ml of acetonitrile,

                    5.8.2.2    Secondary  Dilution  Standard(s)   -   Using  the
            individual  stock standard  solutions,  prepare  secondary  dilution
            standards in acetonitrile containing the DNPH derivatives from the
            target  analytes  mixed together.   Solutions  of  100  ^9/L may be
            prepared  by  placing 100  jjtL of a  100  mg/L  solution  in a 100 ml
            volumetric flask and diluting to the mark with  acetonitrile.

                    5.8.2,3    Calibration   Standards   -   Prepare   a   working
            calibration standard mix  from the secondary dilution standard,  using
            the mixture of DNPH derivatives at concentrations of 0.5-2,0 Mi/L
            (which  spans  the concentration  of interest for  most  indoor  air
            work).  The concentration of the DNPH derivative in the standard mix
            solutions may need to  be  adjusted to reflect relative concentration
            distribution in a real sample.

      5.9   Standard Storage  -  Store all  standard  solutions  at  4°C  in  a  glass
vial  with a Teflon-lined  cap,  with minimum headspace,  and in the dark.   They
should be stable for about 6 weeks.   All  standards should be checked frequently
for signs of  degradation or  evaporation,  especially just  prior  to preparing
calibration  standards from them.

      5.10  Calibration Standards

            5.10.I  Prepare   calibration   solutions  at   a  minimum    of  5
      concentrations for each analyte of interest in organic-free reagent  water
      (or acetonitrile  for  Option 2)  from the stock standard solution.   The
      lowest concentration of each  analyte  should be at,  or  just above, the MDLs
      listed  in  Tables 1 or  2.   The other concentrations of the calibration
      curve  should correspond to the expected range of concentrations found in
      real samples.
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6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1   See the introductory material  to this Chapter, Organic Analytes, Sec.
4.1.

      6.2   Samples  must  be  refrigerated  at 4°C.   Aqueous  samples must  be
derivatized and extracted within 3 days  of sample collection.  The holding times
of leachates of  solid  samples should be  kept  at  a minimum.   All  derivatized
sample extracts should  be analyzed within 3 days after preparation.

      6.3   Samples  collected by Methods 0011 or 0100 must  be  refrigerated at
4°C.   It  is recommended that samples be extracted and analyzed within 30 days of
collection.


7.0   PROCEDURE

      7.1   Extraction  of Solid Samples  (Option  1)

            7.1.1  All  solid samples should be made as homogeneous as possible
      by stirring and  removal  of sticks,  rocks,  and other  extraneous material.
      When the  sample is not dry, determine the dry weight of the sample, using
      a  representative  aliquot.   If particle  size  reduction is  necessary,
      proceed as per Method 1311.

                   7.1.1.1    Determination of dry weight -  In certain  cases,
            sample results  are desired  based on  a  dry  weight basis.   When such
            data are desired or required,  a portion of sample for  dry  weight
            determination should be weighed  out  at the same time as the portion
            used for analytical  determination.

                   WARN I N6 :   The  drying  oven should be  contained  in a hood or
                              vented.  Significant laboratory contamination may
                              result  from   drying   a  heavily   contaminated
                              hazardous  waste sample.

                   7.1.1.2    Immediately  after   weighing   the  sample  for
            extraction,  weigh  5-10 g  of the  sample  into  a  tared  crucible.
            Determine  the %  dry weight of  the  sample by drying  overnight  at
            105°C.  Allow to  cool  in a desiccator before weighing:
                   % dry weight = - x 100
                                      g  of sample

            7.1.2  Measure  25  g  of solid  into  a 500  mL bottle with  a  Teflon
      lined screw cap or crimp top,  and add 500 ml of extraction  fluid (Sec.
      5.5.15).   Extract the solid by rotating the bottle at approximately 30 rpm
      for 18 hours.  Filter  the  extract through glass fiber  filter  paper and
      store in sealed bottles  at  4°C.   Each mL of extract represents  0.050 g
      solid.      Smaller   quantities   of   solid   sample   may  be  used  with
                                  8315 - 10                         Revision 0
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correspondingly reduced volumes of extraction fluid maintaining the 1:20
mass to volume ratio,

7,2   Cleanup and Separation (Option 1)

      7.2.1   Cleanup procedures may not  be necessary for  a relatively
clean sample matrix.  The  cleanup  procedures  recommended in this method
have been used for the analysis of  various  sample  types.  If particular
samples  demand the use of an alternative cleanup procedures the analyst
must determine the elution profile  and demonstrate that  the recovery of
formaldehyde from a spiked sample  is greater than  85%,   Recovery may be
lower for samples which form emulsions.

      7,2.2   If the sample is not clear, or the complexity is unknown, the
entire sample should be centrifuged at 2500 rpm  for 10 minutes.  Decant
the supernatant  liquid  from the  centrifuge bottle, and  filter through
glass fiber filter paper into a container which can be tightly sealed.

7.3   Derivatization (Option 1)

      7.3.1   For  aqueous  samples,  measure an  aliquot of sample which is
appropriate to  the  anticipated analyte  concentration  range (nominally
100 ml).    Quantitatively transfer  the sample aliquot to  the  reaction
vessel (Sec. 4.2).

      7.3.2   For  solid  samples, 1  to  10  ml of extract  (Sec.  7.1)  will
usually be  required.   The amount  used for  a particular  sample must be
determined through preliminary experiments.

      NOTE:   In cases where the selected  sample or  extract volume is less
              than 100 ml, the total volume of the aqueous layer  should be
              adjusted to  100 ml with organic-free reagent water.  Record
              original sample volume prior to dilution.

      7.3.3   Derivatization and extraction  of the target analytes may be
accomplished using the liquid-solid (Sec. 7.3.4)  or liquid-liquid (Sec.
7.3.5) procedures.

      7.3.4   Liquid-Solid  Derivatization  and Extraction

              7,3.4.1    For analytes other than formaldehyde, add 4 ml of
      citrate buffer and  adjust the pH to  3,0 ± 0.1 with 6M HC1  or 6M
      NaOH,  Add  6 ml of  DNPH reagent,  seal  the container, and place in a
      heated (40CC),  orbital shaker  (Sec.  4.2.12) for 1 hour.  Adjust the
      agitation to produce a gentle swirling of the reaction solution.

              7.3.4.2    If formaldehyde is the only analyte of interest,
      add 4 ml acetate buffer and adjust pH to 5.0 + 0.1 with  6M  HC1 or 6M
      NaOH.  Add  6 ml of  ONPH reagent,  seal  the container, and place in a
      heated (40°C),  orbital shaker  (Sec.  4.2.12) for 1 hour.  Adjust the
      agitation to produce a gentle swirling of the reaction solution.
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        7.3.4.3    Assemble  the  vacuum manifold  and connect  to  a
water aspirator or vacuum pump.   Attach a 2 g  sorbent cartridge  to
the vacuum  manifold.   Condition  each  cartridge by passing  10  ml
dilute citrate buffer (10 ml of  1  M citrate  buffer dissolved in 250
ml of organic-free reagent water) through each sorbent cartridge.

        7.3.4.4    Remove  the  reaction  vessel  from  the  shaker
immediately at the end of the one hour reaction period  and add 10 ml
saturated NaCl solution to the vessel.

        7.3.4.5    Quantitatively transfer the reaction solution  to
the sorbent cartridge  and  apply  a vacuum so  that  the solution  is
drawn through the cartridge  at  a  rate  of 3 to 5 mL/min.   Continue
applying the vacuum for about 1 minute after the liquid sample has
passed through the cartridge.

        7.3.4.6    While maintaining the vacuum conditions described
in Sec.  7.3.4.4,  elute each  cartridge train with approximately 9 ml
of acetonitrile  directly into a 10 ml volumetric flask.  Dilute the
solution to volume with acetonitrile, mix thoroughly,  and place  in
a tightly sealed vial until  analyzed.

        NQJE:      Because this method  uses  an  excess  of  DNPH,  the
                  cartridges  will remain  a  yellow  color  after
                  completion of Sec.  7.3.4.5.  The presence of this
                  color  is   not   indicative  of  the  loss  of  the
                  analyte derivatives.

7.3.5   Liquid-Liquid  Derivatization  and  Extraction

        7.3.5.1    For analytes other  than formaldehyde, add 4 mL of
citrate buffer and  adjust the pH to 3.0 + 0.1 with 6M HC1  or  6M
NaOH.   Add 6 mL of DNPH reagent, seal the container, and place in a
heated (40°C),  orbital shaker for 1  hour.  Adjust the agitation  to
produce a gentle swirling of the reaction solution.

        7.3.5.2    If formaldehyde is the only analyte of interest,
add 4  mL acetate  buffer and  adjust pH to 5.0 ± 0.1 with 6M HC1 or 6M
NaOH.   Add 6 mL  of DNPH reagent, seal the container, and place in a
heated (40°C),  orbital shaker for 1  hour.  Adjust the ag:tat:cn  to
produce a gentle swirling of the reaction solution.

        7.3.5.3    Serially  extract the solution with three  20  mL
portions of methylene chloride using a 250 mL separatory funnel.  If
an emulsion forms upon extraction, remove the entire emulsion and
centrifuge  at  2000  rpm for  10  minutes.   Separate  the  layers  and
proceed with the  next extraction.  Combine the methylene chloride
layers  in  a  125  ml Erlenmeyer  flask  containing  5.0  grams  of
anhydrous sodium  sulfate.   Swirl  contents to  complete the extract
drying process.
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        7.3.5.4   Assemble a  Kuderna-Danish  (K-D)  concentrator by
attaching a  10 ml  concentrator  tube  to  a 500 ml evaporator flask.
Pour the extract  into the evaporator flask being  careful to minimize
transfer of sodium sulfate granules.  Wash the Erlenmeyer flask with
30 mL of methylene chloride  and  add wash  to the evaporator flask to
complete quantitative transfer.

        7.3.5.5   Add  one  to  two   clean  boiling  chips  to  the
evaporative flask and attach a three ball  Snyder  column.  Prewet the
Snyder column  by adding about 1  ml methylene chloride to  the top.
Place the K-D  apparatus on  a  hot water  bath  (80-90°C) so  that the
concentrator tube  is partially  immersed in the hot water  and the
entire lower rounded surface of  the flask is bathed with hot vapor.
Adjust  the  vertical  position  of  the   apparatus  and  the  water
temperature, as  required,  to  complete the concentration  in  10-15
min.  At  the proper rate  of distillation the balls of  the column
will  actively chatter,  but  the  chambers  will  not flood  with
condensed solvent.  When the apparent volume of liquid  reaches 5 ml,
remove the K-D apparatus and allow it to  drain and cool for at least
10 min.

        7.3.5.6   Prior to  liquid  chromatographic  analysis,  the
extract solvent must be exchanged to acetonitrile.  The analyst must
ensure  quantitative transfer  of the  extract  concentrate.    The
exchange is performed as follows:

            7.3.5.6.1   Remove  the  three-ball  Snyder column  and
        evaporator flask.   Add 5 ml  of acetonitrile  , a new glass
        bead or boiling chip, and attach the micro-Snyder column to
        the  concentrator tube.   Concentrate the  extract  using 1 ml
        of acetonitrile  to prewet the Snyder  column.   Place the K-D
        apparatus on the water bath so that the concentrator tube is
        partially immersed  in  the hot water.  Adjust  the  vertical
        position  of the  apparatus and  the water temperature,  as
        required,  to complete concentration.  At the proper rate of
        distillation the balls of the column will actively chatter,
        but  the chambers will  not flood.   When the  apparent volume
        of liquid reaches  less  than  5 ml, remove the  K-D apparatus
        and  allow it to drain  and  cool for at  least 10 minutes.

            7.3.5.6.2   Remove the Snyder column and rinse the flask
        and  its lower joint with  1-2 ml of acetonitrile  and add to
        concentrator tube.  Quantitatively transfer the sample to a
        10 ml volumetric flask using a 5 ml syringe with an attached
        Acrodisc  0.45 fim filter cassette.   Adjust the extract volume
        to 10 ml.  Stopper the flask and store refrigerated at 4°C
        if further processing will not be  performed immediately.  If
        the  extract will  be  stored longer than two   (2) days,  it
        should  be transferred  to a vial  with  a  Teflon lined screw
        cap   or  crimp  top.     Proceed with  HPLC  chromatographic
        analysis  if further  cleanup  is not  required.
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7.4   Extraction of Samples from Methods 0011  and  0100 (Options 1  and 2)

      7.4.1  Stack gas samples collected by Method 0011 (Option 1)

             7.4.1.1    Measure  the volume of  the aqueous phase  of  the
      sample prior to extraction (for  moisture  determination  in case  the
      volume was  not  measured in the  field).   Pour  the  sample  into  a
      separatory funnel and drain the methylene  chloride into a volumetric
      flask.

             7.4.1.2    Extract  the aqueous solution  with two  or three
      aliquots  of methylene chloride.  Add the methylene chloride extracts
      to the volumetric flask.

             7.4.1.3    Fill   the  volumetric   flask  to  the  line with
      methylene chloride.   Mix well  and remove  an  aliquot.

             7.4.1.4    If  high  concentrations  of  formaldehyde   are
      present,  the extract can be diluted with mobile phase, otherwise  the
      extract solvent must  be  exchanged  as described in Sec. 7.3.5.5.   If
      low concentrations of formaldehyde are present, the sample should be
      concentrated during  the  solvent  exchange  procedure.

             7.4.1.5    Store  the sample at 4°C.   If the extract will  be
      stored longer than two days, it should be  transferred to a vial with
      a Teflon-lined  screw cap, or a  crimp top with a Teflon-lined septum.
      Proceed with HPLC chromatographic analysis if further cleanup is  not
      required.

      7.4.2  Ambient  air samples collected by Method 0100  (Option 2)

             7.4.2.1    The samples  will be received by the laboratory in
      a friction-top  can containing 2  to 5 cm  of  granular  charcoal,  and
      should be  stored in  this  can, in a refrigerator, until  analysis.
      Alternatively,   the  samples may  also  be stored  alone  in  their
      individual  glass containers.  The time between sampling and analysis
      should not exceed 30 days.

             7.4.2,2    Remove the  sample cartridge  from  the labeled
      culture tube.   Connect  the sample cartridge  (outlet or  long  end
      during sampling) to  a clean  syringe.

             NOTE:      The liquid  flow during desorption should be  in
                        the opposite direction from the air  flow  during
                        sample collection (i.e, backflush the cartridge).

             7.4.2.3    Place  the  cartridge/syringe  in the  syringe rack.

             7.4.2.4    Backflush  the  cartridge (gravity feed) by passing
      6 ml of  acetonitrile from the syringe  through the cartridge to  a
      graduated test  tube,  or  to a 5 ml volumetric flask.
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              NOTE:      A dry cartridge  has an acetonitrile holdup volume
                        slightly greater than 1  ml.   The eluate flow may
                        stop before the  acetonitrile in the  syringe  is
                        completely drained into  the  cartridge because of
                        air trapped between the  cartridge filter and the
                        syringe Luer-Lok tip.  If this happens, displace
                        the  trapped  air  with  the  acetonitrile  in  the
                        syringe  using  a  long-tip   disposable  Pasteur
                        pi pet,

              7.4,2.5    Dilute to the  5 ml mark with acetonitrile.  Label
      the flask  with  sample  identification.    Pipet  two aliquots  into
      sample vials having Teflon-lined septa.

              7.4.2.6    Store  the  sample  at 4°C.    Proceed  with  HPLC
      chromatographic  analysis  of the  first aliquot if further cleanup is
      not required.  Store the  second aliquot in  the  refrigerator until
      the results of the  analysis of  the  first  aliquot  are  complete and
      validated.    The  second  aliquot   can  be  used  for  confirmatory
      analysis,  if necessary.

7.5   Chromatographic  Conditions (Recommended):

      7.5.1    Option 1 -  For  aqueous samples, soil or waste  samples,  and
stack gas samples collected by Method  0011.

      Column:                  CIS,  4,6 ram x 250 ram ID, 5 urn particle size
      Mobile Phase Gradient:   70%/30%  acetonitrile/water (v/v), hold for
                              20 min.
                              70%/30%     acetonitrile/water    to    100%
                              acetonitrile in 15 min.
                              100% acetonitrile  for  15 min.
      Flow Rate:               1.2 mL/min
      Detector:                Ultraviolet, operated  at 360 nm
      Injection  Volume:        20 p.1

      7.5.2    Option 2 -  For ambient air samples collected by Method 0100.

      Column:                  Two  HPLC  columns,  4.6 mm  x  250 mm  ID,
                              (Zorbax  ODS,  or equivalent}  in series
      Mobile Phase Gradient:   60%/40%  CH3CN/H20,  hold  for 0 min.
                              60%/40%  to 75%/25% CH3CN/H20, linearly in 30
                              rain.
                              75%/25%  to  100%/0% CH3CN/H20, linearly in 20
                              min.
                              100% CH3CN  for  5 minutes.
                              100VO%  to 60%/40% CH3CN/H20, linearly in 1
                              min.
                              60%/40%  CH3CN/H20 for 15 minutes.
      Detector:                Ultraviolet, operated  at 360 nm
      Flow Rate:               1.0 mL/min
      Sample Injection volume:25 pi (suggested)

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      NOTE:   For Options 1 and 2, analysts  are  advised  to adjust their
              HPLC systems  to optimize  chromatographic  conditions  for
              their particular  analytical  needs.    The   separation  of
              acrolein,  acetone,  and  propionaldehyde should be a minimum
              criterion  of the optimization  in  Option  2.

      7.5.3   Filter and degas the mobile phase to remove dissolved gasses,
using the following procedure:

              7.5.3.1    Filter  each   solvent  (water   and  acetonitrile)
      through a  0.22  /im polyester membrane  filter, in an all  glass and
      Teflon suction filtration apparatus.

              7.5.3.2    Degas  each  filtered  solution  by purging  with
      helium for 10-15 minutes (100 mL/min) or by heating to 60°C for 5-10
      minutes  in an  Erlentneyer  flask covered  with  a  watch glass.   A
      constant back pressure restrictor (350 kPa) or  15-30 cm of 0.25 mm
      ID Teflon  tubing  should  be  placed  after  the detector to eliminate
      further mobile phase outgassing.

              7.5.3.3    Place  the  mobile  phase  components  in  their
      respective HPLC solvent reservoirs,  and program  the gradient system
      according to the conditions listed  in  Sec.  7.5.2.  Allow the system
      to pump  for 20-30 minutes  at  a  flow  rate of 1.0 mL/min  with the
      initial  solvent mixture ratio  (60%/40%  CH3CN/H20).   Display the
      detector output on a strip chart recorder or similar output device
      to establish a stable baseline.

7.6   Calibration

      7.6.1   Establish  liquid chromatographic operating  conditions  to
produce a  retention  time similar  to  that indicated  in Table  1  for the
liquid-solid derivatization and extraction or in Table  2 for liquid-liquid
derivatization  and extraction.    For determination  of  retention  time
windows,  see  Sec.  7.5  of  Method   8000.    Suggested  chromatographic
conditions are provided  in Sec. 7.5.

      7.6.2   Process    each   calibration   standard   solution   through
derivatization  and extraction,  using the  same  procedure employed  for
sample processing  (Sees. 7.3.4 or 7.3.5).

      7.6.3   Analyze  a  solvent blank to  ensure that the system is clean
and interference free.

      NOTE:   The samples  and standards must be  allowed to  come to ambient
              temperature before  analysis.

      7.6.4   Analyze  each  processed  calibration  standard  using  the
chromatographic  conditions listed in  Sec.  7.5,  and  tabulate  peak area
against calibration solution concentration in iJ.g/1.
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      7.6.5   Tabulate  the peak  area  along with  standard concentration
injected to determine  the response  factor (RF) for the  analyte at each
concentration  (see  Sec.  7.8.1  for  equations).    The percent  relative
standard deviation  (54RSD) of the mean  RF of  the  calibration standards
should be no greater than + 20 percent or a system check will have to be
performed.   If a calibration  check  after  the  system check does not meet
the  criteria, a  recalibration  will  have to  be  performed.    If  the
recalibration does  not meet  the  established  criteria,  new calibration
standards must be made,

      7.6.6   The  working calibration curve must  be  verified  each day,
before  and after  analyses  are   performed,  by  analyzing  one  or  more
calibration standards.   The response obtained  should fall  within  ± 15
percent of the initially established response or a system check will have
to be performed.   If a calibration check after the system check does not
meet the criteria,  the system must be recalibrated.

      7.6.7   After  10  sample runs,  or  less,  one  of  the  calibration
standards must be reanalyzed to ensure that the DNPH derivative response
factors remain within ±15% of the original calibration response factors.

7.7   Sample Analysis

      7.7.1   Analyze samples by HPLC, using conditions established  in Sec.
7,5.  For  analytes to  be analyzed by Option 1, Tables 1  and 2  list the
retention times and MDLs that were obtained under these conditions.  For
Option 2 analytes,  refer to Figure 3 for the sample chromatogram.

      7.7.2   If the peak  area exceeds the  linear range of the calibration
curve, a smaller  sample injection volume should be used.   Alternatively,
the final solution may be diluted with acetonitrile and reanalyzed.

      7.7.3   After   elution   of   the   target   analytes,   calculate  the
concentration of analytes found in the samples using the equations found
in Sec.  7.8 or the specific sampling method used.

      7.7.4   If the peak  area measurement is prevented by the presence of
observed interferences, further cleanup is required.

7.8   Calculations

      7.8.1   Calculate each  response factor,  mean  response  factor,  and
percent relative  standard deviation as follows:

               Concentration  of  standard  injected,
                        Area of signal
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                           IRF:
      Mean RF = RF
                  I (RF, - RFr /N-l
      %RSD    =  	_	  x 100%
                        RF

where:

      RF      =    Mean  response  factor  or mean of  the  response factors
                  using the 5 calibration concentrations.
      RFi      =    Response factor for calibration standard i (i = 1-5).
      %RSD    =    Percent  relative  standard  deviation  of  the response
                  factors.
      N       =    Number of calibration standards.

      7.8.2   Calculate the analyte concentrations  in  liquid samples as
f ol1ows:

      Concentration of aldehydes in fig/I  =  (RF)(Area of signal)(100/VJ

where:

      RF      =    Mean response factor for a particular analyte.
      Vs       =    Number of ml of sample  (unit!ess).

      7.8.3   Calculate the  analyte  concentration  in  solid  samples as
fol1ows:

      Concentration of aldehydes  in  M9/9 - (RF)(Area of signal)(20/ V8X)

where:

      RF      =    Mean response factor for a particular analyte.
      Vex      =    Number of ml extraction fluid aliquot (unitless).

      7.8.4   Calculate the concentration of  formaldehyde  in  stack gas
samples (Method 0011) as follows: (Option 1)
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                    7.8.4.1    Calculation  of  Total  Formaldehyde:   To determine
            the total formaldehyde  in mg,  use the  following  equation:

                                         [g/mole  formaldehyde]
Total mg formaldehyde = Cd x V x DF x 	 x  10"3 mg/^sg
                                        [g/mole DNPH derivative]

            where:

                    Cd   =      measured   concentration   of  DNPH-formaldehyde
                               derivative,  mg/L
                    V   =      organic extract volume,  ml
                    DF   =      dilution  factor

                    7.8.4.2    Formaldehyde concentration in stack gas: Determine
            the formaldehyde concentration in the stack gas using the following
            equation:

                    Cf = K  [total formaldehyde, mg]  / Vmhstd)

            where:

                    K          =     35.31  ft3/m3,   if   Vm(stdl  is  expressed  in
                                    English units
                                    1.00 m3/m3, if Vm(std) is expressed in  metric
                                    units
                    Vm(std!       =     volume of gas sample as measured by dry gas
                                    meter,  corrected  to  standard  conditions,
                                    dscm (dscf)

            7.8.5   Calculation of the Concentration of Formaldehyde and Other
      Carbonyls from Indoor Air Sampling by Method  0100.  (Option 2}

                    7.8.5.1    The concentration of target analyte "a" in air at
            standard conditions  (25°C and  101.3  kPa),   Conc^  in ng/L,  may be
            calculated using the following equation:

                           (AreaJ(RF)(Vol.)(MWJ(1000 ng/Mg)
                    Cone., = 	  x  DF
                               (MWd)(VTolStd)(1000 ml/I)
            where:
                    Areaa      =     Area of the  sample  peak  for  analyte  "a"
                    RF         =     Mean response  factor for analyte  "a"  from
                                    the calibration  in  fig/L. (See Sec. 7.8.1}
                    Vola       =     Total volume of the sample cartridge  eluate
                                    (ml)
                    MWa        =     Molecular weight of analyte  "a"  in g/mole
                    MWd        =     Molecular weight of the  DNPH derivative  of
                                    analyte "a"  in g/mole
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                VTotStd         =     Total  volume  of  air sampled  converted  to
                                    standard  conditions in  liters  (L).  (To
                                    calculate  the concentration  at  sampling
                                    conditions  use  Vtot.)(See  Sec.  9.1,3  of
                                    Method 0100)
                   DF         =     Dilution  Factor  for the sample  cartridge
                                    eluate,  if any.  If there  is  no  dilution,
                                    DF - 1

                   7.8.5.2    The target analyte "a"  concentration at standard
            conditions may be  converted to parts per billion by  volume, Conca in
            ppbv,  using the following equation:

                                      (Cone.) (22.4)
                   Conca in ppbv    = -
                                          (MWJ

            where:

                   Conca      =     Concentration of  analyte "a"  in ng/L
                   22.4       =     Ideal  gas law  volume  (22.4 nL of gas =  1
                                    nmole  at standard conditions)
                   MWa        «     Molecular weight of analyte "a"  in  g/mole
                                    (or ng/nmole)


8.0   QUALITY CONTROL

      8.1   Refer  to Chapter One and  Method 8000 for specific  quality control
procedures.    Refer  to Table  4 for  QC  acceptance  limits  derived  from  the
interlaboratory method validation study on Method 8315.


9.0   METHOD PERFORMANCE

      9.1   The MDLs  for Option  1 listed in Table 1  were  obtained using organic-
free reagent water  and  liquid-solid extraction.  The MDLs for Option 1 listed in
Table 2 were obtained  using organic-free  reagent water  and methylene chloride
extraction.   Results reported ir Tables ! and 2 we^s achieved  using  fortified
reagent water volumes of 100 ml.  Lower detection limits may be obtained using
larger sample volumes.

            9.1.1   Option  1  of this  method  has been tested for  linearity  of
      recovery from spiked organic-free  reagent  water and has been demonstrated
      to be applicable over the range 50-1000
            9.1.2  To generate the MDL and precision and accuracy data reported
      in this section,  analytes were segregated into two spiking groups, A and
      B.   Representative chromatograms  using  liquid-solid  and  liquid-liquid
      extraction  are  presented  in Figures  1   {a  and  b)   and  2  (a and  b) ,
      respectively.
                                   8315  -  20                         Revision 0
                                                                September 1994

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      9.2   The Sensitivity of Option 2 sampling (Method 0100) and analysis is
listed in Table 3.

      9,3   Method 8315, Option 1, was tested by 12 laboratories using reagent
water and ground waters spiked at six concentration levels over the range 30-2200
jug/L.  Method  accuracy  and  precision  were  found to be directly related to the
concentration of the  analyte and independent of the sample matrix.  Mean recovery
weighted  linear  regression  equations,  calculated  as  a   function  of  spike
concentration,  as well  as  overall  and  single-analyst precision  regression
equations, calculated as functions of mean recovery, are presented in Table 5.
These equations  can  be used  to estimate  mean  recovery and  precision  at any
concentration value within the range tested.


10.0  REFERENCES

1.    "OSHA Safety and  Health  Standards,  General Industry",  (29CRF1910).
      Occupational  Safety  and  Health  Administration,  OSHA 2206,  (Revised,
      January 1976).


11,0  SAFETY

      11.1  The toxicity or carcinogenicity of each  reagent  used in this method
has not been precisely defined;  however, each chemical compound should be treated
as a potential  health hazard.   From this viewpoint, exposure to these chemicals
must be reduced to the lowest possible level by whatever means available.  The
laboratory  is  responsible for  maintaining a current  awareness file  of OSHA
regulations regarding  the safe  handling  of the  chemicals specified  in this
method.   A  reference file of material safety data  sheets  should  also  be made
available  to  all   personnel  involved  in  the chemical  analysis.    Additional
references to laboratory safety are available.

      11.2  Formaldehyde has been tentatively classified as a known or suspected,
human or mammalian carcinogen.
                                   8315  -  21                         Revision 0
                                                                September 1994

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                        TABLE 1.

        OPTION 1  -  METHOD DETECTION LIMITS8  USING
                 LIQUID-SOLID EXTRACTION
Analyte             Retention  Time                 MDL
                      (minutes)
Formaldehyde
Acetaldehyde
Propanal
Crotonaldehyde
Butanal
Cyclohexanone
Pentanal
Hexanal
Heptanal
Octanal
Nonanal
Decanal
5.3
7.4
11.7
16.1
18.1
27.6
28.4
34.1
35.0
40.1
40.4
44.1
6.2
43. 7b
11.0
5.9
6.3
5.8
15.3
10.7
10.0
6.9
13.6
4.4
 The  method  detection  limit  (MDL)   is   defined  as  the  minimum
 concentration that  can  be measured  with 99%  confidence  that the
 value  is  above   background  level.     With   the   exception  of
 acetaldehyde, all reported MDLs  are  based upon analyses of 6 to 8
 replicate  blanks  spiked  at  25  M9/L-   The MDL  was  computed  as
 fol1ows:

        MDL = V1-0.01,(Std. Dev.)

 where:

        t(N-i,0,01)    =     The  upper first  percentile point  of the
                         t-distribution with n-1 degrees  of freedom.
         Std.  Dev. =     Standard  deviation.,  calculated  using n-1
                         degrees of freedom.

 The reported MDL is  based upon  analyses  of 3 replicate, fortified
 blanks  at 250 M9/L.
                        8315 -  22                        Revision 0
                                                     September  1994

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                              TABLE  2.

             OPTION 1 - METHOD DETECTION LIMITS" USING
                      LIQUID-LIQUID  EXTRACTION
     Analyte           Retention Time                    MDL
                           (minutes)
Formaldehyde
Acetaldehyde
Propanal
Crotonaldehyde
Butanal
Cyclohexanone
Pentanal
Hexanal
Heptanal
Octanal
Nonanal
Decanal
5.3
7.4
11.7
16.1
18.1
27.6
28.4
34.1
35.0
40.1
40.4
44.1
23.2
110. 2b
8.4
5.9
7.8
6.9
13.4
12.4
6.6
9.9
7.4
13.1
a    The  method  detection   limit   (MDL)   is  defined   as   the   minimum
     concentration that can be measured with 99% confidence that the value
     is above background  level.  With  the  exception  of  acetaldehyde,  all
     reported MDLs  are based  upon  analyses of 6  to 8  replicate  blanks
     spiked at 25 /ug/L.   The MDL was computed  as  follows:

     MDL    =     two,0.oi,(Std. Dev.)

where:

     tjN-t.o.oi!      =  The   upper  first  percentile  point   of  the   t-
                     distribution with n-1  degrees  of freedom.
     Std. Dev.    =  Standard deviation,  calculated using n-1  degrees  of
                     freedom,

 b   The reported  MDL is based  upon analyses  of 3  replicate, fortified
     blanks at 250
                             8315 - 23                         Revision  0
                                                           September  1994

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                                   TABLE 3.

        OPTION 2 - SENSITIVITY (ppb, v/v) OF SAMPLING AND ANALYSIS FOR
        CARBONYL COMPOUNDS IN AMBIENT AIR USING AN ADSORBENT CARTRIDGE
                          FOLLOWED BY GRADIENT HPLC0
Compound
10
     Sample Volume (L)b

20    30    40    50   100   200   300   400   500
Acetaldehyde
Acetone
Acrolein
Benzaldehyde
Butyraldehyde
Crotonaldehyde
2, 5 -Dimethyl -
benzaldehyde
Formaldehyde
Hexanal
Isovaleraldehyde
Propionaldehyde
m-Tolualdehyde
o-Tolualdehyde
p-Tolualdehyde
Valeraldehyde
1
1
1
1
1
1

0
1
1
1
1
1
1
1
1
.36
.28
.29
.07
.21
.22

.97
.45
,09
.15
.28
.02
.02
.02
.15
0.68
0.64
0.65
0.53
0.61
0.51

0.49
0.73
0.55
0.57
0.64
0.51
0.51
0.51
0.57
0.45
0.43
0.43
0.36
0.40
0.41

0.32
0.48
0.36
0.38
0.43
0.34
0.34
0.34
0.38
0.34
0.32
0.32
0.27
0.30
0.31

0.24
0.36
0.27
0.29
0.32
0.25
0.25
0.25
0.29
0.27
0.26
0.26
0.21
0.24
0.24

0.19
0.29
0.22
0.23
0.26
0.20
0.20
0.20
0.23
0.14
0.13
0.13
0.11
0.12
0.12

0.10
0.15
0.11
0.11
0.13
0.10
0.10
0.10
0.11
0.07
0.06
0.06
0.05
0.06
0.06

0.05
0.07
0.05
0.06
0.06
0.05
0.05
0.05
0.06
0.05
0.04
0.04
0.04
0.04
0.04

0.03
0.05
0.04
0.04
0.04
0.03
0.03
0.03
0.04
0.03
0.03
0.03
0.03
0.03
0.03

0.02
0.04
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.03
0.02
0.02
0.02

0.02
0.03
0.02
0.02
0.03
0.02
0.02
0.02
0.02
      The ppb values  are  measured at 1 atm and  25°C. The  sample  cartridge is
      eluted with 5 mL acetonitrile and 25 y,L  is injected  into  the HPLC.   The
      maximum sampling flow through a DNPH-coated Sep-Pak is about 1.5 L/minute.
      A  sample  volume  of  1000  L  was  also  analyzed.    The
      sensitivity of 0.01 ppb for all  the target analytes.
                                           results  show  a
                                   8315  -  24
                                                 Revision 0
                                             September 1994

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                             TABLE 4.

         PERFORMANCE-BASED QC  ACCEPTANCE  LIMITS  CALCULATED
                USING THE COLLABORATIVE STUDY DATA
Spike
Analyte Concentration*
Formaldehyde
Propanal
Crotonaldehyde
Butanal
Cyclohexanone
Hexanal
Qctanal
Decanal
160
160
160
160
160
160
160
160
Xb
154
148
160
151
169
151
145
153
c c
iR
30.5
22.4
34.8
22.7
39.2
34.6
40.1
40.0
Acceptance
Limits, %d
39-153
50-134
35-165
52-137
32-179
30-159
15-166
21-171
Spike concentration,
Mean recovery calculated using  the  reagent  water,  mean recovery, linear
regression equation, (j.g/1.
Overall standard  deviation  calculated using the reagent  water, overall
standard deviation linear regression equation,  /xg/L.
Acceptance limits calculated as (X + 3sR)100/spike  concentration.
                             8315  -  25
    Revision 0
September 1994

-------
                                  TABLE 5.

WEIGHTED LINEAR REGRESSION EQUATIONS FOR MEAN RECOVERY AND PRECISION  (/tg/L)
Analyte
Formaldehyde
Propanal
Crotonaldehyde
Butanal
Cyclohexanone
Hexanal
Octanal
Decanal
Appl i cable
Cone, Range
39.2-2450
31.9-2000
32.4-2030
35.4-2220
31.6-1970
34.1-2130
32.9-2050
33.2-208C

X
SR
Sr
X
%
sr
X
sft
sr
X
SR
sr
X
SR
sr
X
SR
Sf
X
SR
sr
V
A
SR
sr
Reagent Water
0.909C + 8.79
0.185X + 1.988
0.093X + 5.79
0.858C + 10.49
0.140X + 1.63
0.056X + 2,76
0.975C + 4.36
0.185X + 5.15
0.096X + 1.85
0.902C + 6.65
0.149X + 0,21
0.086X - 0.71
0.962C + 14.97
0.204X + 4.738
0.187X +3.46
0.844C + 15.81
0.169X + 9.07
0.098X + 0.37a
0.856C + 7.88
0.200X + 11.17
0.092X + 1.71s
'"* GO"?1*"* - * ^5 -*"*^'s
w.OOOK, -.- ii£.w«
0.225X + 5.52
0.088X + 2.28a
a Variance is not constant over concentration range.
X Mean recovery, ^g/L, exclusive of outliers.
SR Overall standard deviation, ^g/L, exclusive of out!
sr Single-analyst standard deviation, pig/L, exclusive
Ground Water
0.870C +14.84
0.177X + 13.85
0.108X +6.24
0.892C + 22.22
0.180X + 12.37
0.146X + 2.08*
0.971C + 2.94
0.157X + 6.09
0.119X - 2.27
0.925C + 12.71
0.140X + 6.89
0.108X - 1.638
0.946C + 28.95
0.345X + 5.02
0.123X + 7,64
0.926C + 9.16
0.132X + 8.31
0.074X - 0.40a
0.914C + 13.09
0.097X + 12.41
0.039X + 1.14
C.908C -r S.46
0.153X + 2.23
0.052X + 0.37
iers.
of out! iers.
                                 8315 - 26
    Revision 0
September 1994

-------
                                    FIGURE  la.

   OPTION 2 - LIQUID-SOLID PROCEDURAL STANDARD OF GROUP A ANALYTES  AT 625  M9/L
 -l.OOH
,-1.20-
 -l.SO-
-i.tO-
-2.00-1 i    i     t
               1.00
2.00             3.00
       x  10*  «inutt«
4.00
                          Retention Time
                            fminutes)
                               5.33
                              11.68
                              18.13
                              27.93
                              36.60
                              42.99
                    Analyte
                   Derivative
                  Formaldehyde
                  Propanal
                  Butanal
                  Cyclohexanone
                  Heptanal
                  Nonanal
                                     831S  -  27
                                      Revision 0
                                  September 1994

-------
                             FIGURE lb.

  OPTION 1 - LIQUID-SOLID PROCEDURAL STANDARD OF GROUP B ANALYTES AT 625
-O.80
         1.00
                                                       LI
2.00
3.00
4.00
                                i 10* •imitra
                     Retention Time
                       Cminutes)
                         7.50
                        16.68
                        26.88
                        32.53
                        40.36
                        45.49
                  Analyte
                 Derivative
                 Acetaldehyde
                 Crotonaldehyde
                 Pentanal
                 Hexanal
                 Octanal
                 Decanal
                              8315 - 28
                                 Revision 0
                              September 1994

-------
                                 FIGURE 2a.

OPTION 1 - LIQUID-LIQUID PROCEDURAL STANDARD OF GROUP A ANALYTES AT 625
           1.00
                                                              f
                                                *
2.00
          3.00
x i9* •inutts
4.00
                       Retention Time
                          (minutes)
                            5.82
                            13.23
                            20.83
                            29,95
                            37.77
                            43.80
                     Analyte
                    Derivative
                   Formaldehyde
                   Propanal
                   Butanal
                   Cyclohexanone
                   Heptanal
                   Nonanal
                                  8315 - 29
                                       Revision 0
                                   September 1994

-------
                                   FIGURE 2b.

  OPTION 1  -  LIQUID-LIQUID  PROCEDURAL STANDARD OF GROUP B ANALYTES AT 625 M9/L
-f.OO-i
            1.00
J.OO
       3.00
x iQ* alnui**
                          Retention  Time
                            {minutesI
                               7.79
                              17.38
                              27.22
                              32.76
                              40.51
                              45.62
                       Analyte
                      Derivative
                     Acetaldehyde
                     Crotonaldehyde
                     Pentanal
                     Hexanal
                     Octanal
                     Decanal
                                    8311  - 30
                                          Revision  0
                                      September 1994

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                          FIGURE 3.
OPTION 2 - CHROMATOGRAPHIC SEPARATION OF THE  DNPH  DERIVATIVES
                   OF 15 CARBONYL COMPOUNDS
          DNPH
              10
                              20

                                    f\UI. min

                      Peak  Identification
             30
                             40
   Number    Compound
Concentration^/ U
     1       Formaldehyde
     2       Acetaldehyde
     3       Acrolein
     4       Acetone
     5       Propanal
     6       Crotonaldehyde
     7       Butanal
     8       Benzaldehyde
     9       Isoval era!dehyde
    10       Pentanal
    11       o-To!ualdehyde
    12       m-Tolualdehyde
    13       p-Tolualdehyde
    14       Hexanal
    15       2,4-Dimethylbenzaldehyde
       1.140
       1.000
       1.000
       1.000
       1.000
       1.000
       0.905
        .000
        .450
        .485
        .515
        .505
        .510
        .000
1,
0.
0,
0.
0.
0,
1,
       0.510
                          8315 - 31
                           Revision 0
                       September 1914

-------
                                      METHOD  8315

                      DETERMINATION OF CARBONYL  COMPOUNDS
              BY  HIGH PERFORMANCE  LIQUID CHROMATOGRAPHY  (HPLC)
  7.1.1-7.1.1.1
Homogenize simple
 and determine dry
     weight
   7.1.2EMrwt
  sample tor18
  touts,' WtBf and
   store extract
 7.3.2 Measure 1-10
  mL extract: adjust
  volume to100 rnL
     with water
 7,0 Is media
   solid or
  aqueous?
  IE sample
dear or sample
  oomplexily
   known?
 7.0 What is  \S»*Ga»(Optton1)
 "ie sampr
   maWx?



      MedU (Option 1)
                                                                    0
 7.2.2 Centrifuge sample
   at 2500 rpm tor 10
          decant
      and fitter
                   Aqueous
    7.3.1 Measure
   aJiquot o( sample;
   adjust volume to
|   100 ml wflfi water
                                     7.3.5.5 Exctiange
                                    sorvent to meBianol
                                       O
                                     8315  - 32
                                           Revision  0
                                      September  1994

-------
              METHOD 8315
               continued
                         7.4.1,1 Measure volume
                          of aqueous phase of
                        sampte: pour sample into
                         separator? funnel and
                        drain methytene chloride
                         (from Method 0011) Into
                            volumetric flask
                         7 4.1.2 Extract aqueous
                         solution wtth methytene
                         crtonde: add metfryteoe
                           chforide extracts to
                            volumetric Bask
                        with metrytene crtoode;
                        mix wed: remove aSquot
7.4. 1.5 Store
sample at 4C
1
i
                                                        7.4.1.4 Dilute
                                                      extract with mobile
                                                           phase
  7.4.1.4 Exchange
solvent with me thanoi
    a« in 7.3.5.5
hign ccooentraoon
     aldehyde?
    7.4.1.4
    s s3ffl
  have a low
   CBfltTEtlCfl
formaldehyde?
                            7.4.1.4 Concentrate
                              extract during
                            sotvent exchange
               8315  -  33
                                                              Revision 0
                                                         September  1994

-------
               METHOD 8315
                continued
'
h-
7.4.2.2 - 7,4.23
Connect sampte cartridge
tt> dean syringe and
place hi syringe rack
i
t
7.4.2.4 Badrftush
carvidge wtth
acetonitrile
     7.4.2.4
   Doeeehjate
   flo* become
    Nocked?
   7.4.2.4 Dtepiace
   trapped air wtti
    acatanitrfen
syringe using a long-tip
dnpccabte Pasteur pipal
 7.4.2.5 DUMB to S
mLwrthaceionttrite;
 label flask; pipet 2
   sampte viate
   7.4.Z6 Store
   sample at 4C
                8315 -  34
                            Revision 0
                       September 1994

-------
                                      METHOD  8315
                                        continued
7.5.2 Set LC conditions
to produce appropriate
   retention times
        I
                                        7.5.1 Set LC
                                    conditions to produce
                                    appropriate retention
                                           tlnm
   7.5.2.1 Filter and
 degas mobile phase
  7.6.2 Process calibration
  standards through same
processing steps as samples
                                    7.6.3 - 7.6.4
                                Analyze solvent blank
                              and calibration standards;
                                 tabulate peak areas
                               7.S.S Determine response
                              factor at each concentration
                                      7.6.5
                                      Does
                                    calibration
                                   check meet
                                     criteria''
                                    O
                                       7.6.5 Prepare new
                                          calibration
                                          standards
                                        8315  - 35
                                                         Revision  0
                                                   September  1994

-------
                     METHOD 8315
                       continued
                                    O
                                  7.6.S-7.6,7 Verify
                              calibration curve every day;
                                reanalyze 1 calibration
                                  standard altar 10
                                 sample runs or toss
                                  7.7 Analyze samples
                                      byHPLC
 7.7.2 Inject a smaller
volume or dilute sample
     7.7.4 Further
  cleanup is required
   7.7.2
 Does peak
area exceed
 calibration
   curve?
  7.7.4 Are
interferences
  present?
                                 7.8.1 Calculate aa.dr,
                                 response factor, rneart
                                 response factor, and
                                     percent RSD
                                    7.8.2 - 7.8.5
                                  Calculate anatyte
                                   concentrations
                       8315 -
                                    Revision  0
                              September  1994

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                                  APPENDIX A

            RECRYSTALLIZATION OF 2,4-DINITROPHENYLHYDRAZINE-(DNPH)


NOTE: This  procedure  should be  performed under  a properly  ventilated hood,
      Inhalation of acetonitrile  can result in nose and throat  irritation (brief
      exposure  at  500 pprn)  or more  serious  effects  at  higher concentration
      and/or longer exposures.

      A.I   Prepare a  saturated solution of DNPH by boiling excess DNPH in 200 ml
of acetonitrile for approximately 1 hour.

      A.2   After 1 hour, remove and transfer the supernatant to a covered beaker
on  a hot  plate and  allow  gradual  cooling  to  40  to  60°C.    Maintain  this
temperature range until 95% of the solvent has evaporated, leaving crystals.

      A.3   Decant the solution to waste  and rinse the  remaining  crystals twice
with three times their apparent volume of acetonitrile.

      A.4   Transfer the  crystals to a clean beaker, add 200 ml of acetonitrile,
heat to boiling, and again  let  the crystals grow  slowly at 40  to 60°C until 95%
of the solvent has evaporated.   Repeat the rinsing process as in Sec. A.3.

      A.5   Take  an  aliquot  of  the  second  rinse,   dilute  10  times  with
acetonitrile,  acidify  with  1 ml  of 3.8  M perchloric acid per  100  ml of DNPH
solution, and analyze  with  HPLC  as in Sec.  7.0  for Option 2.   An acceptable
impurity level is less than 0.025 ng/^L of formaldehyde in recrystall ized DNPH
reagent or below the sensitivity  (ppb, v/v) level indicated in Table 3 for the
anticipated sample volume.

      A,6   If the  impurity  level  is not satisfactory, pipet off  the solution to
waste, repeat the  recrystall ization  as in Sec.  A.4  but rinse  with  two 25 ml
portions of acetonitrile.  Prep and analyze the second rinse  as  in Sec. A.5.

      A.7   When the impurity level is satisfactory,  place  the  crystals in an
all-glass reagent bottle, add another  25 ml of  acetonitrile, stopper, and shake
the bottle.  Use clean pipets when removing the  saturated DNPH  stock solution to
reduce the possibility of contamination of the solution.  Maintain only a minimum
volume o* *he saturstec! solL'tior  sdsc'US'ts ^or dsv ~tc dsv ODersti"o?i to irnrnnpze
waste of the purified  reagent.
                                  8315  -  37                         Revision 0
                                                                September 1994

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                                  METHOD 8316

          ACRYLAMIDE,  ACRYLONITRILE AND ACROLEIN  BY  HIGH  PERFORMANCE
                         LIQUID CHROMATOGRAPHY (HPLC)
1.0   SCOPE AND APPLICATION

      1.1   The following compounds can be determined by this method:



      Compound Name                                   CAS No.3


      Acrylamide                                       79-06-1
      Acrylonitrile                                   107-13-1
      Acrolein (Propenal)                             107-02-8


      "      Chemical Abstract Services Registry Number.

      1.2   The  method  detection  limits   (MDLs)  for the  target analytes  in
organic-free reagent water are listed in Table  1.  The method may be applicable
to other matrices,

      1.3   This  method  is  restricted to  use  by  or under the  supervision  of
analysts experienced in the  use  of high performance liquid chromatographs and
skilled in the interpretation  of high performance  liquid chromatograms.   Each
analyst must demonstrate  the  ability  to generate  acceptable  results with this
method.
2.0   SUMMARY OF METHOD

      Z.I   Water samples are analyzed by high performance liquid chromatography
(HPLC).  A  ZOO jiL aliquot  is  injected onto a C-18  reverse-phase  column,  and
compounds in the effluent are detected with an ultraviolet (UV) detector.


3.0   INTERFERENCES

      3.1   Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially analyzed.   To reduce carryover,  the
sample syringe must  be  rinsed  out between samples with solvent.   Whenever an
unusually concentrated  sample  is  encountered,  it should  be followed  by  the
analysis of solvent to check for cross contamination.
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4.0   APPARATUS AND MATERIALS

      4.1   HPLC system

            4.1.1 One high pressure pump.

            4.1.2 Octadecyl  Silane  (ODS,  C-18)  reverse phase  HPLC  column,
      25 cm x 4.6 mm, 10 ^m,  (Zorbax, or equivalent).

            4.1.3 Variable wavelength UV detector.

            4.1,4 Data system.

      4.2   Other apparatus

            4.2.1 Water degassing unit - 1 liter filter flask with stopper and
      pressure tubing.

            4.2.2 Analytical  balance - ± 0.0001 g.

            4.2.3 Magnetic stirrer and magnetic stirring bar.

            4.2.4 Sample filtration unit - syringe filter with 0.45  ^m filter
      membrane, or equivalent disposable filter unit.

      4.3   Materials

            4.3.1 Syringes - 10, 25, 50 and 250 pi and  10 ml.

            4.3.2 Volumetric pipettes, Class A, glass -1,5 and 10 ml.

            4.3.3 Volumetric flasks - 5, 10, 50 and  100 mL.

            4.3.4 Vials -  25 ml,  glass with Teflon  lined  screw  caps or crimp
      tops.


5.0   REAGENTS

      5.1   Reagent grade inorganic chemicals sha" be used :n a" tests. Unless
otherwise  indicated,  it  is  intended  that  all   reagents  shall  conform  to  the
specifications of the Committee  on Analytical Reagents of the American Chemical
Society, where  such  specifications are available. Other grades  may  be used,
provided it is  first  ascertained that the reagent is of sufficiently high purity
to permit its use without  lessening the accuracy of the determination.

      5.2   Acrylamide,  CH2:CHCONH2, 99+% purity, electrophoresis reagent grade.

      5.3   Acrylonitrile,  H2C:CHCN,  99+%  purity.

      5.4   Acrolein, CH2:CHCHO, 99+% purity.
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      5.5   Organic-free reagent water.  All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.  Sparge with He
to eliminate 02 to prevent significant absorption interference from 02 at the 195
nm wavelength.

      5.6   Stock standard  solutions  -  Can be  prepared  from pure  standard
materials or can  be  purchased  as  certified solutions.   Commercially  prepared
stock standards  can  be  used  if they are  certified  by  the manufacturer  and
verified against a standard  made from  pure  material.

            5.6.1 Acrylamide

                  5,6.1.1    Weigh 0.0100 g of acrylamide neat standard into a
            100 ml volumetric  flask,  and dilute to the mark  with  organic:free
            reagent water. Calculate the concentration of the standard solution
            from the  actual  weight used.  When compound purity is assayed to be
            96%  or  greater, the  weight can  be  used without correction  to
            calculate the concentration  of  the  stock  standard.

                  5.6.1.2    Transfer the stock solution  into vials with Teflon
            lined screw caps or crimp tops.   Store  at 4°C,  protected from light.

                  5.6.1.3    Stock solutions must  be replaced after six months,
            or   sooner  if comparison  with  the check standards  indicates  a
            problem.

            5.6.2 Acrylonitrile and Acrolein - Prepare separate stock solutions
      for acrylonitrile and  acrolein,

                  5.6.2.1    Place about 9.8 ml of organic-free reagent water
            into a 10 ml volumetric flask before weighing  the flask and stopper.
            Weigh the flask  and record the weight to the nearest 0.0001 g.  Add
            two drops of neat standard, using  a 50  pi syringe, to  the flask.
            The liquid  must  fall directly into the water, without contacting the
            inside wall of the  flask.

                  CAUTION:   Acrylonitrile  and acrolein  are toxic.   Standard
                             preparation should be performed in an  laboratory
                             fume hood.

                  5.6.2.2    Stopper  the flask and then reweigh.  Dilute  to
            volume with organic-free reagent water.  Calculate the concentration
            from the  net gain in weight.  When compound purity is assayed to be
            96%  or  greater, the  weight can  be  used without correction  to
            calculate the concentration  of  the  stock  standard.

                  5.6.2.3    Stock solutions must  be replaced after six months,
            or   sooner  if comparison  with  the check standards  indicates  a
            problem.
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      5.7   Calibration standards

            5.7.1  Prepare   calibration  standards   at   a  minimum   of  five
      concentrations by diluting the stock solutions with organic-free reagent
      water,

            5.7.2  One calibration standard should be prepared at a concentration
near, but  above,  the method  detection limit; the  remaining  standards should
correspond to the range of concentrations  found in real samples, but should not
exceed the working range of the HPLC system (1 mg/L to 10 mg/L).


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to this  chapter,  Organic  Analytes,
Sec. 4.1.
7.0   PROCEDURE

      7.1   HPLC Conditions

      Mobile Phase:                 Degassed organic-free reagent water
      Injection Volume:             200 pL
      Flow Rate:                    2.0 mL/min
      Pressure:                     38 atm
      Temperature:                  25°C
      Detector UV wavelength:       195 nm

      7.2   Calibration:

            7.2.1  Prepare standard solutions of acrylamide  as described in Sec.
      5.7.1.   Inject 200 y.L  aliquots  of  each solution into the chromatograph.
      See Method  8000  for  additional  guidance on calibration  by the external
      standard method.

      7.3   Chromatographic analysis:

            7.3.1  Analyze the samples using the same chromatographic conditions
      used to prepare the standard curve.  Suggested chromatographic conditions
      are given  in Sec. 7.1.   Table 1 provides the retention  times  that were
      obtained under these conditions  during method development.


8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control  procedures.

      8.2   Before processing any samples, the analyst  must demonstrate, through
the analysis of a method blank, that all glassware and  reagents are interference
free.
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9.0   METHOD PERFORMANCE

      9.1   Method performance data are not available.


10.0  REFERENCES

1.     Hayes,  Sam;  "Acrylamide,  Acrylom'trile,  and  Acrolein Determination  in
      Water by  High Pressure Liquid Chromatography,"  USEPA.
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                                   TABLE  1
             ANALYTE RETENTION TIMES  AND METHOD DETECTION LIMITS
                                  Retention             MDL
Compound                          Time  (min)           (M9/L)
Aery1 amide                           3.5                10
Acrylonitrile                        8.9                20
Acrolein (Propenal)                 10.1                30
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                          METHOD 8316
ACRYLAHIDE. ACRYLDNITRILE AND  ACROLEIN BY  HIGH PERFORMANCE
                 LIQUID CHROHATQ6RAPHY (HPLQ
                   f   Stan    j
                     7.1 Set by
                       HPLC
                     Conditions.
                     7,2 Calibrate
                    Chromatograph.
                        7.3
                   Chromatographic
                      analysis.
                        StOD
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                                  METHOD 8318

                N-METHYLCARBAMATES BY HIGH PERFORMANCE LIQUID
                             CHROMATOGRAPHY fHPLCl


1.0   SCOPE AND APPLICATION

      1.1   Method   8318   is   used   to  determine   the   concentration   of
N-methylcarbamates in soil, water and waste  matrices. The following compounds can
be determined by this method:
      Compound Name                                               CAS No.a


      Aldicarb (Temik)                                              116-06-3
      Aldicarb Sulfone                                             1646-88-4
      Carbaryl (Sevin)                                               63-25-2
      Carbofuran (Furadan)                                         1563-66-2
      Dioxacarb                                                    6988-21-2
      3-Hydroxycarbofuran                                         16655-82-6
      Methiocarb (Mesurol)                                         2032-65-7
      Methoinyl (Lannate)                                          16752-77-5
      Promecarb                                                    2631-37-0
      Propoxur (Baygon)                                             114-26-1


      a  Chemical Abstract Services Registry Number.

      1.2   The method detection 1 imits (MDLs) of Method 8318 for determining the
target analytes in organic-free reagent water and in soil are listed in Table  1.

      1.3   This method  is restricted  to  use by,  or under the supervision of,
analysts experienced in the use of high performance liquid chromatography (HPLC)
and  skilled  in  the   interpretation  of  chromatograms.     Each   analyst  must
demonstrate the ability to generate acceptable results with this method.


2.0   SUMMARY OF METHOD

      2.1   N-methylcarbamates are extracted from aqueous samples with methylene
chloride, and  from  soils, oily solid  waste and oils with  acetonitrile.   The
extract solvent is exchanged to methanol/ethylene glycol, and then the extract
is cleaned  up  on  a  C-18 cartridge, filtered, and eluted  on a C-18 analytical
column.  After separation, the  target  analytes  are  hydrolyzed and derivatized
post-column, then quantitated fluorometrically.

      2.2   Due  to  the  specific  nature of  this  analysis, confirmation  by a
secondary method  is  not essential.  However, fluorescence due to post-column
derivatization may be  confirmed  by substituting the NaOH and o-phthalaldehyde
solutions with organic-free  reagent  water  and reanalyzing  the  sample.   If


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fluorescence is still  detected, then a positive interference  is present and care
should be taken in the interpretation of the results.

      2.3   The  sensitivity  of  the  method  usually  depends on  the  level  of
interferences present, rather than on  the instrumental conditions.  Waste samples
with a  high  level  of extractable fluorescent compounds are  expected  to yield
significantly higher detection limits.


3.0   INTERFERENCES

      3.1   Fluorescent compounds, primarily  alky!  amines and  compounds which
yield  primary  alkyl  amines  on   base hydrolysis,  are potential  sources  of
interferences.

      3.2   Coeluting compounds that  are  fluorescence  quenchers  may result in
negative interferences.

      3.3   Impurities  in  solvents  and   reagents  are  additional  sources  of
interferences.   Before processing any samples,  the analyst must  demonstrate
daily,  through the  analysis of solvent blanks, that the entire analytical  system
is interference free.


4.0   APPARATUS AND MATERIALS

      4.1   HPLC system

            4.1.1 An  HPLC  system  capable  of injecting  20 jiL  aliquots  and
      performing multilinear gradients at  a constant flow.  The system must also
      be equipped with a data system  to  measure the peak areas.

            4.1.2 C-18 reverse phase  HPLC column, 25 cm x  4.6 mm (5 ^m}.

            4.1.3 Post Column Reactor with two solvent delivery systems (Kratos
      PCRS 520  with  two Kratos  Spectroflow 400 Solvent Delivery  Systems,  or
      equivalent).

            4.1.4 Fluorescence detector (Kratos Spectroflow 980, or equivalent).

      4.2   Other apparatus

            4,2.1 Centrifuge.

            4.2.2 Analytical  balance  - ± 0.0001 g.

            4.2.3 Top loading balance -  + 0.01 g.

            4.2.4 Platform shaker.

            4.2.5 Heating block,  or equivalent apparatus,  that can accommodate
      10 ml graduated vials (Sec. 4.3.11).
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      4.3   Materials

            4.3.1 HPLC injection syringe - 50 ML.

            4.3.2 Filter paper,  {Whatman #113 or #114,  or equivalent).

            4,3.3 Volumetric pipettes, Class A, glass,  assorted sizes.
                                                        p
            4.3.4 Reverse phase cartridges,  (C-18 Sep-Pak  [Waters Associates],
      or equivalent).

            4.3.5 Glass syringes - 5 ml.

            4.3.6 Volumetric flasks, Class A - Sizes as  appropriate.

            4.3.7 Erlenmeyer flasks with teflon-lined screw caps,  250 ml.

            4.3.8 Assorted glass funnels.

            4.3.9 Separatory funnels,  with ground  glass  stoppers and  teflon
      stopcocks - 250 ml.

            4.3.10      Graduated cylinders - 100 ml.

            4.3.11      Graduated glass vials - 10 ml,  20  ml.

            4.3.12      Centrifuge tubes - 250 ml.

            4.3.13      Vials  -  25 ml,  glass  with  Teflon  lined  screw  caps  or
      crimp tops.

            4.3.14      Positive  displacement  micro-pipettor,  3 to   25   /iL
      displacement, (Gilson Microman [Rainin  #M-25] with tips,  [Rainin #CP-25],
      or equivalent).

            4,3,15      Nylon  filter unit, 25 ram diameter, 0.45 /M pore size,
      disposable (Alltech Associates,  #2047,  or equivalent).


5.0   REAGENTS

      5.1   HPLC grade chemicals shall be used in all tests.  It  is intended that
all reagents shall  conform to the  specifications of the Committee on Analytical
Reagents  of the  American  Chemical  Society,  where such  specifications  are
available.  Other grades may be used,  provided  it is first ascertained that the
reagent is of sufficiently  high purity  to  permit  its use  without  lowering  the
accuracy of the determination.

      5.2   General

            5.2.1 Acetonitrile, CHgCN  -  HPLC grade - minimum UV  cutoff at 203  nm
      (EM Omnisolv #AX0142-1, or equivalent).
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      5,2.2 Methane!, CH3OH - HPLC grade - minimum UV cutoff at 230 nm (EM
Omni sol v #MXQ488-1, or equivalent).

      5.2.3 Methylene chloride,  CH?C1,  - HPLC grade - minimum UV cutoff at
230 nm (EM Omnisolv #0X0831-1, or equivalent).

      5.2.4 Hexane, CgH,. - pesticide grade - (EM Omnisolv IHX0298-1, or
equivalent) .

      5.2.5 Ethylene glycol, HQCHgCH-QH -  Reagent grade -  (EM Science, or
equivalent) .

      5.2.6 Organic-free reagent water - All  references to water in this
method refer to organic-free reagent water, as defined in Chapter One.

      5.2.7 Sodium hydroxide, NaOH -  reagent grade - 0.05N NaOH solution.

      5.2.8 Phosphoric acid, H,PO.  - reagent grade.

      5.2.9 pH 10 borate buffer (J.T. Baker 15609-1, or equivalent).

      5.2.10      o-Phthal aldehyde,  o-CfiHd(CHQ)9 - reagent grade (Fisher
#0-4241,  or equivalent).                 *     L

      5.2.11      2-Mercaptoethanol ,  HSCH?CH?OH - reagent grade (Fisher
#0-3446,  or equivalent).

      5.2.12      N-methylcarbamate   neat  standards  (equivalence  to EPA
standards must be demonstrated for  purchased solutions).

      5.2.13      Chloroacetic acid,  ClCHgCOOH,  0.1  N.

5.3   Reaction solution

      5.3.1 Dissolve 0.500  g of  o-phthalaldehyde in  10 ml  of methanol, in
all  volumetric flask.  To  this solution,  add 900  ml  of organic-free
reagent water, followed  by  50 ml of the  borate buffer  (pH 10).   After
mixing well, add 1 ml  of 2-mercaptoethanol , and dilute to the mark with
organic-free reagent water.   Mix the solution thoroughly.  Prepare fresh
solutions on  a  weekly basis,  as needed.   Protect £v-o~ Vlght  and sto
under refrigeration.

5.4   Standard solutions

      5.4.1 Stock  standard  solutions:  prepare  individual  1000  rng/L
solutions by adding 0.025 g of carbamate to a 25 ml volumetric flask, and
diluting to the mark with methanol.   Store solutions, under refrigeration,
in glass vials with Teflon lined  screw  caps or crimp tops.  Replace every
six months.

      5.4.2 Intermediate  standard  solution:  prepare  a  mixed  50.0  mg/L
solution by adding  2.5  ml of  each  stock solution to  a  50  ml volumetric
flask,  and  diluting to the mark with  methanol.  Store  solutions, under
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      refrigeration, in glass vials with Teflon lined screw caps or crimp tops.
      Replace every three months.

            5.4.3 Working standard solutions: prepare 0.5,  1.0,  2.0, 3.0 and 5.0
      mg/L  solutions  by  adding  0.25,  0.5,  1.0,   1.5   and   2.5  ml  of  the
      intermediate mixed  standard to  respective  25 ml volumetric  flasks,  and
      diluting  each  to  the  mark  with   methanol.    Store  solutions,  under
      refrigeration, in glass vials with Teflon lined screw caps or crimp tops.
      Replace every two months,  or sooner  if necessary.

            5.4.4 Mixed QC standard solution: prepare a 40.0 mg/L solution from
      another set  of  stock  standard  solutions,  prepared similarly to  those
      described in Sec.  5.4.1.   Add 2,0 ml of each stock solution to  a  50 ml
      volumetric  flask and  dilute  to  the  mark  with  methanol.    Store  the
      solution,  under refrigeration,  in a  glass vial  with  a  Teflon  lined screw
      cap or crimp top.  Replace every three months.


6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1   Due to the  extreme  instability of N-methylcarbamates  in  alkaline
media, water, waste water  and leachates should be preserved  immediately  after
collection by acidifying to pH 4-5 with 0.1 N chloroacetic acid.

      6.2   Store samples at 4°C and out of direct sunlight, from  the  time of
collection  through  analysis.   N-methylcarbamates  are  sensitive  to  alkaline
hydrolysis and heat.

      6.3   All  samples must be extracted  within  seven days  of  collection,  and
analyzed within  40 days of extraction.


7.0   PROCEDURE

      7.1   Extraction

            7.1.1 Water, domestic wastewater, aqueous  industrial  wastes,  and
      leachates

                  7.1.1.1     Measure  100  mL  of sample into a 250 mL separatory
            funnel  and extract by shaking vigorously for about 2 minutes with 30
            mL of methylene  chloride.   Repeat  the  extraction  two more  times.
            Combine all three extracts  in  a 100 mL  volumetric flask and dilute
            to volume with methylene chloride.  If cleanup  is  required,  go to
            Sec. 7.2.   If cleanup is  not  required,  proceed directly  to Sec,
            7.3.1.

            7.1.2 Soils, solids, sludges,  and heavy aqueous  suspensions

                  7.1.2.1     Determination of sample % dry weight - In certain
            cases,  sample results are  desired based on dry-weight  basis.   When
            such data  is  desired, a  portion of  sample for  this  determination
            should be  weighed  out  at  the  same  time  as the portion used  for
            analytical determination.

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            WARNING:    The drying oven should be contained in a. hood or
                        vented.  Significant laboratory contamination may
                        result  from  a heavily  contaminated  hazardous
                        waste sample.

                  7.1.2.1.1   Immediately after weighing  the  sample for
            extraction, weigh 5-10 g of the sample into a tared crucible.
            Determine the % dry weight of the sample by drying overnight
            at 105°C.   Allow to cool  in a  desiccator before  weighing;

                  % dry weight = q of dry sample x 100
                                   g of sample

            7.1.2.2     Extraction - Weigh out 20 + 0.1 g of sample into
      a 250 ml Erlenmeyer flask with a  Teflon-lined  screw cap.  Add 50 ml
      of acetonitrile and shake for 2 hours on a platform shaker.   Allow
      the mixture to settle  (5-10 min), then decant the extract into a 250
      ml centrifuge tube.  Repeat the extraction two  more times with 20 ml
      of acetonitrile and 1 hour  shaking  each  time.   Decant and combine
      all three extracts. Centrifuge the combined extract at 200 rpm for
      10 min.   Carefully decant the supernatant into a 100 ml volumetric
      flask and dilute  to volume with acetonitrile.   (Dilution factor = 5}
      Proceed  to  Sec. 7.3.2.

      7.1.3 Soils heavily contaminated with non-aqueous substances, such
as oils

            7.1.3.1     Determination  of  sample %  dry  weight  -  Follow
      Sees. 7.1.2.1 through 7.1.2.1.1.

            7.1.3.2     Extraction - Weigh out 20 + 0.1 g of sample into
      a 250 ml Erlenmeyer flask with  a  Teflon-lined  screw cap.  Add 60 ml
      of hexane and shake for  1 hour on a platform  shaker.  Add  50 ml of
      acetonitrile and  shake for an additional  3 hours.  Allow the mixture
      to settle (5-10 min),  then decant the solvent  layers into  a  250 ml
      separatory  funnel.  Drain the  acetonitrile  (bottom  layer)  through
      filter paper into a 100 ml volumetric flask. Add 60 ml of hexane and
      50 ml of acetonitrile to the sample  extraction flask and shake for
      1 hour.   Allow the mixture to settle, then decant the mixture into
      the  separatory  funnel   containing   the  hexane  from  the   first
      extraction.  Shake the separatory funnel  for  2  minutes, allow the
      phases to  separate,  drain  the  acetonitrile  layer through  filter
      paper into  the   volumetric  flask,  and  dilute  to  volume  with
      acetonitrile.  (Dilution factor = 5)  Proceed  to Sec.  7.3.2.

      7.1,4 Non-aqueous liquids such as oils

            7.1.4.1     Extraction - Weigh out 20 + 0.1 g of sample into
      a  125 ml separatory  funnel.   Add  40 ml of  hexane  and 25  ml  of
      acetonitrile and  vigorously  shake the sample mixture for 2  minutes.
      Allow the phases to separate,  then  drain  the  acetonitrile (bottom
      layer) into a 100 ml volumetric flask. Add 25 ml of acetonitrile to
      the  sample  funnel,  shake  for  2  minutes,  allow  the  phases  to
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            Repeat the extraction with  another  25  ml portion of acetonitrile,
            combining  the  extracts.    Dilute  to   volume  with  acetonitrile.
            (Dilution factor = 5).  Proceed to Sec. 7,3.2,

      7.2   Cleanup  -  Pipet 20.0 ml  of the extract  into  a  20 ml  glass  vial
containing 100 juL of ethylene glycol.   Place the vial  in a heating block set at
50° C, and gently evaporate  the  extract under a stream of  nitrogen  {in a fume
hood) until only  the ethylene glycol  keeper remains.  Dissolve  the  ethylene
glycol residue in 2 ml of methanol,  pass the extract through  a pre-washed C-18
reverse phase  cartridge,  and collect the  eluate in a 5 ml  volumetric flask.
Elute the cartridge with methanol, and collect the eluate until the final volume
of 5.0 ml  is  obtained.   (Dilution factor = 0.25)   Using a disposable  0.45  jum
filter,  filter an  aliquot  of the clean extract directly into a properly labelled
autosampler vial.   The extract is now  ready for  analysis.  Proceed to Sec.  7.4.

      7.3   Solvent Exchange

            7.3.1 Water,   domestic wastewater,  aqueous industrial wastes,  and
      leachates:

            Pipet 10.0 ml of the extract  into   a  10 ml graduated  glass  vial
      containing 100 /jL of ethylene glycol.  Place the vial in a heating block
      set at 50  C,  and gently evaporate the  extract  under a stream of nitrogen
      (in  a  fume  hood) until  only  the  ethylene glycol  keeper remains.   Add
      methanol to the ethylene glycol  residue, dropwise, until the total volume
      is 1.0 ml.   (Dilution factor = 0.1).   Using a disposable 0.45  /urn filter,
      filter this extract directly  into a  properly labelled  autosarnpler vial.
      The extract is now ready for analysis.  Proceed to Sec. 7.4.

            7.3.2 Soils,  solids,  sludges,  heavy aqueous suspensions,  and  non^
      aqueous liquids:

            Elute 15 ml of the acetonitrile extract  through  a C-18 reverse phase
      cartridge,  prewashed with  5 ml of  acetonitrile.  Discard the  first 2 ml of
      eluate and  collect the  remainder.  Pipet 10.0  mL of the clean extract into
      a 10 ml  graduated glass vial containing 100 p.1  of ethylene glycol.  Place
      the vial in  a heating block set at 50   C, and  gently evaporate the extract
      under a  stream of nitrogen  (in a fume  hood) until  only the ethylene glycol
      keeper remains.  Add methanol to  the ethylene glycol  residue, dropwise,
      until the total  volume is  1.0  ml.   (Additional dilution  factor = O.I;
   .   overall  dilution factor = 0.5).  Using a disposable 0.45 /um filter, filter
      this extract  directly into a properly labelled autosampler  vial.   The
      extract is now ready for analysis.  Proceed to Sec.  7.4.

      7.4   Sample Analysis

            7.4.1 Analyze  the samples  using the  chromatographic  conditions,
      post-column reaction parameters and instrument parameters given in Sees.
      7.4.1.1, 7.4.1.2, 7.4.1.3  and 7.4.1.4.    Table 2 provides the retention
      times that were obtained under these conditions during method development.
      A chromatogram of the separation  is shown  in  Figure  1.
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            7.4.1.1
Chroraatographic Conditions  (Recommended)
            Solvent A:        Organic-free reagent water,  acidified with
                              0.4 ml  of  phosphoric  acid per  liter  of
                              water
            Solvent B:        Methanol/acetonitrile  (1:1,  v/v)
            Flow rate:        1.0 mL/min
            Injection Volume:  20 pi
            Solvent delivery system program:
                  Function
                     FR
                     B%
                     B%
                     B%
                     B%
                     B%
                     B%
                   ALARM
      Value
        1.0
       10%
       80%
      100%
      100%
       10%
       10%
Duration
(rain)
  20
   5
   5
   3
   7
   0,01
File
 0
 0
 0
 0
 0
 0
 0
 0
            7.4.1.2
Post-column Hydrolysis  Parameters  (Recommended)
            Solution:
            Flow Rate:
            Temperature:
            Residence Time:
      0.05 N aqueous  sodium  hydroxide
      0.7 mL/min
      95° C
            7.4.1.3
      (Recommended)

            Solution:
      35 seconds  (1  ml  reaction  coil)

Post-column    Derivatization    Parameters
            Flow Rate:
            Temperature:
            Residence time:
      o-phthalaldehyde/2-mercaptoethanol
      5.3.1)
      0.7 mL/min
                         (Sec.
      40° C
            7.4.1.4
      25 seconds  (1  mL  reaction  coil)

Fluorometer Parameters  (Recommended)
            Cell:                   10  ML
            Excitation wavelength:   340 nm
            Emission wavelength:     418 nm cutoff  filter
            Sensitivity wavelength:  0.5 #A
            PMT voltage:            -800 V
            Time constant:           2  sec

      7.4.2 If the peak areas of the  sample signals exceed the calibration
range of the  system,  dilute  the  extract as necessary and reanalyze  the
diluted extract.
                             8318 -  8
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                                  September 1994

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7.5   Calibration:

      7.5.1 Analyze a solvent blank {20 ^L of methanol)  to ensure that the
system is clean.  Analyze the calibration standards  (Sec, 5.4.3), starting
with the 0.5 mg/L standards and ending with the 5.0  mg/L standard.  If the
percent  relative  standard  deviation  (%RSD)  of the mean  response factor
(RF) for each analyte does not exceed  20%,  the system  is  calibrated and
the analysis of samples  may proceed.  If the %RSD for any analyte exceeds
20%,  recheck  the  system  and/or  recalibrate  with  freshly  prepared
calibration solutions.

      7.5.2 Using the established calibration mean response factors, check
the  calibration  of  the  instrument  at  the  beginning  of  each  day  by
analyzing  the  2.0 mg/L mixed  standard.  If  the concentration  of  each
analyte falls within  the range of 1.70 to 2.30 mg/L  (i.e., within + 15% of
the true value),  the instrument  is  considered to  be calibrated  and the
analysis of  samples  may proceed.   If the observed value of any  analyte
exceeds  its  true  value by  more than  + 15%,  the  instrument must  be
recalibrated (Sec. 7.5.1).

      7.5.3 After 10  sample runs,  or  less, the 2.0 mg/L standards must be
analyzed to ensure  that  the retention times and response factors are still
within  acceptable  limits.    Significant  variations   (i.e.,  observed
concentrations exceeding the true concentrations by more  than + 15%) may
require a re-analysis of the samples.

7.6   Calculations

      7,6.1 Calculate each  response factor as follows  (mean value based on
5 points):
      RF =
concentration of standard

  area of the signal
                       5
                      (I
                       i
      mean RF = RF =
                   [(I RFi - RF)2]1/2 / 4
      %RSD of RF =
                                  X 100%
                            RF
      7.6.2 Calculate  the concentration  of  each  N-methylcarbarnate  as
follows:

           or mg/L =  (RF) (area of signal) (dilution factor)
                             8318 - 9
                                                  Revision 0
                                              September 1994

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8.0   QUALITY CONTROL

      8.1   Before processing any samples, the analyst must demonstrate, through
the analysis  of  a method blank  for  each  matrix type, that  all  glassware and
reagents are  interference free.    Each time there  is  a  change of reagents, a
method blank must be processed as a safeguard against laboratory contamination.

      8.2   A QC check solution must be prepared and analyzed with each sample
batch that is processed.   Prepare this  solution,  at  a concentration of 2.0 mg/L
of each analyte,  from the 40.0 mg/L mixed QC standard solution (Sec. 5.4.4).  The
acceptable response range is 1.7 to 2.3 mg/L for each analyte.

      8.3   Negative interference due to quenching may be examined by spiking the
extract with  the appropriate  standard,  at  an appropriate  concentration,  and
examining the observed response against the expected response.

      8.4   Confirm any  detected analytes  by substituting  the NaOH  and  OPA
reagents in the post column  reaction  system with  deionized water, and reanalyze
the suspected extract.   Continued  fluorescence  response  will  indicate that a
positive interference is  present (since the fluorescence  response is not due to
the post column derivatization). Exercise caution in the  interpretation of the
chromatogratn.


9.0   METHOD PERFORMANCE

      9.1   Table 1 lists the single operator method detection limit (MDL) for
each  compound  in organic-free  reagent water  and  soil.    Seven/ten  replicate
samples were  analyzed,  as  indicated in the  table.   See  reference  7  for more
details.

      9.2   Tables 23 3 and  4  list the single  operator average recoveries and
standard deviations for organic-free reagent water,  wastewater and  soil.   Ten
replicate samples were analyzed at each indicated spike concentration for each
matrix type.

      9.3   The method detection limit, accuracy  and precision  obtained will be
determined by the sample matrix.


10.0  REFERENCES

1.    California Department  of Health Services, Hazardous Materials Laboratory,
      "N-Methylcarbamates by HPLC", Revision No.  1.0, September 14,  1989.

2.    Krause, R.T. Journal  of Chromatographic Science, 1978, vol. 16, pg 281.

3.    Klotter,  Kevin,  and   Robert  Cunico,  "HPLC  Post   Column  Detection  of
      Carbamate Pesticides", Varian Instrument Group, Walnut Creek,  CA  94598.

4.    USEPA,  "Method  531.     Measurement  of  N-Methylcarbomyloximes  and  N-
      Methylcarbamates in Drinking Water by Direct Aqueous Injection HPLC with
      Post Column Derivatization",   EPA 600/4-85-054, Environmental  Monitoring
      and Support Laboratory, Cincinnati, OH  45268.

                                   8318 -  10                         Revision 0
                                                                September 1994

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5,    USEPA, "Method 632.  The Determination of Carbamate and Urea  Pesticides in
      Industrial  and Municipal  Wastewater",  EPA  600/4-21-014,   Environmental
      Monitoring and Support Laboratory, Cincinnati, OH  45268.

6.    Federal Register, "Appendix B to Part 136 - Definition and  Procedure for
      the Determination of the Method Detection  Limit -  Revision 1.11", Friday,
      October 26, 1984, 49, No. 209, 198-199.

7.    Qkamoto, H.S.,  D.  Wijekoon, C. Esperanza, J. Cheng, S.  Park,  J. Garcha, S.
      Gill, K.  Perera "Analysis for  N-Methylcarbamate Pesticides by  HPLC in
      Environmental  Samples",  Proceedings of the Fifth Annual USEPA Symposium on
      Waste Testing and Quality Assurance,  July 24-28,   1989, Vol. II, 57-71.
                                   8318  -  11                         Revision 0
                                                                September 1994

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                                    TABLE  1
                     ELUTION ORDER, RETENTION TIMES3 AND
                    SINGLE OPERATOR METHOD DETECTION  LIMITS
Method Detection Limits
Compound


Aldicarb Sulfone
Methomyl (Lannate)
3-Hydroxycarbofuran
Dioxacarb
Aldicarb (Temik)
Propoxur (Baygon)
Carbofuran (Furadan)
Carbaryl (Sevin)
a-Naphthol
Hethiocarb (Mesurol)
Promecarb
Retention
Time
(min)
9.59
9.59
12.70
13.50
16.05
18.06
18.28
19.13
20.30
22.56
23.02
Organic- free
Reagent Water
(M9/U
1.9C
1.7
2.6
2.2
9.4C
2.4
2.0
1.7
-
3.1
2.5

Soil
(M9/kg)
44C
12
10*
>50C
12C
17
22
31
-
32
17
c

d
See Sec. 7.4 for chromatographic conditions

MDL  for  organic-free  reagent  water,  sand,   soil  were  determined  by
analyzing  10  low  concentration spike  replicate  for  each matrix  type
(except where noted).  See reference 7 for more details.

MDL determined by analyzing 7 spiked replicates.

Breakdown product of Carbaryl.
                                   8318  -  12
                                                              Revision 0
                                                          September 1994

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                                TABLE 2
                 SINGLE OPERATOR AVERAGE RECOVERY AND
            PRECISION DATA3 FOR ORGANIC-FREE  REAGENT WATER
Compound
Aldicarb Sulfone
Methomyl (Lannate)
3-Hydroxycarbofuran
Dioxacarb
Aldicarb (Temik)
Propoxur (Baygon)
Carbofuran (Furadan)
Carbaryl (Sevin)
Methiocarb (Mesurol)
Promecarb
Recovered
225
244
210
241
224
232
239
242
231
227
% Recovery
75.0
81.3
70.0
80.3
74.7
77.3
79.6
80.7
77.0
75.7
SD
7.28
8.34
7.85
8.13
13.5
10.6
9.23
8.56
8.09
9.43
%RSD
3.24
3.42
3.74
3.54
6.03
4.57
3.86
3.54
3.50
4.1
Spike Concentration = 300 #g/L of each compound,  n = 10
                               8318 -  13
    Revision 0
September 1994

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              TABLE 3
SINGLE OPERATOR AVERAGE RECOVERY AND
   PRECISION DATA3 FOR WASTEWATER
Compound
         Recovered
% Recovery
SD
Aldicarb Sulfone
Methomyl (Lannate)
3 -Hydroxycarbof uran
Dioxacarb
Aldicarb (Temik)
Propoxur (Baygon)
Carbofuran (Furadan)
Carbaryl (Sevin)
Methiocarb (Mesurol)
Promecarb
a Spike Concentration =
No recovery
235
247
251
D
258
263
262
262
254
263
300 Mg/L of

78.3
82.3
83.7
-
86.0
87,7
87,3
87.3
84.7
87.7
each compound, n = 10

17.6
29.9
25.4
-
16.4
16.7
15.7
17.2
19.9
15,1


7.49
12.10
10.11
-
6.36
6.47
5.99
6.56
7.83
5,74


             8318  - 14
                       Revision  0
                   September 1994

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                                TABLE 4
                 SINGLE OPERATOR AVERAGE RECOVERY AND
                       PRECISION DATA3 FOR SOIL
Compound
Aldicarb Sulfone
Methomyl (Lannate)
3-Hydroxycarbofuran
Dioxacarb
Aldicarb (Ternik)
Propoxur (Baygon)
Carbofuran (Furadan)
Carbaryl (Sevin)
Methiocarb (Mesurol)
Promecarb
Recovered
1.57
1.48
1.60
1.51
1.29
1.33
1.46
1.53
1.45
1.29
% Recovery
78.5
74.0
80.0
75.5
64.5
66.5
73.0
76.5
72.5
64.7
SD
0.069
0.086
0.071
0.073
0.142
0.126
0.092
0.076
0.071
0.124
%RSD
4.39
5.81
4.44
4.83
11.0
9.47
6.30
4.90
4.90
9.61
Spike Concentration =2.00 mg/kg of each compound,  n = 10
                               8318 -  15
    Revision 0
September 1994

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                                    FIGURE  1
   100 r
 E
 E
 S
 P
 S
 E
                               TIKE (MIN)
1.00 M9/mL EACH OF:

1.  ALDICARB  SULFONE

2.  METHOMYL

3.  3-HYDROXYCARBOFURAN

4.  DIOXACARB

5.  ALDICARB
6.    PROPOXUR

7,    CARBOFURAN

8.    CARBARYL

9.    METHIOCARB

10.  PROMECARB
                                  8318  -  16
                      Revision 0
                  September 1994

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                                                           METHOD  8318
              N-METHYLCARBAMATES  BY  HIGH  PERFORMANCE  LIQUID  CHROMATOGRAPHY  (HPLC)
                                                              71 Extraction
  7.1.1 Water, domestic
  wastewater. aqueous
  industrial wastes and
      leachates.
 1  Extract too ml sample
 w/30 ml MeCI 3x in sep.
tunnel: combine extracts In
tOOmLvol flask and dilute
        to mark
 7.
   .2 Soils, solid!;, sludges, and heavy
       aqueous suspensions  	
.1 Determine % dry wt.:
  .1 Weigh 5 10 gr sample Into crucible:
  oven dry overnight at 105 C: cool in
  dessicator: reweigh
.2 Extraction:
  Weigh 20 g sample into 250 ml
  Erlenmeyer: add 50 ml acetonltrile,
  shake (or 2 hrs.: decant extract into
  centrifuge tube: repeat extraction 2x
  w/20 mL acetonltrile.  shake 1 hr.;
  combine oxtracte and centrifuge
  10 mlns  at 200 rpm: decant supernatant
  to 100 ml. vol flask and dilute to mark
7.2 Cleanup
Combine 20 ml extract
and 100 uL ethylene glycol
In a glass vial: Slowdown
mixture w/N2 In heating
block set at 50 C: dissolve
residue In 2 ml MeOH,
pass soln through pre
washed C18 cartridge: collect
elute in 5 ml vol. flask: elute
cartridge w/MeOH into vol flask
up to mark, (liter MeOH soln
through 0 45 um tiller into
autosample vial



7.3 1 \

                                        7.3 Solvent Exchange
                                  7.3 1 Water, domestic, wastewater.
                                      aqueous Industrial wastes.
                                      andleachales:  Combine
                                      10 ml extract and 100 uL
                                      othylene glycol in a glass
                                      vial: blowdown mixture w/N2
                                      in heating block at 50 C: add
                                      MeOH to residue to total
                                      volume of 1 ml: tiller
                                      MeOH soln through 0.4B urn
                                        |pr Into autosampier vial
    713 Soils heavily contaminated with
    non aqueous substances, such as oils
.1 Determine % dry wt:  Follow Section 7121
2 Extraction: Weigh 20 gr sample Into 250 ml
  Erlenmeyer. add 60 ml hexane. shake
  1 hr.: add 50 ml acentonitrile. shake
  3 hrs ; let settle, decant extract layers
  to 250 ml sep funnel; litter bottom
  aoetonitrile layer into 100 ml vol  flask:
  repeat sample flask extraction w/same
  volumes: decant extract layers on top of
  first hexane  layer, shake funnel: filter bottom
  layer into vol flask; dilute to mark
714 Non aqueous liquids such as oils
1 Extraction Weigh 20 gr sample into
 125 ml sep funnel, add 40 ml
 hexane and 25 ml acetonilrite. shake.
 settle and drain bottom acetonitrile
 layer into 100 ml vol flask: repeat
 extraction 2x by adding 25 ml
 acetonltrile to initial flask mix:
 combine acetonilrile layers into vol
 flask: dilute to mark
                                                                                                                7.3 Solvent Exchange
                                                                           732 Soils, solids, sludges, heavy
                                                                                aqueous suspensions, and non
                                                                                aqueous liquids: Elute 15 ml extract
                                                                                through acetonitrile prewashed C18
                                                                                cartridge, collect latter 13 ml; combine
                                                                                10 ml cleaned extract and 100 uL
                                                                                ethylene glycol in glass vial; blowdown
                                                                                mixture w/N2 In heating block at
                                                                                50 C; add MeOH to residue to
                                                                                total volume of 1 ml; tiller MpOH
                                                                                soln through 0 45 um filter into
                                                                                autosampier vial
                                                             8318   -   17
                                                                                                              Revision 0
                                                                                                        September  1994

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                                                            METHOD  8318
                                                            (continued)
        I  74 Sample Analysis

                  *
7 4 I Initialize Instrumentation:
    1 Set chromatographic parameters
    2 Set Post column Hydrolysis parameters
    3 Set Post column Derivatization parameters
    4 Set Ruorometer parameters
742 Dilute sample extract and reanalyze II
    calibration range fs exceeded
                                                                    75 Calibration
                                                     7.5.1 Analyze a solvent blank then the calibration
                                                          stds ol Section 543: ensure that %RSO ol
                                                          each analyte response factor (RF) is <20%;
                                                          recheck system and recalibrate w/fresh
                                                          solns it %RSD > 20%
                                                      752 Check calibration daily w/2 ug/mL sld ;
                                                          ensure that individual analyte cones lall
                                                          w/ln W 15% ol true value; recalibrate
                                                          it observed difference > 15%
                                                     753 Check calibration every 10 samples or less
                                                          w/2 ug/mL std ; variations > 15% may
                                                          require re analysis of samples
                                                                                                                 J    7 6 Calculations
                                                                                                                         T
                                                                                                           7 6.1 Calculate response factors and % RSD
                                                                                                               according to equation
                                                                                                                          JL
                                                                                                          762 Calculate sample analyte cones according
                                                                                                              to equation
                                                              8318  -   18
      Revision  0
September  1994

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                                  METHOD  8321

                SOLVENT EXTRACTABLE NON-VOLATILE COMPOUNDS BY
     HIGH PERFORMANCE LIQUID CHROHATOGRAPHY/THERHOSPRAY/MASS SPECTRQMETRY
                 fHPLC/TSP/HS) OR ULTRAVIOLET (UV) DETECTION
1.0   SCOPE AND APPLICATION

      1.1   This method covers the use of high performance liquid chromatography
(HPLC),  coupled with  either thermospray-mass  spectrometry  {TSP-MSJ,  and/or
ultraviolet (UV), for the determination of disperse azo dyes, organophosphorus
compounds, and  Tris-(2,3-dibromopropy1)phosphate  in wastewater,  ground water,
sludge, and soil/sediment matrices,  and  chlorinated phenoxyacid  compounds and
their esters in wastewater,  ground water,  and soil/sediment matrices.  Data are
also provided for chlorophenoxy  acid  herbicides  in fly ash (Table 15), however,
recoveries for most compounds are very poor indicating poor extraction efficiency
for  these analytes using the extraction procedure included in this  method.
Additionally,  this method may apply  to other non-volatile  compounds that are
solvent extractable,  are amenable to  HPLC, and are ionizable under thermospray
introduction for mass spectrometric detection.   The following compounds can be
determined by this method:
      Compound Name
      (F1uorescent Brighteners)
      Fluorescent Brightener 61
      Fluorescent Brightener 236

      Alkaloids
      Caffeine
      Strychnine
  CAS No.'
Azo Dyes
Disperse Red 1
Disperse Red 5
Disperse Red 13
Disperse Yellow 5
Disperse Orange 3
Disperse Orange 30
Disperse Brown 1
Solvent Red 3
Solvent Red 23
Anthraquinone Dyes
Disperse Blue 3
Disperse Blue 14
Disperse Red 60
Coumarin Dyes
2872-52-8
3180-81-2
2832-40-8
6439-53-8
730-40-5
5261-31-4
17464-91-4
6535-42-8
85-86-9
2475-46-9
2475-44-7
17418-58-5
 8066-05-5
63590-17-0
   58-08-2
   57-24-9
                                   8321 - 1
           Revision  0
       September  1994

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      Compound Name                                        CAS No.8
      Organophosphgrus Compounds
      Methomyl                                           16752-77-5
      Thiofanox                                          39196-18-4
      Famphur                                               52-85-7
      Asulam                                              3337-71-1
      Dichlorvos                                            62-73-7
      Dimethoate                                            60-51-5
      Disulfoton                                           298-04-4
      Fensulfothion                                        115-90-2
      Merphos                                              150-50-5
      Methyl parathion                                     298-00-0
      Monocrotophos                                        919-44-8
      Naled                                                300-76-5
      Phorate                                              298-02-2
      Trichlorfon                                           52-68-6
      Tris-(2,3-Dibromopropyl) phosphate, (Tris-BP)        126-72-7

      Chlorinated PhenoxyacidCompounds
      Dalapon             *                                  75-99-0
      Dicamba                                             1918-00-9
      2,4-D                                                 94-75-7
      MCPA                                                  94-74-6
      MCPP                                                7085-19-0
      Dichlorprop                                          120-36-5
      2,4,5-T                                               93-76-5
      Silvex (2,4,5-TP)                                     93-72-1
      Dinoseb                                               88-85-7
      2,4-DB                                                94-82-6
      2,4-D, butoxyethanol ester                          1929-73-3
      2,4-D, ethylhexyl ester                             1928-43-4
      2,4,5-T,  butyl ester                                  93-79-8
      2,4,5-T,  butoxyethanol ester                        2545-59-7
      a  Chemical  Abstract  Services  Registry  Number.

      1.2   This method may be applicable  to  the analysis of other non-volatile
or semi volatile compounds.

      1.3   Tris-BP has  been classified  as  a carcinogen.   Purified standard
material  and stock standard solutions should be handled in a hood.

      1.4   Method  8321  is  designed  to  detect  the  chlorinated  phenoxyacid
compounds (free acid form) and their esters  without  the use of hydrolysis and
esterification in the extraction procedure.
                                   8321 - 2                         Revision 0
                                                                September 1994

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      1.5   The compounds were chosen for analysis by  HPLC/MS because they have
been designated as  problem compounds that are  hard to  analyze by traditional
chromatographic methods  (e.g.  gas  chromatography).   The  sensitivity  of this
method is dependent upon the  level  of interferants within a given matrix, and
varies  with  compound  class   and  even   with   compounds  within  that  class.
Additionally,  the limit  of detection  (LOD)  is  dependent upon  the  mode  of
operation of the  mass  spectrometer.   For example, the LOD for caffeine in the
selected reaction monitoring  (SRM)  mode  is 45 pg  of  standard  injected (10  juL
injection), while for  Disperse Red  1  the LOD is 180 pg.   The  LOD for caffeine
under single quadrupole scanning  is  84 pg and is 600 pg for Disperse Red 1 under
similar scanning conditions.

      1.6   The experimentally  determined limits of  detection  (LOD)  for the
target analytes are  presented  in Tables 3, 10, 13,  and  14.   For further compound
identification, MS/MS  (CAD  - collision activated dissociation)  can be used as an
optional  extension of this method.

      1,7   This  method  is restricted to  use  by  or  under  the supervision  of
analysts experienced in the use of high performance liquid chromatographs/mass
spectrometers and  skilled in the interpretation of  liquid ehromatograms and mass
spectra.    Each analyst  must  demonstrate  the  ability to  generate  acceptable
results with this  method.
2.0   SUMMARY OF METHOD

      2.1   This  method  provides   reverse   phase  high  performance  liquid
chromatographic  (RP/HPLC)  and  thermospray  (TSP)  mass  spectrometric  (MS)
conditions for the detection of the target analytes.  Quantitative analysis is
performed by TSP/MS, using an external  standard approach.  Sample extracts can
be  analyzed  by direct   injection  into  the  thermospray  or  onto  a  liquid
chromatographic-thermospray interface.  A gradient elution program is used on the
chromatograph to separate  the compounds.  Detection is achieved both by negative
ionization  (discharge  electrode)   and   positive   ionization,  with  a  single
quadrupole mass spectrometer.   Since this method  is  based on an HPLC technique,
the use of ultraviolet (UV)  detection is optional on routine samples.

      2.2   Prior to  the  use  of  this  method, appropriate  sample preparation
techniques must be used.

            2.2.1  Samples for analysis of chlorinated phenoxyacid compounds are
      prepared by a modification of Method 8151 (see Sec. 7.1.2).  In general,
      one  liter of  aqueous sample  or  fifty grams  of solid  sample are  pH
      adjusted, extracted  with diethyl ether,  concentrated and solvent exchanged
      to acetonitrile.

            2.2.2  Samples for analysis of the other target analytes are prepared
      by  established  extraction techniques.   In  general,  water  samples  are
      extracted at  a  neutral  pH with  methylene  chloride,  using  a  separatory
      funnel  (Method  3510)  or a  continuous liquid-liquid extractor  (Method
      3520).  Soxhlet  (Methods 3540/3541) or ultrasonic (Method 3550) extraction
      using methylene  chloride/acetone  (1:1)  is  used  for  solid samples.   A
                                   8321 - 3                         Revision 0
                                                                September 1994

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      micro-extraction technique is included for the  extraction of Tris-BP from
      aqueous and non-aqueous matrices.

      2,3   An   optional   thermospray-mass   spectrometry/mass   spectrometry
 (TS-MS/MS) confirmatory method is provided.  Confirmation is obtained by using
 MS/MS collision activated dissociation (CAD) or wire-repeller CAD.


 3.0   INTERFERENCES

      3,1   Refer to Methods 3500, 3600, 8000  and 8150/8151.

      3.2   The  use  of  Florisil  Column  Cleanup  (Method  3620)  has  been
 demonstrated to yield recoveries  less than 85% for some  of the compounds in this
 method, and is therefore  not recommended for all compounds.  Refer to Table 2 of
 Method  3620  for  recoveries  of  organophosphorus  compounds  as  a  function  of
 Fieri si 1 fractions.

      3.3   Compounds with  high  proton affinity  may mask some  of  the  target
 analytes.  Therefore, an HPLC must be used as a chromatographic separator,  for
 quantitative analysis.

      3.4   Analytical difficulties encountered with specific organophosphorus
 compounds, as applied in this method, may include (but are not limited to)  the
 following:

            3.4.1  Methyl parathion  shows  some  minor degradation upon analysis.

            3.4.2  Naled  can  undergo debromination to form dichlorvos.

            3.4.3  Merphos often  contains  contamination  from tnerphos  oxide.
      Oxidation  of  merphos   can occur   during   storage,  and  possibly  upon
      introduction into the mass spectrometer.

            Refer to Method 8141 for other compound problems as related to the
      various extraction methods.

      3.5   The chlorinated phenoxy acid  compounds, being  strong organic acids,
 react  readily with  alkaline  substances  and  may  be  lost  during  analysis.
Therefore, glassware and  glass wool must be acid-rinsed,  and sodium sulfate must
be acidified with sulfuric acid prior to use to avoid this possibility.

      3.6   Due to the reactivity of the chlorinated herbicides,  the standards
must  be  prepared  in acetonitrile.   Methylation  will   occur  if  prepared  in
methanol.

      3.7   Solvents, reagents, glassware, and  other  sample processing hardware
may  yield  discrete  artifacts   or   elevated   baselines,  or  both,   causing
misinterpretation of chromatograms or spectra.   All of these materials must be
demonstrated to be free  from  interferences under the  conditions of the analysis
by running reagent blanks.  Specific selection of reagents and purification of
 solvents by distillation in all-glass systems may be required.
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      3.8   Interferants  co-extracted  from the sample  will  vary considerably
from source to source.  Retention times of target analytes must be verified by
using reference standards.

      3,9   The optional use of HPLC/MS/MS methods aids in the confirmation of
specific analytes.  These methods  are less  subject to chemical noise than other
mass spectrometric methods.


4.0   APPARATUS AND MATERIALS

      4.1   HPLC/MS

            4.1.1  High Performance  Liquid  Chromatograph (HPLC) - An analytical
      system  with  programmable  solvent   delivery  system  and  all  required
      accessories including 10 /nL injection  loop,  analytical  columns,  purging
      gases, etc.  The solvent delivery system must be capable, at a minimum, of
      a binary solvent  system.  The chromatographic system  must  be capable of
      interfacing with a Mass Spectrometer (MS).

                   4.1.1,1      HPLC Post-Column Addition Pump - A  pump for post-
            column  addition  should  be  used.   Ideally,  this pump  should  be a
            syringe   pump,  and  does  not  have  to  be  capable  of  solvent
            programming.

                   4.1.1.2      Recommended  HPLC  Columns  - A guard column and an
            analytical column are required.

                        4.1.1.2.1   Guard  Column  -  C18  reverse phase  guard
                   column,  10  mm x 2.6  mm  ID,  0.5  jum frit,  or equivalent.

                        4.1.1.2.2   Analytical  Column  -  C18  reverse  phase
                   column,  100 mm  x 2 mm ID, 5 /Ltm particle size of ODS-Hypersil;
                   or C8 reversed  phase column, 100 mm x 2  mm ID,  3  ^m particle
                   size of  MOS2-Hypersil, or  equivalent.

            4.1.2  HPLC/MS  interface^}

                   4.1.2.1      Microtnixer - 10 /uL, interfaces HPLC column system
            with HPLC post-column  addition  solvent system.

                   4.1.2.2      Interface -  Thermospray ionization interface and
            source  that  will  give  acceptable calibration  response for  each
            analyte of interest  at the  concentration required.  The source must
            be capable of generating both  positive and  negative  ions,  and have
            a discharge electrode  or filament.

            4.1.3  Mass  spectrometer   system  -  A  single   quadrupole   mass
      spectrometer capable of scanning  from  1  to 1000  amu.   The spectrometer
      must  also be capable of scanning  from 150  to 450  amu in 1.5 sec or less,
      using 70  volts  (nominal) electron  energy in the positive or  negative
      electron impact modes.  In addition, the mass spectrometer must be capable
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      of producing a calibrated mass spectrum for PEG 400,  600, or 800 (see Sec,
      5.14).

                   4.1.3.1      Optional  triple quadrupole mass  spectrometer -
            capable of generating daughter ion spectra with a collision gas in
            the second quadrupole and operation in the single quadrupole mode.

            4.1.4  Data  System -  A computer system  that  allows  the continuous
      acquisition and storage on machine-readable  media  of all mass  spectra
      obtained throughout the duration of the  chromatographic program  must be
      interfaced to the mass spectrometer.  The computer must have software that
      allows any MS data file to  be searched for ions of a specified mass, and
      such ion abundances to be plotted  versus time or scan  number.  This type
      of plot is defined as an Extracted Ion Current Profile (EICP).  Software
      must also be available  that allows  integration  of  the  abundances in any
      EICP between specified time or scan-number limits.  There must be computer
      software available to operate the specific modes of the mass spectrometer.

      4.2   HPLC  with  UV  detector  -   An  analytical   system  with  solvent
programmable  pumping  system  for  at  least  a  binary  solvent  system,  and all
required  accessories  including  syringes,  10  ^l  injection  loop,  analytical
columns, purging gases,  etc.   An  automatic injector is optional, but is useful
for multiple samples.  The columns specified in Sec. 4.1.1.2 are also used with
this system.

            4.2.1  If  the  UV  detector   is  to  be  used  in  tandem with  the
      thermospray  interface,   then  the  detector   cell  must  be  capable  of
      withstanding high  pressures (up to 6000  psi).   However, the  UV detector
      may be  attached to an HPLC independent  of  the HPLC/TS/MS and,  in that
      case,  standard HPLC pressures  are  acceptable.

      4.3   Purification Equipment for Azo Dye Standards

            4.3.1  Soxhlet extraction  apparatus.

            4.3.2  Extraction  thimbles,  single  thickness,  43  x 123  mm.

            4.3.3  Filter  paper,   9.0  cm  (Whatman  qualitative   No.   1  or
      equivalent).

            4.3.4  Silica-gel  column  - 3  in.  x 8 in., packed with Silica gel
      (Type 60,  EM reagent 70/230 mesh).

      4.4   Extraction equipment  for Chlorinated Phenoxyacid Compounds

            4.4.1  Erlenmeyer  flasks  - 500-mL wide-mouth  Pyrex,  500-mL Pyrex,
      with 24/40 ground  glass joint,  1000-mL pyrex.

            4.4.2  Separatory  funnel  - 2000 ml.

            4.4.3  Graduated  cylinder  -  1000 ml.

            4.4.4  Funnel  -  75 mm  diameter.
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             4.4,5  Wrist shaker - Burrell  Model  75 or equivalent.

             4.4.6  pH meter.

      4,5    Kuderna-Danish  (K-D) apparatus (optional).

             4.5.1  Concentrator tube  -  10 ml  graduated (Kontes K-57QQ50-1025 or
      equivalent).   A ground glass stopper  is used  to prevent  evaporation of
      extracts.

             4.5.2  Evaporation   flask -   500 ml (Kontes   K-570001-500   or
      equivalent).    Attach to  concentrator tube  with  springs,  clamps,  or
      equivalent.

             4.5.3  Snyder column -   Two  ball  micro  (Kontes  K-569Q01-0219 or
      equivalent).

             4.5.4  Springs -  1/2 in.  (Kontes K-662750 or equivalent).

      4.6    Disposable serological  pipets - 5 ml x 1/10, 5.5 mm  ID.

      4.7    Collection tube - 15 ml  conical,  graduated (Kimble No.  45165 or
equivalent).

      4.8    Vials - 5 ml conical, glass,  with Teflon lined screw-caps or crimp
tops.

      4,9    Glass wool - Supelco No.  2-0411 or equivalent.

      4.10  Micro syringes - 100 #L, 50 jtL, 10 pi (Hamilton 701 N or equivalent),
and 50 pi (Blunted, Hamilton 705SNR or equivalent).

      4.11   Rotary evaporator  - Equipped with 1000 ml receiving  flask.

      4.12   Balances - Analytical,  0.0001 g,  Top-loading, 0.01 g.

      4.13   Volumetric flasks, Class A -  10 ml to 1000 ml.

      4.14   Graduated cylinder - 100 ml.

      4.15  Separatory funnel  - 250 ml.


5.0   REAGENTS

      5.1    Reagent  grade  inorganic  chemicals  shall  be used  in  all  tests.
Unless otherwise indicated,  it  is intended that all reagents shall  conform to the
specifications of the Committee on Analytical Reagents of the American Chemical
Society,  where  such  specifications are available.  Other grades may be used,
provided it  is first  ascertained that the  reagent  is of sufficiently high purity
to permit its use without lessening the accuracy  of the determination.
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      5.2   Organic  free  reagent water.  All references to water in  this method
refer to organic-free  reagent  water,  as defined  in  Chapter  One.

      5.3   Sodium sulfate (granular, anhydrous),  Na2S04. Purify by  heating  at
400°C for 4 hours in a shallow tray,  or by  precleaning the  sodium sulfate with
methylene chloride.

      5.4   Ammonium acetate, NH4OOCCH3, solution (0.1 M).  Filter through a 0.45
micron membrane filter (Millipore HA  or equivalent).

      5.5   Acetic acid,  CH3C02H

      5.6   Sulfuric acid  solution

            5.6.1  {(1:1)  (v/v)) - Slowly add 50 ml H2S04  (sp. gr. 1.84) to   50
      ml of water.

            5.6.2  ((1:3)  (v/v)) - slowly add 25 ml H2S04  (sp. gr. 1.84) to   75
      ml of water.

      5.7   Argon gas, 99+%  pure.

      5.8   Solvents

            5.8.1  Methylene chloride, CH2C12 - Pesticide  quality or equivalent.

            5.8.2  Toluene, C6HSCH3 -  Pesticide quality or equivalent.

            5.8.3  Acetone, CH3COCH3  - Pesticide  quality  or  equivalent.

            5.8.4  Diethyl Ether, C2HSOC2H5  -  Pesticide quality or equivalent.
      Must be  free  of  peroxides as  indicated by  test  strips (EM  Quant,   or
      equivalent).   Procedures  for  removal  of peroxides  are provided with the
      test strips.  After cleanup, 20 ml of ethyl alcohol preservative must  be
      added to each liter of ether.

            5.8,5  Methanol,  CH3OH -  HPLC  quality or equivalent.

            5.8.5  Acetcr.ltr'le, CK CKf -  HPLC "ua^'ty cr  scu'Vcls^t.

            5.8.7  Ethyl  acetate CH3C02C2H5 - Pesticide quality or equivalent.

      5.9   Standard Materials - pure standard materials  or  certified solutions
of each  analyte targeted for analysis.  Disperse azo dyes must be  purified before
use according to Sec. 5.10.

      5.10  Disperse Azo Dye Purification

            5.10.1      Two  procedures are  involved.   The first step  is the
      Soxhlet extraction  of. the dye for 24 hours with toluene and evaporation  of
      the liquid extract  to  dryness,  using  a rotary evaporator.  The solid  is
      then recrystal1ized  from  toluene,  and dried  in an  oven at approximately
      100°C.   If  this  step   does   not   give  the  required  purity,  column

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      chromatography  should be employed.   Load the solid  onto a 3  x  8 inch
      silica  gel  column (Sec.  4.3.4),  and elute with diethyl ether.   Separate
      impurities  chromatographically, and collect the major dye fraction.

      5.11  Stock standard  solutions  -  Can  be  prepared  from  pure  standard
materials or  can  be purchased  as certified solutions.

            5.11.1       Prepare stock standard solutions by accurately weighing
      0.0100  g  of pure material.   Dissolve the material  in  methanol  or other
      suitable  solvent  (e.g.  prepare Tris-BP  in ethyl  acetate), and  dilute to
      known volume in a volumetric flask.

            NOTE:  Due  to  the reactivity of  the chlorinated  herbicides,  the
                   standards must be  prepared in acetonitrile. Methylation will
                   occur if prepared in methanol.

            If  compound purity is  certified  at  96%  or  greater,  the weight can
      be used without correction  to calculate  the  concentration  of  the stock
      standard.   Commercially  prepared  stock  standards can be  used  at  any
      concentration  if  they  are  certified  by  the  manufacturer or  by  an
      independent source.

            5.11.2       Transfer the stock standard solutions into glass vials
      with Teflon lined screw-caps  or crimp-tops.  Store at 4DC and protect from
      light.  Stock standard solutions should be checked frequently  for signs of
      degradation or evaporation, especially just prior  to preparing calibration
      standards,

      5.12  Calibration standards  -  A  minimum of five  concentrations  for each
parameter of interest should be prepared through dilution of the  stock standards
with methanol  (or other suitable solvent).  One of these concentrations should
be near, but above,  the MDL.  The remaining concentrations should correspond to
the expected range of concentrations  found in real samples, or should define the
working range of the HPLC-UV/VIS or HPLC-TSP/MS. Calibration standards must be
replaced after one or two months,  or sooner if  comparison with check  standards
indicates a problem.

      5.13  Surrogate standards -  The analyst  should monitor the performance of
the  extraction,  cleanup (when  used),  and analytical  system,   along  with  the
effectiveness of the method in dealing  with each sample matrix, by spiking each
sample,  standard, and blank with one or two surrogates  (e.g., organophosphorus
or chlorinated phenoxyacid compounds not  expected to be present  in the sample).

      5.14  HPLC/MS tuning standard - Polyethylene glycol  400  (PEG-400), PEG-600
or PEG-800.   Dilute  to 10 percent (v/v)  in methanol.   Dependent  upon analyte
molecular weight range:  m.w. < 500 amu,  use PEG-4QO; m.w. > 500 amu, use PEG-600,
or PEG-800.
6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See  the  introductory material to this  Chapter,  Organic Analytes,
Sec. 4.1.
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7.0   PROCEDURE

      7.1   Sample preparation - Samples for analysis of disperse azo dyes and
organophosphorus compounds must be prepared by one of the  following methods prior
to HPLC/MS analysis:

      Matrix                                    Methods

      Water                                     3510, 3520
      Soil/sediment                             3540, 3541, 3550
      Waste                                     3540, 3541, 3550, 3580

      Samples for the analysis of Tris-(2,3-dibromopropyl }phosphate in wastewater
must be  prepared according to Sec. 7.1.1  prior to HPLC/MS analysis.  Samples for
the analysis  of chlorinated phenoxyacid  compounds  and their esters  should be
prepared according to Sec, 7.1.2 prior to HPLC/MS  analysis.

            7.1.1   Microextraction for Tris-BP:

                   7.1.1.1      Solid  Samples

                        7.1.1.1.1   Weigh a 1 gram  portion  of  the  sample into
                   a  tared  beaker.    If  the  sample  appears  moist,  add  an
                   equivalent  amount  of  anhydrous  sodium sulfate  and mix well.
                   Add  100 /^L  of Tris-BP  (approximate concentration 1000 mg/L}
                   to the  sample  selected  for spiking;  the  amount  added should
                   result  in  a final  concentration  of 100  ng//iL  in the  1  mL
                   extract.

                        7.1.1.1.2   Remove the glass wool plug from a disposable
                   serological  pipet.   Insert  a  1  cm  plug  of  clean  silane
                   treated glass  wool  to  the bottom  (narrow end)  of the pipet.
                   Pack 2  cm of  anhydrous  sodium  sulfate onto the  top  of the
                   glass  wool.   Wash pipet and  contents   with  3  -  5  ml  of
                   methanol.

                        7.1.1.1.3   Pack  the  sample  into  the pipet  prepared
                   according to Sec. 7.1.1.1.2.   If packing  material  has dried,
                   wet  with  a  few mL of  methanol  first,  then pack  sample into
                   the  pipet.

                        7.1.1.1.4   Extract the sample  with 3 mL  of  methanol
                   followed  by 4 mL  of  50% (v/v)  methanol/methylene  chloride
                   (rinse  the   sample  beaker with  each  volume of  extraction
                   solvent  prior  to   adding  it  to  the  pipet  containing  the
                   sample).   Collect  the  extract  in  a  15  mL  graduated  glass
                   tube.

                        7.1.1.1.5   Evaporate the  extract  to  1  mL using  the
                   nitrogen  blowdown  technique  (Sec.  7.1.1.1.6).    Record  the
                   volume.   It may  not  be possible  to  evaporate  some  sludge
                   samples to  a reasonable  concentration.
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      7.1.1.1.6   Nitrogen Slowdown Technique

            7.1.1.1.6.1       Place the concentrator tube  in
      a warm water bath {approximately 35°C) and evaporate the
      solvent  volume  to  the required  level  using a  gentle
      stream  of  clean,  dry nitrogen  (filtered  through   a
      column of activated carbon).

            CAUTION:     Do   not   use   plasticized   tubing
                         between  the  carbon  trap  and the
                         sample.

            7.1.1.1.6.2       The internal wall of the  tube
      must  be  rinsed  down  several  times  with  methylene
      chloride  during  the operation.  During evaporation, the
      solvent level in the tube must be positioned  to  prevent
      water  from  condensing  into  the  sample  (i.e.,  the
      solvent  level  should be below the  level  of the  water
      bath}.       Under  normal   operating  conditions,  the
      extract  should  not  be allowed to become dry.   Proceed
      to  Sec.  7.1.1.1.7.

      7.1.1.1.7   Transfer the  extract to a  glass vial  with
a Teflon lined screw-cap  or crimp-top and  store refrigerated
at 4°C.  Proceed  with HPLC analysis.

      7.1.1.1.8   Determination  of  percent  dry  weight  -  In
certain  cases,  sample results  are desired  based  on a dry
weight basis.    When  such data  are desired,  or required,   a
portion  of sample for this determination should be  weighed
out  at the same  time as  the  portion used  for  analytical
determination.

      WARN1NG:     The drying oven  should  be contained  in  a
                  hood or  vented.    Significant  laboratory
                  contamination  may result  from  drying   a
                  heavily   contaminated    hazardous    waste
                  sample.

      7.1.1.1.9   Immediately  after weighing the sample for
extraction, weigh 5-10 g  of the sample into a tared crucible.
Determine the  % dry weight of the  sample  by  drying overnight
at 105°C. Allow  to cool  in a desiccator  before weighing:

      % dry weight =  q of dry sample x  100
                       g  of sample
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             7.1.1.2     Aqueous Samples

                   7.1.1.2.1    Using  a  100 ml graduated cylinder, measure
             100 ml  of sample  and  transfer it  to a  250  ml separatory
             funnel.   Add  200 juL of Tris-BP (approximate concentration
             1000 mg/L) to  the sample selected  for  spiking;  the amount
             added should  result in a final  concentration of 200 ng//zL in
             the 1 ml extract.

                   7.1.1.2.2    Add  10  ml  of methylene chloride  to  the
             separatory funnel.   Seal  and  shake  the  separatory funnel
             three  times,   approximately  30 seconds  each  time,  with
             periodic venting to release excess pressure.  NOTE: Methylene
             chloride  creates  excessive  pressure rapidly;  therefore,
             initial  venting  should  be  done  immediately  after  the
             separatory funnel has been sealed and shaken  once.  Methylene
             chloride  is  a  suspected  carcinogen,  use  necessary safety
             precautions.

                   7.1.1.2.3    Allow the organic  layer to separate from the
             water phase for  a minimum of 10 minutes.   If the emulsion
             interface between layers is more than one-third the size of
             the  solvent   layer,  the  analyst   must  employ  mechanical
             techniques to  complete  phase  separation.   See  Sec.  7.5,
             Method 3510.

                   7.1.1.2.4    Collect  the  extract in  a  15 ml graduated
             glass tube. Proceed as  in Sec.  7.1.1.1.5.

      7.1.2  Extraction for chlorinated phenoxyacid compounds - Preparation
of soil, sediment,  and other solid samples   must  follow Method 8151, with
the exception of no hydrolysis or esterification.  Sec. 7.1.2.1 presents
an outline of  the  procedure with the  appropriate  changes  necessary for
determination  by  Method 8321.   Sec.  7.1.2.2  describes the  extraction
procedure for aqueous samples.

             7.1.2.1     Extraction  of solid samples

                   7,1.2.1.1    Add 50 g of  soil/sediment  sample to a 500
             mi_,  wide  mouth  Erlenmeyer,    Add  spiking  solutions  if
             required, mix  well  and allow to stand for  15  minutes.  Add 50
             ml of organic-free  reagent  water  and stir  for  30 minutes.
             Determine the  pH of the  sample  with  a  glass electrode and pH
             meter, while stirring.   Adjust the pH to 2 with  cold  H2S04
             (1:1)  and monitor the pH for 15 minutes,  with stirring.  If
             necessary, add additional  H2SO« until  the  pH remains  at 2.

                   7.1.2.1.2    Add 20 ml of  acetone to the flask, and mix
             the contents with the wrist shaker for 20  minutes.   Add 80 ml
             of diethyl ether  to the  same flask, and  shake again for 20
             minutes.    Decant  the  extract  and measure  the  volume  of
             solvent recovered.
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      7.1.2.1.3   Extract the sample twice more using  20  ml
of  acetone  followed  by  80 ml  of  diethyl  ether.    After
addition of  each solvent, the mixture  should be shaken with
the wrist shaker for 10 minutes and the acetone-ether extract
decanted.

      7.1.2.1.4   After the third extraction, the volume  of
extract  recovered  should be at least  75%  of the volume  of
added  solvent.    If  this  is  not  the   case,  additional
extractions may be necessary.  Combine the extracts  in a 2000
ml separatory funnel containing 250 ml of reagent water.   If
an emulsion forms,  slowly add 5 g of acidified sodium sulfate
(anhydrous)  until  the solvent-water mixture  separates.   A
quantity of  acidified sodium sulfate equal  to the weight  of
the sample may be added,  if necessary.

      7.1.2.1.5   Check the  pH  of  the extract.   If it is not
at or below pH 2, add more concentrated HC1  until the extract
is stabilized at the desired pH.   Gently mix  the contents  of
the separatory funnel  for 1  minute and allow the layers  to
separate.  Collect the aqueous phase in a clean beaker, and
the  extract  phase  (top  layer)  in  a  500 ml  ground-glass
Erlentneyer  flask.   Place the  aqueous phase back  into the
separatory  funnel  and  re-extract  using 25  ml  of   diethyl
ether. Allow  the layers to separate  and discard the  aqueous
layer. Combine the  ether extracts in the  500 ml Erlenmeyer
flask.

      7.1.2.1.6   Add  45  -  50  g  acidified  anhydrous  sodium
sulfate to the combined ether extracts.  Allow the extract  to
remain in contact with the sodium sulfate for approximately
2 hours.

      NOTE:  The drying step is very  critical.  Any moisture
            remaining  in  the   ether  will   result   in low
            recoveries.  The amount of sodium  sulfate used  is
            adequate  if  some   free  flowing  crystals are
            visible when  swirling the flask.   If all of the
            sodium sulfate  solidifies  in a cake,  add  a few
            additional grams of acidified sodium sulfate and
            again test by swirling. The 2 hour drying time  is
            a  minimum;  however,  the extracts  may  be held
            overnight in contact with the sodium sulfate.

      7.1.2.1.7   Transfer the ether extract, through a funnel
plugged with acid-washed glass  wool, into a 500 ml K-D  flask
equipped with a 10 ml  concentrator tube.  Use a glass rod  to
crush caked  sodium  sulfate  during the transfer.   Rinse the
Erlenmeyer flask and column with 20-30 mL of diethyl  ether  to
complete the quantitative transfer.  Reduce  the volume of the
extract using the macro K-D technique (Sec. 7.1.2.1.8).

      7.1.2.1.8   Add  one or two clean boiling chips to the
flask and attach  a  three ball  macro-Snyder column,   Prewet

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the Snyder  column by  adding  about  1  ml of diethyl ether  to
the top.  Place the apparatus on a hot water bath (60°-65°C)
so that  the concentrator  tube is partially immersed in the
hot water and the entire lower rounded surface of the  flask
is bathed  in vapor.   Adjust the vertical  position  of the
apparatus and the water temperature, as required,  to complete
the concentration in  15^20 minutes.   At  the proper rate  of
distillation the balls of the column will actively chatter,
but the chambers will  not flood.  When the apparent volume  of
liquid reaches 5 ml, remove the K-D apparatus  from the  water
bath and allow it to drain and cool for at least  10 minutes.

      7.1.2,1.9    Exchange  the  solvent  of  the  extract  to
acetonitrile by quantitatively transferring  the extract with
acetonitrile to a blow-down apparatus.  Add a total of 5  ml
acetonitrile.   Reduce the extract  volume according to Sec.
7.1.1.1.6,  and adjust the final  volume to 1 ml.

7.1.2.2     Preparation of aqueous samples

      7.1.2.2.1    Using a 1000 ml  graduated cylinder, measure
1 liter (nominal)  of sample,  record the sample volume to the
nearest 5 ml,  and  transfer  it to a  separatory  funnel.   If
high concentrations  are anticipated,  a  smaller volume may  be
used and then diluted with organic-free  reagent  water to  1
liter. Adjust the pH to less than 2 with sulfuric  acid (1:1).

      7.1.2.2.2   Add  150 ml  of  diethyl  ether to the sample
bottle, seal, and shake for  30  seconds  to rinse the walls.
Transfer  the solvent  wash   to  the  separatory  funnel and
extract the sample by shaking the funnel  for 2 minutes with
periodic  venting  to  release excess  pressure.    Allow the
organic layer to separate  from the water  layer for a minimum
of 10 minutes.  If the  emulsion  interface between layers  is
more  than   one-third  the  size  of the  solvent  layer, the
analyst must  employ mechanical  techniques  to  complete the
phase  separation.  The optimum  technique depends  upon the
sample, and may include  stirring, filtration of the emulsion
through  glass  wool,  centrifugation,  or  other  physical
methods.  Drain the aqueous  phase into a 1000 ml Erlenmeyer
flask.

      7.1.2.2.3    Repeat the  extraction two more  times  using
100 ml of diethyl  ether each time.   Combine the  extracts  in
a 500  ml  Erlenmeyer flask.    (Rinse the  1000  ml  flask with
each  additional  aliquot of  extracting  solvent  to make   a
quantitative transfer.)

      7.1.2.2.4    Proceed  to  Sec.   7.1.2.1.6   (drying, K-D
concentration,   solvent   exchange,    and   final   volume
adjustment).
                8321  -  14-                        Revision 0
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      7.2   Prior to HPLC analysts,  the extraction solvent must be exchanged to
methanol or acetonitrile (Sec.  7.1.2.1.9).  The exchange is performed using the
K-D procedures listed in all of the extraction methods.

      7.3   HPLC Chromatographic Conditions:

            7.3.1  Analyte-specific  chromatographic  conditions  are shown  in
      Table 1. Chromatographic conditions which are not analyte-specific are as
      follows:

            Flow rate:                     0.4 mL/min
            Post-column mobile phase:       0.1 M ammonium acetate (1% methanol)
                                           (0.1   M    ammonium   acetate   for
                                           phenoxyacid compounds)
            Post-column flow rate:          0.8 mL/min

            7.3.2  If there  is a chromatographic problem from compound retention
      when analyzing  for disperse  azo  dyes,  organophosphorus  compounds,  or
      Tris-(2,3-dibromopropylJphosphate,   a  2%  constant   flow  of  methylene
      chloride may be applied as needed.   Methylene  chloride/aqueous methanol
      solutions must be used with caution  as  HPLC eluants.   Acetic acid (1%),
      another mobile  phase modifier, can be  used  with  compounds  with  acid
      functional  groups.

            7.3.3  A total   flow  rate of  1.0  to  1.5 mL/min  is necessary  to
      maintain thermospray  ionization.

            7.3.4  Retention times   for   organophosphorus   compounds  on   the
      specified analytical  column are  presented in Table  9.

      7.4   Recommended HPLC/Thermospray/MS operating conditions:

            7.4.1  Positive  Ionization mode

            Repeller (wire  or plate, optional): 170  to  250   v   (sensitivity
      optimized). See Figure 2  for  schematic  of source with  wire repeller.

            Mass  range:  150 to 450 amu (compound  dependent,  expect  1 to 18  amu
                        higher than molecular weight  of  the compound).
            Scan  time:  I.5C sec/scan.

            7.4.2  Negative  Ionization mode

            Discharge electrode:     on
            Filament:               off
            Mass  Range:              135  to 450 amu
            Scan  time:              1.50 sec/scan.

            7.4.3  Thermospray temperatures:

            Vaporizer control   110DC to 130°C.
            Vaporizer tip      200°C to 215°C,
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      Jet                210°C to 220°C.
      Source block       230°C to 265°C.  (Some  compounds  may degrade in
                         the  source  block  at  higher  temperatures,  the
                         operator  should   use   knowledge  of  chemical
                         properties    to    estimate    proper    source
                         temperature).

      7,4.4  Sample injection  volume:  20  nl is  necessary  in  order to
overfill the 10 ^L injection loop.  If  solids are present  in  the extract,
allow them to settle or centrifuge the  extract and withdraw the injection
volume from the clear layer.

7.5   Calibration:

      7,5.1  Thermospray/MS system -  Must  be  hardware-tuned on quadrupole
1 (and quadrupole 3 for triple quadrupoles)  for  accurate mass assignment,
sensitivity, and  resolution.    This  is accomplished  using  polyethylene
glycol (PEG) 400,  600,  or 800  (see Sec.  5.14) which have average molecular
weights of 400, 600, and 800, respectively.  A mixture of these PEGs can
be made such that it will approximate the  expected working mass range for
the  analyses.   Use  PEG  400  for  analysis  of  chlorinated  phenoxyacid
compounds.    The  PEG  is   introduced   via   the  thermospray  interface,
circumventing the HPLC.

             7.5.1.1     The mass calibration parameters  are as  follows:

             for PEG 400 and 600                 for PEG 800
             Mass range:  15 to 765 amu            Mass range:  15 to 900 amu
             Scan time: 5.00 sec/scan            Scan time: 5,00 sec/scan

             Approximately   100  scans  should be acquired, with  2  to  3
      injections made.  The scan  with  the best  fit  to the accurate mass
      table (see Tables 7 and  8)  should be used  as the calibration table.

             7.5.1.2     The low mass range  from 15 to 100 amu is covered
      by the ions  from the ammonium acetate buffer used  in the thermospray
      process:   NH/  (18 amu},  NH/-H20 (36), CH3OH'NH4+ (50)  (methanol),
      or  CH3CNNH4+  (59)  (acetonitrile),   and  CH3COOHNH4+  (78)  (acetic
      acid). The appearance of the m/z 50 or 59 ion depends upon the use
      of methanol or  acetonitrile as the organic modifier.   The higher
      mass range  is covered by the  ammonium ion adducts  of  the various
      ethylene  glycols   (e.g.   H(OCH2CH2)nOH   where   n=4,   gives   the
      H(OCH2CH2)4OH'NH4+ ion at m/z 212).

      7.5.2  Liquid  Chromatograph

             7.5.2.1      Prepare calibration standards as outlined  in Sec,
      5.12.

             7.5.2.2     Choose  the  proper  ionization  conditions,  as
      outlined  in Sec.  7.4.  Inject each  calibration  standard  onto the
      HPLC,  using  the chromatographic  conditions  outlined  in  Table 1.
      Calculate the area under the curve for the  mass chromatogram of each


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quantitation ion.   For example, Table  9  lists the retention times
and  the  major  ions  (>5%)  present  in  the  positive  ionization
thermospray  single  quadrupole  spectra  of  the  organophosphorus
compounds.  In most cases the (M+H)*  and (M*NH4)+ adduct ions are
the only  ions  of significant abundance.   Plot  these  ions as area
response versus  the amount  injected.   The  points should fall on a
straight line,  with a correlation coefficient of at least 0,99 (0.97
for chlorinated phenoxyacid analytes).

       7.5.2.3      If  HPLC-UV  detection  is   also   being  used,
calibrate  the  instrument  by preparing  calibration   standards  as
outlined in Sec.  5.12, and injecting each calibration standard onto
the HPLC using the chromatographic conditions outlined in Table 1.
Integrate  the  area under the full  chromatographic peak  for each
concentration.    Quantitation by HPLC-UV  may  be  preferred if it is
known that sample  interference and/or  analyte  coelution are not a
problem.

       7.5.2.4      For  the methods  specified  in  Sec.  7.5.2.2  and
7.5.2.3,  the  retention  time of  the  chromatographic  peak  is  an
important variable in analyte identification.  Therefore, the ratio
of the retention  time of  the  sample analyte to the standard analyte
should be 1.0 - 0.1.

       7.5.2.5      The concentration of the  sample analyte will  be
determined by  using the  calibration   curves  determined  in  Sees.
7.5.2.2 and 7,5.2.3. These calibration curves must be generated on
the  same  day  as each sample is  analyzed.    At least  duplicate
determinations should be made for  each  sample  extract.   Samples
whose concentrations exceed  the standard calibration  range should
be diluted to fall within the range.

       7.5.2.6      Refer  to  Method 8000 for further information on
calculations.

       7.5.2.7      Precision  can also  be  calculated  from the ratio
of response (area) to the amount  injected; this is defined as  the
calibration factor  (CF)  for each  standard concentration.   If  the
percent relative standard deviation (%RSD) of  the CF  is less than
20 percent over the working range, ":nearfty through the cr:gi:: can
be assumed, and the average calibration factor can be used in place
of a  calibration curve.    The CF  and %RSD  can be calculated  as
fol1ows:

       CF  = Total  Area of Peak/Mass  injected  (ng)

       %RSD = SD/CF x 100

where:

       SD  = Standard deviation between  CFs

       CF  = Average CF
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      7.6   Sample Analysis

            7.6.1  Once the LC/HS  system has been calibrated as  outlined in Sec.
      7.5, it is ready for sample  analysis.   It  is recommended  that the samples
      initially be analyzed in the negative ionization mode.   If low levels of
      compounds are suspected, then the samples should also be screened in the
      positive ionization mode.

                   7.6.1,1     A  blank 20  pi  injection  (methanol)  must  be
            analyzed after the standard(s) analyses, in order to determine any
            residual contamination of the Therraospray/HPLC/MS  system.

                   7.6.1.2     Take a 20 jil aliquot of the sample extract from
            Sec. 7.4.4.   Start the HPLC  gradient  elution,  load and inject the
            sample  aliquot,  and   start  the  mass  spectrometer  data  system
            analysis.

      7.7   Calculations

            7.7.1  Using the  external  standard calibration  procedure  (Method
      8000),  determine the identity and quantity of each component peak in the
      sample reconstructed ion chromatogram which corresponds to the compounds
      used  for  calibration  processes.    See  Method  8000   for  calculation
      equations.

            7.7.2  The retention time of the chromatographic peak is an important
      parameter for  the  identity of  the analyte.    However,   because  matrix
      interferences can change chromatographic column conditions, the retention
      times are  not as  significant,  and the  mass  spectra  confirmations  are
      important criteria for analyte identification.


8.0   QUALITY CONTROL

      8.1   Refer to Chapter  One  and  Method  8000  for  specific  quality  control
procedures.

      8.2   Tables 4,  5,  6,  11, 12, and 15 indicate the single operator accuracy
and precision  for this  method.  Compare the results obtained with the results in
the tables to determine if the data quality Is acceptable.   Tables 4, 5,  and 5
provide  single  lab data  for Disperse  Red  1,  Table  11 with  organophoshorus
pesticides, Table 12 with Tris-BP and Table 15 with chlorophenoxyacid herbicides.

            8.2.1  If  recovery is  not  acceptable,  check  the following:

                   8.2.1.1      Check  to be sure  that there  are  no errors in the
            calculations, surrogate solutions  or internal standards.  If errors
            are found, recalculate the data accordingly.

                   8.2.1.2     Check  instrument  performance.   If an instrument
            performance  problem  is   identified,   correct  the  problem  and
            re-analyze the extract.
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                   8.2.1.3     If no problem is found,  re-extract and re-analyze
            the sample.

                   8.2,1.4     If, upon re-analysis,  the recovery is again not
            within limits, flag the data as "estimated concentration".

      8.3   Instrument  performance  -  Check  the  performance  of  the  entire
analytical system daily using data gathered from analyses of blanks, standards,
and replicate samples.

            8,3.1  See Sec. 7.5.2.7 for required HPLC/MS parameters for standard
      calibration curve %RSD limits.

            8.3.2  See Sec.  7.5.2.4 regarding  retention  time window QC limits.

            8.3.3  If any of the  chromatographic QC  limits  are  not  met,  the
      analyst should examine the LC system for:

            •      Leaks,
            •      Proper  pressure delivery,
            *      A dirty guard column; may need  replacing or  repacking,  and
            *      Possible  partial thermospray plugging.

            Any of the above items will necessitate shutting  down the HPLC/TSP
      system,  making repairs  and/or  replacements,  and  then  restarting  the
      analyses.  The  calibration standard should be reanalyzed before any sample
      analyses,  as described in Sec.  7.5,

            8.3.4   The   experience    of   the   analyst   performing   liquid
      chromatography is invaluable to the success of the method.  Each day that
      analysis is  performed,  the daily  calibration standard should be evaluated
      to determine if the  chromatographic system is operating properly.  If any
      changes are made to the  system (e.g. column change), the system must be
      recalibrated.

      8.4   Optional Thermospray HPLC/MS/MS confirmation

            8.4.1   With respect to this method, MS/MS shall be defined as the
      daughter ion collision  activated  dissociation acquisition with quadrupole
      one set on one mass (parent  Ion}, quadrupole two  pressurized w!th argcr
      and with a higher offset  voltage  than normal, and quadrupole three set to
      scan desired mass range.

            8,4.2  Since the  thermospray process often  generates only one or two
      ions per compound,  the  use of MS/MS is a more specific mode  of operation,
      yielding molecular structural information.   In  this mode, fast screening
      of samples can  be accomplished through direct injection of the sample into
      the thermospray.

            8.4.3  For MS/MS  experiments, the first quadrupole should be set to
      the protonated molecule or ammoniated adduct of the analyte of interest.
      The third quadrupole should  be  set to scan  from  30 amu  to just above the
      mass region  of the protonated molecule.


                                   8321 - 19                         Revision 0
                                                               September 1994

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            8.4.4  The collision gas pressure  (Ar)  should  be  set at about 1.0
      mTorr and the collision energy  at 20 eV.  If these  parameters fail to give
      considerable  fragmentation,  they may  be raised above these  settings to
      create more and stronger collisions.

            8.4.5  For analytical determinations, the base peak of the collision
      spectrum shall be taken as the quantification ion.   For extra specificity,
      a second ion should be chosen as a backup quantification ion.

            8.4.6  Generate a calibration  curve as outlined in Sec.  7.5.2.

            8.4.7  For analytical determinations, calibration blanks  must be run
      in  the  MS/MS  mode  to determine  specific  ion   interferences.   If  no
      calibration  blanks are  available,  chromatographic  separation must  be
      performed  to  assure  no  interferences  at  specific  masses.   For  fast
      screening, the  MS/MS  spectra of the  standard and the  analyte  could be
      compared and the ratios of the three major (most  intense) ions examined.
      These  ratios  should   be  approximately  the   same,  unless  there  is  an
      interference.     If  an  interference   appears,  chromatography  must  be
      utilized.

            8.4.8  For unknown concentrations, the total area of the quantitation
      ion(s) is calculated and the calibration curves generated as in Sec.  7.5
      are used to attain an  injected weight number.

            8.4.9  MS/MS techniques  can  also  be  used  to  perform  structural
      analysis on ions represented  by unassigned  m/z ratios.  The procedure for
      compounds of unknown structures is  to set up a CAD experiment  on the ion
      of interest.   The  spectrum generated from this experiment  will reflect the
      structure of the compound by its fragmentation pattern.   A trained  mass
      spectroscopist  and some  history  of  the  sample  are  usually   needed  to
      interpret  the spectrum.  (CAD  experiments  on actual standards  of  the
      expected  compound are necessary for confirmation  or   denial  of  that
      substance.)

      8.5   Optional wire-repeller CAD confirmation

            8.5.1  See Figure 3 for the correct position  of the wire-repeller in
      the thermospray source block.

            8.5.2  Once the wire-repeller is inserted into the thermospray flow,
      the voltage can  be increased to approximately 500 - 700 v.  Enough voltage
      is necessary  to  create  fragment  ions,  but  not  so  much  that  shorting
      occurs.

            8.5.3  Continue  as outlined in Sec.  7.6,
9.0   METHOD PERFORMANCE

      9.1   Single operator accuracy and precision studies have been conducted
using spiked sediment, wastewater, sludge,  and water samples.   The results are
presented in Tables 4, 5,  6,  11,  12,  and  15.  Tables 4, 5, and 6 provide single


                                   8321  - 20                         Revision 0
                                                                September 1994

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 lab data  for  Disperse Red  1, Table 11 for organophoshorus pesticides, Table  12
 for Tris-BP and  Table 15 with chlorophenoxyacid herbicides,

      9.2   LODs should be calculated for the known analytes,  on each  instrument
 to be used. Tables 3, 10, and 13  list  limits of detection (LOD)  and/or estimated
 quantitation  limits  (EQL)  that are typical with this method.

            9.2.1  The LODs presented in this method were calculated by analyzing
      three  replicates  of  four  standard  concentrations,  with  the  lowest
      concentration  being near  the  instrument  detection  limit.   A  linear
      regression was performed  on  the data  set to  calculate the  slope and
      intercept.  Three  times the standard deviation (3cr) of the lowest standard
      amount, along with the calculated slope and intercept, were used to find
      the  LOD.   The  LOD was not  calculated using the specifications  in Chapter
      One, but according to the  ACS guidelines specified in Reference 4.

            9.2.2  Table 17 presents  a comparison of the LODs from Method 8151
      and  Method 8321 for  the chlorinated phenoxyacid compounds.

      9.3   Table 16 presents multilaboratory  accuracy  and  precision data for
 the chlorinated phenoxyacid herbicides.  The data  summary is based on data from
 three   laboratories  that   analyzed   duplicate   solvent  solutions   at  each
 concentration specified in the Table.


 10.0  REFERENCES

 1.    Voyksner, R.D.; Haney,  C.A. "Optimization and Application of Thermospray
      High-Performance  Liquid  Chromatography/Mass Spectrometry";  An a].  Chejn.
      1985, 57, 991-996.

 2,    Blakley,   C.R.;   Vestal,   H.L.     "Thermospray   Interface   for   Liquid
      Chromatography/Mass Spectrometry"; Anal.  Chem.  1983,  55,  750-754.

3.    Taylor,  V.; Hickey, D. M., Marsden, P. J.  "Single Laboratory Validation of
      EPA Method 8140";  EPA-600/4-87/009, U.S. Environmental Protection Agency,
      Las Vegas, NV,  1987,  144 pp.

4.    "Guidelines  for  Data  Acquisition  and  Data  Quality   Evaluation  in
      Environmental  Chemistry";  Anal. Cheg.  IS8C,  52,  Z242-224S.

5.    Betowski, L.  D.; Jones, T.  L. "The Analysis of Organophosphorus Pesticide
      Samples  by HPLC/MS and HPLC/MS/MS"; Environmental Science and Technology,
      1988,

8.    EPA;  2nd Annual Report onCarcinogens, NTP 81-43,  Dec. 1981, pp. 236-237.

9.    Blum, A.; Ames, B. N. Science  195. 1977,  17.

10.    Zweidinger, R.  A.;  Cooper,  S. D.;  Pellazari,  E.  D.,   Measurements  of
      Organic  Pollutants in Water and Mastewater,  ASTM 686.

11.    Cremlyn, R. Pesticides:  Preparation and modeof  Action;  John  Wiley and
      Sons:  Chichester, 1978;  p. 142.

                                  8321  - 21                         Revision 0
                                                                September 1994

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12,   Cotterill,  E.  G.;   Byast,   T.   H.   "HPLC  of  Pesticide  Residues  in
      Environmental  Samples,"    in  Liquid   Chromatography  in  Environmental
      Analysis; Laurence, J. F., Ed.; Humana  Press:  Clifton, NO, 1984.

13,   Voyksner, R. D. "Thermospray HPLC/MS  for Monitoring the Environment,"  In
      Applications of New Mass SpectrometryTechniques jn Pesticide Chemistry;
      Rosen, J, D,, Ed,, John Wiley and Sons:  New York, 1987,

14.   Yinon, J.; Jones,  T. L.; Betowski, L. D. Rap, Comm. Mass Spectrom. 1989,
      3, 38.

15.   Shore, F. L.; Amick,  E, N.,  Pan,  S.  T,, Gurka,  D.  F.  "Single Laboratory
      Validation of EPA Method 8150 for the Analysis of Chlorinated Herbicides
      in  Hazardous  Waste";  EPA/600/4-85/060,  U.S.  Environmental  Protection
      Agency, Las Vegas, NV, 1985.

16.   "Development and Evaluations of an LC/MS/MS Protocol",  EPA/60Q/X-86/328,
      Dec. 1986.

17.   "An LC/MS Performance  Evaldation  Study of Organophosphorus Pesticides",
      EPA/600/X-89/006,  Jan. 1989.

18,   "A  Performance   Evaluation   Study  of   a  Liquid  Chromatography/Mass
      Spectrometry    Method    for    Tris-(2,3-Dibromopropyl)    Phosphate",
      EPA/600/X-89/135,  June 1989.

19.   "Liquid  Chromatography/Mass  Spectrometry  Performance   Evaluation  of
      Chlorinated Phenoxyacid Herbicides and  Their Esters",  EPA/6QQ/X-89/176,
      July 1989.

20,   "An Inter!aboratory Comparison of  an SW-846 Method for the Analysis of the
      Chlorinated Phenoxyacid Herbicides by LC/MS",  EPA/600/X-90/133, June 1990.
                                   8321  -  22                         Revision 0
                                                                September 1994

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                                            TABLE 1.
                           RECOMMENDED HPLC  CHROMATOGRAPHIC CONDITIONS



Analytes
Organophosphorus
Compounds

Initial
Mobile
Phase
(%)
50/50
(water/
methanol)

Initial
Time
(min)
0



Gradient
(linear)
(min)
10


Final
Mobile
Phase
(%)
100
(methanol)


Final
Time
(min)
5


Azo Dyes (e.g.
Disperse Red 1)
50/50
(water/CH3CN)
                 100            5
                 (CH3CN)
Tris-(2,3-dibromo-
propyl)phosphate
50/50             0
(water/methanol)
10
100            5
(methanol)
Chlorinated
phenoxyacid
compounds

* Where A = 0.01
75/25
(A/methanol)
40/60
(A/methanol)
M ammonium acetate
2 15
3 5
(1% acetic acid)
40/60
(A/methanol)*
75/25
(A/methanol)*


10

                                            8321 -  23
                                                                    Revision 0
                                                                September 1994

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                                   TABLE 2.
              COMPOUNDS AMENABLE TO THERMOSPRAY MASS SPECTROMETRY
      Disperse Azo Dyes        Alkaloids
      Methine Dyes             Aromatic ureas
      Arylmethane Dyes         Amides
      Coumarin Dyes            Amines
      Anthraquinone Dyes       Amino acids
      Xanthene Dyes            Organophosphorus Compounds
      Flame retardants         Chlorinated  Phenoxyacid Compounds
                                   TABLE 3.
              LIMITS OF DETECTION (LOD) AND METHOD SENSITIVITIES
                        FOR DISPERSE  RED 1  AND CAFFEINE
Compound

Disperse Red 1


Caffeine


Mode

SRM
Single Quad
CAD
SRM
Single Quad
CAD
LOD
(pg)
180
600
2,000
45
84
240
EQL(7s)
(pg)
420
1400
4700
115
200
560
EQL(lOs)
(Pi)
600
2000
6700
150
280
800
EQL = Estimated Quantitation Limit

Data from Reference 16.
                                   8321  -  24                         Revision 0
                                                                September 1994

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                                   TABLE 4,
            PRECISION AND ACCURACY  COMPARISONS  OF  MS AND  MS/MS  WITH
       HPLC/UV FOR ORGANIC-FREE REAGENT  WATER SPIKED WITH DISPERSE RED 1
Sample
Spike 1
Spike 2
RPD

HPLC/UV
82.2 ± 0.2
87.4 ± 0.6
6.1%
Percent
MS
92.5 ± 3.7
90.2 + 4.7
2.5%
Recovery
CAD
87.6 ± 4.6
90.4 + 9.9
3.2%

SRM
95.5 ± 1
90.0 ± 5
5.9%


7.1
.9

Data from Reference 16.
                                   TABLE 5.
           PRECISION AND ACCURACY COMPARISONS OF MS AND MS/MS WITH
          HPLC/UV  FOR  MUNICIPAL  WASTEWATER  SPIKED WITH  DISPERSE  RED  1
Percent Recovery
Sample
Spike 1
Spike 2
RPD
HPLC/UV
93.4 + 0.3
96,2 ± 0.1
3.0%
MS
102.0 ± 31
79.7 ± 15
25%
CAD
82.7 ± 13
83.7 ± 5.2
1 . 2%
Data from Reference 16.
                                   8321  -  25
    Revision 0
September 1994

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                                   TABLE 6.
         RESULTS FROM ANALYSES OF ACTIVATED SLUDGE PROCESS WASTEWATER
Sample
5 rag/L Spiking
Concentration
1
1-D
2
3
RPD
Unspiked
Sample
1
1-D
2
3
RPD
Recovery
HPLC/UV

0.721 + 0.003
0.731 + 0.021
0.279 + 0.000
0.482 + 0.001
1.3%

0.000
0.000
0.000
0.000
--
of Disperse Red 1
MS

0.664 + 0.030
0.600 + 0.068
0.253 + 0.052
0.449 ± 0.016
10.1%

0.005 ± 0.0007
0.006 ± 0.001
0.002 + 0.0003
0.003 + 0.0004
18.2%
(mq/L)
CAD

0.796 + 0.008
0.768 ± 0.093
0.301 + 0.042
0.510 + 0.091
3.6%

<0.001
<0.001
<0.001
<0.001
__
Data from Reference 16.
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                  TABLE 7.
CALIBRATION MASSES AND % RELATIVE ABUNDANCES
                 OF PEG 400
Mass
18.0
35.06
36.04
50.06
77.04
168.12
212.14
256.17
300.20
344.22
388.25
432.28
476.30
520.33
564.35
608.38
652.41
653.41
696.43
697.44
% Relative
Abundances8
32.3
13.5
40.5
94.6
27.0
5.4
10.3
17.6
27.0
45.9
64.9
100
94.6
81.1
67.6
32.4
16.2
4.1
8.1
2.7
   Intensity is normalized to mass 432,
                  8321 - 27                        Revision 0
                                               September 1994

-------
                  TABLE 8.
CALIBRATION MASSES AND % RELATIVE ABUNDANCES
                 OF PEG 600
Mass
18.0
36.04
50.06
' 77.04
168.12
212.14
256.17
300.20
344.22
388.25
432.28
476.30
520.33
564.35
608.38
652.41
653.41
696.43
. % Relative
Abundances8
4.7
11.4
64.9
17.5
9.3
43.9
56.1
22.8
28.1
38.6
54.4
64.9
86.0
100
63.2
17.5
5.6
1.8
         Intensity  is normalized to mass  564.
                 8321 - 28                         Revision 0
                                               September 1994

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                                   TABLE 9.
                 RETENTION TIMES AND THERMOSPRAY MASS SPECJRA
                         OF ORGANOPHOSPHORUS  COMPOUNDS
Compound
Monocrotophos
Trichlorfon
Dimethoate
Diehlorvos
Naled
Fensulfothion
Methyl parathion
Phorate
Disul foton
Merphos
Retention Time
(minutes)
1:09
1:22
1:28
4:40
9:16
9:52
10:52
13:30
13:55
18:51
Mass Spectra
(% Relative Abundance)8
241 (100), 224 (14)
274 (100), 257 (19), 238 (19)
230 (100), 247 (20)
238 (100), 221 (40)
398 (100), 381 (23), 238 (5),
221 (2)
326 (10), 309 (100)
281 (100), 264 (8), 251 (21),
234 (48)
278 (4), 261 (100)
292 (10), 275 (100)
315 (100), 299 (15)
  a  For molecules containing Cl,  Br and S, only the base peak of the isotopic
  cluster is listed.

Data from Reference 17.
                                   8321  -  29
    Revision 0
September 1994

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                                   TABLE 10.
               PRECISION AND METHOD DETECTION LIMITS (MDLs) FOR
                      ORGANOPHOSPHORUS COMPOUND  STANDARDS
Compound Ion
Dichlorvos 238
Dimethoate 230
Phorate 261
Disulfoton 275
Fensulfothion 309
Naled 398
Merphos 299
Methyl 281
parathion
Standard
Quantitation
Concentration
(ng//iL)
2
12.5
25
50
2
12.5
25
50
2
12.5
25
50
2
12.5
25
50
2
12.5
25
50
2
12,5
25
50
2
12.5
25
50
2
12.5
25
50
%RSD
16
13
5.7
4.2
2.2
4.2
13
7.3
0.84
14
7.1
4.0
2.2
14
6.7
3.0
4.1
9.2
9.8
2.5
9.5
9.6
5,2
6.3
5.5
17
3.9
5.3
7.1
4.8
1.5
HDL (ng)
4
2
2
1
0.4
0.2
1
30
Data from Reference 17.
                                  8321  - 30
    Revision 0
September 1994

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                                   TABLE  11.
     SINGLE OPERATOR ACCURACY AND PRECISION FOR LOW  CONCENTRATION  DRINKING
     WATER  (A), LOW CONCENTRATION SOIL (B), MEDIUM CONCENTRATION DRINKING
                 WATER (C), MEDIUM CONCENTRATION SEDIMENT (D)
Average
Recovery
Compound (%)
A
Dimethoate
Dichlorvos
Naled
Fensul fothion
Methyl parathion
Phorate
Disul foton
Merphos
B
Dimethoate
Dichlorvos
Naled
Fensul fothion
Methyl parathion
Phorate
Disul foton
Merphos
C
Dimethoate
Dichlorvos
Naled
Fensul fothion
Methyl parathion
Phorate
Disul foton
Merphos
D
Dimethoate
Dichlorvos
Naled
Fensul fothion
Methyl parathion
Phorate
Disul foton
Merphos

70
40
0,5
112
50
16
3.5
237

16
ND
ND
45
ND
78
36
118

52
146
4
65
85
10
2
101

74
166
ND
72
84
58
56
78
Standard
Deviation

7,7
12
1.0
3.3
28
35
8
25

4
--
--
5
--
15
7
19

4
29
3
7
24
15
1
13

8.5
25
--
8.6
9
6
5
4
Spike
Amount
UQ/L
5
5
• 5
5
10
5
5
5
Mq/kq
50
50
50
50
100
50
50
50
UQ/l
50
50
50
50
100
50
50
50
nig/kg
2
2
2
2
3
2
2
2
Range of
Recovery

54
14
0
106
0
0
0
187

7
-
-
34
-
48
22
81

43
89
0
51
37
0
0
75

57
115
-
55
66
46
47
70

- 85
- 64
- 2
- 119
- 105
- 86
- 19
-287

- 24
-
-
- 56
-
- 109
- 49
- 155

- 61
- 204
- 9'
- 79
- 133
. 41
. 4
- 126

- 91
- 216
-
- 90
- 102
- 70
- 66
- 86
Number
of
Analyses

15
15
15
15
15
15
15
15

15
15
15
15
15
15
15
15

12
12
12
12
12
12
12
12

15
15
15
15
15
15
15
12
Data from Reference 17.
                                  8321  - 31
    Revision 0
September 1994

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                                   TABLE 12
          SINGLE OPERATOR ACCURACY AND PRECISION FOR MUNICIPAL WASTE
           WATER (A), DRINKING WATER (B), CHEMICAL SLUDGE WASTE (C)
Average
Recovery
Compound (%)
Tris-BP (A) 25
(B) 40
(C) 63
Spike Range
Standard Amount of % Number of
Deviation (ng/nl) Recovery Analyses
8.0 2 41 - 9.0 15
5.0 2 50-30 12
11 100 84-42 8
Data from Reference 18.
                                   8321  - 32                         Revision 0
                                                                September 1994

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                                                 TABLE  13.
                    SINGLE OPERATOR ESTIMATED QUANTITATION LIMIT (EQL) TABLE FOR TRIS-BP
Concentration
(ng/ML)

50
100
150
200
Average
Area

2675
5091
7674
8379
Standard 3*Std 7*Std
Deviation Dev. Dev.

782 2347 5476
558
2090
2030
10*Std
Dev. LOD
(ng/ML)
7823 33



Lower
EQL
(ng/ML)
113



Upper
EQL
(ng/ML)
172



Data from Reference 18.
                                                  8321  -  33                                        Revision 0
                                                                                              September 1994

-------
                                   TABLE 14
       LIMITS OF DETECTION  (LOD)  IN THE POSITIVE AND NEGATIVE  ION MODES
          FOR THE  CHLORINATED  PHENOXYACID HERBICIDES AND FOUR  ESTERS
Compound
Dalapon
Oicamba
2,4-D
MCPA
Dichlorprop
MCPP
2,4,5-T
2,4,5-TP (Silvex)
Dinoseb
2,4-DB
2,4-D,Butoxy
ethanol ester
2,4,S-T,Butoxy
ethanol ester
2,4,5-T, Butyl
ester
2,4-D,ethyl-
hexyl ester
Positive Mode
Quantitation
Ion
Not defected
238 (M+NH4)+
238 (M+NH4)+
218 (M+NH4)+
252 (M+NH4)+
232 (M+NH4)+
272 (M+NH4)+
286 (M+NHJ +
228 (M+NH4-NO)+
266 (M+NHJ*
321 (M+H)+

372 (M+NH4)+

328 (M+NH4)+

350 (M+NHJ*

LOD
(ng)

13
2,9
120
2,7
5.0
170
160
24
3.4
1.4

0.6

8.6

1.2

Negative Mode
Quantitation
Ion
141 (M-H)'
184 (M-HC1)'
184 (M-HC1)-
199 (M-l)-
235 (M-l)'
213 (M-l)-
218 (M-HC1)-
269 (M-l)-
240 (M)-
247 (M-l)-
185 (M-CeH^O,)"

195 (M-C8H1S03)-

195 (M-CeH,^)-

161 (M-C10H1903)-

LOD
(ng)
11
3.0
50
28
25
12
6.5
43
19
110








Data from Reference 19.
                                   8321  -  34
    Revision 0
September 1994

-------
                                    TABLE  15
               SINGLE LABORATORY OPERATOR ACCURACY AND PRECISION
                   FOR THE  CHLORINATED  PHENOXYACID HERBICIDES
Compound

Dicamba
2,4-D
MCPA
MCPP
Dichlorprop
2,4,5-T
Sil vex
2,4-DB
Dinoseb
Dalapon
2,4-D, ester

Dicamba
2,4-D
MCPA
MCPP
Dichlorprop
2,4,5-T
Sil vex
2,4-DB
Dinoseb
Dalapon
2,4-D, ester

Dicamba
2,4-D
MCPA
MCPP
Dichlorprop
2,4,5-T
Sil vex
2,4-DB
Dinoseb
Dalapon
2,4-D, ester
(a)
Average Standard
Recovery(%) Deviation
LOW LEVEL
63
26
60
78
43
72
62
29
73
ND
73
HIGH LEVEL
54
60
67
66
66
61
74
83
91
43
97
LOW
117
147
167
142
ND
134
121
199
76
ND
180
DRINKING WATER
22
13
23
21
18
31
14
24
11
ND
17
DRINKING WATER
30
35
41
33
33
23
35
25
10
9.6
19
LEVEL SAND
26
23
79
39
ND
27
23
86
74
ND
58
Spike
Amount
M9A
5
5
5
5
5
5
5
5
5
5
5
M9/L
50
50
50
50
50
50
50
50
50
50
50
M9/9
.1
.1
.1
.1
.1
.1
.1
.1
.1
.1
.1
Range of
Recovery
(%)

33
0
37
54
0
43
46
0
49

48

26 -
35 -
32 -
35 -
27 -
44 -
45 -
52 -
76 -
31 -
76 -

82
118
78
81

99
85
0
6

59

- 86
- 37
- 92
- 116
- 61
- 138
- 88
- 62
- 85
ND
- 104

103
119
128
122
116
99
132
120
102
56
130

- 147
- 180
- 280
- 192
ND
- 171
- 154
- 245
- 210
ND
- 239
Number
of
Analyses

9
9
9
9
9
9
9
9
9
9
9

9
9
9
9
9
9
9
9
9
6
9

10
10
10
10
10
10
10
10
10
10
7
ia!All  recoveries  are in  negative ionization  mode,  except  for 2,4-D,ester.
ND = Not Detected,
                                   8321  -  35
    Revision 0
September 1994

-------
                               TABLE 15  (cent.)
               SINGLE LABORATORY OPERATOR ACCURACY'AND PRECISION
                  FOR THE CHLORINATED PHENOXYACID HERBICIDES


Compound

-------
                                   TABLE 16
                  MULTI LABORATORY  ACCURACY  AND  PRECISION  DATA
                  FOR THE CHLORINATED PHENOXYACID HERBICIDES
Compounds

2,4,5-T
2,4,5-T,butoxy
2,4-D
2,4-DB
Dalapon
Dicamba
Dichlorprop
Dinoseb
MCPA
MCPP
Sil vex

2,4,5-T
2,4,5-T,butoxy
2,4-D
2,4-DB
Dal apon
Dicamba
Dichlorprop
Dinoseb
MCPA
MCPP
Silvex

2,4,5-T
2,4,5-7,butoxy
2,4-D
2,4-DB
Dalapon
Dicamba
Dichlorprop
Dinoseb
MCPA
MCPP
Sil vex
Spiking Mean
Concentration (% Recovery}8
500 mq/L
90
90
86
95
83
77
84
78
89
86
96
50 mq/L
62
85
64
104
121
90
96
86
96
76
65
5 mg/L
90
9S
103
96
150
105
102
108
94
98
87
% Relative
Standard Deviation1*

23
29
17
22
13
25
20
15
11
12
27

68
9
80
28
99
23
15
57
20
74
71

28
17
31
21
4
12
22
30
18
15
15
Data from Reference 20.
8  Mean  of duplicate  data  from 3  laboratories.
b  % RSD of duplicate data from 3 laboratories.
                                  8321  - 37
    Revision 0
September 1994

-------
                                   TABLE 17
           COMPARISON OF LODs: METHOD 815! vs. METHOD 8321
Compound
Method 8151
 LOD(Mg/L)
Method 8321
LOO
lonization
   Mode
Dalapon
Dicamba
2,4-D
MCPA
Dichloroprop
MCPP
2,4,5-T
2,4,5-TP (Silvex)
2,4-DB
Dinoseb
     1,3
     0.8
     0.2
     0,06
     0.26
     0.09
     0.08
     0.17
     0.8
     0.19
  1.1
  0.3
  0.29
  2.8
  0.27
  0.50
  0.65
  4.3
  0.34
  1.9
                                   8321  -  38
                                       Revision 0
                                   September 1994

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                    FIGURE 1,
SCHEMATIC OF THE THERMOSPRAY PROBE AND  ION SOURCE
I
                  Flange
   Source
  Mounting
    Plate
               Ion Sampling
                  Cone
Ions
Electron  Vaporizer
 Seem  ^ Probe
  /_^1_T,
                                                                —1C
            Temperature
             TM
                   Coupling
                       Slock
                    Temperature
                     T.
                    8321 - 39
                                      Revision 0
                                  September  1994

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            FIGURE 2.
THERMOSPRAY SOURCE WITH WIRE-REPEUER
   (High sensitivity configuration)
    CERAMIC INSULATOR
    WIRE REPELLER
             8321  - 40
   Revision 0
September  1994

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           FIGURE 3.
THERHOSPRAY SOURCE WITH WIRE-REPELLER
        (CAD configuration)
  CERAMIC INSULATOR
  WIRE REPELLER
            8321 - 41
   Revision 0
September 1994

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                             METHOD 8321
           SOLVENT  EXTRACTABLE  NON-VOLATILE COMPOUNDS BY
HIGH PERFORMANCE LIQUID  CHROMATOGRAPHY/THERMOSPRAY/HASS SPECTROMETRY
             (HPLC/TSP/MS) OR ULTRAVIOLET  (UV) DETECTION
7.3 Sat HPtC
Chrom*iographic
condition*.



74- Set HPIC/
Th«rmQ spray /MS
Operating
condition*.



7,5
Calibration
pracadure,



7,6 Perform
LC.'WS
1
f
                                                                     7 7 Use
                                                                    Methoa 8000
                                                                   concentration
                              8321 - 42
    Revision 0
September 1994

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                                  METHOD  8330

                     NITROAROHATICS AND NITRAHINES  BY HIGH
                   PERFORMANCE LIQUID CHROHAT06RAPHY (HPLC)
1.0   SCOPE AND APPLICATION

      1.1   Method 8330 is intended for the trace analysis of explosives residues
by high performance liquid chromatography using a UV detector.   This method is
used to determine the  concentration of the following compounds in a water, soil,
or sediment matrix:
Compound
Abbreviation
CAS No8
Octahydro~l,3,5,7-tetranitro-l,3,5,7-tetrazocine
Hexahydro-l,3,5-trinitro-l,3,5-triazine
1, 3, 5-Tri nitrobenzene
1 ,3-Di ni trobenzene
Methyl -2,4,6-trinitrophenylnitramine
Nitrobenzene
2,4,6-Trinitrotoluene
4-Amino-2,6-dinitrotoluene
2-Amino-4, 6-dinitrotoluene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
2-Nitrotoluene
3-Nitrotoluene
4-Nitrotoluene
HMX
RDX
1,3,5-TNB
1,3-DNB
Tetryl
NB
2,4,6-TNT
4-Am-DNT
2-Am-DNT
2,4-DNT
2,6-DNT
2-NT
3-NT
4-NT
2691-41-0
121-82-4
99-35-4
99-65-0
479-45-8
98-95-3
118-96-7
1946-51-0
355-72-78-2
121-14-2
606-20-2
88-72-2
99-08-1
99-99-0
a  Chemical Abstracts Service Registry number

      1.2   Method 8330  provides a  salting-out  extraction procedure  for  low
concentration (parts  per trillion, or nanograms per liter)  of explosives residues
in surface  or  ground water.   Direct injection  of diluted and  filtered water
samples can be used for water samples of higher concentration (See Table 1).

      1.3   All  of  these  compounds  are  either  used  in  the manufacture  of
explosives or are the degradation products of compounds used  for that purpose.
When making stock solutions for calibration, treat each explosive compound with
caution.  See NOTE in Sec. 5.3.1 and Sec. 11 on Safety.

      1.4   The  estimated  quantitation  limits  (EQLs)   of   target  analytes
determined by Method 8330  in water and soil are presented in  Table 1.

      1.5   This method  is restricted to  use  by or under the  supervision  of
analysts  experienced in  the  use of HPLC, skilled  in the  interpretation  of
chromatograms, and experienced in handling explosive  materials.  (See Sec. 11.0
                                   8330 - 1
                 Revision  0
             September 1994

-------
on SAFETY,)  Each  analyst  must  demonstrate  the  ability  to generate acceptable
results with this method.
2.0   SUMMARY OF METHOD

      2.1   Method 8330 provides high performance liquid chromatographic (HPLC)
conditions for the  detection  of ppb levels of certain explosives  residues in
water, soil  and sediment matrix.  Prior to use of this method, appropriate sample
preparation techniques must be used.

      2.2   Low-Level Salting-out Method With No  Evaporation:   Aqueous samples
of low concentration are extracted  by a  salting-out  extraction procedure with
acetonitrile and  sodium chloride.  The small  volume of acetonitrile that remains
undissolved above  the  salt water  is  drawn off  and  transferred to  a smaller
volumetric flask.   It  is  back-extracted by vigorous stirring  with  a specific
volume of salt water.  After equilibration,  the phases  are allowed  to separate
and  the  small volume   of  acetonitrile   residing  in the  narrow neck of  the
volumetric flask is removed using a  Pasteur  pi pet.  The concentrated extract is
diluted 1:1  with  reagent grade water.  An aliquot  is separated on a C-18 reverse
phase column,  determined at 254 nm,  and confirmed on a CN reverse phase column.

      2.3   High-level   Direct  Injection Method:   Aqueous  samples  of  higher
concentration can be diluted 1/1  (v/v) with methanol or acetonitrile, filtered,
separated on a C-18 reverse phase column, determine at 254 nm, and confirmed on
a CN reverse phase column.   If HMX is an important  target analyte,  methanol is
preferred.

      2.4   Soil  and sediment  samples  are  extracted using acetonitrile  in an
ultrasonic bath,  filtered and chromatographed as  in Sec.  2.3.


3.0   INTERFERENCES

      3.1   Solvents, reagents, glassware and other sample processing hardware
may yield discrete artifacts and/or elevated baselines, causing misinterpretation
of the chromatograms.  All  of  these materials  must be  demonstrated to be free
from interferences.

      3.2   2,4-ONT and 2,6-DNT elute at similar retention  times  (retention time
difference of 0.2 minutes).  A  large concentration of  one isomer may mask the
response of the  other  isomer.   If it is not  apparent that both  isoraers  are
present (or are not detected), an isomeric mixture  should be reported.

      3.3   Tetryl  decomposes rapidly in methanol/water  solutions,  as well as
with heat.  All aqueous samples expected to contain tetryl  should be diluted with
acetonitrile prior to filtration and acidified to pH <3.   All  samples expected
to contain tetryl should not be exposed to temperatures  above room temperature.

      3.4   Degradation products of  tetryl appear as a shoulder  on the 2,4,6-TNT
peak.  Peak  heights  rather  than peak areas should  be used when tetryl  is present
in  concentrations   that are  significant  relative  to the  concentration  of
2,4,6-TNT.

                                   8330 - 2                         Revision 0
                                                                September 1994

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4.0   APPARATUS AND MATERIALS

      4.1   HPLC system

            4.1.1 HPLC - equipped with a pump capable of achieving 4000 psl, a
      100 /il loop injector and a 254 nrn  UV detector   (Perkin Elmer Series 3, or
      equivalent).   For the  low concentration option,  the  detector  must be
      capable of a stable baseline at  0.001  absorbance units  full scale.

            4.1.2 Recommended Columns;

                  4.1.2.1     Primary  column:  C-18 Reverse phase HPLC column,
            25 cm x 4.6 mm (5 jim), (Supelco LC-18, or equivalent).
                  4.1.2.2     Secondary column:   CN Reverse phase HPLC column,
            25 cm x 4.6 mm (5 pm) , (Supelco LC-CN, or equivalent).

            4.1.3 Strip chart recorder.

            4.1.4 Digital integrator (optional).

            4.1.5 Autosampler (optional).

      4,2   Other Equipment

            4.2.1 Temperature controlled ultrasonic bath.

            4.2.2 Vortex mixer.

            4.2.3 Balance, ± 0.0001 g.

            4.2.4 Magnetic stirrer with stirring  pellets.

            4.2.5 Water bath - Heated, with concentric  ring  cover,  capable of
      temperature control (± 5°C),   The bath should be used in a hood.

            4.2.6 Oven - Forced  air,  without heating.

      4.3   Materials

            4.3.1 High pressure  injection  syringe - 500 ptL,  (Hamilton liquid
      syringe or equivalent).

            4.3.2 Disposable cartridge filters -  0.45 pm Teflon filter.

            4.3.3 Pipets - Class A, glass,  Appropriate sizes.

            4.3.4 Pasteur pipets.

            4.3.5 Scintillation  Vials - 20 mL, glass.

            4.3.6 Vials - 15 mL, glass, Teflon-lined cap.


                                   8330 - 3                         Revision 0
                                                                September 1994

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            4.3.7 Vials- 40 ml, glass, Teflon-lined cap.

            4.3.8 Disposable syringes - Plastipak, 3 ml and  10 ml or equivalent.

            4.3.9 Volumetric  flasks   -  Appropriate  sizes  with  ground  glass
      stoppers, Class A.

            NOT E: The 100 ml and 1 L volumetric flasks used for magnetic stirrer
                  extraction must be round.

            4.3.10      Vacuum desiccator - Glass.

            4.3.11      Mortar and pestle - Steel.

            4.3.12      Sieve - 30 mesh.

            4.3.13      Graduated cylinders - Appropriate sizes.

      4.4   Preparation of Materials

            4.4.1 Prepare all materials to be used as described  in Chapter 4 for
      semi volatile organics.


5.0   REAGENTS

      5.1   Reagent grade inorganic chemicals shall  be used in  all tests.  Unless
otherwise indicated,  it is  intended  that  all  reagents  shall  conform  to  the
specifications of the Committee on Analytical  Reagents of the American Chemical
Society, where such  specifications  are  available.    Other grades may  be used,
provided it  is first  ascertained that the reagent is of sufficiently high purity
to permit its use without lowering the accuracy of the determination.

            5,1.1 Acetonitrile, CH3CN -  HPLC  grade.

            5.1.2 Methanol, CH3OH  -  HPLC  grade.

            5.1.3 Calcium chloride,  CaCl2 - Reagent grade.   Prepare an aqueous
      solution of 5 g/L,

            5.1.4 Sodium  chloride,  NaCl,  shipped  in glass bottles  -  reagent
      grade.

      5.2   Organic-free reagent  water -  All  references to water in this method
refer to organic-free reagent water,  as defined in Chapter One.

      5.3   Stock Standard Solutions

            5.3.1 Dry each solid analyte standard to constant weight  in a vacuum
      desiccator in the dark.  Place  about 0,100 g (weighed  to 0.0001  g) of a
      single analyte into  a  100 ml volumetric flask and  dilute to  volume with
      acetonitrile.   Invert flask  several  times  until  dissolved.    Store  in


                                   8330 - 4                         Revision 0
                                                                September 1994

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refrigerator at 4°C  in the dark.  Calculate the concentration of the stock
solution from the actual weight used (nominal  concentration = 1,000 mg/L).
Stock solutions may be used for up to one year.

      NOTE: The  HMX,  RDX,  Tetryl,  and 2,4,6-TNT are  explosives  and the
            neat material  should be handled carefully.  See SAFETY in Sec.
            11 for  guidance,   HMX,  RDX,   and Tetryl reference materials
            are  shipped under  water.    Drying  at  ambient  temperature
            requires several days.  DO NOT DRY AT HEATED TEMPERATURES!

5.4   Intermediate Standards Solutions

      5.4.1 If both 2,4-DNT and 2,6-DNT  are to be determined, prepare two
separate intermediate stock solutions  containing  (1)  HMX,  RDX, 1,3,5-TNB,
1,3-DNB, NB, 2,4,6-TNT, and 2,4-DNT and (Z) Tetryl, 2,6-DNT, 2-NT,  3-NT,
and 4-NT.   Intermediate stock standard solutions  should  be prepared at
1,000 M9/L, in acetonitrile when analyzing soil samples, and in methane!
when analyzing aqueous samples.

      5.4.2 Dilute the two concentrated intermediate stock  solutions, with
the appropriate solvent, to prepare intermediate standard solutions that
cover  the  range of  2.5  -  1,000  jig/L.    These   solutions  should  be
refrigerated on preparation, and may be used for 30 days.

      5.4.3 For the low-level method, the analyst must conduct a detection
limit study and devise dilution series appropriate  to the desired range.
Standards for the low level method must be prepared immediately prior to
use.

5.5   Working standards

      5.5.1 Calibration  standards  at  a  minimum  of  five concentration
levels should be prepared through dilution of the intermediate standards
solutions by 50% (v/v) with 5  g/L calcium  chloride solution (Sec. 5.1.3).
These solutions must be refrigerated and stored in the dark, and prepared
fresh on the day of calibration.

5.6   Surrogate Spiking Solution

      5.6.1 The analyst should monitor the performance of the extraction
and  analytical  system  as  well as  the  effectiveness  of  the method in
dealing with  each  sample  matrix  by  spiking  each   sample,  standard and
reagent water blank  with  one  or  two  surrogates  (e.g.,  analytes  not
expected to be present in the sample).

5.7   Matrix Spiking Solutions

      5.7.1 Prepare matrix  spiking  solutions  in methanol  such  that the
concentration in the sample  is five times the  Estimated Quantitation Limit
(Table 1).  All target analytes should be included.
                             8330 - 5                         Revision 0
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      5.8   HPLC Mobile Phase

            5.8.1 To prepare 1 liter of mobile phase, add 500 mL of methanol to
      500 ml of organic-free reagent water.


6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1   Follow  conventional  sampling and  sample  handling procedures  as
specified for semivolatile organics in  Chapter Four.

      6.2   Samples and  sample extracts must  be  stored in  the dark  at  4"C.
Holding times are the same as for semivolatile organics.


7.0   PROCEDURE

      7.1   Sample Preparation

            7.1.1 Aqueous Samples;   It is highly recommended that process waste
      samples be screened with the high-level  method to determine  if  the low
      level  method  (1-50 M9/L) is required.  Most groundwater samples will  fall
      into the low level method.

                  7.1.1.1     Low-Level  Method (salting-out extraction)

                        7.1.1.1.1    Add  251.3 g  of sodium  chloride to a  1  L
                  volumetric  flask  (round).   Measure  out  770  mL  of  a  water
                  sample (using all graduated cylinder)  and transfer it to the
                  volumetric flask  containing  the salt.  Add a stir bar and mix
                  the contents at maximum speed on a magnetic stirrer until the
                  salt is completely dissolved.

                        7.1.1.1.2    Add  164 mL of acetonitrile  (measured with a
                  250 mL graduated cylinder) while the solution  is being stirred
                  and stir for an  additional  15 minutes.  Turn  off the stirrer
                  and allow the phases  to separate  for  10 minutes.

                        7.1.1.1.3    Remove the acetonitrile  (upper) layer (about
                  8 ml)  with  a  Pasteur pi pet  and transfer  it to  a ICC  m_
                  volumetric flask  (round).  Add 10 ml of fresh  acetonitrile to
                  the water  sample  in the 1 L flask.  Again stir the contents of
                  the flask  for  15 minutes followed by  10 minutes  for  phase
                  separation.  Combine the second acetonitrile portion with the
                  initial extract.   The  inclusion  of  a  few  drops of salt water
                  at this point is  unimportant.

                        7.1.1.1.4    Add  84 mL of salt water  (325 g NaCl per 1000
                  mL of reagent water) to the acetonitrile extract in the 100 mL
                  volumetric flask.  Add a stir bar and stir the contents  on a
                  magnetic stirrer for 15 minutes, followed by 10  minutes for
                  phase separation.  Carefully transfer the acetonitrile phase


                                   8330  - 6                         Revision 0
                                                                September 1994

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      to a 10 ml graduated cylinder using  a Pasteur pipet.  At this
      stage, the amount of water transferred with the acetonitrile
      must be minimized.  The water contains a high concentration of
      NaCl  that produces  a  large  peak  at  the  beginning of  the
      chromatogram,  where   it   could  interfere  with   the   HMX
      determination.

            7.1.1.1.5   Add an additional  1.0 ml of acetonitrile to
      the 100 ml volumetric flask.  Again stir the contents of the
      flask  for 15  minutes,  followed by  10 minutes  for  phase
      separation.  Combine the second  acetonitrile portion with the
      initial extract in the 10 ml graduated cylinder (transfer to
      a  25  ml  graduated  cylinder  if the volume  exceeds 5  ml).
      Record the total volume of acetonitrile  extract  to the nearest
      0.1 ml.   (Use this as the volume of total extract  [Vt] in the
      calculation of concentration  after  converting  to ^L).   The
      resulting extract, about 5-6  ml,  is  then  diluted  1:1  with
      organic-free  reagent  water  (with  pH  <3   if  tetryl  is  a
      suspected analyte) prior to analysis.

            7.1.1.1.6   If the diluted extract is turbid, filter it
      through a 0.45 - pm Teflon  filter using a disposable syringe.
      Discard the first  0.5 ml of filtrate, and retain the remainder
      in a Teflon-capped vial for RP-HPLC analysis as in Sec.  7.4.

      7.1.1.2     High-level  Method

            7.1.1.2.1   Sample filtration: Place  a 5 ml aliquot of
      each  water sample  in   a  scintillation vial,  add  5 ml  of
      acetonitrile, shake thoroughly,  and filter  through a 0.45-fim
      Teflon filter using a disposable syringe.   Discard the  first
      3 ml of filtrate,  and retain the remainder in a Teflon-capped
      vial for  RP-HPLC analysis  as  in Sec. 7.4.   HMX quantisation
      can  be  improved   with  the  use of  methanol   rather  than
      acetonitrile for dilution before filtration.

7.1.2 Soil and Sediment Samples

      7.1.2.1     Sample homogenization:   Dry soil  samples  in air at
room temperature or colder tc £ constant weight,  being careful  net
to expose the samples to direct sunlight.  Grind and homogenize the
dried sample thoroughly in an acetonitrile-rinsed mortar to pass a
30 mesh sieve.

      NOTE:  Soil samples should be screened by Method 8515 prior to
            grinding in  a mortar  and pestle (See Safety Sec. 11.2).

      7.1.2.2     Sample extraction

            7.1.2.2.1   Place a 2.0 g  subsample of each soil sample
      in a 15 ml glass vial.   Add  10.0 ml  of acetonitrile, cap with
                       8330 - 7                         Revision 0
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            Teflon-lined cap, vortex swirl  for one minute, and place in a
            cooled ultrasonic bath for 18 hours.

                  7.1.2.2.2   After sonication, allow sample to settle for
            30 minutes.  Remove 5.0  ml  of  supernatant,  and  combine with
            5.0 ml of  calcium chloride  solution (Sec.  5.1.3)  in a 20 ml
            vial.  Shake, and let stand for 15 minutes.

                  7.1.2.2.3   Place  supernatant  in  a  disposable syringe
            and filter through a Q.45-/jm Teflon filter.  Discard first 3
            ml and retain remainder  in  a Teflon-capped  vial for RP-HPLC
            analysis as in Sec.  7.4.

7,2   Chromatographic Conditions (Recommended)

      Primary Column:   C-18 reverse phase  HPLC column, 25-cm
                        x 4.6-mm,  5 ^m, (Supelco LC-18 or equivalent).

      Secondary Column: CN reverse phase HPLC column,  25-cm x
                        4.6-mm,  5 /*m, (Supelco  LC-CN or
                        equivalent).

      Mobile Phase:     50/50 (v/v) methanol/organic-free
                        reagent  water.

      Flow Rate:        1.5 mL/nnn

      Injection volume: 100-^L

      UV Detector:      254 nra

7.3   Calibration of HPLC

      7.3.1 All electronic equipment  is allowed to warm up for 30 minutes.
During this period,  at least  15 void volumes  of mobile phase are passed
through the  column   (approximately 20 min  at  1.5 mL/min)  and  continued
until the baseline is level  at the UV detector's greatest sensitivity.

      7.3.2 Initial Calibration.   Injections of each calibration standard
over the concentration range of interest are  made  sequentially  Into the
HPLC in random order.  Peak  heights  or  peak  areas  are obtained  for each
analyte.  Experience indicates that a linear calibration curve with zero
intercept is appropriate for each analyte.   Therefore, a response factor
for  each analyte  can be taken as  the slope of  the best-fit regression
1 ine.

      7.3.3 Daily Calibration.  Analyze midpoint calibration  standards, at
a minimum,  at the  beginning of the day, singly at the midpoint of the run,
and singly after the  last sample of the day  (assuming a sample group of 10
samples or less).  Obtain the response  factor for  each analyte  from the
mean peak heights or peak areas and  compare  it with the response factor
obtained for the  initial calibration.   The mean response  factor for the
                             8330 - 8                         Revision 0
                                                          September 1994

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      daily calibration must  agree  within ±15% of the  response  factor of the
      initial  calibration.    The same  criteria  is  required for  subsequent
      standard  responses  compared  to  the mean  response  of the  triplicate
      standards beginning the day.   If this criterion  is not met, a new initial
      calibration must be obtained.

      7A   HPLC Analysis

            7.4.1 Analyze the samples using the chromatographic conditions given
      in Sec. 7.2.  All positive measurements observed on the C-18 column must
      be confirmed by injection onto the CN column.

            7.4.2 Follow  Sec. 7.0  in  Method 8000  for  instructions on  the
      analysis  sequence,  appropriate  dilutions,  establishing daily retention
      time windows, and identification criteria.   Include a mid-level standard
      after each  group of  10 samples  in  the analysis  sequence.    If column
      temperature control  is not  employed,  special care must be taken to ensure
      that temperature shifts do not cause peak misidentification.

            7.4.3 Table 2  summarizes the estimated retention times on both C-18
      and CN columns for a number of analytes  analyzable using this method.  An
      example of the separation achieved by Column 1 is shown in Figure 1.

            7.4.4 Record the resulting peak sizes in  peak heights  or area units.
      The use of peak heights is recommended  to improve reproducibility of low
      level samples.

            7.4.5 Calculation of concentration is  covered  in Sec. 7.0 of Method
      8000.
8.0   QUALITY CONTROL

      8.1   Refer  to Chapter  One  for  specific  quality control  procedures.
Quality control to validate sample extraction is covered in Method 3500,

      8.2   Quality control required to validate  the  HPLC  system operation is
found in Method 8000, Sec. 8.0.
      g "?   Dv-: nv 4-r* r
water blanks  should be run  to  determine possible interferences  with analyte
peaks.   If  the acetonitrile, methanol,  or water blanks  show contamination, a
different batch should be used.


9.0   METHOD PERFORMANCE

      9.1   Table 3 presents the single  laboratory precision  based on data from
the analysis  of  blind duplicates of four  spiked  soil samples  and  four field
contaminated samples analyzed by seven laboratories.
                                   8330 - 9                         Revision 0
                                                                September 1994

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      9.2   Table 4 presents the multllaboratory  error based on data from the
analysis  of blind  duplicates  of  four  spiked soil   samples  and  four  field
contaminated samples analyzed by seven laboratories.

      9.3   Table  5  presents  the   mul tilaboratory   variance  of  the  high
concentration method for water based on data from nine laboratories.

      9.4   Table 6 presents multi laboratory recovery  data  from the  analysis of
spiked soil samples by seven laboratories.

      9.5   Table 7 presents a comparison of method accuracy for soil  and aqueous
samples (high concentration method).

      9.6   Table 8 contains  precision and accuracy  data  for the  salting-out
extraction method.
10.0  REFERENCES

1.    Bauer, C.F., T.F. Jenkins, S.M.  Koza,  P.M.  Schumacher,  P.H. Hiyares and
      M.E.  Walsh  (1989).     Development   of  an  analytical  method  for  the
      determination of explosive residues  in  soil.   Part 3.  Collaborative test
      results and final performance evaluation.  USA Cold Regions Research and
      Engineering Laboratory, CRREL Report 89-9.

2.    Grant,  C.L.,  A.D.  Hewitt and  T.F. Jenkins   (1989)  Comparison  of  low
      concentration measurement capability estimates in trace analysis:  Method
      Detection  Limits and  Certified  Reporting  Limits.    USA  Cold  Regions
      Research and Engineering Laboratory, Special Report 89-20.

3.    Jenkins,  T.F.,   C.F.   Bauer,   D.C.   Leggett  and   C.L.   Grant  (1984)
      Reversed-phased HPLC method for analysis of  TNT, RDX, HMX  and 2,4-DNT in
      munitions  wastewater.    USA  Cold  Regions  Research  and  Engineering
      Laboratory, CRREL Report 84-29.

4.    Jenkins, T.F. and M.E.  Walsh  (1987)  Development  of an analytical  method
      for explosive residues in  soil.  USA Cold Regions Research  and Engineering
      Laboratory, CRREL Report 87-7.

5.    Jenkins, T.F.,  P.H.  Mlyares  and ME. Walsh  (!988a;   An  -mp-ovec! RP-HPLC
      method for determining nitroaromatics and nitratnines in water.  USA Cold
      Regions Research and Engineering Laboratory, Special Report 88-23.

6.    Jenkins,  T.F.   and  P.H.  Miyares  (1992)   Comparison  of Cartridge  and
      Membrane Solid-Phase  Extraction  with Salting-out  Solvent Extraction for
      Preconcentration  of  Nitroaromatic and  Nitramine Explosives from  Water.
      USA Cold Regions Research and  Engineering Laboratory, Draft  CRREL Special
      Report.

7.    Jenkins,  T.F.,   P.M.   Schumacher,  M.E.  Walsh  and   C.F.  Bauer   (1988b)
      Development of  an analytical  method for  the  determination  of explosive
      residues in soil.  Part II:  Further development and ruggedness testing.
      USA Cold Regions Research and Engineering Laboratory, CRREL Report 88-8.

                                   8330 -  10                         Revision 0
                                                                September 1994

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8.    Leggett, D.C., T.F. Jenkins  and  P.H.  Miyares  (1990)  Salting-out solvent
      extraction for  preconcentration of neutral  polar organic  solutes  from
      water.  Analytical Chemistry, 62:  1355-1356.

9.    Miyares, P.H. and T.F. Jenkins (1990)  Salting-out solvent extraction for
      determining  low  levels  of nitroaromatics and nitramines  in  water.   USA
      Cold Regions Research and Engineering  Laboratory, Special Report 90-30.


11.0  SAFETY

      11.1  Standard precautionary measures used  for handling  other organic
compounds should be sufficient for  the safe handling  of the analytes targeted by
Method 8330.  The only extra caution that should be taken is when handling the
analytical standard neat material for the  explosives themselves and in rare cases
where soil or  waste samples are highly contaminated with the explosives.  Follow
the note for drying the neat materials at ambient temperatures.

      11.2  It is advisable  to screen soil or waste samples using Method 8515 to
determine whether high concentrations of explosives are present.  Soil samples
as high  as  2% 2,4,6-TNT have been safely ground.  Samples  containing higher
concentrations should not be ground in the mortar and pestle.   Method 8515 is for
2,4,6-TNT,  however, the other  nitroaromatics  will  also cause a  color  to  be
developed and  provide  a rough  estimation  of  their concentrations.  2,4,6-TNT is
the analyte most often  detected  in  high concentrations  in soil  samples.  Visual
observation of a soil  sample is also important when the sample  is taken from a
site expected to contain  explosives.   Lumps of material that  have a chemical
appearance should  be suspect and not  ground.   Explosives  are generally a very
finely ground  grayish-white material.
                                   8330 -  11                         Revision 0
                                                                September 1994

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           TABLE 1
ESTIMATED QUANTITATION LIMITS
Compounds
HMX
RDX
1,3,5-TNB
1,3-DNB
Tetryl
NB
2,4,6-TNT
4-Am-DNT
2-Am-DNT
2,6-DNT
2,4-DNT
2-NT
4-NT
3-NT
Water
Low-Level
-
0.84
0.26
0.11
-
-
0.11
0.060
0.035
0.31
0.020
-
-
-
(uq/U
High-Level
13.0
14.0
7.3
4.0
4.0
6.4
6.9
-
-
9.4
5.7
12.0
8.5
7.9
Soil (mg/kg)
2.2
1.0
0.25
0.25
0.65
0.26
0.25
-
-
0.26
0.25
0.25
0.25
0,25
          8330 -  12
    Revision 0
September 1994

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                                    TABLE  2
        RETENTION TIMES AND CAPACITY FACTORS  ON  LC-18 AND  LC-CN  COLUMNS
Retention time
{min)
Compound
HMX
RDX
1,3,5-TNB
1,3-DNB
Tetryl
NB
2,4,6-TNT
4-Am-DNT
2-Am-DNT
2,6-DNT
2,4-DNT
2-NT
4-NT
3-NT
LC-18
2.44
3.73
5.11
6.16
6.93
7.23
8.42
8.88
9.12
9.82
10.05
12.26
13.26
14.23
LC-CN
8.35
6.15
4.05
4.18
7.36
3.81
5.00
5.10
5.65
4.61
4.87
4.37
4.41
4.45
Capaci
LC-18
0.49
1.27
2.12
2.76
3.23
3.41
4.13
4.41
4.56
4.99
5.13
6.48
7.09
7.68
ty factor
(k)*
LC-CN
2.52
1.59
0.71
0.76
2.11
0.61
1.11
1.15
1.38
0.95
1.05
0.84
0.86
0.88
* Capacity factors are based on an  tmretained peak  for  nitrate at 1.71 min on
LC-18 and at 2.00 min on LC-CN.
                                   8330  -  13                         Revision 0
                                                                September 1994

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                                   TABLE 3
            SINGLE LABORATORY PRECISION OF METHOD FOR SOIL SAMPLES
                   Sulked Soils
                  Mean Cone.
             {mg/kg}        SD
                   %RSD
                    Field-Contaminated Soils
                             Mean Cone,
                   (mg/kg}     SD         %RSD
HMX


RDX


1,3,5-TNB


1,3-DNB

Tetryl

2,4,6-TNT


2,4-DNT
46


60


 8.6
46

 3.5

17

40


 5.0
1.7


1,4


0,4
1.9

0.14

3.1

1.4


0.17
 3.7


 2.3


 4.6
 4.1

 4.0

17,9

 3.5


 3,4
 14
153

104
877

  2.8
 72

  1.1

  2.3

  7.0
669

  1.0
 1.8
21.6

12
29.6

 0.2
 6,0

 0.11

 0.41

 0.61
55

 0.44
12.8
14.1

11.5
 3.4

 7.1
 8.3

 9.8

18.0

 9.0
 8.2

42.3
                                  8330 - 14
                                                    Revision 0
                                                September 1994

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                       TABLE 4
  MULTILABORATORY ERROR OF METHOD FOR SOIL SAMPLES
Spiked Soils

HMX
RDX
1,3,5-TNB
1,3-DNB
Tetryl
2,4,6-TNT
2,4-DNT
Mean
(mg/kg)
46
60
8,6
46
3.5
17
40
5.0
Cone.
SD
2.6
2.6
0.61
2.97
0.24
5.22
1.88
0.22
%RSD
5.7
4.4
7.1
6.5
6.9
30.7
4.7
4.4
Field-Contaminated Soils
(rag/kg)
14
153
104
877
2.8
72
1.1
2.3
7.0
669
1.0
Mean Cone.
SD %RSD
3.7
37.3
17.4
67.3
0.23
8.8
0.16
0.49
1.27
63.4
0.74
26.0
24.0
17.0
7.7
8.2
12.2
14.5
21.3
18.0
9.5
74.0
                       TABLE 5
MULTILABORATORY VARIANCE OF METHOD FOR WATER SAMPLES8
Compounds
HMX
RDX
2,4-DNT
2,4,6-TNT
Mean Cone.
(M9/LJ
203
274
107
107
SD
14.8
20.8
7.7
11.1
%RSD
7.3
7.6
7.2
10.4
8 Nine Laboratories
                      8330 - 15
    Revision 0
September 1994

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                                       TABLE  6
                MULTILABORATORY RECOVERY  DATA FOR SPIKED SOIL SAMPLES
Laboratory
1
3
4
5
6
7
8
True Cone
Mean
Std Dev
% RSD
% Diff*
Mean %
Recovery

44
50
42
46
55
41
52
50
47
5
11
5
95
HMX
.97
.25
.40
.50
.20
.50
.70
.35
.79
.46
.42
.08

Concentration (/ug/g)
1,3,5- 1,3-
RDX TNB DNB
48.78
48.50
44.00
48.40
55.00
41.50
52.20
50.20
48.34
4.57
9.45
3.71
96
48
45
43
46
41
38
48
50
44
3
8
10
89
.99
.85
.40
.90
.60
.00
.00
.15
.68
.91
.75
.91

49.
45.
49.
48.
46.
44.
48.
50.
47.
2.
4.
4.
95
94
96
50
80
30
50
30
05
67
09
39
76

Tetryl
32.48
47.91
31.60
32.10
13.20
2.60
44.80
50,35
29.24
16.24
55.53
41.93
58
2,4,6-
TNT
49.73
46.25
53.50
55.80
56.80
36.00
51.30
50.65
49.91
7.11
14.26
1.46
98
2,4-
DNT
51
48
50
49
45
43
49
50
48
2
5
3
96
.05
.37
.90
.60
.70
.50
.10
.05
.32
.78
.76
.46

* Between true value and mean determined value.
                                      8330  -  16
    Revision 0
September 1994

-------
Analyte
                                    TABLE 7
          COMPARISON OF METHOD ACCURACY  FOR SOIL AND AQUEOUS SAMPLES
                          (HIGH CONCENTRATION  METHOD)
                                                Recovery(%)
Soil Method*
Aqueous Method**
2,4-DNT

2,4,6-TNT

RDX

HMX
    96,0

    96.8

    96.8

    95.4
      98,6

      94.4

      99.6

      95.5
*  Taken from Bauer et al. (1989), Reference 1.
** Taken from Jenkins et al. (1984), Reference 3.
                                   8330  -  17
                                 Rev i s i on  0
                             September  1994

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                                   TABLE 8
       PRECISION AND ACCURACY DATA FOR THE SALTING-OUT  EXTRACTION  METHOD
Analyte
HMX
RDX
1,3,5-TNB
1,3-DNB
Tetryl
2,4,6-TNT
2-Am-DNT
2,4-DNT
1,2-NT
1,4-NT
1,3-NT
No. of Samples1
20
20
20
20
20
20
20
20
20
20
20
Preci si on
(% RSD)
10.5
8.7
7.6
6.6
16,4
7.6
9.1
5.8
9.1
18.1
12.4
Ave. Recovery
(%)
106
106
119
102
93
105
102
101
102
96
97
Cone. Range
(M9/L)
0-1.14
0-1.04
0-0.82
0-1.04
0-0.93
0-0.98
0-1.04
0-1.01
0-1.07
0-1.06
0-1.23
1Reagent water
                                  8330 - 18
    Revision 0
September 1994

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 EXPLOSIVES ON A
 CIS COLUMN
                                          /.A.
                                                      11.
EXPLOSIVES ON A
CN COLUMN
                                        1
                                                                1 *
                            FIGURE 1
       CHROMATOGRAMS FOR COLUMNS DESCRIBED IN Sec. 4.1.2.
      COURTESY OF U.S. ARMY CORPS OF ENGINEERS, OMAHA, NE.
                            8330 -  19
    Revision 0
September 1994

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                 METHOD 8330
  NITROAROMATICS AND NITRAMINES BY  HIGH
PERFORMANCE LIQUID CHROMATOGRAPHY  (HPLC)
       Low
Sailing dm
7 1 1.1.1 Add 2S1.3 got soft
and 1 1. of water sample to a
1 L vol. (task Mm the contents

!'
71,1 1.2 Add 164mLot
acwonrtf* lACN) ana stir
foMSmins.
•

71 1.1.3 Transfer ACN layer
to 100 mL «)l. task. Add 10 ml
of trash ACN 10 i L tlask and
stir, Transfer 2nd portion and
combine witti 1st in 100 ml flask.
1
<
7 1.1.1 4 Add 84 mL of sal
waief to the ACN axtract and stir.
Trans*' ACN extract lo 1 0 mL
grad. cylinder
i

71115 Add 1 mL ot ACN to
100 mL vol. flask. SBr and
transfer 10 the 10 mL grafl,
cylinder Record volume.
Dilute 1 1 with reagent water
1 '

7 1 1.1 6 Filter if turbid.
Transfer to a vial tar
RP-HPLC analysis.
                                    7111 Sample Rhrauon:
                                     Place 5 mL sample in
                                    santfci wn voi AddSmL
                                     meifiarwl: shake. Her
                                  mrourjh O.S urn KRsr. Discard
                                   tirsl 3 mL Retain remainder
                                        tor use
                  8330 - 20
     Revision 0
September  1994

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                            METHOD  8330
                            (continued)
~ i 2.1 Sample riomog&nizason
Air dry sample at room Temp
or below  Avoid exposure to
direct sunlignt Grind sample
m an acetontfnl* rinsed mortar.
   7 1,2.2 Sample Extraction
 7 i 2,2.1
 Place 2 g soil subsample,
 10 mLs acetoniOTt in 15 ml
 glass vial. Cap, vortex, svnn,
 piaca in room Temp, or below
 ultrasonic Oath tar 18 hrs.
7 1 2.2.2
Let sdn. serte,  Add S mL
supernatant to 5 mL calcium
cnlonae soln, in  20 ml vial.
Shake let stand i S mins.
7 1 2,2,3
Filter supernatant through
0.5 urn filler. Discard initial
3 mL. retarn remainder
tor analysis.
7 2 Sal Crsrotiatograpnic Conditions
     7 3 Calibration ot HPLC
 73.2
 Run working s&ds. in Bipiicate
 Plot rig. vs. paaK area ar ht
 Curve snaulfl be linear wim
 zero intercept.
  733
  Analyze midrange calibration
  std, at beginning, middle.
  and end of sarnpla analyses.
  Redo Section 7 3 1 if peak
  areas or Ms. do not agree
  to w/in w- 20% of initial
  calibration values.
                                                          7 4 Sample Analysis
  74.1
  Analyze samples Confirm
  measurment w/infecnon onto
  CN column,
74,3
Refer to TaMe 2 tor typical
anaiyte retention times.
I

                                                                Stop
                             8330  -  21
                                Revision  0
                          September  1994

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                                  METHOD 8331

                          TETRAZENE  BY  REVERSE  PHASE
                 HIGH PERFORMANCE LIQUID CHRQMATQGRAPHY  (HPLC)


1.0   SCOPE AND APPLICATION

      1.1   This method is intended  for the  analysis of tetrazene, an explosive
residue,  in  soil  and  water.    This  method  is  limited  to  use by  analysts
experienced  in  handling  and analyzing  explosive materials.    The  following
compounds can be determined by this method:
      Compound                                              CAS No*
      Tetrazene                                             31330-63-9
      a  Chemical  Abstracts Service Registry  number

      1.2   Tetrazene degrades rapidly in water and methanol  at room temperature.
Special care must be taken to refrigerate or cool  all  solutions throughout the
analytical process.

      1.3   Tetrazene, in its dry form, is extremely explosive.  Caution must be
taken during preparation of standards.

      1.4   The estimated quantitation 1 imit (EQL) of Method 8331 for determining
the  concentration  of   tetrazene   is  approximately  7  /ig/L   in  water  and
approximately 1 mg/kg in soil.

      1.5   This method  is restricted to use by  or under the  supervision of
analysts  experienced  in the  use  of  HPLC,  skilled  in  the interpretation of
chromatograms, and experienced  in  handling explosive materials.   Each analyst
must demonstrate the ability to generate acceptable results with this method.


2.0   SUMMARY OF METHOD

      2.1   A 10 ml water sample is filtered, eluted on a C-18 column using ion
pairing reverse phase HPLC, and quantitated at 280 nm.

      2.2   2  g of  soil  are  extracted with  55:45 v/v  methanol-water  and
1-decanesulfonic acid  on  a platform shaker, filtered, and eluted  on a  C-18 column
using ion pairing reverse phase HPLC, and quantitated at 280 nm.
                                   8331 - 1                         Revision 0
                                                                September 1994

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3.0   INTERFERENCES

      3,1   No interferences  are known.  Tetrazene elutes  early, however, and if
a computing integrator  is used for peak quantification, the baseline setting may
have to  be set to exclude baseline aberrations.  Baseline setting is particularly
important at low concentrations of analyte.


4.0   APPARATUS AND MATERIALS

      4.1   HPLC system

            4.1.1   HPLC - Pump capable of achieving 4000 psi.

            4.1.2   100 /xL loop injector.

            4.1.3   Variable or fixed wavelength detector capable  of reading
      280 nm.

            4.1.4   C-18 reverse  phase HPLC  column,  25 cm  x 4.6  mm (5  ^,m)
      (Supelco LC-18,  or  equivalent).

            4.1.5   Digital integrator - HP 3390A (or equivalent)

            4.1.6   Strip chart recorder.

      4.2   Other apparatus

            4.2.1   Platform orbital shaker.

            4.2.2   Analytical  balance - + 0.0001 g.

            4.2.3   Desiccator.

      4.3   Materials

            4.3.1   Injection syringe - 500 jxL.

            4.3.2   Filters - 0.5 pm Millex-SR and 0.5 urn Millex-HV, disposable,
      or equivalent.

            4.3.3   Pipets - volumetric, glass, Class A.

            4.3.4   Scintillation vials - 20 mL, glass.

            4.3.5   Syringes -  10 mL.

            4.3.6   Volumetric  flasks, Class A - 100 mL,  200 mL.

            4.3.7   Erlenmeyer  flasks with ground glass stoppers - 125 mL.
                                   8331  -  2                          Revision 0
                                                                September 1994

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      4.4   Preparation

            4.4.1   Prepare all materials  as described in Chapter 4 for volatile
      organics.


5.0   REAGENTS

      5.1   HPLC grade  chemicals shall be used  in all tests.  It  is intended that
all reagents shall  conform to  the  specifications of the Committee on Analytical
Reagents  of the  American  Chemical  Society,, where  such  specifications  are
available.  Other grades  may be used, provided it is first ascertained that the
reagent is of sufficiently high purity  to  permit  its  use without lowering the
accuracy of the determination,

      5.2   General

            5.2.1   Methanol,   CH3OH - HPLC grade.

            5.2.2   Organic-free reagent water - All references  to water in this
      method refer'to  organic-free reagent water,  as defined in Chapter One.

            5.2.3   1-Decanesulfonic acid,  sodium salt, C10H21S03Na - HPLC grade.

            5.2.4   Acetic acid (glacial), CH3COOH - reagent grade.

      5.3   Standard Solutions

            5.3.1   Tetrazene  - Standard Analytical Reference Material.

            5.3.2   Stock standard solution -  Dry tetrazene to  constant weight
      in a vacuum desiccator in the dark.   (Tetrazene is extremely explosive in
      the dry  state.  Do not dry more reagent than  is necessary to prepare stock
      solutions.)   Place  about 0.0010  g  (weighed  to  0.0001 g)  into  a  100-ml
      volumetric flask  and dilute to volume with methane!.  Invert flask several
      times until tetrazene is  dissolved.   Store  in freezer at  -10"C.   Stock
      solution is about 100 mg/L.   Replace stock  standard solution every week.

            5.3.3   Intermediate standard  solutions

                    5.3.3.1   Prepare a 4 mg/L standard  by  diluting  the stock
            solution 1/25 v/v  with methane!.

                    5.3.3.2   Pipet 0.5, 1.0,  2.0, 5.0, 10.0,  and 20.0 ml of the
            4  mg/L standard solution into  6 separate 100 mL volumetric flasks,
            and make up to volume with methane!.    Pipet  25.0 mL of  the  4 mg/L
            standard solution  into  a 50 mL volumetric  flask,  and make  up to
            volume with methane!.   This results  in intermediate  standards of
            about 0.02, 0.04,  0.08,  0.2, 0.4,  0.8,  2 and 4 mg/L.

                    5.3.3.3   Cool immediately on preparation in  refrigerator or
            ice bath.
                                   8331 -  3                         Revision 0
                                                                September 1994

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            5.3.4    Working  standard  solutions

                     5.3.4.1    Inject 4 ml of each of the intermediate standard
            solutions into 6.0 mL of water.  This results in concentrations of
            about 0.008, 0.016, 0.032, 0.08, 0.16, 0.3, 0.8 and 1.6 mg/L.

                     5.3.4.2   Cool immediately on preparation in refrigerator or
            ice bath.

      5.5   QC spike concentrate solution

            5.5.1    Dry  tetrazene to constant weight in a vacuum desiccator in
      the dark.  (Tetrazene is  extremely explosive in the dry state.  Do not dry
      any more than necessary  to  prepare standards.)   Place about  0.0011  g
      (weighed to 0.0001 g) into a 200-ml  volumetric flask and dilute to volume
      with methanol.  Invert flask several times until  tetrazene is dissolved.
      Store in  freezer  at -10"C.  QC  spike concentrate solution  is  about 55
      mg/L.   Replace stock standard solution every week.

            5.5.2    Prepare spiking solutions, at  concentrations appropriate to
      the concentration range of the  samples  being analyzed, by diluting the QC
      spike  concentrate  solution  with  methanol.   Cool  on  preparation  in
      refrigerator or ice bath.

      5.6   Eluent

            5.6.1    To   make   about   1  liter  of  eluent,   add   2.44   g  of
      1-decanesulfonic acid,  sodium  salt to  400/600 v/v methanol/water, and add
      2.0 ml of glacial  acetic acid.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to this Chapter,  Organic Analytes,
Section 4.1.

      6,2   Samples must be collected  and  stored  in glass  containers.  Follow
conventional sampling procedures.

      6.3   Samples must be kept below 4°C from the  time of collection through
analysis.


7.0   PROCEDURE

      7.1   Sample Preparation

            7.1.1    Filtration  of Water Samples

                     7.1.1,1   Place a  10 mL  portion of  each water  sample in a
            syringe and filter through a 0.5  pm Millex-HV filter unit.  Discard
            first 5 mL of filtrate,  and retain 5 mL for analysis.
                                   8331-4                         Revision 0
                                                                September 1994

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7.1.2    Extraction  and  Filtration of Soil Samples

         7.1.2.1   Determination of sample % dry weight - In certain
cases, sample results are desired based on dry-weight basis.  When
such data  is  desired,  a portion of sample for  this determination
should be  weighed out  at  the  same time  as  the portion  used for
analytical determination.

         WARNING:  The drying oven should be  contained in a hood or
                  vented.  Significant  laboratory contamination may
                  result  from   a heavily  contaminated  hazardous
                  waste sample.

            7.1.2.1.1   Immediately after weighing  the  sample for
         extraction,  weigh  5-10 g  of  the   sample  into  a  tared
         crucible.   Determine  the  % dry  weight  of the sample by
         drying overnight  at  105°C.  Allow to  cool  in a desiccator
         before weighing:

            % dry weight = g	of dry sample x  100
                               g of sample
fl
               7.1.2.2   Weigh 2 g soil subsamples into 125 ml Erlenmeyer
        asks with ground glass stoppers.

               7.1.2.3   Add  50  ml  of  55/45  v/v  methanol-water  with
      1-decanesulfonic acid, sodium salt added to make a 0.1 M solution.

               7.1.2.4   Vortex for 15 seconds.

               7.1.2.5   Shake for 5 hr at 2000 rpm on platform shaker.

               7.1.2.6   Place a 10 ml portion of  each  soil sample extract
      in a  syringe  and filter through  a 0.5  IJM Hillex-SR  filter unit.
      Discard first 5 ml of filtrate, and retain 5 ml for analysis.

7.2   Sample Analysis

      7.2.1    Analyze  the samples using  the  chromatographic  conditions
given in Section 7.2.1.1.  Under* these conditions,  the r*etentjon time GC
tetrazene is 2.8 min.  A  sample  chromatogram,  including other compounds
likely  to   be  present  in  samples  containing  tetrazene,  is shown  in
Figure 1.

               7.2.1.1   Chromatographic Conditions

               Solvent:              0.01  M  1-decanesulfonic  acid,  in
                                    acidic methanol/water (Section 5.5)
               Flow  rate:            1.5 mL/min
               Injection volume:     100 /iL
               UV Detector:          280 nm
                       8331 - 5                         Revision 0
                                                    September 1994

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      7.3   Calibration of HPLC

            7.3.1    Initial  Calibration  -    Analyze  the  working  standards
      (Section 5.3.4), starting with the  0.008 mg/L  standards and ending with
      the 0.30 mg/L standard.   If the percent relative standard deviation (%RSD)
      of the mean response  factor (RF) for each analyte  does  not exceed 20%, the
      system is calibrated  and  the analysis of samples may proceed.   If the %RSD
      for any  analyte exceeds  20%,  recheck  the system  and/or recalibrate with
      freshly prepared calibration solutions.

            7.3.2    Continuing Calibration - On a daily basis, inject 250 nl of
      stock standard  into  20 ml water.   Keep solution  in  refrigerator until
      analysis.  Analyze  in triplicate (by overfilling loop)  at the beginning of
      the day, singly after each  five samples,  and singly after the last sample
      of the  day.   Compare response factors  from the  mean peak  area  or peak
      height  obtained over  the  day  with  the  response   factor  at  initial
      calibration.  If these values do  not agree within 10%, recalibrate.


8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control  procedures.

      8.2   Prior to preparation of stock solutions, methanol should be analyzed
to determine possible interferences with  the  tetrazene peak.   If the methanol
shows contamination, a different batch  of methanol should be used.

      8.3   Method Blanks

            8.3.1   Method blanks for the analysis of  water samples should be
      organic-free reagent water carried through all sample storage and handling
      procedures.

            8.3.2   Method blanks  for  the analysis of soil  samples  should be
      uncontaminated soil carried through all  sample storage, extraction,  and
      handling procedures.


9.0   METHOD PERFORMANCE

      9.1   Method 8331  was tested  in a laboratory over a period of four days.
Spiked organic-free reagent water and standard soil were  analyzed in duplicate
each  day  for  four  days.   The  HPLC  was  calibrated  daily  according  to  the
procedures given  in Section 7.1. Method performance data are  presented in Tables
1 and 2.
10.0  REFERENCES

1.    Walsh,   M.E.,   and   T.F.
      Tetrazene in Water," U.S
Jenkins,   "Analytical   Method  for  Determining
Army Corps of  Engineers,  Cold  Regions  Research
      & Engineering Laboratory, Special  Report 87-25,  1987.
                                   8331 - 6
                                     Revision  0
                                 September 1994

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2.    Walsh,  H.E.,  and  T.F.   Jenkins,   "Analytical  Method  for  Determining
      Tetrazene in Soil," U.S.  Army  Corps  of  Engineers, Cold Regions Research &
      Engineering Laboratory, Special Report 88-15, 1988.


11.0  SAFETY

      11.1   Standard  precautionary  measures  used  for handling  other organic
compounds should  be sufficient  for  safe handling of  the  analytes  targeted by
Method 8331.
                                   8331  -  7
    Revision 0
September 1994

-------
               FIGURE 1
                            TNT
    12
£
I  8
                     0.064
                Absorbonc* Units
                8331  - 8
    Revision 0
September  1994

-------
            TABLE 1.
METHOD PERFORMANCE,  WATER MATRIX
Spike
Cone.
(M9/U
0.00



7.25



14.5



29



72.5



145



290



725



OVERALL
Avq % Recovery
Repl icate
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Repl icate 2
% Recovery
Repl icate 1
% Recovery
Repl icate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate !
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery

Day 1
0.0
NA
0.0
NA
8.9
122
6.6
91
14.6
101
14.8
102
31.8
110
29.5
102
71.1
98
71.2
98
140.6
97
138.5
96
289.4
100
282.0
97
737.6
102
700. Z
97

Day 2
0.0
NA
0.0
NA
7.8
108
9.9
137
14.6
101
14.1
97
30.0
103
29.7
102
73.6
102
71.3
98
143.8
99
140.8
97
288.5
99
284.2
98
707.2
98
695.8
96

Day 3
0.0
NA
0.0
NA
7.4
102
8.5
117
13.8
95
14.1
98 .
30.8
106
30.4
105
75.7
104
70.7
98
144.7
100
140.9
97
997 _ ^
100
281.9
97
714.3
99
714.2
99

Average
Day 4 %
0.0
NA
0.0
NA
9.4
130
6.7
92
14.6
101
15.2
105
28.7
99
30.7
106
73.9'
102
71.6
99
142.1
98
136.9
94
289.8
100
282.5
97
722.0
100
716.3
99

Recovery

NA

NA

116

109

99

100

105

104

101

98

98

96

100

97

99

97
102
            8331  -  9
    Revision 0
September 1994

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            TABLE 2
METHOD PERFORMANCE, SOIL MATRIX
Spike
Cone.
(M9/L)
0.00



1.28



2.56



5.12



12.8



25.6



OVERALL
Avq % Recovery
Repl icate
Replicate 1
% Recovery
Replicate 2
% Recovery
Repl icate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery

Day 1
0.0
NA
0.0
NA
0.6
49
1.2
92
1.4
56
1.5
59
2.9
57
3.0
58
7.8
61
8.0
62
17.2
67
16.7
65

Day 2
0.0
NA
0.0
NA
0.9
73
0.7
56
1.5
58
2.0
79
3.0
58
3.0
59
7.6
59
8.4-
66
16.7
65
16.8
66

Day 3
0.0
NA
0.0
NA
0.6
48
0.8
63
1.6
61
1.4
56
2.9
55
3.5
69
7.8
61
7.7
60
17.4
68
17.6
69

Average
Day 4
0.0
NA
0.0
NA
1.0
74
0.7
56
1.6
61
1.3
50
2.9
56
3.1
60
8.1
63
8.2
64
17.3
68
17.2
67

% Recovery

NA

NA

61

67

59

61

57

61

61 .

63

67

67
52
           8331  -  10
    Revision 0
September 1994

-------
                                     HETHOD 8331
                           TETRAZENE  BY REVERSE  PHASE
                HIGH  PERFORMANCE  LIQUID CHROHATOGRAPHY (HPLC)
  r
        Start
   7.1 .1 Filter 10 ml
 water sample; discard
first 5 rnL; analyze last 5.
  7.1.2.1  Determine
    % dry weight.
  7.1.2.2 - 7.1.2.5
   Extract 2 g soil
 with 50 ml solvent.
  7.1 .2.6 Filter 10 rnL
 extract; discard 5 mL;
   analyze last 5 mL.
 7.2 Analyze samples
using chrornatographic
    conditions in
   Section 7.2.1 .1.
                                     7.3.1 Initial calibration:
                                        Analyze working
                                           standards
                                        {Section 5.3.3}.
                                                                       7.3.1 Recheck system/
                                                                        recalibrate with new
                                                                        calibration solution.
                                              7.3.2
                                            Continuing
                                            Calibration
                                        c
                                               Stop
                                      8331  -  11
                                           Revision  0
                                      September 1994

-------

-------
                                  METHOD  8410

                 GAS  CHROMATOGRAPHY/FOURIER TRANSFORM  INFRARED
              (GC/FT-IR) SPECTRQHETRY FOR SEMIVOLATILE ORGANICS:
                               CAPILLARY COLUMN
1.0   SCOPE AND APPLICATION

      1.1   This method covers the automated identification, or compound class
assignment  of  unidentifiable compounds,  of solvent extractable  semivolatile
organic  compounds  which  are  amenable  to  gas  chromatography,  by  GC/FT-IR.
GC/FT-IR can be  a  useful  complement to GC/MS  analysis  (Method 8270).   It is
particularly well suited for the identification of specific  isomers that are not
differentiated  using  GC/MS.   Compound class  assignments are made using infrared
group  absorption   frequencies.    The  presence  of  an  infrared  band  in  the
appropriate group  frequency  region may  be  taken  as evidence  of the possible
presence of a particular compound class,  while its absence may be construed as
evidence that the compound class in question is  not present.  This evidence will
be further strengthened by the presence  of confirmatory  group frequency bands.
Identification  limits of the  following compounds have been demonstrated by this
method.
      Compound Name                               CAS No.'
      Acenaphthene                                 83-32-9
      Acenaphthylene                              208-96-8
      Anthracene                                  120-12-7
      Benzo(a)anthracene                           56-55-3
      Benzo(a)pyrene                               50-32-8
      Benzoic acid                                 65-85-0
      Bis(2-chloroethoxy)methane                  111-91-1
      Bis(2-chloroethyl) ether                    111-44-4
      Bis(2-chloroisopropy1) ether              39638-32-9
      Bis(2-ethylhexyl) phthalate                 117-81-7
      4-Bromophenyl  phenyl ether                  101-55-3
      Butyl  benzyl phthalate                       85-58-7
      4-Chloroaniline                             106-47-8
      4-Chloro-3-methylphenol                       59-50-7
      2-Chloronaphthalene                          91-58-7
      2-Chlorophenol                               95-57-8
      4-Chlorophenol                              106-48-9
      4-Chlorophenyl phenyl  ether                7005-72-3
      Chrysene                                    218-01-9
      Dibenzofuran                                132-64-9
      Di-n-butyl phthalate                         84-74-2
      1,2-Dichlorobenzene                          95-50-1
      1,3-Dichlorobenzene                         541-73-1
      1,4-Dichlorobenzene                         106-46-7
      2,4-Dichlorophenol  .                        120-83-2
                                   8410 -  1                          Revision 0
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      Compound Name                               CAS No.a


      Dimethyl phthalate                          131-11-3
      Diethyl phthalate                            84-66-2
      4,6-Dinitro-2-methyl phenol                  534-52-1
      2,4-Dinitrophenol                            51-28-5
      2,4-Dinitrotoluene                          121-14-2
      2,6-Dinitrotoluene                          606-20-2
      Di-n-octyl phthalate                        117-84-0
      Di-n-propyl phthalate                       131-16-8
      Fluoranthene                                206-44-0
      Fluorene                                     86-73-7
      Hexachlorobenzene                           118-74-1
      1,3-Hexachlorobutadiene                      87-68-3
      Hexachlorocyclopentadiene                    77.47.4
      Hexachloroethane                             67-72-1
      Isophorone                                   78-59-1
      2-Methylnaphthalene                          91-57-6
      2-Methylphenol                                95-48-7
      4-Methylphenol                               106-44-5
      Naphthalene                                  91-20-3
      2-Nitroaniline                               88-74-4
      3-Nitroaniline                               99-09-2
      4-Nitroaniline                              100-01-6
      Nitrobenzene                                 98-95-3
      2-Nitrophenol                                88-75-5
      4-Nitrophenol                               100-02-7
      N-Nitrosoditnethylamine                       62-75-9
      N-Nitrosodiphenylamine                       86-30-9
      N-Nitroso-di-n-propylamine                  621-64-7
      Pentachlorophenol                            87-86-5
      Phenanthrene                                 85-01-8
      Phenol                                      108-95-2
      Pyrene                                      129-00-0
      1,2,4-Trichlorobenzene                      120-82-1
      2,4,5-Trichlorophenol                         95-95-4
      2,4,6-Trich'Orophenc":                         88-05-2


      a  Chemical  Abstract Services  Registry Number.

      1.2    This method is applicable to  the determination of most extractable,
semivolatile-organic  compounds  in wastewater,  soils and  sediments,  and solid
wastes.  Benzidine can  be  subject to losses  during solvent concentration and GC
analysis;   a-BHC,  jS-BHC,  Endosulfan I  and  II,  and  Endrin  are  subject  to
decomposition under the alkaline conditions of the  extraction step; Endrin is
subject to decomposition during GC analysis; and Hexachlorocyclopentadiene and
N-Nitrosodiphenylamine may decompose during extraction and GC analysis.  Other
extraction and/or instrumentation procedures should be considered for unstable
analytes.


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      1.3   The identification limit of this method may depend  strongly upon the
level and  type of gas  chromatographable  (GC)  semivolatile extractants.   The
values listed in Tables  1 and 2 represent the minimum quantities of semivolatile
organic compounds which have been identified by the specified GC/FT-IR system,
using this  method and under routine environmental analysis conditions.  Capillary
GC/FT-IR wastewater identification limits of 25 pg/L  may be achieved for weak
infrared absorbers  with this  method,  while the  corresponding  identification
limits for strong infrared  absorbers is 2 M9A-   Identification limits for other
sample matrices can be calculated from the wastewater  values  after choice of the
proper sample workup procedure {see Sec. 7.1}.


2.0   SUMMARY OF METHOD

      2.1   Prior to  using this method,  the  samples  should  be prepared  for
chromatography  using the  appropriate  sample preparation  and  cleanup methods.
This  method describes  chromatographic  conditions  that  will  allow for  the
separation  of  the  compounds in the extract  and  uses FT-IR for  detection  and
quantitation of the target analytes.


3.0   INTERFERENCES

      3.1   Glassware  and other sample  processing hardware  must  be thoroughly
cleaned to  prevent contamination and misinterpretation.  All of these materials
must be demonstrated to be free from interferences under the conditions of the
analysis  by  running   method   blanks.    Specific  selection  of  reagents  or
purification of solvents by distillation in  all-glass systems  may be required.

      3.2   Matrix  interference will  vary considerably  from source to  source,
depending upon  the diversity of the residual  waste  being  sampled.  While general
cleanup techniques  are  provided as part  of this  method, unique  samples  may
require additional cleanup to isolate the analytes of interest from interferences
in order to achieve maximum sensitivity.

      3.3   4-Chlorophenol  and 2-m'trophenol  are subject to interference from co-
el ut ing compounds.

      3,4   Clean all glassware as soon as possible after use by rinsing with the
Isst solvent used.  GIssswsrs should  be sss^sd/stcrsd  ^r  s. c^esn  srw"*"0!n?ier!'t
immediately  after   drying   to prevent  any  accumulation  of  dust  or  other
contaminants.
4.0   APPARATUS AND MATERIALS

      4.1   Gas  Chromatographic/Fourier   Transform   Infrared   Spectrometric
Equipment

            4.1.1   Fourier Transform-Infrared  Spectrometer  -  A  spectrometer
      capable of collecting at least one scan set per second at 8 cm"1 resolution
      is  required.    In  general,   a  spectrometer  purchased  after  1985,  or
      retrofitted  to meet  post-1985 FT-IR improvements, will  be  necessary to


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            meet the detection limits  of this  protocol.  A state-of-the-art A/D
            converter is required, since it has been shown that the signal-to-
            noise  ratio of  single  beam  GC/FT-IR  systems  is A/D  converter
            1imi ted.

            4,1.2  GC/FT-IR Interface - The interface should be lightpipe volume-
      optimized for the  selected chromatographic conditions (lightpipe volume of
      100-200 pi for capillary columns).  The shortest possible inert transfer
      line (preferably fused silica)  should be used to interface the end of the
      chromatographic column  to  the  lightpipe.   If  fused silica  capillary
      columns are employed, the end of the GC column can serve as the transfer
      line  if  it  is  adequately  heated.   It  has  been  demonstrated that  the
      optimum lightpipe  volume is  equal  to  the full width at half height of the
      GC eluate peak.

            4.1.3  Capillary Column  -  A fused  silica  DB-5  30  m  x 0.32  mm
      capillary column with 1.0 ^m film thickness (or equivalent).

            4.1.4  Data  Acquisition - A computer system dedicated to the GC/FT-IR
      system  to  allow  the continuous  acquisition  of  scan sets  for  a  full
      chromatographic run.   Peripheral data storage systems  should be available
      (magnetic  tape and/or  disk)  for  the  storage  of  all  acquired  data.
      Software should be available to allow the acquisition and  storage of every
      scan set to locate the  file  numbers  and  transform high S/N scan sets,  and
      to provide a real  time reconstructed chromatogram,

            4.1.5  Detector - A cryoscopic, medium-band  HgCdTe (MCT)  detector
      with the smallest  practical focal area.  Typical narrow-band MCT detectors
      operate  from 3800-800  cm"1,  but   medium-band  MCT  detectors  can  reach
      650 cm"1.   A  750 cm"1 cutoff  (or lower)  is  desirable  since  it  allows  the
      detection of  typical  carbon-chlorine stretch and  aromatic  out-of-plane
      carbon-hydrogen vibrations  of environmentally  important  organo-chlorine
      and polynuclear aromatic  compounds.   The  MCT detector sensitivity (D)"
      should be > 1 x 1010  cm.

            4.1.6  Lightpipe -  Constructed  of  inert materials, gold coated,  and
      volume-optimized  for  the desired  chromatographic  conditions  (see  Sec.
      7.3).

            4.1.7  Gas  Chrornatograph   - The   FT-13  spectrometer  shcu'ld   be
      interfaced to a temperature  programmable gas  chromatograph  equipped with
      a  Grob-type (or equivalent) purged splitless injection  system suitable for
      capillary glass columns or an on-column  injector system.

            A short,  inert  transfer line should interface the gas  chromatograph
      to the  FT-JR  lightpipe  and, if applicable,  to  the GC detector.   Fused
      silica GC columns  may be directly interfaced to the lightpipe  inlet  and
      outlet,

      4.2   Dry Purge Gas - If the spectrometer  is  the  purge-type,  provisions
should be made to provide  a suitable  continuous source of dry purge-gas  to  the
FT-IR spectrometer.
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      4,3   Dry  Carrier Gas  -  The  carrier  gas should  be passed  through  an
efficient cartridge-type drier.

      4.4   Syringes -  1-^U  10-ML-


5.0   REAGENTS

      5.1   Reagent grade inorganic chemicals shall be used in  all tests. Unless
otherwise  indicated,  it is  intended that all  reagents  shall conform  to the
specifications of the Committee on Analytical Reagents of the American Chemical
Society, where  such specifications  are  available.  Other grades may  be used,
provided it is first ascertained that the reagent is  of sufficiently high purity
to permit its use without lessening the accuracy of the determination.

      5.2   Organic-free reagent water.   All  references to water in this method
refer to organic-free reagent water, as defined in Chapter One,

      5.3   Solvents

            5.3.1  Acetone,  CH3COCH3  - Pesticide quality, or equivalent.

            5.3,2  Hethylene chloride, CH2C12  - Pesticide quality, or equivalent.

      5.4   Stock Standard  Solutions  (1000  mg/L)  - Standard  solutions  can  be
prepared from pure standard materials or purchased as a certified solution.

            5.4,1  Prepare stock standard sol utions by accurately weighing 0.1000
      + 0.0010 g of pure material.  Dissolve the material  in pesticide quality
      acetone  or other  suitable  solvent and  dilute to  volume  in  a  100  ml
      volumetric flask.  Larger volumes  can  be  used at  the convenience of the
      analyst.  When compound  purity  is assayed to be 96 percent or greater, the
      weight may be  used without  correction  to  calculate  the  concentration  of
      the stock standard. Commercially  prepared stock standards may be used at
      any concentration if  they  are certified  by  the  manufacturer or  by  an
      independent source,

            5.4.2  Transfer  the stock standard solutions into bottles with Teflon
      lined screw-caps.  Store at  4°C and protect  from  light.   Stock standard
      solutions  should  be  checked  frequant'y  rcr~  signs  cf degradation  or
      evaporation, especially just prior to preparing calibration standards from
      them.

            5.4.3  Stock standard solutions  must be replaced after 6 months  or
      sooner if  comparison  with  .quality  control  reference samples indicates a
      problem.

      5.5   Calibration Standards and Internal Standards -  For  use in situations
where GC/FT-IR will  be used for primary quantitation of  analytes  rather than
confirmation of GC/MS identification,

            5.5.1  Prepare calibration  standards that contain  the compounds  of
      interest,  either singly or mixed  together.   The  standards  should  be


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      prepared at concentrations that will  completely bracket the working range
      of  the  chromatographic   system  (at  least  one  order of magnitude  is
      suggested).

            5.5.2  Prepare  internal  standard  solutions.    Suggested  internal
      standards  are   1-Fluoronaphthalene,  Terphenyl,  2-Chlorophenol,  Phenol,
      Bis(2-chloroethoxy)methane, 2,4-Dichlorophenol, Phenanthrene, Anthracene,
      and Butyl benzyl  phthalate.  Determine the internal standard concentration
      levels from the minimum identifiable quantities.   See Tables 1 and 2.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the introductory material  to this chapter, Organic Analytes, Sec.
4.1.


7.0   PROCEDURE

      7.1   Sample Preparation - Samples must be prepared by one  of the following
methods prior to GC/FT-IR analysis.

      Matrix                        Methods

      Water                         3510,  3520
      Soil/sediment                 3540,  3541, 3550
      Waste                         3540,  3541, 3550, 3580

      7.2   Extracts  may be cleaned up by Method 3640,  Gel-Permeation Cleanup.

      7.3.   Initial  Calibration - Recommended GC/FT-IR  conditions:

      Scan time:                                At least 2 scan/sec.
      Initial column  temperature and hold time: 40°C for 1 minute.
      Column temperature program:               40-280DC at 10°C/min.
      Final column temperature hold:            280°C.
      Injector temperature:                     280-300°C.
      Transfer line temperature:                270°C.
      Lightpipe:                                280°C.
      Injector:                                 Grab-type,  split"ess  or  on-
                                                column.
      Sample volume:                             2-3 ^L.
      Carrier gas:                              Dry helium at about 1 mL/rain.

      7.4   With an oscilloscope, check the detector centerburst  intensity versus
the manufacturer's specifications.  Increase the source voltage, if necessary,
to  meet  these  specifications.    For  reference purposes,   laboratories  should
prepare a plot of time versus detector voltage over at  least a  5 day period.

      7.5   Capillary  Column  Interface Sensitivity Test  -  Install  a 30  m x
0.32 mm  fused  silica  capillary  column   coated  with  1.0  Mm  of  DB-5  (or
equivalent).   Set the lightpipe and transfer  lines at  280°C,  the  injector at
225°C and  the GC detector  at 280°C  (if used).  Under splitless Grob-type or on-


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column injection conditions,  inject  25 ng of nitrobenzene, dissolved in 1 pi of
methylene chloride.  The nitrobenzene should be identified by the on-line library
software search within  the  first five hits (nitrobenzene  should  be  contained
within the search library).

      7.6   Interferometer -  If  the interferometer is air-driven, adjust  the
interferometer drive air pressure to manufacturer's specifications.

      7.7   MCT Detector Check -  If the  centerburst intensity is  75  percent or
less of the mean intensity of the plot maximum  obtained by the procedure of Sec.
7.4, install a new  source  and check the MCT centerburst with  an  oscilloscope
versus the manufacturer's specifications (if available).   Allow  at  least five
hours of new source operation before data acquisition.

      7.8   Frequency Calibration - At  the  present time,  no consensus  exists
within the  spectroseopic community on a suitable frequency reference standard for
vapor-phase FT-IR.  One reviewer has  suggested the use of indene as an  on-the-fly
standard.

      7.9   Minimum  Identifiable  Quantities  -  Using the  GC/FT-IR  operating
parameters specified in  Sec.  7.3, determine the minimum identifiable  quantities
for the compounds  of interest.

            7.9.1   Prepare a plot of  lightpipe temperature versus MCT centerburst
      intensity (in volts or  other  vertical height units).  This plot  should
      span the temperature range between  ambient and the lightpipe thermal limit
      in increments of about 20°C.  Use this plot for daily QA/QC (see Sec-. 8.4).
      Note that modern GC/FT-IR interfaces (1985 and later)  may have  eliminated
      most of this  temperature effect.

      7.10  GC/FT-IR Extract  Analysis

            7.10.1       Analysis  - Analyze the dried methylene chloride extract
      using the chromatographic  conditions  specified  in  Sec.  7.3  for  capillary
      column interfaces.

            7.10.2       GC/FT-IR  Identification  -  Visually  compare the analyte
      infrared  (IR)  spectrum  versus the search library  spectrum of  the most
      promising  on-line  library  search   hits.   Report,  as  identified,  those
      analytes with  IR frequencies for the five  (maximum number) most  intense IR
      bands (S/N >  5) which are within ±  5.0 cm"1 of the  corresponding bands in
      the library spectrum.   Choose  IR bands which are sharp and well  resolved.
      The software  used  to locate spectral peaks should employ the peak "center
      of gravity" technique.  In addition, the  IR frequencies of the analyte and
      library spectra should  be  determined with the same  computer software.

            7.10.3       Retention Time Confirmation - After  visual  comparison of
      the analyte and library  spectrum as described in Sec.  7.10.2, compare the
      relative retention times (RRT) of the analyte  and an authentic standard of
      the most promising  library search hit.   The  standard and analyte  RRT
      should agree  within + 0.01 RRT units when both are determined at the same
      chromatographic conditions.
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            7.10.4      Compound Class  or Functionality  Assignment  -  If  the
      analyte cannot be unequivocally identified, report its compound class or
      functionality.  See Table  3  for gas-phase group frequencies to be used as
      an aid for compound class  assignment.   It should be noted that FT-IR gas-
      phase group stretching frequencies are  0-30 cm"1 higher in frequency than
      those of the condensed phase.

            7.10.5      Quantitation - This protocol  can be used to confirm GC/MS
      identifications, with  subsequent quantitation.  Two FT-IR quantitation and
      a supplemental GC detector technique are also provided.

                   7.10.5.1    Integrated Absorbance Technique  - After analyte
            identification,   construct   a   standard   calibration  curve   of
            concentration versus  integrated  infrared  absorbance.    For  this
            purpose, choose  for  integration only  those FT-IR  scans which are at
            or above the peak half-height.  The calibration curve should span at
            least one order of magnitude  and  the working range should bracket
            the analyte concentration.

                   7.10.5.2   Maximum  Absorbance Infrared   Band  Technique  -
            Following analyte identification, construct a standard calibration
            curve of concentration  versus  maximum infrared band intensity.  For
            this purpose, choose an intense,  symmetrical  and well  resolved IR
            absorbance band.

                   (Note that IR transmission  is  not proportional to concentra-
            tion).  Select the FT-IR scan with the  highest  absorbance to plot
            against concentration.   The  calibration curve should span at least
            one order  of  magnitude and  the  working range should  bracket  the
            analyte  concentration.    This   method  is   most   practical   for
            repetitive, target compound analyses.  It is more  sensitive than the
            integrated absorbance  technique.

                   7.10.5.3   Supplemental  GC  Detector  Technique  -  If a  GC
            detector is used in tandem with  the  FT-IR  detector,  the following
            technique may be used:  following analyte identification,  construct
            a standard calibration curve  of concentration  versus integrated peak
            area.   The calibration curve  should span   at  least one  order of
            magnitude  and  the   working  range  should  bracket  the  analyte
            concentration.  This methoo is most practical  for  repetitive, target
            compound analyses.


8.0   QUALITY CONTROL

      8.1   Refer  to Chapter One   for  specific  quality control  procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized.  If extract cleanup was performed, follow the QC
in Method 3600 and in the specific cleanup method.

      8.2   One Hundred Percent Line Test - Set the GC/FT-IR operating conditions
to those employed  for the Sensitivity Test  (see Sec. 7.5).  Collect 16 scans over
the entire detector spectral  range.  Plot  the  test and measure the peak-to-peak


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noise between 1800 and 2000  cm"1.  This  noise should be <0.15%.  Store this plot
for future reference.

      8.3   Single Beam Test - With the GC/FT-IR at  analysis conditions, collect
16 scans  in  the  single beam mode.  Plot the  co-added  file  and compare with a
subsequent file acquired in  the  same fashion several minutes  later.  Note if the
spectrometer  is   at  purge  equilibrium.    Also check  the plot  for  signs  of
deterioration of the lightpipe potassium bromide windows.  Store this plot for
future reference.

      8.4   Align  Test  -  With  the lightpipe and  MCT  detector  at  thermal
equilibrium, check the  intensity of the  centerburst versus the signal temperature
calibration curve.  Signal  intensity deviation from the predicted intensity may
mean thermal equilibrium has not  yet been  achieved,  loss of detector coolant,
decrease  in  source  output, or  a  loss  in signal  throughput resulting  from
lightpipe deterioration.

      8.5   Mirror Alignment -  Adjust the interferometer mirrors to attain the
most  intense signal.    Data collection  should not  be  initiated until  the
interferogram is  stable.   If necessary,  align the mirrors  prior  to each GC/FT-IR
run.

      8.6   Lightpipe - The  lightpipe and lightpipe windows should be protected
from moisture and  other  corrosive substances  at all  times.   For this  purpose,
maintain the lightpipe temperature above the maximum GC program temperature but
below its thermal  degradation limit.   When  not in  use,  maintain  the lightpipe
temperature slightly above ambient.  At  all times, maintain a  flow of dry, inert,
carrier gas through the lightpipe.

      8.7   Beamsplitter -  If  the spectrometer is thermostated, maintain the
beamsplitter at  a temperature  slightly  above ambient at all  times.    If the
spectrometer is  not thermostated,  minimize  exposure  of the  beamsplitter  to
atmospheric water vapor.


9.0   METHOD PERFORMANCE

      9.1   Method 8410  has  been  in use at the U.S.  Environmental  Protection
Agency Environmental  Monitoring  Systems Laboratory  for  more  than  two years.
Portions of  it have been reviewed  by  key  members  of  the FT-IR  spectroscopic
community (9).   Side-by-side comparisons  with  6C/MS  sample  analyses  indicate
similar demands  upon analytical  personnel   for the two  techniques.   Extracts
previously subjected to 6C/MS analysis  are  generally compatible with GC/FT-IR.
However,  it should be  kept  in mind  that  lightpipe  windows are typically water
soluble.   Thus,  extracts must be  vigorously dried  prior to analysis,

      9.2   Table 4 provides performance data  for  this method.
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10.0  REFERENCES

1.    Handbook  for  AnalyticalQuality   Control   In  Water  and  Wastewater
      Laboratories;  U.S.  Environmental  Protection  Agency.    Environmental
      Monitoring and Support Laboratory.  ORD Publication Offices of Center for
      Environmental Research  Information:  Cincinnati,  OH,  March  1979; Sec. 4,
      EPA-600/4-79-019.

2.    Freeman, R.R.  Hewlett  Packard  Application  Note:  Quan titative Analy s i s
      Using a Purged Splitless Injection •Technique; ANGC 7-76.

3.    Cole,  R.H.    Tables  of Wavenumbers   for  the  Calibrat Ion   of  Infrared
      Spectrometers; Pergamon:  New York, 1977.

4.    Grasselli,  J.G.;  Griffiths,  P.R.; Hannah, R.W.  "Criteria for Presentation
      of Spectra from Computerized IR Instruments"; AppJ. Spectrgsc.  1982, 36,
      87.

5.    Nyquist, R.A.  The I n t e rp r e t a t ion	of	Vapor-Ph. a s e	In f r a red Spectra.  Group
      Frequency. Data; Volume I. Sadtler Laboratories:  Philadelphia,  PA, 1984.

6.    Socrates,  G.  Infrared  Characieri s.ti c  Group  Frequencies;  John  Wiley and
      Sons:  New York,  NY, 1980.

7.    Bellamy, L.J. The Infrared Spectra of Complex Organic Molecules; 2nd ed.;
      John Wiley and Sons:  New York,  NY,  1958.

8.    Szymanski,  H.A.   Infrared Band  Handbook, Volumes I  and II;  Plenum:  New
      York, NY,  1965.

9,    Gurka, D.F.   "Interim Protocol for the  Automated Analysis of Semivolatile       \
      Organic  Compounds  by   Gas  Chromatography/Fourier  Transform-Infrared
      Spectrometry"; Appl. Spectrosc.  1985, 39, 826.

10.    Griffiths,  P.R.;   de Haseth,  J.A.; Azarraga,  L.V.  "Capillary GC/FT-IR";
      Anal. Chem.  1983, 55,  1361A.

11.    Griffiths,  P.R.;  de Haseth, J.A.  Fourier Transform-Infrared Spectrometry;
      Wiley-Interscience:   New York,  NY, 1986.

12.    Gurka, D.  F.; Farnham,  I.; Potter, B. B.; Pyle,  S.; Titus, R. and Duncan,
      W.    "Quantitation     Capability     of   a     Directly    Linked    Gas
      Chromatography/Fourier Transform Infrared/Mass Spectrometry System"; Anal.
      Chem., 1989, 6_i,  1584.
                                   8410  -  10                         Revision 0
                                                                September 1994

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                             TABLE 1,
FUSED SILICA CAPILLARY COLUMN  GAS  CHROMATOGRAPHIC/FOURIER TRANSFORM
   INFRARED  IDENTIFICATION LIMITS FOR BASE/NEUTRAL EXTRACTABLES
Compound
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a}anthracene
Benzo(a)pyrene
Bis(2-chloroethyl} ether
Bis(Z-chloroeth'oxy) methane
Bis(2-chloroisopropyl ) ether
Butyl benzyl phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chloroanil ine
4-Chlorophenyl phenyl ether
Chrysene
Di-n-butyl phthalate
Dibenzofuran
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Di-n-propyl phthalate
1 , 2 -Di ch 1 orobenzene
1 , 3 -Di chl orobenzene
1 ,4-Dichlorobenzene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Bis-(2-ethylhexyl) phthalate
Fluoranthene
Fluorene
Hexachl orobenzene
Hexachl orocycl opentadiene
Hexachl oroethane
I , 3 -Hexachl orobut ad iene
Isophorone
2-Methyl naphthalene
Naphthalene
Nitrobenzene
N-Nitrosodi methyl ami ne
N-Nitrosodi -n-propyl amine
N-Nitrosodi phenyl ami ned
2-Nitroanil ine
3-Nitroaniline
Identification
ng injected8
40(25}
50(50}
40(50)
(50}
(100)
70(10)
50(10)
50(10}
25(10}
40(5)
110
40
20(5)
(100)
20(5}
40
20(5)
20(5)
25(10)
25(5)
50
50
50
20
20
25(10}
100(50}
40(50)
40
120
50
120
40
110
40(25)
25
20(5}
50(5)
40
40
40
Limit
M9/Lb
20(12.5}
25(25)
20(25)
(25)
(50)
35(5)
25(5}
25(5}
12.5(5}
20(2.5}
55
20
10(2.5)
(50)
10(2.5)
20
10(2.5)
10(2.5}
12.5(5}
12.5(2.5}
25
25
25
10
10
12.5(5)
50(25)
20(25)
20
60
25
60
20
55
20(12.5)
12.5
10(2.5}
25(2.5}
20
20
20
j>max, cm"
799
799
874
745
756
1115
1084
1088
1748
1238
851
1543
1242
757
1748
1192
1748
1751
1748
1748
1458
779
1474
1547
1551
1748
773
737
1346
814
783
853
1690
3069
779
1539
1483
1485
1501
1564
1583
                             8410  - 11
    Revision 0
September 1994

-------
                                    TABLE  1.
                                  (Continued)
      Compound
                              Identification  Li mit
                            ng injected3        ~--
i/max, cm
4-Nitroanil ine
Phenanthrene
Pyrene
1 , 2 , 4-Trichl orobenzene
40
50(50)
100(50)
50(25)
20
25(25)
50(25)
25(12,5)
1362
729
820
750
   Determined using on-column injection and the conditions of Sec,  7.3.  A medium
   band HgCdTe detector [3800-700 cm"1;  D'value  (,ipeak  1000  Hz,  1)  4.5  x  1010 cm
   Hz1/2W"1] type with  a  0.25  mm2 focal chip was  used.   The GC/FT-IR system is a
   1976 retrofitted model.   Values in  parentheses  were determined  with a new
   (1986)  GC/FT-IR system. A narrow band HgCdTe detector  [3800-750cm"1; D'value
   (ylpeak 1000 Hz, 1)  4 x 1010 cm Hz1'2!*!"1] was  used.   Chromatographic conditions
   are those of Sec. 7.3.  ,
   Based on a 2 /iL injection of  a one liter  sample  that has been extracted and
   concentrated to a volume of  1.0  ml.   Values in  parentheses  were determined
   with a new (1986) GC/FT-IR system. A narrow band HgCdTe detector  [380Q-75Qcnf
   1    '                               10      1/2"1
   Dvalue  (/Ipeak  1000  Hz,  1)  4  x  10
conditions are those of Sec. 7.3.
                                         cm Hz1/2W"]  was used.   Chromatographic
c  Most intense IR peak and suggested quantitation peak.

d  Detected as diphenylamine,
                                   8410 - 12
                                                                  Revision 0
                                                              September 1994

-------
                                   TABLE 2.
      FUSED SILICA CAPILLARY COLUMN GAS CHROMATOGRAPHIC/FOURIER TRANSFORM
   INFRARED ON-LINE AUTOMATED IDENTIFICATION LIMITS FOR ACIDIC EXTRACTABLES
                                    Identification Limit
Compound
ng injected8
j/max, cm
                                                                             1c
Benzoic acid
2-Chlorophenol
4-Chlorophenold
4-Chloro -3 -methyl phenol
2~Methylphenol
4-Methyl phenol
2,4-Dichlorophenol
2,4-Dinitrophenol
4, 6-Dinitro-2 -methyl phenol
2-Nitrophenold
4-Nitrophenol
Pentachl orophenol
Phenol
2, 4, 6-Trichl orophenol
2,4,5-Trichlorophenol
70
50
100
25
50
50
50
60
60
40
50
50
70
120
120
35
25
50
12.5
25
25
25
30
30
20
25
25
35
60
60
1751
1485
1500
1177
748
1177
1481
1346
1346
1335
1350
1381
1184
1470
1458
a  Operating conditions are the same as those cited in Sec. 7.3.

b  Based on a 2 j^L injection of a one liter sample that has been extracted and
   concentrated to a volume of 1.0 mL.

c  Most intense IR peak and suggested quantitation peak.

d  Subject to interference from co-eluting compounds.
                                   8410 -  13
                                      Revision 0
                                  September  1994

-------
         TABLE 3.
GAS-PHASE GROUP FREQUENCIES
Number of
Functionality Class Compounds
Ether





Ester


Nitro





Nitrile

Ketone


Amide
Al kyne
Acid




Phenol







Aryl , Al kyl
Benzyl , Al kyl
Diaryl
Dial kyl
Alkyl, Vinyl

Unsubstituted Aliphatic
Aromatic
Monosubstituted Acetate
Aliphatic



Aromatic

Al iphatic
Aromatic
Aliphatic (acyclic)
(a,@ unsaturated)
Aromatic
Substituted Acetamides
Al iphatic
Aliphatic

D imeri zed- Al iphatic
Aromatic

1,4-Disubstituted


1,3-Disubstituted


1,2-Di substituted

14
3
5
12
3

29
11
34
5



18

9
9
13
2
16
8
8
24
22
2
10
10
15
15
15
10
10
10
6

Frequency
Range, van"1
1215-1275
1103-1117
1238-1250
1084-1130
1204-1207
1128-1142
1748-1761
1703-1759
1753-1788
1566-1594
1548-1589
1377-1408
1327-1381
1535-1566
1335-1358
2240-2265
2234-2245
1726-1732
1638-1699
1701-1722
1710-1724
3323-3329
3574-3580
1770-1782
3586-3595
3574-3586
1757-1774
3645-3657
1233-1269
1171-1190
3643-3655
1256-1315
1157-1198
3582-3595
1255-1274
                                    (continued)
         8410  -  14
    Revision 0
September 1994

-------
TABLE 3.
(Continued)
Functionality
Alcohol






Araine


Al kane



Aldehyde





Benzene





Class
Primary Aliphatic


Secondary Aliphatic

Tertiary Al iphatic

Primary Aromatic
Secondary Aromatic
Al iphatic




Aromatic


Aliphatic


Monosubstituted





Number of
Compounds
20
11
16
17
10
10
6
15
5
10
14



12
12
12
6
6
6
7
24
24
11
23
25
Frequency
Range, ^cm1
3630-3680
1206-1270
1026-1094
3604-3665
1231-1270
3640-3670
1213-1245
3480-3532
3387-3480
760- 785
2930-2970
2851-2884
1450-1475
1355-1389
1703-1749
2820-2866
2720-2760
1742-1744
2802-2877
2698-2712
1707-1737
1582-1630
1470-1510
831- 893
735- 790
675- 698
8410 - 15
    Revision 0
September 1994

-------
TABLE 4.  FUSED SILICA CAPILLARY COLUMN 6C/FT-IR QUANTITATION RESULTS

Concentration
'Range, and
Identification
Compound Limit, nga
Acenaphthene
Acenaphthylene
Anthracene
Benzo( a) anthracene
Benzole acid
Benzo(a)pyrene
Bi s (2-chl oroethoxy) methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
4-Chloroaniline
4-Chl oro-3-rnethyl phenol
2-Chl oronaphthal ene
2-Chlorophenol
4-Chlorophenole
4-Chlorophenyl phenyl ether
Chrysene
Dibenzofuran
Di-n-butyl phthalate
1 , 2-Di chl orobenzene
1 ,3-Dichlorobenzene
1 5 4-Di chl orobenzene
2,4-Dichlorophenol
Dimethyl phthalate
Dimethyl phthalate
Dinitro-2-methyl phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Oinltrotol uene
Di-n-octyl phthalate
Bis(2-ethylhexyl) phthalate
Fluoranthene
Fluorene
Hexachl orobenzene
1 ,3-Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachl oroethane
Isophorone
2 -Methyl naphthalene
25-250
25-250
50-250
50-250
50-250
100-250
25-250
25-250
50-250
25-250
25-250
25-250
25-250
100-250
25-250

25-250
100-250
25-250
25-250
25-250
25-250
25-250
25-250
25-250
25-250
50-250
50-250
25-250
25-25C
25-250
25-250
25-250
25-250
50-250
50-250
100-250
25-250
25-250
50-250
Maximum
Absorbanceb
Correlation
Coefficient51
0.9995
0.9959
0.9969
0.9918
0.9864
0.9966
0.9992
0.9955
0.9981
0.9995
0.9999
0,9991
0.9975
0.9897
0.9976

0.9999
0.9985
0.9697
0.9998
0.9937
0.9985
0.9994
0.9964
0.9998
0.9998
0 . 9936
0.9920
0.9966
D. 9947
0^9983
0.9991
0.9983
0.9987
0.9981
0.9960
0.9862
0.9986
0.9984
0.9981
Integrated
Absorbance0
Correlation
Coefficientd
0.9985
0.9985
0.9971
0.9921
0.9892
0.9074
0.9991
0.9992
0.9998
0.9996
0.9994
0.9965
0.9946
0.9988
0.9965

0.9997
0.9984
0.8579
0.9996
0.9947
0.9950
0.9994
0.9969
0.9996
0.9997
0.9967
0.9916
0.9928
0.9966
0.9991
0.9993
0.9966
0.9989
0.9995
0.9979
0.9845
0.9992
0.9990
0.9950
                                                               (continued)
                              8410 -  16
    Revision 0
September 1994

-------
                             TABLE  4.   (Continued)




Compound
2-Methylphenol
4-Methylphenol
Naphthalene
2-Nitroanil ine
3-Nitroanil ine
4-Nitroanil ine
Nitrobenzene
2-Nitrophenole
4-Nitrophenol
N-Nitrosodimethyl amine
N-Nitrosodiphenyl amine
N-Nitrosodi -n-propyl amine
Pentachlorophenol
Phenanthrene
Phenol
Pyrene
1,2,4-Trichlorobenzene
25455-Trichlorophenol
2,4,6-Trichlorophenol
Concentration
Range, and
Identification
Limit, nga
25-250
25-250
25-250
25-250
25-250
25-250
25-250

50-250
25-250
25-250
25-250
50-250
25-250
25-250
50-250
50-250
25-250
25-250
Maximum
Absorbanceb
Correl ation
Coefficientd
0.9972
0.9972
0.9956
0.9996
0.9985
0,9936
0.9997

0.9951
0.9982
0.9994
0.9991
0.9859
0.9941
0.9978
0.9971
0.9969
0.9952
0.9969
Integrated
Absorbancec
Correlation
Coefficient51
0.9964
0.9959
0.9954
0.9994
0.9990
0.9992
0.9979

0.9953
0.9993
0.9971
0.9995
0.9883
0 . 9989
0.9966
0.9977
0,991
0.9966
0.9965
a  Lower end of range is at or near the identification limit.

fa  FT-IR scan with highest absorbance plotted against concentration,

c  Integrated absorbance of combined  FT-IR  scans which occur at  or  above the
   chromatogram peak half-height.

d  Regression analysis  carried out  at four concentration levels.   Each  level
   analyzed in duplicate.   Chromatographic conditions are stated in Sec.  7.3.

e  Subject to interference from co-eluting compounds.
                                  8410  -  17
    Revision 0
September 1994

-------
                                            METHOD  8410
              GAS  CHROMATOGRAPHY/FOURIER TRANSFORM  INFRARED  (GC/FT-IR)
             SPECTROMETRY FOR  SEMIVOLATILE  ORGANICS:   CAPILLARY  COLUMN
^
t
7,1 Sample
preparation
prior to
GC/FT-tft
analysrs.
^
1
7.2 Optional
Permeation
Cleanup of
extracts.
                       7.6 Adjust
                     interfBrorriBttr
                        drive air
                       pressure.
                                     Yes
  I
  7.3 Initial
 Calibration;
recommended
  GC/FT-IR
 conditions.
  7.4 Check
  detector
 eenterburst
  intensity.
                      7.7 Replace
                        Source.
7.5 Column
 Interface
Sensitivity.
                     7.8 Frequency
                      Calibration.
                    7.9 Determine
                    min. identifiable
                     quantities of
                      analyte of
                       interest.
                     7.9.1 Prepare
                        plot of
                     lightpipe T vs.
                   MCT centerburst
                       intensity.
                                             7.10.1  Analyze
                                              extracts using
                                              conditions of
                                              Section 7.3.
                                           7.10.2 OC/FT-IR
                                            identification;
                                           compare analyte
                                             IR spectrum;
                                               report.
                                               7.10.3
                                           Retention Time;
                                           compare RRT of
                                             analyte with
                                              standard.
                                           7.10.4 Report
                                           compound class
                                            if no library
                                           match is found.
                                           7.10.7 Standard
                                              calibration
                                            curve of cone.
                                           vs. max. iR band
                                              intensity.
                                             8410  -  18
                                                                   7.10.6 Standard
                                                                   calibration curve
                                                                     of cone. vs.
                                                                     integrated IR
                                                                     afasorbance.
                                                                      7.10.8 Is
                                                                     GC Detector
                                                                    used in tandem
                                                                      with FT-IR
                                                                      detector?
   7.10.8
Supplemental
GC Detector
 Technique.
                                                                                           Revision  0
                                                                                     September  1994

-------
                                 METHOD 9020B

                          TOTAL ORGANIC HALIDES (TOX)


1.0   SCOPE AND APPLICATION

      1.1    Method 9020  determines Total Organic Hal ides  (TOX) as chloride in
drinking water  and ground waters.  The method uses carbon  adsorption  with a
microcoulometric-titration detector.

      1.2    Method  9020  detects  all  organic  halides containing  chlorine,
bromine, and  iodine that  are adsorbed  by granular  activated carbon under the
conditions of the method.  Fluorine-containing species are not determined  by this
method.

      1.3    Method 9020 is applicable to samples whose  inorganic-halide concen-
tration does  not  exceed the organic-halide  concentration  by more than  20,000
times.

      1.4    Method  9020  does  not  measure  TOX   of   compounds  adsorbed  to
undissolved solids.

      1.5    Method 9020  is restricted  to use by, or under the supervision of,
analysts experienced in the operation of a pyrolysis/microcoulometer and in the
interpretation of the results.

      1.6    This method is provided as  a recommended procedure.  It  may  be used
as a  reference  for comparing the  suitability of other methods thought to be
appropriate for measurement of TOX (i.e., by comparison of sensitivity, accuracy,
and precision of data).

2.0   SUMMARY OF METHOD

      2.1    A  sample  of water  that  has been  protected  against the loss of
volatiles by the elimination of headspace in the sampling container,  and that is
free  of  undissolved  solids,  is  passed through a  column  containing 40  mg of
activated carbon.   The  column is  washed  to remove any trapped inorganic halides
and is then  combusted  to convert  the  adsorbed organohalides  to  HX, which is
trapped and titrated electrolytica'Ty ys'ng a mlcrocoulometrlc detector.

3.0   INTERFERENCES

      3.1    Method  interferences may  be  caused  by  contaminants,  reagents,
glassware,  and other sample-processing  hardware.   All  these materials  must be
routinely demonstrated  to  be free from interferences under the conditions of the
analysis by running method blanks.

             3.1.1   Glassware   must   be  scrupulously  cleaned.    Clean  all
      glassware as soon as possible after use by treating with chromate cleaning
      solution.    This  should be  followed  by detergent washing in  hot  water.
      Rinse with tap water and distilled water and drain dry;  glassware which is
      not volumetric should,  in addition, be heated in a muffle  furnace at 400°C
      for 15  to  30 min.   (Volumetric  ware  should  not be  heated in  a  muffle

                                   9020B -  1                      Revision 2
                                                                  Septenfcer 1994

-------
      furnace.)   Glassware  should  be  sealed and stored in a clean environment
      after  drying  and cooling to  prevent  any accumulation of  dust  or other
      contaminants.

             3.1.2    The use of high-purity reagents and gases helps to minimize
      interference problems.

      3.2    Purity of the  activated carbon must be verified before use.  Only
carbon samples that register less than  1,000 ng CV/40 mg should be used.  The
stock of  activated  carbon  should  be  stored in its  granular form in  a glass
container with a Teflon seal.  Exposure to the air must be minimized, especially
during and after milling  and sieving the activated  carbon.  No more than a 2-wk
supply should  be prepared  in advance.   Protect carbon at all  times  from all
sources of halogenated organic vapors.  Store prepared  carbon  and packed columns
in glass containers with Teflon seals.

      3.3    Particulate matter will prevent the passage of the sample through
the adsorption  column.   Particulates  must, therefore, be  eliminated  from the
sample.   This must be  done as gently as possible, with  the least possible sample
manipulation, in  order to  minimize the loss of volatiles.   It  should  also be
noted that the measured TOX will  be  biased by the exclusion of  TOX from compounds
adsorbed onto the particulates.  The following  techniques may be used to remove
particulates; however, data users must  be  informed of the techniques  used and
their possible effects on  the  data.  These techniques are listed  in  order of
preference:

             3.3.1    Allow the  particulates to settle in the sample container
      and decant the  supernatant liquid  into the adsorption system.

             3.3.2    Centrifuge sample and  decant  the supernatant liquid into
      the adsorption  system.

             3.3.3    Measure Purgeable Organic Hal ides (POX)  of sample (see SW-
      846 Method 9021) and Non-Purgeable Organic Hal ides  (NPOX, that is, TOX of
      sample that  has been purged  of  volatiles)  separately,  where the  NPOX
      sample is centrifuged or filtered.

4.0   APPARATUS AND MATERIALS

      4.1    Adsorption system (a  schematic diagram of the adsorption system Is
shown in Figure 1):

             4.1.1    Adsorption module:  Pressurized  sample and nitrate-wash
      reservoirs.

             4.1.2    Adsorption columns:  Pyrex, 5-cm-long x 6-mm-O.D.  x
      2-mm-I.D.

             4.1.3    Granular activated  carbon  (GAC):  Filtrasorb-400,  Calgon-
      APC or equivalent,  ground or milled, and screened to a 100/200 mesh range.
      Upon combustion of  40 mg of GAC, the apparent halide background should be
      1,000 ng Cl" equivalent or less.
                                   9020B  -  2                       Revision 2
                                                                  September 1994

-------
              4.1.4   Cerafelt  (available  from Johns-Manville) or  equivalent:
       Form  this  material  into  plugs  to  fit the adsorption module  and  to  hold
       40 mg of GAC in the  adsorption columns.

              CAUTION: Do not touch this  material with your fingers. Oily residue
              will  contaminate  carbon.

              4.1.5   Column holders.

              4.1.6   Class A volumetric flasks:  100-mL and 50-mL.

       4.2     Analytical  system:

              4.2.1   Microcoulometric-titration   system:      Containing  the
       following  components (a  flowchart of the analytical  system is  shown in
       Figure  2):

                      4.2.1.1    Boat sampler:  Muffled at 800°C for at least 2-
              4 min and  cleaned  of any residue  by  vacuuming  after  each run.

                      4.2.1.2    Pyrolysis  furnace.

                      4.2.1.3    Hicrocoulometer with  integrator,

                      4.2.1.4    Titration  cell.

              4.2.2   Recording device.

5.0    REAGENTS

       5.1     Reagent  grade  chemicals  shall  be  used  in all  tests.    Unless
otherwise  indicated,  it is  intended that all  reagents shall  conform to the
specifications of the Committee on Analytical  Reagents  of the American  Chemical
Society, where such specifications are available.  Other grades  may  be used,
provided it is first ascertained that the reagent is of sufficiently high  purity
to permit its use  without  lessening  the accuracy of the  determination.

       5.2     Reagent water.   All references to water  in this method  refer to
reagent water, as  defined  in Chapter One.

       5.3     Sodium sulfite  (0.1  H), Na2S03:   Dissolve  12.6  g ACS  reagent grade
Na2S03  in  reagent water  and dilute to 1  L,

       5.4     Concentrated  nitric acid (HN03).

       5.5     Nitrate-wash  solution (5,000 mg N03~/L), KN03:  Prepare a  nitrate-
wash solution by transferring  approximately  8.2 g of potassium nitrate  (KN03)
into a 1-liter  Class A volumetric  flask and  diluting  to volume  with reagent
water.

       5.6     Carbon dioxide  (C02):  Gas, 99.9% purity.

       5.7     Oxygen (02):  99.9%  purity.


                                   9020B -  3                        Revision 2
                                                                   September 1994

-------
      5.8     Nitrogen  (N2):  Prepurified.

      5.9     Acetic  acid  in water (70%), C2H402:   Dilute 7 volumes of glacial
acetic acid with 3 volumes  of reagent water.

      5.10    Trichlorophenol solution, stock (1 nL = 10 ^tg Cl ):  Prepare a  stock
solution fay accurately  weighing accurately 1.856 g  of trichlorophenol into a 100-
mL Class A volumetric  flask.  Dilute to  volume with methanol.

      5.11    Trichlorophenol solution, calibration (1  iA. - 500 ng CV), C6H3C130:
Dilute 5 mL of the trichlorophenol stock solution  to  100 ml with methanol.

      5.12    Trichlorophenol standard, instrument calibration:  First, nitrate-
wash a single column packed with  40  mg  of activated carbon,  as instructed for
sample analysis,  and  then  inject the  column  with 10  /uL of the calibration
solution.

      5.13    Trichlorophenol standard, adsorption  efficiency (100 y,g CV/liter):
Prepare an adsorption-efficiency standard by injecting 10 jiL  of stock solution
into 1 liter  of reagent water.

      5.14    Blank  standard:   The  methanol used to  prepare the calibration
standard should be used as the blank standard.

6.0   SAMPLE  COLLECTION, PRESERVATION, AND HANDLING

      6.1     All samples must be collected using a sampling plan that addresses
the considerations discussed in Chapter Nine.

      6.2     All samples should be collected in bottles with Teflon  septa (e.g..,
Pierce #12722 or equivalent)  and be protected  from  light.   If  this  is not
possible, use  amber glass 250-mL bottles  fitted with Teflon-lined caps.   Foil may
be substituted  for  Teflon  if  the sample is not  corrosive.    Samples  must be
preserved by  acidification  to  pH  
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 may  increase  on  storage  of the sample.   Samples should be stored at 4'C
 without  headspace,

 7.2     Calibration:

        7.2.1    Check the  adsorption  efficiency of  each  newly prepared
 batch of carbon by analyzing 100 ml of the adsorption  efficiency standard,
 in  duplicate, along  with  duplicates of the  blank  standard.   The net
 recovery should  be within  10%  of the standard  value.

        7.2.2    Nitrate-wash  blanks  (method  blanks):     Establish  the
 repeatability of the method background each day by first  analyzing several
 nitrate-wash  blanks.   Monitor this background  by  spacing nitrate-wash
 blanks between each group  of ten pyrolysis determinations.  The nitrate-
 wash  blank values  are  obtained on  single columns  packed with40mgof
 activated  carbon.   Wash  with the  nitrate  solution, as  instructed for
 sample analysis, and then  pyrolyze the carbon.

       7.2.3    Pyrolyze duplicate instrument-calibration standards and the
 blank  standard  each  day  before  beginning  sample   analysis.   The  net
 response  to  the  calibration  standard  should  be   within  10%  of  the
 calibration-standard value. Repeat analysis of the instrument-calibration
 standard after each  group of ten  pyrolysis  determinations  and  before
 resuming  sample  analysis, and  after  cleaning  or   reconditioning  the
 titration cell or pyrolysis system.

 7.3    Adsorption  procedure:

       7.3.1    Connect  two columns in series,  each  containing  40 mg of
 100/200-mesh activated carbon.

       7.3,2    Fill  the sample reservoir  and pass   a metered amount of
 sample through the activated-carbon columns at a rate of approximately
 3 mL/tnin.

       NOTE:  100 ml of sample  is the preferred volume for concentrations
       of TOX between 5 and 500 M9/U 50 ml for 501  to 1000 M9/U and 25
       ml for 1001 to 2000 ^g/L.  If the anticipated TOX is greater than
       2000 M9/U  dilute  the  sample so  that 100 ml  will contain between
       1 and 50  pg TOX.

       7.3.3    Wash  the columns-in-series  with  2 ml of  the 5,000-mg/L
 nitrate solution at a  rate  of approximately 2 mL/min to displace inorganic
 chloride ions.

 7.4    Pyrolysis procedure:

       7.4.1    The contents  of  each column  are pyrolyzed  separately.
After being  rinsed with  the  nitrate  solution,  the columns  should be
 protected from the  atmosphere  and other sources  of  contamination until
 ready for further analysis.
                            9020B  -  5                       Revision 2
                                                            September 1994

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              7,4,2    Pyrolysis of the sample is accomplished in two stages.  The
      volatile  components  are  pyrolyzed in  a CQ2-rieh  atmosphere  at  a  low
      temperature to  ensure the conversion  of brominated trihalomethanes to a
      titratable species.  The less volatile components  are then pyrolyzed at a
      high temperature in an 02-rich atmosphere.

              7.4.3    Transfer the contents of each column to the quartz boat for
      individual analysis.

              7.4,4    Adjust gas flow according to manufacturer's  directions.

              7,4.5    Position the sample for  2 min in the 200°C  zone  of the
      pyrolysis tube.

              7.4.6    After Z min, advance the boat into  the 800°C zone (center)
      of the  pyrolysis furnace.   This  second and  final  stage  of pyrolysis may
      require from 6 to 10 min to complete.

      7.5     Detection:  The effluent gases  are directly analyzed in the micro-
coulometric-titration cell.   Carefully follow manual instructions for optimizing
cell performance.

      7.6     Breakthrough:   The  unpredictable  nature  of the  background bias
makes  it  especially  difficult  to  recognize  the extent  of   breakthrough  of
organohalides from one column to another.  All  second-column measurements for a
properly  operating   system   should  not  exceed 10%  of  the  two-column  total
measurement.   If  the 10% figure  is  exceeded,  one of three events  could have
happened:    (1)  the  first  column was overloaded  and  a legitimate measure  of
breakthrough  was  obtained,  in  which  case  taking a  smaller  sample  may  be
necessary;  (2)  channeling or some other  failure  occurred,  in which  case  the
sample may need to be rerun; or (3) a high random  bias occurred, and the result
should be rejected  and  the  sample rerun.   Because it  may not  be  possible  to
determine which event occurred, a sample analysis should be repeated often enough
to gain confidence in results.  As a general  rule,  any analysis that is rejected
should be repeated whenever a sample is available.  In  the event that repeated
analyses show that the second column consistently exceeds the 10% figure and the
total is too  low for  the  first  column to  be saturated  and the  inorganic Cl  is
less than 20,000  times the  organic chlorine value, then  the result  should  be
reported,  but the data user should be informed of the problem.   If the second-
column measurement is equal  to  or "ess than the nitrate-wash  blank value,  the
second-column value should be disregarded.
                                   9020B  -  6                       Revision 2
                                                                  September 1994

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       7.7     Calculations:  TOX as Cl" is calculated using the following formula:

           (C, - C3) + (C2 -  C3)
           	 =  M9/L Total  Organic Halide
                    V

       where:

              C., =  /ig CV on the first column in series;

              Cz =  /ig Cl" on the second column in series;

              C3 =  predetermined,  daily,  average, method-blank value
                    (nitrate-wash blank for a  40-mg carbon  column);  and

                V =  the  sample  volume  in liters.

8.0    QUALITY CONTROL

       8.1     Refer  to Chapter  One  for specific  quality  control guidelines.

       8.2     This method requires  that all  samples be run  in  duplicate.

       8.3     Employ a minimum  of two  blanks to establish the repeatability  of
the  method background,  and monitor  the  background  by  spacing  method  blanks
between each group  of eight analytical  determinations.

      8.4     After  calibration,  verify it with  an independently prepared check
standard.

      8.5     Run matrix  spike between every 10 samples and  bring  it  through the
entire sample preparation and  analytical  process.

9.0   METHOD PERFORMANCE

       9.1     Under  conditions of duplicate analysis,  the method detection limit
is 10 jLtg/L-

      9,2     Analyses of distilled  water,  uncontaminated  ground  water,  and
ground  water from  RCRA waste  management  facilities   spiked  with   volatile
chlorinated  organics  generally  gave  recoveries  between  75-100%  over  the
concentration range  10-500  p.g/1.  Relative standard  deviations were  generally
20% at concentrationssgreater  than 25 #g/L.  These  data are shown  in  Tables  1
and 2.

10.0  REFERENCES

1.    Gaskill, A. s   Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA  Contract No. 68-01-7075,  September 1986.
                                   9020B - 7                      Revision 2
                                                                  September 1994

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2.    Stevens, A.A., R.C. Dressman, R,K. Sorrel!,  and H.J. Brass, Organic Halogen
Measurements: Current Uses and Future  Prospects, Journal of  the  American Water
Works Association, pp. 146-154, April  1985.

3.    Tate, C.,  B.  Chow, et al., EPA Method  Study 32, Method 450.1, Total Organic
Hal ides (TOX), EPA/600/S4-85/080, NTIS: PB 86 136538/AS.
                                  9020B  - 8                       Revision  2
                                                                  Septenter 1994

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                       TABLE  1.  METHOD  PERFORMANCE DATA*
Spiked
Compound
Bromobenzene
Bromodichloromethane
Bromoform
Bromoform
Bromoform
Bromoform
Bromoform
Chloroform
Chloroform
Chloroform
Chloroform
Chloroform
Dibromodichloromethane
Dibromodichloromethane
Tetrachl oroethyl ene
Tetrachl oroethyl ene
Tetrachl oroethyl ene
trans -Di chl oroethyl ene
trans -Di chl oroethyl ene
trans -Di chl oroethyl ene
Matrix15
D.W.
D.W
D.W.
D.W.
G.W,
6.W.
G.W.
D.W.
D.W.
G.W.
G.W.
G.W.
D.W,
D.W.
G.W,
G.W.
G.W.
G.W.
G.W.
G.W.
TOX
Concentration
(M9/L)
443
160
160
238
10
31
100
98
112
10
30
100
155
374
10
30
101
10
30
98
Percent
Recovery
95
98
110
100
140
93
120
89
94
79
75
81
86
73
79
75
78
84
63
60
Results from Reference 2,

bG.W.  = Ground Water.
 D.W.  = Distilled Water.
                                   9020B - 9
Revision 2
Septetrfcer 1994

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                       TABLE 2. METHOD PERFORMANCE DATA3
Sample                   Unspiked                Spike                 Percent
Matrix                  TOX Levels               Level                Recoveries
                           (WJ/D


Ground Water               68, 69                  100                  98, 99
Ground Water               5, 12                  100                 110, 110
Ground Water               5, 10                  100                  95, 105
Ground Water               54, 37                  100                 111, 106
Ground Water               17, 15                  100                  98, 89
Ground Water               11, 21                  100                  97, 89
aResults  from Reference 3.
                                  9020B -  10                       Revision  2
                                                                   September 1994

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 Fig. 1. Schematic Diagram of Adsorption  System
*	D*3	-i
   S ample
   Reservoir
   (1  of 4)
Nitratt Wash
Reservoir
 GAC Column 1
 GAC Column I
                   9020B -  11
Revision 2
September 1994

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Fig. 2. Flowchart of Analytical System
                Sparging
                Device


T-itration
Cell


Pyrolysis
Furnace
                                Boat
                                Inlet


Mlcrocoulonieter
with Integrator


Strip Chart
Recorder
                                                     Adsorption
                                                     Nodule
                  9020B -  12
Revision 2
September 1994

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START
                                         METHOD  9020B

                                TOTAL ORGANIC HALIDES  (TOX)

7.1.1 Ta ke special
ear* in handl ing
mraple ta mm insure
vo la ti ie 1 as *
,,
7 1.2 ftdd »uifit«
to roduee res idual
chlorine; store at
4 C without
heads pace

7.2 1 Check
absorption
batch ol carbon

? 2 2 Analyze
nitrate-waak blanks
to es tab 1 ish
hackgr ound

72.3 Pyrclyre
dupi tea te
i n at t r uiti en t
calibratiar. -and
each day

7.3 I Connec t in
a e r i ea twc; coi utnr.s —
containing
activated ea? bon

7 3 2 Fill jamcle
reacrveir ; pass
•* sample thraugh
ac ti va ted ca arbors
coi xirens

7 3 3 Wash columns
wi th ni trate
sslutien

7 ^ 1 Protect
corvtassina ti on,

742 Pyroiyze
volatile component a
in C02-rich
atmosphere at low
t Empera tur 
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                                  METHOD 9056

            DETERMINATION OF INORGANIC AN IONS BY ION CHROHATOGRAPHY
 1.0   SCOPE AND APPLICATION

      1.1   This  method  addresses the sequential determination  of the anions
 chloride,  fluoride,  bromide,  nitrate, nitrite, phosphate,  and  sulfate in the
 collection solutions from the  bomb combustion of solid waste samples,  as well as
 all water samples.

      1,2   The method detection  limit (MDL),  the minimum concentration  of a
 substance that can be measured and reported with 99% confidence that the value
 is  above  zero,   varies  for  anions   as  a  function  of  sample  size  and  the
 conductivity scale used.  Generally, minimum detectable concentrations are in the
 range of 0.05 mg/L for F" and 0.1 mg/L  for Br", Cl",  N03",  N02", P043",  and S042" with
 a  100-#L sample  loop and  a  10-jumho  full-scale  setting  on  the conductivity
 detector.  Similar values may  be achieved by using a higher  scale setting and an
 electronic integrator. Idealized detection limits  of an order of magnitude lower
 have been determined  in  reagent water by  using  a  1-pmho/cm full-scale setting
 (Table  1).    The  upper  limit  of  the method  is  dependent  on   total  anion
 concentration and  may  be determined experimentally.  These limits may be  extended
 by appropriate dilution.

 2.0   SUMMARY OF METHOD

      2.1   A small  volume of combustate  collection solution or other water
 sample,  typically 2 to 3  ml, is  injected into an ion chromatograph to flush and
 fill a constant volume sample loop.   The sample is then injected  into  a stream
 of carbonate-bicarbonate eluent  of the same strength as the collection  solution
 or water sample.

      2.2   The sample is pumped through three different ion  exchange columns and
 into a conductivity detector.  The first two columns,  a precolumn or guard column
 and a  separator  column,  are  packed  with  low-capacity,  strongly basic anion
exchanger.  Ions are separated into  discrete bands based on their affinity for
 the exchange sites of the  resin.  The last column is a suppressor column that
 reduces  the background conductivity  of the eluent to  a low or negligible level
 and converts  the  anions  in  the  sample  tc  their corresponding  acids.   The
 separated anions in their acid  form are measured  using an electrical ^conductivity.
 cell.   Anions are  identified  based on their  retention  times compared  to known
 standards. Quantitation  is accomplished by measuring the peak height or  area and
 comparing it to a calibration curve  generated from known standards.

3.0   INTERFERENCES

      3.1   Any species with a retention time similar  to that of the desired ion
will interfere.   Large quantities of  ions  eluting close to the ion of  interest
will also result in an interference.  Separation can be improved by  adjusting the
eluent concentration and/or flow rate. Sample dilution  and/or the use of the
method of  standard additions  can also be  used.   For example, high  levels of
 organic  acids may be present in  industrial  wastes,  which  may  interfere  with


                                   9056 -  1                       Revision 0
                                                                  September 1994

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 inorganic anion analysis. Two common  species, formate and acetate,  elute between
 fluoride and chloride,

      3.2   Because  bromide and nitrate  elute very close  together,  they  are
 potential  interferences  for  each  other.   It is advisable not to have Br'/NQ3"
 ratios higher than 1:10 or 10:1  if  both anions are to be quantified.   If nitrate
 is observed to  be an interference with bromide,  use of an alternate  detector
 (e.g., electrochemical detector) is  recommended.

      3.3   Method interferences may be  caused by contaminants in the  reagent
water, reagents, glassware,  and other sample processing apparatus that  lead to
discrete artifacts or elevated baseline in  ion chromatograms.

      3.4   Samples  that contain  particles larger  than  0,45 pm  and  reagent
 solutions that  contain  particles  larger  than 0.20  urn require  filtration to
prevent damage to instrument columns and flow systems.

      3.5   If a packed bed  suppressor column is used, it will be slowly  consumed
during analysis and,  therefore, will need to be regenerated.  Use of either an
anion fiber  suppressor or an anion micromembrane suppressor eliminates the time-
consuming regeneration step through the use  of  a continuous  flow of regenerant.

4.0   APPARATUS AND MATERIALS

      4.1   Ion chromatograph,  capable  of delivering 2 to  5  ml  of eluent per
minute at a pressure of 200 to 700 psi  (1.3 to 4.8 MPa).   The  chromatograph shall
be equipped  with an injection valve, a IQQ-/J.L sample loop, and set up with the
following components, as schematically illustrated in Figure  1.

            4.1.1    Precolumn, a guard column placed before the separator column
      to protect  the separator  column from being  fouled by particulates or
      certain  organic constituents (4 x 50 mm,  Dionex P/N 030825 [normal run],
      or P/N 030830 [fast run], or equivalent).

            4.1.2   Separator   column,   a  column  packed  with  low-capacity
      pellicular anion exchange resin that  is styrene divinylbenzene-based has
      been found to be suitable for  resolving  F\  Cl", N02",  P04"3,  Br',  N03", and
      SQ4~2 (see Figure 2)  (4  x 250 mm, Dionex P/N  03827  [normal  run],  or P/N
      030831  [fast run],  or equivalent).

            4.1.3   Suppressor column,  a  column  that is capable of converting
      the eluent  and  separated anions to their  respective  acid forms (fiber,
      Dionex  P/N 35350, micromembrane, Dionex P/N 38019 or equivalent).

            4.1.4   Detector,    a    low-volume,    flowthrough,   temperature-
      compensated, electrical  conductivity cell  (approximately 6  /j.1 volume,
      Dionex,  or equivalent) equipped with a meter capable of  reading  from 0 to
      1,000 ^seconds/cm on  a linear  scale.

            4.1.5   Pump, capable of delivering a constant flow of approximately
      2 to 5  mL/min throughout the test and tolerating a pressure of  200 to
      700 psi  (1.3 to 4.8 MPa).
                                   9056 - 2                       Revision 0
                                                                  September 1994

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      4.2   Recorder,  compatible with  the  detector output  with  a full-scale
response time  in 2 seconds  or  less.

      4.3   Syringe, minimum capacity of 2 ml and equipped  with  a male pressure
fitting.

      4.4   Eluent and  regenerant  reservoirs,  suitable containers for storing
eluents and regenerant.   For example, 4 L collapsible bags can  be used.

      4.5   Integrator, to integrate the area under the chrornatogram.  Different
integrators can perform this  task  when  compatible with the electronics of the
detector  meter or  recorder.     If  an  integrator  is used,  the maximum  area
measurement must be within  the linear range of the integrator.

      4.6   Analytical  balance,  capable of weighing to the nearest 0.0001 g.

      4.7   Pipets, Class A volumetric flasks, beakers:  assorted sizes.

5.0   REAGENTS

      5.1   Reagent grade chemicals shall be used in all tests. Unless otherwise
indicated, it is intended that all  reagents  shall  conform to  the specifications
of the Committee on Analytical  Reagents  of the American Chemical Society, where
such specifications  are available.   Other grades may  be  used,  provided it is
first ascertained that the reagent  is of sufficiently high  purity to permit its
use without lessening the accuracy of the determination.

      5.2   Reagent water.   All  references  to  water in this method  refer to
reagent water,  as defined in Chapter One.  Column life may be extended by passing
reagent water through a 0.22-^im  filter  prior to use.

      5.3   Eluent, 0.003M  NaHC03/0.0024M Na2C03.   Dissolve 1.0080 g of sodium
bicarbonate (0.003M NaHCD3)  and 1.0176 g of sodium carbonate (0.0024M Na2C03) in
reagent water and dilute to 4 L with reagent water.

      5.4   Suppressor  regenerant solution.  Add  100 ml of IN H2S04 to  3  L of
reagent water in a collapsible bag and dilute to 4 L with reagent water.

      5.5   Stock solutions (1,000 mg/L).

            5.5.1    Bromide stock  solution (1.00  ml  =  1.00  mg  Br").    Dry
      approximately 2 g of sodium bromide  (NaBr) for 6 hours at 150°C, and cool
      in a desiccator.   Dissolve 1.2877 g of the  dried salt  in  reagent water,
      and dilute to 1 L with reagent water.

            5.5.2    Chloride stock solution (1.00 ml = 1.00 mg CV).  Dry sodium
      chloride (NaCl) for 1 hour at 600°C, and cool in a desiccator.  Dissolve
      1.6484 g of the dry salt in reagent  water, and dilute to 1 L with reagent
      water.

            5.5.3    Fluoride  stock  solution (1.00 ml = 1.00 mg F").   Dissolve
      2.2100 g of sodium fluoride (NaF)  in reagent water, and  dilute to 1 L with
      reagent water.   Store in chemical-resistant glass or polyethylene.

                                   9056 - 3                       Revision 0
                                                                  September 1994

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             5.5.4    Nitrate stock  solution  (1.00  ml =  1.00  mg  N03").    Dry
       approximately  2  g  of sodium nitrate  (NaN03)  at  105DC for  24  hours.
       Dissolve exactly  1.3707 g of  the dried  salt in  reagent water,  and  dilute
       to  1  L with reagent water.

             5.5.5    Nitrite stock  solution  (1.00 ml =  1.00 mg NO/).    Place
       approximately  2 g of sodium nitrate (NaN02)  in a 125 ml beaker  and  dry to
       constant weight (about 24 hours) in a desiccator containing concentrated
       H2S04.  Dissolve 1.4998 g of the dried salt in  reagent water,  and  dilute
       to  1  L with  reagent  water.   Store  in  a  sterilized glass  bottle.
       Refrigerate and prepare monthly.

             NOTE: Nitrite  is easily  oxidized,  especially in  the  presence  of
             moisture, and only fresh reagents are to  be used.

             NOTE:  Prepare  sterile  bottles  for  storing   nitrite  solutions  by
             heating  for 1 hour at 170°C  in  an air oven.

             5.5.6    Phosphate stock solution (1.00 ml = 1.00 mg P043"). Dissolve
       1,4330 g of potassium dihydrogen phosphate (KH2P04)  in reagent  water,  and
       dilute to 1 L with reagent water.   Dry sodium  sulfate (Na2S04)  for  1  hour
       at  105°C and cool in a desiccator.

             5.5.7    Sulfate  stock solution  (1.00 ml  = 1.00 mg  S042").  Dissolve
       1.4790  g  of the  dried  salt  in  reagent water, and dilute  to  1  L  with
       reagent water.

       5.6   Anion working  solutions.    Prepare  a  blank  and  at   least   three
different working solutions containing the following combinations of anions.  The
combination anion solutions must be  prepared in Class A volumetric flasks.   See
Table  2.

            5.6.1    Prepare  a  high-range  standard  solution  by diluting  the
       volumes of each anion specified in  Table  2  together to 1 L  with reagent
      water.

            5.6.2    Prepare the intermediate-range standard solution by diluting
       10.0 ml of the high-range standard solution (see Table 2) to 100 ml  with
       reagent water.

            5.6.3    Prepare the low-range standard solution by  diluting 20.0 ml
      of the intermediate-range standard solution (see Table 2) to 100 ml  with
      reagent water.

      5.7   Stability of standards.   Stock standards  are  stable for  at least 1
month when stored at 4°C.  Dilute working standards should be prepared weekly,
except those that contain nitrite  and  phosphate, which should be prepared  fresh
daily.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All  samples must  have  been  collected  using  a sampling  plan  that
addresses the considerations discussed in Chapter Nine of this manual.

                                   9056 - 4                       Revision  0
                                                                  September 1994

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      6.2   Analyze the  samples  as soon as possible after collection.  Preserve
by refrigeration at 4°C.

7.0   PROCEDURE

      7.1   Calibration

            7.1.1   Establish   ion   chromatographic   operating   parameters
      equivalent to those  indicated  in  Table  1.

            7.1.2   For each analyte of interest, prepare calibration standards
      at  a  minimum  of three   concentration  levels  and  a  blank  by  adding
      accurately measured  volumes of one or more stock standards to  a  Class  A
      volumetric flask  and  diluting to  volume with  reagent  water.    If  the
      working  range exceeds  the  linear range of the system,  a sufficient number
      of standards  must be analyzed to allow an accurate calibration curve to be
      established.   One  of the  standards  should  be  representative of a  concen-
      tration  near, but  above,  the method detection limit if  the  system is
      operated on an applicable attenuator range.  The other standards should
      correspond to the range of concentrations expected in the sample or should
      define the working range  of the  detector.   Unless the attenuator range
      settings  are proven  to   be  linear, each setting  must  be   calibrated
      individually.

            7.1.3   Using injections of 0.1 to  1.0  ml (determined by injection
      loop volume)  of each calibration  standard, tabulate peak height  or area
      responses against  the  concentration.   The results are used to  prepare  a
      calibration curve for  each  analyte.    During  this procedure,  retention
      times  must be recorded.

            7.1.4   The working  calibration  curve  must  be verified  on  each
      working  day,  or whenever  the anion  eluent  strength  is  changed,  and  for
      every  batch of samples.  If the response or retention time  for  any  analyte
      varies from  the expected  values  by more  than  + 10%, the  test  must be
      repeated,  using  fresh  calibration standards.   If the results  are still
      more than + 10%,  an entirely new calibration curve must be prepared  for
      that analyte.

            7.1.5   Nonlinear response  can  result when the  separator  column
      capacity is exceeded (overloading}.  Maximum column loading (all  anions)
      should not exceed  about 400 ppm.

      7.2   Analyses

            7.2.1    Sample preparation.  When aqueous samples  are injected,  the
      water  passes  rapidly through  the  columns,  and a negative "water  dip" is
      observed  that  may  interfere  with  the  early-eluting  fluoride   and/or
      chloride ions.  The water dip should not  be  observed in the  combustate
      samples;  the  collecting solution  is a concentrated eluent  solution that
      will  "match"  the eluent strength when diluted to 100-mL with reagent water
      according to  the bomb combustion procedure.   Any dilutions required in
      analyzing other  water  samples should be made  with the  eluent  solution.
      The water dip, if present,  may be removed by adding concentrated eluent to


                                  9056  - 5                       Revision  0
                                                                 September 1994

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all samples and standards.   When a  manual  system  is used, it is necessary
to  micropipet  concentrated  buffer into  each  sample.    The  recommended
procedures follow:

(1)   Prepare a 100-mL stock of eluent 100 times normal concentration by
      dissolving  2.5202  g  NaHC03 and 2.5438 g  NazC03  in  100-mL  reagent
      water.  Protect the volumetric flask from air.

(2)   Pipet 5 ml  of each sample into a  clean  polystyrene  micro-beaker.
      Micropipet 50 /iL of the concentrated buffer into the beaker and stir
      well.

Dilute the samples with eluent, if necessary,  to concentrations within the
linear range of the calibration,

      7.2.2   Sample  analysis.

              7.2.2.1    Start   the  flow of   regenerant   through  the
      suppressor column.

              7.2.2.2    Set up the recorder range for maximum sensitivity
      and any additional  ranges needed.

              7.2.2.3    Begin  to  pump  the eluent through  the  columns.
      After a stable baseline is obtained, inject a midrange standard.  If
      the peak  height  deviates  by more than 10% from that of the previous
      run, prepare fresh  standards.

              7.2.2.4    Begin  to  inject standards  starting  with  the
      highest concentration  standard and decreasing in concentration.  The
      first sample should be a quality control  reference sample  to check
      the calibrat ion.

              7.2.2.5    Using  the procedures  described in Step  7.2.1,
      calculate the regression  parameters  for the initial standard curve.
      Compare  these values  with those  obtained  in  the  past.    If they
      exceed the  control limits,  stop  the  analysis  and  look  for  the
      problem.

              7.2.2.6    Inject  a  quality control  reference sample.   A
      spiked sample or a sample of known content must  be  analyzed with
      each  batch  of  samples.    Calculate  the  concentration  from  the
      calibration curve  and compare the  known value.    If the  control
      limits are exceeded,  stop the analysis  until  the  problem is found.
      Recalibration is necessary.

              7.2.2.7    When an acceptable value has  been  obtained  for
      the quality control sample, begin  to inject the samples.

              7.2.2.8    Load  and  inject a  fixed  amount of  well-mixed
      sample.   Flush  injection  loop  thoroughly,  using each new  sample.
      Use the  same size loop  for standards  and samples.   Record  the
                             9056  -  6                       Revision 0
                                                            September 1994

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       resulting  peak size  in  area  or peak height  units.   An  automated
       constant volume  injection  system may also be  used,

               7.2.2.9     The width  of the retention time window used to
       make  identifications  should  be based  on measurements  of  actual
       retention  time variations of standards over  the  course  of  a day.
       Three times the  standard deviation  of a retention time can be used
       to calculate a suggested window size for  a compound.  However, the
       experience of the analyst should weigh heavily in the interpretation
       of chromatograins.

               7.2.2.10   If the  response for the peak exceeds the working
       range of the system, dilute the sample with an appropriate  amount of
       reagent water  and reanalyze.

               7,2.2.11   If the  resulting chromatogram  fails to produce
       adequate resolution,  or  if  identification  of specific  anions  is
       questionable,  spike  the  sample  with  an  appropriate amount  of
       standard and reanalyze.

       NOTE : Nitrate  and sulfate exhibit  the  greatest  amount of change,
       although all anions are affected to some degree.   In some  cases,
       this    peak    migration   can   produce    poor    resolution   or
       misidentification.

7.3    Calculation

       7.3.1    Prepare   separate  calibration  curves for  each   anion  of
interest by plotting peak size in area, or peak  height units of  standards
against concentration values.  Compute sample concentration by  comparing
sample peak response with the standard curve.

       7.3.2    Enter  the  calibration  standard  concentrations   and peak
heights from  the integrator  or  recorder  into a  calculator with  linear
least  squares capabilities.

       7.3.3    Calculate the following parameters:   slope (s),   intercept
(I), and correlation coefficient (r).  The  slope  and intercept  define a
relationship  between the concentration and  instrument  response  of the
form:
where:
       yj = predicted  instrument  response
       Sj = response slope
       Xj = concentration of  standard  i
       I = intercept
                             9056 - 7                       Revision 0
                                                            September 1994

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      Rearrangement of the above equation yields the concentration corresponding
      to an instrumental measurement:
                             Xj =  (ys - D/SJ   {2}

      where:

             ^  =  calculated  concentration  for a  sample
             y-t  =  actual  instrument  response  for  a  sample
             Sj  and  I are calculated slope and intercept  from calibration above.

            7.3.4    Enter the  sample peak  height  into  the  calculator,  and
      calculate the sample concentration in milligrams per liter.

8.0   QUALITY CONTROL

      8.1   All quality control data should be maintained and available for easy
reference and inspection.  Refer to Chapter One for additional quality control
guidelines.

      8.2   After every 10 injections,  analyze a midrange calibration standard.
If the instrument response has changed by more than 5%,  recalibrate.

      8.3   Analyze one in every ten samples in duplicate.  Take the duplicate
sample through the entire sample preparation and analytical process.

      8.4   A matrix spiked  sample  should  be run for each analytical  batch or
twenty samples, whatever is more frequent, to determine matrix effects.

9.0   METHOD PERFORMANCE

      9.1   Single-operator  accuracy  and precision for reagent,  drinking  and
surface water,  and mixed domestic  and  industrial wastewater are listed in Table
3.

      9.2   Combustate samples. These  data are based on  41 data points obtained
by six laboratories  who each analyzed four used crankcase oils  and  three fuel oil
blends with crankcase in duplicate.  The oil samples were combusted using Method
5050.  A data  point represents one duplicate analysis of a  sample.   One data
point was judged to be an outlier and was not included in the results.

            9.2.1    Precision.  The precision of the method as  determined by the
      statistical examination of interlaboratory test results is as follows:

            Repeatability - The difference between successive results obtained
      by the sample operator with  the  same apparatus under constant operating
      conditions on identical  test  material  would  exceed,  in  the long  run, in
      the normal and correct  operation  of the test  method, the following values
      only in 1 case in 20 (see Table 4):


      *where x is the average of two results in /ug/g.


                                    9056  - 8                       Revision 0
                                                                  September 1994

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                         Repeatability =20.9

            Reproducibllity - The difference between two single and independent
      results obtained by different operators working in different laboratories
      on identical test material would exceed, in the  long  run,  the  following
      values only in 1 case in 20:
                        Reproducibllity = 42.1


      *where x is the average value of two results  in M9/9-

            9.2.2    Bias.  The  bias  of  this method  varies with  concentration,
      as shown in Table 5:

                     Bias  = Amount  found - Amount expected

10.0  REFERENCES

1,    Environmental  Protection Agency.  Test Method for the Determination  of
Inorganic Anions in Water  by  Ion Chromatography.  EPA Method  300.0.   EPA-600/4-
84-017.  1984.

2.    Annual Book  of ASTM Standards,  Volume 11.01  Water D4327, Standard  Test
Method for Anions in Water by Ion  Chromatography, pp.  696-703.   1988.

3.    Standard Methods for the Examination of Water and Wastewater,  Method  429,
"Determination of Anions by Ion  Chromatography with  Conductivity Measurement,"
16th Edition of Standard Methods.

4.    Dionex, 1C 16  Operation and  Maintenance Manual, PN 30579, Dionex  Corp.,
Sunnyvale, CA  94086.

5.    Method  detection  limit   (MDL)  as  described  in  "Trace Analyses   for
Wastewater," J,  Glaser, D. Foerst,  G.  McKee, S.  Quave,  W. Budde, Environmental
Science and Technology, Vol.  15, Number  12,  p.  1426,  December 1981.

6.    Gaskill, A.;  Estes,  E.  D.; Hardison,  D.  L.; and  Myers, L.  E.   Validation
of Methods for Determining Chlorine in Used Oils and Oil Fuels.  Prepared for
U.S. Environmental  Protection Agency Office of Solid Waste.  EPA Contract No. 68-
01-7075, WA 80.   July 1988.
                                   9056 -  9                       Revision  0
                                                                  September 1994

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                                   TABLE  1.
                CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION
                            LIMITS IN REAGENT WATER
Retention8 Relative
time retention
Analyte min time
Fluoride 1
Chlorine 3
Nitrite-N 4
o-Phosphate-P 9
Nitrate-N 11
Sulfate 21
Standard conditions:
.2 1.0
.4 2.8
.5 3.8
.0 7.5
.3 9.4
.4 17.8

Columns - As specified in 4.1.1-4.1.3
Detector - As specified in 4.1.4
Eluent - As specified in 5.3
Methodb
detection limit,
mg/L
0.005
0.015
0.004
0.061
0.013
0.206

Sample loop - 1
Pump volume - 2.
Concentrations of mixed standard (mg/L)
            Fluoride 3.0
            Chloride 4.0
            Nitrite-N 10.0
o-Phosphate-P 9.0
Nitrate-N 30.0
Sulfate 50.0
"The retention time given for each anion  is based on the equipment and  analytical
conditions described in the method.  Use  of other analytical columns or different
elutant concentrations will effect retention times accordingly.

bMDL calculated from data obtained using  an attentuator setting of l-/umho/crti full
scale.   Other settings would produce an MDL proportional to their value.
                                   9055  -  10
            Revision 0
            Septentser 1994

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                                    TABLE  2.
         PREPARATION OF STANDARD  SOLUTIONS  FOR INSTRUMENT CALIBRATION
High
Range
Standard1
Fluoride (F")
Chloride (CT)
Nitrite (N02'J
Phosphate (PO/)
Bromide (Br")
Nitrate (N03'}
Sulfate (S042-)
10
10
20
50
10
30
100
Anion
concentration
mg/L
10
10
20
50
10
30
100
Intermediate- Low-range
range standard, standard,
mg/L mg/L (see
(see 5.6.2) 5.6.3)
1.0
1.0
2.0
5.0
1.0
3.0
10.0
0.2
0.2
0.4
1.0
0.2
0.6
2.0
'Milliliters of each  stock solution  (1.00 mL = 1.00 mg) diluted to 1 L (see sec.
 5.6,1).
                                   9056 -  11
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September 1994

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                                    TABLE  3.
                     SINGLE-OPERATOR ACCURACY  AND PRECISION
Sample
Analyte type
Chloride



Fluoride



Nitrate-N



Nitrite-N



o-Phosphate-P



Sulfate



RW
DW
SW
ww
RW
DW
SW
WW
RW
DW
SW
WW
RW
DW
SW
WW
RW
DE
SW
WW
RW
DW
SW
WW
Spike
mg/L
0,050
10,0
1.0
7.5
0.24
9.3
0.50
1.0
0.10
31.0
0.50
4.0
0.10
19.6
0.51
0.52
0.50
45.7
0.51
4.0
1.02
98,5
IC.C
12.5
Number
of
replicates
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
/
7
Mean
recovery,
%
97.7
98.2
105.0
82.7
103.1
87.7
74.0
92.0
100.9
100.7
100.0
94.3
97.7
103.3
88.2
100.0
100.4
102.5
94.1
97.3
102.1
104.3
» i _ . 5
134.9
Standard
deviation,
mg/L
0.0047
0.289
0.139
0.445
0.0009
0.075
0.0038
0.011
0.0041
0.356
0.0058
0.058
0.0014
0.150
0.0053
0.018
0.019
0.386
0.020
0.04
0.066
1.475
f\ -? rtr*
w , / Wh?
0.466
RW = Reagent water.
DW = Drinking water.
SW = Surface water.
WW = Wastewater.
                                   9056 - 12
                                        Revision 0
                                        Septerrter 1994

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                                   TABLE 4.
               REPEATABILITY  AND REPRODUCIBILITY  FOR CHLORINE  IN
              USED OILS BY BOMB OXIDATION AND ION CHROMATOGRAPHY
Average value,             Repeatability,          Reproducibility,
     M9/9                      M9/9                       M9/9
500
1,000
1,500
2,000
2,500
3,000
467
661
809
935
1,045
1,145
941
1,331
1,631
1,883
2,105
2,306
                                   TABLE 5.
              RECOVERY AND BIAS  DATA  FOR CHLORINE  IN USED OILS  BY
                    BOMB OXIDATION AND ION CHROMATOGRAPHY
            Amount        Amount
          Expected •         found           Bias,     Percent,
             M9/9           M9/g           M9/g         bias
               320            567             247          +77
               480            773             293          +61
               920          1,050             130          +14
             1,498          1,694             196          +13
             1,527          1,772             245          +16
             3,029          3,026              -3            0
             3,045          2,745            -300          -10
                                  9056  -  13                       Revision 0
                                                                  September 1994

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           FIGURE 1
SCHEMATIC OF ION CHROMATOGRAPH
                                                      WASTE
(I) Eluent reservoir
(2) Pump
(3) Precolumn
(4) Separator column
(5) Suppressor column
(6) Detector
(7) Recorder or  integrator,  or both
          9056 - 14
Revision 0
September 1994

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       FIGURE  2
TYPICAL ANION PROFILE
         uiNuns
       9056 - 15
Revision 0
September 1994

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(    Start     |


       ~^
             DETERMINATION OF
     METHOD 9056
INORGANIC ANIONS BY
ION CHROMATOGRAPHY
7.1 .1 Establish ion
chromatographte
operating
parameters.
V
7,1 .2 Prepare
calibration
standards al a
minimum of three
concentration
levels and a blank.
If
7.1 .3 Prepare
calibration curve.
V
7.1.4 Verify the
calibration curves
each working day or
whenever the anion
eluent is changed,
and for every batch
of samples.
I

/ ^^ 7.2,1 tf a dilution
/ 7.2.1 Are\ Aqueous is "«oe88a'V the
/samples aqueousN 	 w. dilution should
\ or extracts? / ^ be ma£lv range? /
\Ho
V
7.3.1 Prepare
sample calibration
curves for each
anion of interest
and compute sample
concentration.


7.2.2.10 Dilute
, 1^ sample with
reagent water.

7.3.3 Calculate
w concentrations
r from instrumental
response.
V
      9056  -  16
                                                                      Revision 0
                                                                      September 1994

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                                 METHOD  9Q71A

       OIL AND GREASE EXTRACTION METHOD  FOR  SLUDGE AND SEDIMENT SAMPLES


 1.0  SCOPE AND APPLICATION

       1.1     Method  9071 is  used  to  quantify  low concentrations  of oil and
 grease (10 mg/L)  by chemically drying a wet sludge sample and then extracting via
 the  Soxhlet  apparatus.   It  is  also  used to recover  oil  and grease  levels in
 sediment and  soil samples,

       1.2     Method  9071  is  used  when  relatively  polar,   heavy  petroleum
 fractions are present, or when the levels of nonvolatile greases challenge the
 solubility limit of the solvent.

       1.3     Specifically,  Method  9071   is  suitable  for  biological lipids,
 mineral hydrocarbons, and some industrial wastewaters.

       1.4     Method  9071 is  not  recommended  for measurement  of  low-boiling
 fractions that volatilize at temperatures below 70°C.

 2.0  SUMMARY OF METHOD

      2.1     A 20-g  sample  of wet  sludge with a  known  dry-solids  content is
 acidified to pH 2.0 with 0.3 mL concentrated HC1.

      2.2     Magnesium  sulfate  monohydrate  will  combine with 75%  of its own
weight in water in forming MgS04 « 7H20 and is used to dry the acidified sludge
 sample.

      2.3    Anhydrous  sodium  sulfate  is  used  to  dry  samples  of  soil  and
sediment.

      2.4    After   drying,    the    oil   and   grease   are   extracted   with
trichlorotrifluoroethane (Fluorocarbon-113)1  using the Soxhlet apparatus.

3.0  INTERFERENCES

      3.1    The method  is  entirely  empirical,  and duplicate results  can be
obtained only by strict adherence to all  details of the processes,

      3.2    The rate and time  of extraction in  the Soxhlet apparatus must be
exactly as directed because of varying solubilities of the different  greases.

      3.3    The  length of  time  required  for drying  and  cooling  extracted
material  must be constant.

      3.4    A gradual  increase in weight may  result  due to the absorption of
oxygen; a gradual loss of weight may result due to volatilization.
     Replacement solvent will  be specified in a forthcoming regulation.
                                   9071A  -  1                       Revision 1
                                                                  September 1994

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4.0  APPARATUS AND  MATERIALS
      4.1     Soxhlet  extraction  apparatus.
      4.2     Analytical  balance.
      4.3     Vacuum pump or some other  vacuum source.
      4.4     Extraction  thimble:  Filter paper.
      4.5     Glass  wool  or small  glass  beads  to  fill thimble.
      4.6     Grease-free cotton:   Extract nonabsorbent cotton with  solvent.
      4.7     Beaker:  150-mL.
      4.8     pH  Indicator to determine  acidity.
      4.9     Porcelain mortar.
      4,10    Extraction  flask: 150-mL.
      4.11    Distilling  apparatus:  Waterbath at 7Q°C.
      4.12    Desiccator.
5.0  REAGENTS
      5.1     Reagent  grade  chemicals   shall  be  used  in all  tests.   Unless
otherwise  indicated,  it  is  intended  that  all  reagents  shall  conform  to the
specifications of the Committee on Analytical  Reagents of the American Chemical
Society, where such specifications are available.   Other grades  may be used,
provided it is first ascertained  that the reagent is of sufficiently  high purity
to permit its use without  lessening the accuracy of the determination.
      5.2     Reagent  water.   All references  to water in this  method refer to
reagent water, as defined  in Chapter One.
      5.3     Concentrated  hydrochloric  acid {HC1},
      5.4     Magnesium sulfate monohydrate:   Prepare MgS04 * H20 by  spreading a
thin layer in a dish and drying in an oven at ISO^C overnight.
      5.5     Sodium sulfate, granular,  anhydrous  (Na2S04): Purify  by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride.  If the sodium sulfate is precleaned with methylene chloride,
a method blank must  be analyzed, demonstrating  that there is no interference from
the sodium sulfate.
                                   9071A  -  2                      Revision 1
                                                                  September 1994

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      5.6    Trichlorotrifluoroethane (l,l,2-trichloro-l,2,2-trifluoroethane):
Boiling  point, 47°C.    The  solvent  should  leave  no  measurable  residue  on
evaporation;  distill if necessary.2

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6,1    Transfers  of  the  solvent trichlorotrifluoroethane   should  not
involve any plastic tubing in the assembly.

      6.2    Sample  transfer  implements:   Implements  are required to transfer
portions  of solid,  semisolid,  and  liquid  wastes  from  sample  containers  to
laboratory  glassware.   Liquids  may be transferred using a  glass  hypodermic
syringe.  Solids may be transferred using a spatula, spoon, or coring device.

      6.3    Any turbidity  or suspended solids  in the extraction flask should
be removed by filtering through grease-free cotton or glass wool.

7.0  PROCEDURE

      7.1    Determination of Sample Dry Weight Fraction

      Weigh 5-10 g  of the sample into a tared crucible.   Determine  the dry weight
fraction of the sample by drying overnight at 105°C.

             NOTE:   The  drying  oven should be contained  in a hood  or vented.
             Significant  laboratory contamination  may  result from  a heavily
             contaminated hazardous waste sample.

      Allow to cool in a desiccator before weighing:

                      dry  weight  fraction =    q  of dry sample
                                                g  of sample

      7.2    Sample Handling

             7.2.1    Sludge Samples

                      7.2.1.1    Weigh out 20 + 0.5 g of wet sludge with a known
             dry-weight fraction (Section 7.1).  Place in a 150-mL beaker.

                      7.2.1.2    Acidify to a pH of 2 with approximately 0.3 mL
             concentrated HC1.

                      7.2.1.3    Add  25  g  prepared Mg2S04 * H20 and  stir  to  a
             smooth paste.

                      7.2.1.4    Spread  paste  on  sides of beaker  to  facilitate
             evaporation.   Let stand about  15-30  min  or until   substance  is
             solidified.
     Replacement  solvent  will  be  specified  in  a  forthcoming  regulation.

                                  9071A - 3                       Revision 1
                                                                  September 1994

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                 7.2,1.5    Remove  solids and  grind  to fine  powder in a
        mortar.

                 7.2.1.6    Add the powder to the paper extraction thimble.

                 7.2.1.7    Wipe  beaker and mortar with  pieces of  filter
        paper moistened with solvent and add to  thimble.

                 7.2.1.8    Fill  thimble with glass wool (or glass beads).

        7.2.2    Sediment/Soil  Samples

                 7.2.2.1    Decant and discard any water layer on a sediment
        sample.   Mix  sample  thoroughly,  especially  composited samples.
        Discard  any foreign objects such as sticks, leaves, and rocks.

                 7.2.2.2    Blend  10  g of  the  solid  sample of known dry
        weight fraction with 10  g  of  anhydrous sodium sulfate, and place
        in an extraction thimble.  The extraction thimble must  drain  freely
        for the  duration of the extraction period.

 7.3    Extraction

        7.3.1    Extract in Soxhlet apparatus using trichlorotrifluorocarbon
 at a rate of 20 cycles/hr for 4 hr.

        7.3.2    Using grease-free  cotton,  filter the extract into  a pre-
 weighed 250-mL boiling flask.  Use gloves to avoid adding fingerprints to
 the flask.

        7.3.3    Rinse flask and  cotton with  solvent.

        7.3.4    Connect the boiling   flask  to  the  distilling head  and
 evaporate the solvent by immersing the lower half of the flask in water at
 70°C.  Collect  the solvent  for  reuse.   A  solvent blank should accompany
 each analytical  batch of samples.

        7.3.5    When  the temperature  in  the  distilling head reaches 50°C
 or the flask appears dry,  remove the distilling head.  To remove solvent
 vapor, sweep out the flask for 15 sec with air by inserting  a glass tube
 that is connected to a vacuum source.   Immediately remove the flask from
 the  heat  source  and wipe  the  outside  to remove  excess moisture  and
 fingerprints.

        7.3.6    Cool  the  boiling  flask  in a  desiccator  for  30  min and
 weigh,

        7.3.7    Calculate  oil and grease as a percentage of the total dry
 solids.  Generally:

% of oil and grease  =      gain  in weight offlask(g)^  x  100
                        wt. of wet solids (g) x dry weight fraction
                              9071A  -  4                       Revision 1
                                                             September 1994

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8.0  QUALITY CONTROL

      8.1    All  quality  control  data should  be  maintained and available  for
easy reference  and inspection.   Refer to Chapter  One  for additional  quality
control guidelines.

      8.2    Employ  a minimum  of one  blank  per  analytical  batch  or  twenty
samples, whichever is  more frequent, to determine if contamination has  occurred.

      8.3    Run  one  matrix  duplicate and  matrix spike  sample every  twenty
samples or analytical  batch,  whichever is  more frequent.   Matrix duplicates  and
spikes are brought through the whole sample preparation and analytical  process.

      8.4    The use of corn oil  is recommended as  a reference sample  solution.

9.0  METHOD PERFORMANCE

      9.1    Two oil and grease methods (Methods 9070 and  9071)  were  tested on
sewage by a single laboratory.  When 1-liter portions of the sewage were dosed
with 14.0 mg of a mixture of No.  2  fuel oil and Wesson oil,  the recovery was 93%,
with a standard deviation of ± 0.9 mg/L.

10.0 REFERENCES

1.    Blum, K.A.  and H.J, Taras, "Determination of Emulsifying Oil in Industrial
Wastewater," JWPCF Research Suppl., 40, R404 (1968).

2.    Standard  Methods for the Examination  of Water and Wastewater,   14th ed.,
p. 515,  Method  502A (1975).
                                  9071A  -  5                       Revision 1
                                                                  September 1994

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                                  METHOD 9071A
 OIL AND GREASE  EXTRACTION  METHOD FOR SLUDGE  AND  SEDIMENT SAMPLES
                                     7.1 Determine
                                   dry weight fraction
                                       of earnpte.
  7.2.1,1 Weigh
   a sample of
   wet sludge
   and place in
    beaker.
Sludge
                            Soil/Sediment
7.2.2.1 Decant
  watar; mix
sample; discard
foreign objects.
     7.2.1.2
    Acidify to
      pH 2.
                                                7.2.2.2 Blend
                                                 with sodium
                                                 •ulfate; add
                                                 to extraction
                                                   thimble.
   7.2.1.3 Add
     and stir
magnesium eulfate
  monohydrate.
                                                   o
     7.2.1.5
   Remove and
   grind solicit
     to a fine
     powder.
                                   9071A -  6
                                                Revision 1
                                                Septatter 1994

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                                 METHOD 9071A
OIL AND GREASE  EXTRACTION  METHOD FOR SLUDGE AND SEDIMENT SAMPLES
                                 (Continued)
      7,2.1.6 Add
       powder to
         paper
       extraction
        thimble.
      7.2.1.7 Wipe
       beaker and
       mortar;  add
       to thimble.
       7.2.1.8 Fill
      thimble with
       glass wool.
7.3.1 Extract
 in Soxhiet
apparatus for
  4 hours.
 7.3.2 Film
 extract into
boiling flask.
 7.3.3 Ririee
  flask with
   solvent,
                                      7.3.4
                                  Evaporate and
                                     collect
                                 solvent for reuse.
                                   7.3.5 Remove
                                   solvent vapor.
 7.3.6 Cool
 and weigh
boiling flask.
   7.3.7
 Calculate %
   oil and
   grease.
                                                                I      Slop      J
                                  9071A  - 7
                                        Revision 1
                                        September 1994

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                                  METHOD 9075

                TEST METHOD FOR TOTAL CHLORINE  IN NEW AND USED
          PETROLEUM PRODUCTS BY X-RAY FLUORESCENCE SPECTROMETRY fXRF)


 1.0   SCOPE AND APPLICATION

      1.1   This test method covers the determination of total chlorine in new
 and  used  oils,  fuels,  and related materials,  including crankcase,  hydraulic,
 diesel,  lubricating and  fuel  oils,  and  kerosene.    The chlorine  content of
 petroleum products  is often required prior to their use as a fuel.

      1.2   The applicable  range  of this method  is  from 200  ^9/9 to percent
 levels,

      1,3   Method  9075  is restricted to  use by,  or  under the supervision of,
 analysts experienced in the operation of an X-ray fluorescence spectrometer and
 in the interpretation of the results.

 2,0   SUMMARY OF METHOD

      2.1   A well-mixed sample, contained in a disposable plastic sample cup,
 is loaded into an X-ray fluorescence (XRF)  spectrometer.   The  intensities of the
 chlorine  Ka  and  sulfur  Ka  lines  are  measured,  as are  the  intensities  of
 appropriate background lines.   After  background  correction, the net intensities
 are  used with  a calibration  equation to determine the  chlorine  content.   The
 sulfur intensity is used to correct for absorption by sulfur,

 3.0   INTERFERENCES

      3.1   Possible interferences include metals, water, and  sediment in the
 oil.  Results  of spike recovery measurements  and  measurements  on diluted samples
 can be used to check for interferences.

      Each sample,  or one sample from a  group of  closely  related samples, should
 be spiked  to  confirm that matrix  effects are  not  significant.   Dilution  of
 samples that may contain water or sediment  can produce incorrect results,  so
 dilution should be undertaken with  caution and  checked  by spiking.   Sulfur
 interferes with the chlorine determination,  but  a correction Is made.

      Spike recovery measurements  of used crankcase oil  showed  that diluting
 samples five to one allowed accurate measurements on  approximately 80% of the
 samples.   The other 20% of the samples  were  not  accurately analyzed by XRF.

      3.2   Water  in samples  absorbs X-rays emmitted  by chlorine.   For  this
 inter-ference, use  of as  short an X-ray  counting  time as  possible is beneficial.
This  appears  to be related  to  stratification  of  samples  into  aqueous  and
nonaqueous layers  while in the analyzer.

      Although a  correction  for  water  may be possible,  none  is  currently
available.   In general,  the presence  of  any free water as a separate phase or a
                                   9075 - 1                     Revision 0
                                                                September 1994

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water content greater than 25% will reduce the chlorine signal by 50 to 90%.  See
Sec. 6.4.
4.0   APPARATUS AND MATERIALS

      4.1   XRF spectrometer, either energy dispersive or wavelength dispersive.
The instrument must be able  to accurately resolve and measure the intensity of
the chlorine and sulfur lines with  acceptable precision.

      4.2   Disposable sample cups  with suitable plastic film such as Mylar*.

5.0   REAGENTS

      5.1   Purity of reagents.   Reagent-grade  chemicals shall  be used in all
tests.   Unless otherwise  indicated,  it is  intended that  all  reagents shall
conform to  the  specifications of the Committee on  Analytical  Reagents of the
American Chemical Society, where such specifications  are available. Other grades
may be used, provided it is first  ascertained that the reagent is  of sufficiently
high  purity  to  permit  its  use  without  lessening  the  accuracy  of  the
determination.

      5.2   Mineral oil,  mineral  spirits or paraffin oil  {sulfur- and chlorine-
free), for preparing standards and  dilutions.

      5.3   1-Chlorodecane  {Aldrich Chemical Co.),  20.1% chlorine,  or similar
chlorine compound.

      5.4   Di-n-butyl  sulfide {Aldrich Chemical Co.), 21.9% sulfur by weight.

      5.5   Quality control  standards such as the standard reference materials
NBS 1620,  1621, 1622, 1623,  and 1624 for sulfur in oil standards; and NBS 1818
for chlorine in oil standards.

6.0   SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1    All samples must be collected using a sampling plan that addresses
the considerations  discussed in Chapter Nine.

      6.2   The collected sample  should be kept headspace free prior to prepara-
tion and analysis to minimize volatilization losses of organic halogens.  Because
waste oils may contain  toxic and/or carcinogenic substances, appropriate field
and laboratory safety procedures should be followed.

      6.3    Laboratory  sampling of the sample  should be performed on a well-mixed
sample of  oil.   The mixing should be kept to  a minimum and carried out as nearly
headspace  free as possible to minimize volatilization losses of organic halogens.

      6.4    Free water, as  a separate phase, should  be  removed and  cannot be
analyzed by this method.
                                   9075 - 2                     Revision 0
                                                                September 1994

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7.0   PROCEDURE
      7.1   Calibration and standardization.

            7.1.1     Prepare  primary  calibration  standards  by diluting  the
      chlorodecane and n-butyl sulfidewith mineral  spirits or similar material.

            7.1.2     Prepare working calibration standards that contain sulfur,
      chlorine,  or both according to the following  table:
      Cl:
       S:

      1.
      2.
      3.
      4.
      500, 1,000, 2,000, 4,000, and 6,000 /jg/g
      0.5, 1.0, and 1.5% sulfur
      0.5% s, 1,000
      0.5% S, 4,000 jig/g Cl
      1.0% S,   500 jig/g Cl
      1.0% S, 2,000 ng/g Cl
5.   1.0% s,  6,000 ^g/g ci
6.   1.5% s,  1,000 Mg/g ci
7.   1.5% S,  4,000 M9/g Cl
8.   1.5% S,  6,000 jug/g Cl
Once  the  correction  factor for  sulfur  interference
determined, fewer standards may be required.
                                                             with  chlorine  is
            7,1.3    Measure  the intensity of  the chlorine KG  line and  the
      sulfur Ka line as well  as the intensity  of a suitably chosen background.
      Based  on counting statistics, the relative  standard deviation of each peak
      measurement should be 1% or less.

            7.1.4    Determine  the  net  chlorine  and sulfur  intensities  by
      correcting  each peak for background.   Do this for all  of  the calibration
      standards  as well  as for a paraffin  blank.

            7.1.5    Obtain a linear calibration curve for sulfur by performing
      a  least squares fit of the net sulfur  intensity to the standard concentra-
      tions,  including the blank.   The  chlorine content  of a  standard  should
      have little effect on the net sulfur  intensity.

            7.1.6    The  calibration equation  for  chlorine  must  include  a
      correction   term  for  the  sulfur  concentration.   A  suitable  equation
      follows:
                           Cl = (ml + b) (1 + k*S)                (1)
     where:
            I          = net chlorine intensity
            m,  b,  k*  = adjustable parameters
            S          = sulfer concentration

     Using  a  least  squares procedure,  the  above equation  or  a  suitable
     substitute  should  be fitted  to the  data.    Many XRF  instruments  are
     equipped  with suitable  computer  programs to perform this  fit.    In  any
     case,  the resulting equation should be shown  to be accurate by analysis of
     suitable  standard  materials.
                                   9075  -  3
                                                          Revision 0
                                                          September 1994

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       7.2   Analysis.

            7,2.1     Prepare a calibration curve  as  described  in Sec. 7.1.  By
       periodically  measuring  a very stable sample containing  both sulfur and
       chlorine,  it  may be possible to use  the  calibration  equations for more
       than  1  day.   During each day, the  suitability of the calibration curve
       should  be checked by analyzing standards.

            7.2.2     Determine the net chlorine  and sulfur intensities for a
       sample  in the same manner as done for the standards.

            7.2.3     Determine the chlorine and  sulfur concentrations  of the
       samples from the calibration equations.  If the sample concentration for
       either element is beyond the range of the standards, the  sample should be
       diluted with mineral oil and reanalyzed.

8.0    QUALITY CONTROL

       8.1   Refer to Chapter One for specific quality control procedures.

       8.2   One sample in ten should be analyzed in triplicate  and  the relative
standard deviation reported.  For each triplicate,  a separate preparation should
be made, starting from the original sample.

       8.3   Each sample, or one sample in ten from a group of similar samples,
should  be  spiked with the  elements of interest  by  adding   a  known  amount of
chlorine or sulfur to the sample.  The spiked amount should  be between 50% and
200% of the sample  concentration,  but  the minimum addition  should  be at least
five times the limit of detection.   The percent recovery should be  reported and
should be between 80% and 120%.  Any sample suspected of containing >25% water
should also be spiked with organic chlorine.

       8.4   Quality control  standard check samples should  be analyzed every day
and should agree within 10% of the expected value of the standard.

9.0   METHOD PERFORMANCE

      9.1   These data are based on 47 data points obtained by seven  laboratories
who each  analyzed four  used crankcase oils  and  three  fuel oil  blends  with
crankcase in  duplicate.   A  data point represents one duplicate  analysis  of a
sample.  Two data points were determined to  be outliers  and  are not included in
these results.

      9.2   Precision.   The  precision of  the method  as  determined  by  the
statistical  examination of inter!aboratory test results is as follows:

            Repeatabilit.y -  The difference between successive results obtained
      by the  same  operator  with  the  same apparatus under  constant  operating
      conditions on identical test material would exceed, in the long run, in
      the normal  and correct  operation  of  the test method, the following values
      only in 1 case in 20 (see Table 1):
                                   9075 - 4                     Revision  0
                                                                September 1994

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                         Repeatability = 5.72

      *where x is the average  of  two  results in  M9/9-

            Reprpducibilit.y - The difference between two single and independent
      results obtained  by different operators working in different laboratories
      on identical test material  would exceed,  in the long run,  the following
      values only in 1  case in  20:


                        Repzoducibility =9.83 /ar*


      *where x is the average  value of two results  in jug/g,

      9.3   Bias.  The bias of this  test method varies with concentration, as
shown in Table 2:

                    Bias =  Amount found  - Amount expected.

10.0  REFERENCE

1.     Gaskill,  A.; Estes, E.D.; Hardison, D.L.;  and Myers, I.E.   Validation of
      Methods for Determining Chlorine in Used Oils and Oil  Fuels.  Prepared for
      U.S.  Environmental Protection Agency, Office of Solid Waste.  EPA Contract
      No. 68-01-7075, WA 80.  July 1988.
                                  9075 - 5                     Revision 0
                                                               September 1994

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                  TABLE 1.   REPEATABILITY AND REPRODUCIBILITY
                         FOR CHLORINE IN USED OILS BY
                        X-RAY  FLUORESCENCE SPECTROMETRY
Average value,              Repeatability,            Reproducibility,
     500                          128                       220
   1,000                          181                       311
   1,500                          222                       381
   2,000                          256                       440
   2,500                          286                       492
   3,000                          313                       538
               TABLE 2.  RECOVERY AND BIAS DATA FOR CHLORINE IN
                 USED OILS BY X-RAY FLUORESCENCE SPECTROMETRY
 Amount           Amount
expected,          found,             Bias,                Percent
 M9/9             M9/9               M9/9                  bias
   320              278               -42                   -13
   480              461               -19                    -4
   920              879               -41                    -4
 1,498            1,414               -84                    -5
 1,527            1,299              -228                   -15
 3,029            2,806              -223                    -7
 3,045            2,811              -234                    -8
                                   9075 - 6                       Revision 0
                                                                  September 1994

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                             METHOD  9075
        TEST HETHOD  FOR TOTAL  CHLORINE  IN NEW AND USED
PETROLEUM PRODUCTS BY  X-RAY FLUORESCENCE  SPECTRQMETRY  (XRF)
              STA8T
          711-71.2
        Pr*p«r« calibrati
            m la fid a ret a
          713 M**»ur«
          intensity el
          a tandarcj* and
           background
7  1 4 Dnicrnxn* net
  int*«*ity for
  standards and A
  paraffin blank
          715-716
            Cons £. rue t
       e*l ibratxan curv»i
         far »aifur and
           ? 2  1 CK«ek
       calibration curv«§
          periodical 1y
       thrDu^haut thv  day
                       ? 2  2 0»t»r»m« n«t
                       chlarin» ind *ulfur
                         int»n*i hiaar for
                         723 D«t«rinin*
                       cKlonn* and sulfur
                       concert tra tion* t c on
                       calibration eurvw*
                                                       2 3 Dtlut*  aaapl
                                                      with (ti i n» r a I  oil
                              9075  - 7
                                                           Revision  0
                                                           September 1994

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                                  METHOD 9076

           TEST METHOD  FDR  TOTAL  CHLORINE  IN NEK AND USED PETROLEUM
              PRODUCTS BY  OXIDATIVE COMBUSTION AND HICROCOULOMETRY
 1.0   SCOPE AND APPLICATION

      1.1   This test method  covers the determination of total chlorine in new
 and  used  oils, fuels  and related materials,  including  crankcase, hydraulic,
 diesel,  lubricating and  fuel  oils,  and kerosene  by  oxidative combustion and
 microcoulometry.  The chlorine content of petroleum products is often required
 prior to their use  as a  fuel.

      1.2   The  applicable range  of  this method  is from  10  to  10,000  /ng/g
 chlorine.

 2.0   SUMMARY OF METHOD

      2.1   The  sample   is placed  in  a quartz boat at  the inlet  of  a high-
 temperature quartz combustion tube.  An inert carrier gas such  as argon, carbon
 dioxide, or nitrogen sweeps across the inlet  while  oxygen flows into the center
 of the combustion tube.   The  boat and sample are advanced  into a vaporization
 zone of  approximately  300°C  to volatilize the light ends.  Then  the  boat is
 advanced to the center of the combustion tube,  which  is at  1,000*C.  The oxygen
 is diverted to pass  directly over the sample to oxidize any  remaining refractory
 material.  All during this complete combustion cycle, the chlorine  is converted
 to chloride and oxychlorides, which then  flow into an attached titration cell
 where they quantitatively react with silver ions.  The silver ions thus consumed
 are coulometrically replaced.  The total current required to  replace the silver
 ions is a measure of the  chlorine present in the injected  samples.

      2.2   The reaction  occurring in  the  titration cell as chloride enters is:

                           Cl" +  Ag+ ------- > AgCl                  (1)

      The silver ion consumed  in the above  reaction  is generated coulometrically
 thus:

                              Ag°  ------- >  AS" -r e"                  ;z;
      2.3   These microequivalents of silver are equal to the number of micro-
equivalents of titratable sample ion entering the titration cell.

3.0   INTERFERENCES

      3.1   Other titratable ha! ides will  also  give  a  positive response.  These
titratable halides include HBr  and  HI  (HOBr +  HOI  do  not precipitate silver).
Because these oxyhalides do not react in the titration cell, approximately 50%
microequivalent response is detected from bromine and iodine.

      3.2   Fluorine as fluoride does not  precipitate silver,  so it is not an
interferant nor is it detected.


                                   9076 - 1                       Revision 0
                                                                  September 1994

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      3.3   This  test method  is  applicable in  the  presence of  total  sulfur
 concentrations of up  to 10,000 times the chlorine level,

 4.0   APPARATUS AND MATERIALS1

      4.1   Combustion furnace.   The  sample should  be  oxidized  in an electric
 furnace capable of maintaining a temperature of 1,000°C to oxidize the organic
 matrix.

      4.2   Combustion tube,  fabricated from quartz  and  constructed so that a
 sample, which is vaporized  completely  in  the inlet  section,  is  swept into the
 oxidation zone by an  inert  gas where  it mixes  with  oxygen  and is  burned.   The
 inlet end of the tube connects to a boat insertion device where the sample can
 be  placed  on  a  quartz   boat by  syringe,  micropipet,  or  by  being  weighed
 externally.  Two gas  ports are provided, one for an inert  gas  to flow across the
 boat and one for oxygen to enter the combustion tube.

      4.3   Hicrocoulometer,  Stroehlein Coulomat  702 CL  or equivalent,  having
 variable gain and bias control, and capable of measuring the potential  of the
 sensing-reference electrode pair, and  comparing this potential  with  a  bias
 potential,  and   applying  the  amplified  difference  to  the  working-auxiliary
 electrode pair so as to generate a titrant.   The microcoulometer output signal
 shall be proportional to the generating current.  The raicrocoulometer may have
 a digital meter and circuitry to convert this output signal directly to a mass
 of chlorine (e.g., nanograms) or to a concentration of chlorine (e.g., micrograms
 of chlorine or micrograms per gram).

      4.4   Titration cell.   Two different configurations have been applied to
 couloraetrically titrate chlorine for this method.

            4.4.1     Type I uses a sensor-reference pair of electrodes to detect
      changes in silver ion  concentration  and a generator anode-cathode pair of
      electrodes to  maintain constant  silver ion concentration and an inlet for
      a gaseous  sample  from the  pyrolysis  tube.   The sensor,  reference,  and
      anode electrodes  are  silver  electrodes.   The  cathode  electrode  is  a
      platinum wire.   The reference  electrode  resides in a saturated  silver
      acetate half-cell.   The electrolyte contains 70% acetic acid in water.

            4.4.2     Type II  uses  a  sensor-reference pair  of electrodes  to
      detect changes in silver ion concentration and a generates anode-cathode
      pair of electrodes to maintain constant silver  ion concentration, an inlet
      for a gaseous  sample that passes through  a 95% sulfuric acid dehydrating
      tube from the  pyrolysis tube,  and a sealed two-piece titration cell  with
      an exhaust tube to  vent fumes to an external exhaust.  All  electrodes can
      be removed  and replaced independently without reconstructing the  cell
      assembly.   The  anode  electrode  is  constructed  of  silver.   The  cathode
      electrode  is constructed of platinum.   The anode  is separated  from the
     1Any apparatus that meets the performance  criteria  of  this  section  may be
used to conduct analyses by this methodology.   Three commercial  analyzers that
fulfill the requirements for apparatus Steps 4.1  through 4,4 are:  Dohrmann
Models DX-20B and MCTS-20 and Mitsubishi  Model  TSX-10 available  from Cosa
T  I . .    .1
Instrument.
                                   9076 - 2                       Revision 0
                                                                  September 1994

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      cathode by a 10% KN03 agar bridge, and continuity is maintained through  an
      aqueous  10% KN03 salt bridge.   The sensor electrode  is constructed  of
      silver.  The reference electrode is  a silver/silver chloride ground glass
      sleeve, double-junction electrode with aqueous 1M KN03 in the outer chamber
      and  aqueous  1M KCl in the inner  chamber.

      4.5   Sampling syringe, a micro!iter syringe of 10  j*L capacity capable  of
accurately delivering  2 to 5 /uL of  a  viscous  sample  into the  sample boat.

      4.6   Micropipet, a positive displacement micropipet capable of accurately
delivering 2 to 5 jxL of a viscous sample  into the sample boat.

      4.7   Analytical balance.  When  used to weigh a sample of 2  to 5 mg onto
the boat, the  balance shall be accurate to  + 0.01 mg.  When used to  determine the
density of the sample,  typically 8 g per 10 ml, the balance shall  be accurate  to
± 0.1 g.

      4.8   Class A volumetric flasks:  100 ml.

5.0   REAGENTS

      5.1   Purity of  Reagents.  Reagent-grade  chemicals shall  be used in all
tests.   Unless otherwise indicated,  it  is  intended that all  reagents  shall
conform to the  specifications  of  the Committee on Analytical  Reagents of the
American Chemical  Society, where such specifications are available.  Other grades
may be used, provided it is first ascertained that the reagent  is of sufficiently
high  purity  to  permit  its  use  without  lessening  the  accuracy  of  the
determination.

      5.2   Reagent water.   All  references to  water in  this  method refer  to
reagent water, as defined in Chapter One.

      5.3   Acetic acid, CH3C02H.  Glacial.

      5.4   Isooctane,  (CH3)2CHCH2C(CH3)3 (2,2,4-Trimethylpentane).

      5.5   Chlorobenzene,  C6H5C1.

      5.6   Chlorine,   standard  stock  solution  -   10,000   ng  Cl/^L,  weigh
accurately 3.174 g of Chlorobenzene into IOO-mL Class A volumetric flask.  Dilute
to the mark with isooctane.

      5.7   Chlorine,   standard  solution.    1,000  ng Cl//uL,  pipet  10.0  ml  of
chlorine stock solution (Sec.  5.6} into a  100-mL volumetric flask  and dilute  to
volume with isooctane.

      5.8   Argon, helium,  nitrogen, or carbon dioxide, high-purity grade (HP)
used as  the carrier gas.  High-purity grade gas has a minimum purity of 99.995%.

      5.9   Oxygen, high-purity grade (HP), used as  the reactant gas.

      5.10  Gas regulators.  Two-stage regulator must  be used on the reactant and
carrier gas.

                                   9076 -  3                        Revision 0
                                                                   September 1994

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      5.11  Cell Type 1.

            5.11.1    Cell  electrolyte solution.  70% acetic acid: combine 300
      ml reagent water with 700 ml acetic acid  (Sec. 5.3) and mix well.

            5.11.2    Silver acetate, CH3C02Ag.   Powder purified for  saturated
      reference electrode.

      5.12  Cell Type 2.

            5.12.1    Sodium acetate, CH3C02Na.

            5.12.2    Potassium nitrate,  KN03.

            5.12.3    Potassium chloride,  KC1.

            5.12.4    Sulfuric acid (concentrated),  H2S04.

            5.12.5    Agar,  (jelly strength  450 to 600  g/cm2).

            5.12.6    Cell  electrolyte solution -  85% acetic  acid:  combine 150
      ml reagent water with  1.35  g sodium acetate (Sec. 5.12.1) and  mix well;
      add 850 ml acetic acid  (Sec. 5.3) and mix well.

            5.12.7    Dehydrating solution - Combine 95 ml sulfuric acid (Sec.
      5.12.4) with 5 ml reagent water and mix well.

            CAUTION: This is an exothermic reaction and  may proceed with bumping
            unless  controlled by the addition  of sulfuric  acid.   Slowly add
            sulfuric acid to reagent water.   Do not  add  water to sulfuric acid.

            5.12.8    Potassium nitrate  (10%), KN03.  Add 10 g potassium nitrate
      (Sec. 5.12.2) to 100 ml reagent water and mix well.

            5.12.9    Potassium nitrate  (1M),   KN03.    Add  10.11 g   potassium
      nitrate (Sec. 5.12.2) to 100 ml reagent water and mix well.

            5.12.10   Potassium chloride  (1M),  KC1.   Add  7.46 g   potassium
      chloride (Sec. 5.12.3) to 100 ml reagent water and mix well.

            5.12.11   Agar  bridge  solution -  Mix 0.7  g agar (Sec. 5.12.5), 2.5g
      potassium nitrate  (Sec. 5.12.2),  and 25 ml  reagent  water and heat to
      boil ing.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All  samples must be collected using a sampling plan that  addresses
the considerations discussed  in Chapter Nine.

      6.2   Because the  collected  sample will be analyzed for  total halogens, it
should be kept headspace free  and refrigerated prior to preparation and analysis
to minimize volatilization losses of organic halogens.   Because waste oils may
                                   9076 - 4                       Revision 0
                                                                  September 1994

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contain toxic and/or carcinogenic substances, appropriate field and laboratory
safety procedures should be followed.

      6,3   Laboratory subsampling of the sample should  be performed on a well-
mixed sample of oil.

7.0   PROCEDURES

      7.1   Preparation of apparatus,

            7.1.1     Set  up the analyzer as  per the  equipment manufacturer's
      instructions.

            7.1.2     Typical  operating  conditions:  Type  1.

                      Furnace  temperature	   1,000°C
                      Carrier  gas  flow	      43 cm3/min
                      Oxygen gas flow	     160 cm3/min
                      Coulometer
                        Bias..	     250 mV
                        Gain...	      25%

            7.1.3     Typical  operating  conditions:  Type  2.

                      Furnace  temperature	   H-l  850°C
                                                          H-2  1,000°C
                      Carrier  gas  flow		   250  cm3/min
                      Oxygen gas flow.	   250  cm3/min
                      Coulometer
                        End  point  potential  (bias)	   300  mV
                      Gain G-l	     1.5 coulombs/A mV
                          G-2	     3.0 coulombs/A mV
                          G-3	     3.0 coulombs/A mV
                      ES-1 (range  1)	   25  mV
                      ES-2 (range  2)	   30  mV

            NOTE:  Other  conditions  may  be   appropriate.     Refer   to  the
            instrumentation  manual.

      7.2   Sample introduction.

            7.H.I     Carefully fill  a 10-^1- syringe with 2 to  5 pi of sample
      depending  on the  expected concentration of total  chlorine.   Inject the
      sample through the septum onto the cool boat,  being  certain to touch the
      boat with  the needle tip to  displace the last  droplet.

            7.2.2     For viscous  samples that cannot be drawn into the syringe
      barrel,  a  positive displacement micropipet  may be used.  Here,  the 2-5 fiL
      of sample  is placed on  the  boat from the  micropipet  through  the opened
      hatch port.  The same technique as with the syringe is  used  to  displace
      the last droplet into  the boat.  A tuft of  quartz wool  in  the boat can aid
      in completely transferring the sample from the micropipet into the boat.
                                   9076 - 5                       Revision 0
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      NOTE: Dilution of samples  to reduce viscosity is not recommended due
      to  uncertainty  about  the  solubility  of  the  sample  and  its
      chlorinated constituents.  If a positive displacement micropipet is
      not  available,  dilution may  be attempted to  enable  injection of
      viscous samples.

      7.2.3     Alternatively, the  sample  boat  may  be  removed  from the
instrument  and  tared  on an analytical  balance.   A  sample of  2-5 mg is
accurately weighed directly into the  boat and the boat and sample returned
to the inlet of the instrument.

                          2-5  ML =  2-5 mg

      NOTE: Sample dilution may be required to ensure that the titration
      system  is  not overloaded  with chlorine.    This will  be  somewhat
      system  dependent  and  should   be  determined  before   analysis  is
      attempted.   For  example,  the MCTS-20 can  titrate up  to  10,000 ng
      chlorine in a single injection or weighed sample, while the DX-20B
      has an  upper  limit of 50,000  ng  chlorine.   For 2 to  5 /it sample
      sizes, these correspond to nominal concentrations in the sample of
      800 to 2,000 /ig/g  and 4,000  to 10,000  M9/9>  respectively.   If the
      system is overloaded, especially with inorganic chloride,  residual
      chloride may persist in  the system and affect results of subsequent
      samples.  In general, the  analyst should  ensure that  the baseline
      returns to normal  before running the next sample. To speed baseline
      recovery, the electrolyte can be drained from the cell and replaced
      with fresh electrolyte.

      NOTE: To determine total  chlorine, do not extract the sample either
      with reagent water or with an organic solvent  such  as toluene or
      isooctane.  This may  lower the inorganic chlorine content as well as
      result in losses of volatile solvents.

      7.2.4     Follow the manufacturer's recommended  procedure for moving
the sample and boat into the combustion tube.

7.3   Calibration and standardization.

      7.3.1     System  recovery  -  The fraction of chlorine  in a standard
that  is  titrated  should  be  verified  every  4   hours  by  analyzing  the
standard solution (Sec.  5.7).  System recovery is typically 85% or better.
The pyrolysis tube should be replaced whenever system  recovery drops below
75%.

      NOTE: The  1,000  ^g/g system  recovery  sample  is  suitable  for all
      systems except the MCTS-20  for which a 100 jug/g  sample  should be
      used.

      7.3.2     Repeat  the measurement  of  this  standard at  least three
times.
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                                                            September 1994

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            7.3.3     System blank  -  The blank  should be  checked  daily with
       isooctane.   It  is typically less than 1 M9/9 chlorine.  The system  blank
       should be subtracted from both samples and standards.

       7.4   Calculations.

            7.4.1     For systems  that  read  directly  in mass  units of chloride,
       the following equations apply:
                Chlorine, M9/9 (wt/wt) =                 - B                (3)
or
where :
                Chlorine,  Mg/9 (wt/wt) = — (H)P{RF)      ' B
Display     =   Integrated value in nanograms  (when  the  integrated values are
                displayed in micrograms,  they must  be multiplied by 103)
                DisplayB  = blank measurement    Displays = sample measurement

      V     =   Volume of sample injected in  micro! iters
                VB  =  blank volume               Vs =  sample volume

      D     =   Density of sample,  grams  per  cubic  centimeters
                DB  =  blank density              Ds =  sample density

     RF     =   Recovery  factor =  ratio of chlorine        =    Found - Blank
                determined in standard  minus  the  system           Known
                blank,  divided by  known standard  content

      B     =   System blank,  ^tg/g chlorine               =      DisplayB
                                                                 IVBJ  (UBJ

      M     =   Mass  of sample,  mg

            7.4.2     Other systems  internally compensate for recovery factor,
      volume, density, or  mass  and  blank,  and thus  ""ead out directly '.r. oarts
      per million chlorine units.  Refer to instrumentation manual.

8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control procedures.

      8.2   Each sample should be analyzed twice.  If the results do not agree
to within  10%,  expressed  as the  relative percent difference  of the results,
repeat the analysis.

      8.3   Analyze matrix spike and matrix spike duplicates - spike samples with
a chlorinated organic at a level  of  total  chlorine commensurate with the levels
being determined.  The spike recovery should be reported and should be between
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80 and 120% of the expected value.  Any sample suspected of containing >25% water
should also be spiked with organic chlorine,

9.0   METHOD  PERFORMANCE

      9.1   These data are based on 66 data points obtained by 10 laboratories
who  each  analyzed four  used crankcase  oils  and three  fuel  oil  blends  with
crankcase  in  duplicate.   A data point represents one  duplicate  analysis  of a
sample.  One  laboratory  and  four  additional data points  were  determined to be
outliers and  are not included in these results.

      9.2   Precision.   The  precision   of  the  method as  determined   by  the
statistical examination of interlaboratory test results is as  follows:

      Repeatability - The difference between successive results obtained by the
same operator with the  same apparatus under constant  operating  conditions on
identical  test material would exceed, in the long run,  in the normal and correct
operation of the test method the following values only in 1 case in 20 (see Table
1):

                         Repeatability - 0.137 x*
      *where x is the average of two results in M9/9-
            Regrgducibi1i ty - The difference between two single and independent
      results obtained by  different operators working in different laboratories
      on identical test material would exceed,  in  the  long  run,  the following
      values only in 1 case in 20:


                        Reproducibility = 0.455 x*


      *where x is the average value of two results  in  M9/9-

      9.3   Bias.  The bias of this test  method  varies with  concentration,  as
shown in Table 2:

                     Bias  = Amount found - Amount expected

10.0  REFERENCE

I.    Gaskill, A.; Estes,  E.D.; Hardison,  D.L.; and Myers, L.E.  "Validation of
      Methods for Determining Chlorine in Used Oils and Oil  Fuels."   Prepared
      for U.S.  Environmental  Protection  Agency, Office  of  Solid Waste.   EPA
      Contract No. 68-01-7075, WA80.   July 1988.

2.    Rohrobough, W.6.; et al.   Reagent  Chemicals, American  Chemical  Society
      Specifications, 7th  ed.; American Chemical  Society:  Washington, DC, 1986.

3.    Standard Instrumentation, 3322 Pennsylvania Avenue, Charleston, WV 25302.
                                   9076 -  8                       Revision 0
                                                                  September 1994

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                                   TABLE 1.
               REPEATABILITY AND REPRQDUCIBILITY FOR CHLORINE IN
                    USED OILS BY MICROCOULOMETRIC TITRATION
Average value               Repeatability,                 Reproducibility,
    Mi/i                         M9/9                           M9/9
500
1,000
1,500
2,000
2,500
3,000
69
137
206
274
343
411
228
455
683
910
1,138
1,365
                                   TABLE 2,
               RECOVERY AND BIAS DATA FOR CHLORINE IN USED OILS
                         BY MICROCOULOMETRIC  TITRATION
Amount
expected,
M9/9
320
480
920
1,498
1,527
3,029
3,045
Amount
found
M9/9
312
443
841
1,483
1,446
3,016
2,916

Bias,
M9/9
-8
-37
-79
-15
-81
-13
-129

Percent
bias
-3
-8
-9
-1
-5
0
-4
                                   9076 - 9                       Revision 0
                                                                  September 1994

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                       METHOD  9076
TEST METHOD FOR TOTAL CHLORINE IN NEW AND USED PETROLEUM
  PRODUCTS BY OXIDATIVE COMBUSTION AND MICROCOULOMETRY
                      9076 - 10
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September 1994

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                                  METHOD 9077

           TEST METHODS FOR TOTAL CHLORINE IN NEW AND USED PETROLEUM
                       PRODUCTS (FIELD TEST KIT METHODS)
1.0   SCOPE AND APPLICATION

      1,1    The  method may be used  to  determine if a new  or used petroleum
product meets  or  exceeds  requirements for total  halogen measured as chloride.
An analysis of  the chlorine content of petroleum products is often  required prior
to  their  use as  a  fuel.   The method is specifically designed  for used oils
permitting onsite testing at remote locations by nontechnical  personnel to avoid
the delays for laboratory testing,

      1.2    In  these  field  test  methods,  the  entire  analytical  sequence,
including  sampling,  sample pretreatment, chemical reactions,  extraction,  and
quantification, are combined in a single kit using  predispensed  and encapsulated
reagents.  The overall objective is to provide  a simple, easy to  use procedure,
permitting nontechnical  personnel  to perform a test  with analytical accuracy
outside of a laboratory environment in under 10 minutes.  One of the kits is
preset at  1,000  pg/g total chlorine  to  meet regulatory  requirements for used
oils.  The other kits provide quantitative results  over  a range of  750  to
7,000 /ig/g and 300 to 4,000 Mg/g.

2.0   SUMMARY OF METHOD

      2.1    The  oil sample (around 0.4 g by volume) is dispersed in a solvent
and reacted with  a  mixture of metallic  sodium catalyzed  with  naphthalene and
diglyme at ambient temperature.  This process converts all organic halogens to
their respective sodium halides.   All  ha!ides in the treated mixture, including
those present prior to the reaction,  are  then extracted into an aqueous buffer,
which is then  titrated  with  mercuric nitrate using diphenyl carbazone  as the
indicator.  The end point of the titration is the formation of the blue-violet
mercury diphenylcarbazone complex.  Bromide and iodide are  titrated and reported
as chloride.

      2.2    Reagent quantities are  preset  in  the fixed  end  point kit (Method
A)  so that the color of the  solution at  the  end of the titration indicates
whether the sample  is  above  I,OOC /ig/g chlorine  (yeT.ow;  or below  1,000 ^g/g
chlorine (blue),

      2.3    The first quantitative kit (Method B)  involves a reverse titration
of a fixed  volume of mercuric nitrate with the extracted sample such that the end
point is  denoted  by a change from blue to yellow in the titration vessel over the
range of the kit  (750  to 7,000  M9/9)-  The final  calculation  is based  on the
assumption that the oil  has a specific gravity of 0.9 g/cm3.

      2.4    The second quantitative kit  (Method C) involves a  titration of the
extracted sample with mercuric nitrate by means  of a 1-ml microburette such that
the end point  is  denoted by  a change from pale yellow to red-violet over the
range of the kit (300 to 4,000 M9/g)-   The concentration of  chlorine  in the
original  oil  is then read from a scale on the microburette.


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             NOTE: Warning—All reagents are encapsulated  or  contained  within
             ampoules.  Strict adherence to the operational procedures included
             with the kits as well as accepted safety procedures (safety glasses
             and gloves)  should be observed.

             NOTE: Warning—When crushing the glass ampoules,  press  firmly in
             the center of the ampoule once.  Never attempt to recrush  broken
             glass  because the glass  may  come  through the  plastic and  cut
             fingers.

             NOTE:  Warning—In  case  of  accidental  breakage  onto  skin  or
             clothing, wash with large amounts  of water.  All  the ampoules are
             poisonous and should not be taken  internally.

             NOTE: Warning--The gray ampoules contain metallic sodium.  Metallic
             sodium is a flammable water-reactive solid.

             NOTE: Warning—Do not ship kits on passenger aircraft.  Dispose of
             used kits properly.

             NOTE: Caution--When the sodium ampoule in  either  kit  is crushed,
             oils that contain more than 25% water will cause the sample to turn
             clear to light gray.  Under these circumstances,  the  results may
             be biased excessively low and  should be  disregarded.

3.0   INTERFERENCES

      3.1    Free water, as a second phase, should be removed.   However,  this
second phase can be analyzed  separately for chloride content if desired.
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                                   METHOD A

                        FIXED END POINT TEST KIT METHOD


4.0A  APPARATUS AND MATERIALS

      4.1A   The  CLOR-D-TECT  10001  is  a  complete  self-contained  kit.    It
includes:   a  sampling  tube to withdraw a fixed  sample volume for analysis; a
polyethylene test tube #1 into which the sample  is introduced for dilution and
reaction with metallic sodium; and a  polyethylene tube  #2 containing a buffered
aqueous  extractant,  the  mercuric  nitrate  titrant,  and  diphenyl  carbazone
indicator.  Included are instructions to conduct the test and a color chart  to
aid in determining the end point.

5.0A  REAGENTS

      5.1A   Purity of reagents.  Reagent-grade  chemicals shall be used  in all
tests.   Unless otherwise  indicated,  it is  intended that all  reagents shall
conform to  the  specifications of the Committee  on Analytical  Reagents of the
American Chemical  Society, where such  specifications are available. Other grades
may be used, provided it is first ascertained that the reagent  is of sufficiently
high purity to permit its use without lessening the accuracy of the determina-
tion.

      5.2A   All necessary reagents are contained within the kit.

      5,3A   The  kit  should  be examined upon  opening  to see that  all  of the
components  are  present and  that all the  ampoules   (4)  are  in place  and  not
leaking.  The  liquid  in  Tube #2  (yellow cap)  should be approximately 1/2 in.
above the 5-mL line and the  tube should not be leaking.  The ampoules are not
supposed to be completely full.

6.0A  SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

      6.1A   All samples must be collected using  a sampling plan that addresses
the considerations discussed in Chapter Nine.

      6.2A   Because the collected sample will be analyzed for total halogens,
it should be kept  headspace  free and refrigerated   prior   to preparation and
analysis to minimize  volatilization losses of organic  halogens.  Because waste
oils may  contain  toxic  and/or carcinogenic  substances,  appropriate field  and
laboratory safety procedures should be followed.

7.0A  PROCEDURE

      7.1A   Preparation.  Open analysis carton,  remove  contents, mount plastic
test tubes in  the  provided  holder.  Remove syringe and glass sampling capillary
from foil  pouch.
     Available from Dexsil Corporation, One Hamden Park Drive, Hamden,  CT 06517.

                                   9077 - 3                       Revision 0
                                                                  September 1994

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              NOTE:  Perform the test in a warm,  dry  area with adequate light.
              In  cold weather,  a truck cab is sufficient.   If  a warm area is not
              available,  Step  7.3A  should be performed while warming Tube #1 in
              palm of  hand.

      7.2A    Sample  introduction.   Remove white cap from  Tube  #1.   Using the
plastic syringe,  slowly draw the oil up the  capillary tube  until it reaches the
flexible adapter  tube.  Wipe excess oil  from the  tube with  the provided tissue,
keeping capillary vertical.   Position  capillary  tube  into Tube #1,  and detach
adapter tubing,  allowing capillary  to drop to the bottom of the tube.  Replace
white cap on tube. Crush the capillary  by squeezing the test tube several times,
being careful not to break the glass reagent ampoules.

      7.3A    Reaction.  Break the lower  (colorless) capsule containing the clear
diluent solvent  by squeezing the  sides of  the test tube.   Mix  thoroughly by
shaking the tube  vigorously  for  30 seconds.    Crush  the upper  grey  ampoule
containing metallic sodium,  again by squeezing the sides of the test tube.  Shake
vigorously  for 20 seconds.   Allow  reaction  to proceed  for 60 seconds,  shaking
intermittently several times while  timing with a watch.

              NOTE: Caution--Always  crush the clear ampoule in each tube first.
              Otherwise, stop the test and start over using another complete kit.
              False  (low) results may occur  and allow  a contaminated sample to
              pass without detection if  clear ampoule is  not crushed first.

      7.4A    Extraction.  Remove caps from both tubes.  Pour the clear buffered
extraction solution from Tube  #2 into Tube  II.  Replace the white cap on Tube #1,
and shake  vigorously  for 10  seconds.   Vent tube by partially  unscrewing the
dispenser cap. Close cap securely,  and  shake for an additional  10 seconds.  Vent
again, tighten cap, and  stand  tube  upside down on  white  cap.   Allow phases to
separate for 2 minutes.

      7.5A   Analysis.   Put  filtration  funnel  into  Tube  #2.   Position  Tube #1
over funnel and open nozzle on dispenser cap.   Squeeze the sides of Tube II to
dispense the  clear aqueous  lower phase  through the  filter into  Tube  #2 to the
5 ml line  on Tube #2.  Remove the filter funnel.  Replace  the yellow cap on Tube
#2 and close the  nozzle on the dispenser cap.   Break the colorless lower capsule
containing  mercuric nitrate  solution  by squeezing the sides  of the  tube, and
shake for  10 seconds.   Then break the upper colored ampoule containing the
diphenylcarbazone  indicator,  and  shake   for  10  seconds.     Observe  color
immediately.

      7.6A    Interpretation of results

              7.6.1A Because all reagent levels are preset,  calculations are not
      required.  A blue solution in Tube #2  indicates a chlorine content in the
      original oil of less than 1,000 ^9/9? and  a yellow color indicates that
      the chlorine concentration is  greater than 1,000 /jg/g.  Refer to the color
      chart enclosed with the kit  in interpreting the titration end point.

             7.6.2A Report the results as  <  or >  1,000 M9/S chlorine in the oil
      sample.
                                   9077 - 4                       Revision 0
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8.0A  QUALITY CONTROL

      8.1A   Refer to Chapter One for  specific quality control procedures.

      8.2A   Each .sample should be tested  two  times.   If the  results  do not
agree, then a third test must be performed.   Report the results of the two that
agree.

9.0A  METHOD PERFORMANCE

      9.1A   No formal  statement is made about either the precision or bias of
the overall  test  kit  method for determining chlorine in  used  oil  because the
result merely states whether there  is  conformance  to the  criteria for success
specified in the procedure,  (i,e., a blue or yellow color in the final solution).
In a collaborative study, eight laboratories analyzed four used crankcase oils
and three fuel oil blends with crankcase in duplicate  using the test kit.  Of the
resulting 56 data points, 3 resulted  in incorrect  classification  of the oil's
chlorine content (Table 1).  A data point represents one duplicate analysis of
a sample.   There  were  no disagreements within  a laboratory on  any duplicate
determinations.
                                   9077 - 5                       Revision 0
                                                                  September 1994

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                                   TABLE  1.
                 PRECISION AND BIAS  INFORMATION  FOR METHOD A-
                        FIXED END POINT TEST KIT METHOD
  Expected
concentration,
                              Percent agreement
Expected results,   Percent
     jjg/g           correct3  Within     Between
320
480
920
1,498
1,527
3,029
3,045
< 1,000
< 1,000
< 1,000
> 1,000
> 1,000
> 1,000
> 1,000
100
100
100
87
75
100
100
100
100
100
100
100
100
100
100
100
100
87
75
100
100
8Percent correct--percent correctly Identified as above or  below
   1,000 /tg/g.

bPercent agreement--percent agreement within or between laboratories,
                                   9077  - 6
                                                 Revision  0
                                                 Septenfcer 1994

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       STURT
                             METHOD 9077,  METHOD  A
                       FIXED  END  POINT TEST  KIT  METHOD
  1A Open le>»t  kit
~ , 2A Draw oil into
  capillary  tube;
remove exceaa oil;
drop capillary tube
  into Tube #1 and
cap Tub* £1; cruah
  capillary  tube
    7.3A  Break
color]*** capsule;
  mm;  ctuah grey
cap*ule,  miK, a 11ov
raaclion  to proceed
    for 60 aec.
 7 4fi Paur Tube f2
scluiion  into Tube
  ^X,  mix, v*nt;
  alIOM phaiea  to
     *eparmtc
? 5A Fi 1 t*r aquisoua
lower pha>e in Tube
 /I into Tube #2,
   remove  £i Her
   funnel, break
eoioricax  capsule;
 ffiiK; break upper
 BOlured capiule;
ma.it,  ob>«rve color
                                   9077  - 7
                                                                           Revision  0
                                                                           Septenter 1994

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                                   METHOD B

            REVERSE TITRATION QUANTITATIVE END  POINT TEST KIT METHOD

 4.OB APPARATUS AND MATERIALS

       4.IB     QuantiClor2  kit  components  (see  Figure  1).

               4.1.IB  Plastic reaction bottle:  1 oz, with flip-top dropper cap
       and a crushable glass ampoule containing sodium.

               4.1.2B  Plastic buffer bottle:   contains 9.5 ml of aqueous buffer
       solution.

               4.1.3B  Titration vial:  contains buffer bottle and  indicator-
       impregnated paper.

               4.1.4B  Glass vial:  contains 2.0 ml of solvents.

               4.1.5B  Micropipet and plunger,  0.25 ml.

               4.1.6B  Activated carbon filtering column.

               4.1.7B  Titret and valve assembly,

       4.2B     The  reagents  needed  for the  test  are packaged  in  disposable
containers.

       4.3B     The  procedure  utilizes  a  Titret.    Titrets   are   hand-held,
disposable  cells  for titrimetric analysis.   A  Titret is an  evacuated  glass
ampoule (13 mm diameter)  that contains an  exact amount of a standardized liquid
titrante   A flexible valve  assembly  is attached  to  the  tip  of the ampoule.
Titrets  employ the  principle  of reverse titration;  that is,  small doses of
sample are added to the titrant to the appearance of the end point color.  The
color change indicates that the equivalency point has been  reached.  The flow of
the sample  into  the  Titret may  be controlled  by using an  accessory called a
Titrettor* .

5.OB   REAGENTS

       5.IB    The crushable glass ampoule, which  is inside the reaction bottle,
contains 85 mg of metallic sodium in  a light oil  dispersion.

      5.2B    The buffer bottle contains 0.44 g of NaH.PO,  «  2H?0  and  0.32 ml of
HN03 in distilled water.                               z        £

      5.3B    The glass  vial  contains 770 mg  Stoddard  Solvent  (CAS  No.  8052-
41-3),  260 mg toluene,  260 mg butyl  ether, 260  mg diglyme,  130 mg naphthalene,
and 70 mg demulsifier.
     2Quanti-Chlor Kit, Titrets8, and Titrettor*  are manufactured by Chemetrlcs,
Inc., Calverton,  VA  22016.  U.S. Patent No.  4,332,769.

                                   9077 - 8                       Revision 0
                                                                  September 1994

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      5.4B    The Titret  contains 1.12 mg mercuric nitrate In distilled water.

      5.5B    The indicator-impregnated paper contains approximately 0.3 mg of
diphenylcarbazone and 0,2 mg of brilliant yellow.

S.OB  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      See Section 6.0A of Method A.

7,OB PROCEDURE

      7.IB    Shake  the glass  vial  and pour  its  contents into  the  reaction
bottle.

      7.2B    Fill the micropipet with a well-shaken oil sample by pulling the
plunger until  its top edge is even with the top edge of the micropipet.  Wipe off
the excess oil and transfer the sample  into the reaction bottle  (see Figure 2.1).

      7.3B    Gently squeeze  most  of  the air out of the reaction bottle {see
Figure 2.2),  Cap the bottle securely, and shake vigorously for 30 seconds.

      7.4B    Crush the sodium  ampoule by pressing against the outside wall of
the reaction bottle (see Figure 2.3).

              CAUTION:  Samples  containing  a  high  percentage  of water  will
              generate  heat  and  gas, causing  the reaction  bottle walls  to
              expand.  To release the gas, briefly loosen  the cap.

      7.5B    Shake the reaction bottle vigorously for 30  seconds.

      7.6B    Wait 1 minute.  Shake the reaction bottle occasionally during this
time.

      7.7B    Remove the buffer bottle from the  titration vial, and slowly pour
its contents into the reaction bottle  (see Figure 2.4).

      7.8B    Cap the reaction  bottle and  shake gently  for a  few seconds.   As
soon as the foam subsides,  release the gas by  loosening  the cap.   Tighten the
cap, and shake vigorously for 30 seconds.   As before,  release  any gas that has
formed, then turn the reaction bottle  upsidedown (see Figure  2.5).

      7.9B    Wait 1 minute.

      7.10B   While holding the filtering column in a vertical  position, remove
the plug.  Gently tap the column to settle the carbon particles.

      7.1 IB   Keeping the reaction bottle upside down,  insert the  flip top into
the end of the filtering column and position the column over the titration vial
(see Figure 2.6).  Slowly squeeze the lower  aqueous  layer  out of the reaction
bottle and into the filtering column.   Keep squeezing until the  first drop of oil
is squeezed out.
                                   9077 - 9                       Revision 0
                                                                  September 1994

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               NOTE: Caution—The aqueous layer should flow through the filtering
               column  Into  the titration vial in about 1 minute.  In rare cases,
               it  may  be necessary to gently tap the column to begin the flow.
               The indicator paper should  remain in  the titration vial.

      7.12B    Cap the titration  vial  and  shake  it vigorously  for 10 seconds.

      7.13B    Slide the flexible end of the valve assembly  over the tapered tip
of the Titret so that  it fits snugly  (see Figure 3.1).

      7.14B    Lift (see Figure 3.2) the  control bar  and  insert  the assembled
Titret into the Titrettor* .

      7.15B    Hold the Titrettor"1  with the sample pipe in  the  sample, and press
the control bar to snap the pre-scored tip of the Titret (see Figure 3.3).

               NOTE:  Caution—Because the  Titret is sealed under  vacuum,  the
               fluid inside may be agitated when the tip snaps.

      7.16B    With the tip of the  sample  pipe in the sample, briefly press  the
control  bar to pull in a SHALL  amount of sample  (see Figure 3.3).   The contents
of the Titret will turn purple.

               CAUTION: During  the  titration,  there will   be  some  undissolved
               powder   inside the  Titret.    This does .not interfere with  the
               accuracy of  the test.

      7.17B    Wait 30 seconds.

      7.18B    Gently  press the control bar again to allow another SMALL amount
of the sample to be drawn  into the Titret.

               CAUTION: Do  not  press the  control bar unless the sample  pipe is
               immersed in  the sample.  This prevents air from being drawn into
               the  Titret.

      7.19B   After each addition, rock the entire assembly to mix the contents
of the Titret.  Watch  for  a color change from purple to very pale yellow.

      7.20B    Repeat  Steps 7.I8B  and  7.19B unti" the color change occurs.

               CAUTION: The end point color change (from purple to pale yellow)
               actually goes through an intermediate gray  color.   During  this
               intermediate stage,  extra  caution should  be taken to bring  in
              SMALL amounts  of sample and to mix the Titret contents well.

      7.21B   When the color of the liquid in the Titret changes to PALE YELLOW,
remove the Titret  from the Titrettor" .  Hold the Titret in a vertical  position
and carefully read the test result on the scale opposite the liquid level.

      7.22B   Calculation

               7.22.IB  To obtain  results  in micrograms per gram total chlorine,
      multiply scale units on the Titret by 1.3 and then subtract 200.

                                   9077 -  10                       Revision  0
                                                                  September 1994

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8.OB  QUALITY CONTROL

      8.IB     Refer to  Chapter  One  for  specific quality control procedures.

      8.2B     Each  sample should be tested two times.  If the  results  do  not
agree to within 10%, expressed as the relative percent difference  of the results,
a third test must be performed.  Report the results of the two that  agree.

9.OB  METHOD PERFORMANCE

      9.IB     These data  are  based  on  49  data  points  obtained  by  seven
laboratories who each analyzed four used  crankcase oils and  three  fuel oil blends
with crankcase in duplicate.   A  data point represents one duplicate analysis of
a sample.   There were no outlier data points or laboratories.

      9.2B     Precision.   The  precision  of the method as  determined by  the
statistical examination of inter!aboratory test results is as  follows:

               Repeatability - The difference between successive results obtained
               by  the same  operator with  the same  apparatus  under  constant
               operating conditions  on identical test material  would  exceed,  in
               the long  run,  in  the normal  and correct operation of the test
               method, the following values only in 1 case  in 20  (see Table  2):


                          Repeatability = 0.31  x*
      *where x is the average of two results  in

              Reproducibilitv   -   The  difference  between  two  single   and
              independent  results  obtained  by different operators working  in
              different  laboratories  on  identical test  material would  exceed,
              in the long  run,  the following values only in 1 case in 20:

                         Reproducibi lity = 0.60 x*


      *where x is the average value of two results in  Mi/9-

      9.3B    Bias.  The bias of this  test method varies with concentration,  as
shown in Table 3:

                    Bias = Amount  found  - Amount expected
                                  9077 - 11                       Revision  0
                                                                  September 1994

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                                   TABLE 2.
            REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN USED
              OILS BY THE QUANTITATIVE END POINT TEST KIT METHOD
Average value,                Repeatability,        Reproducibility,
                                                          M9/g
1,000
1,500
2,000
2,500
3,000
310
465
620
775
930
600
900
1,200
1,500
1,800
                                   TABLE 3.
            RECOVERY AND  BIAS  DATA  FOR  CHLORINE  IN  USED OILS BY THE
                    QUANTITATIVE END POINT TEST KIT METHOD
Amount
expected,
Mg/g
320 (< 750)a
480 (< 750)a
920
1,498
1,527
3,029
3,045
Amount
found ,
#g/g
776
782
1,020
1,129
1,434
1,853
2,380

Bias,
Mg/g
+16
+32
+100
-369
-93
-1,176
-665

Percent
bias
+3
+4
+11
-25
_c
-39
-22
  The  lower limit  of the kit is 750
                                   9077  -  12                       Revision 0
                                                                  September 1994

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         p*===
         L_j_fjj//
                     Titret
                   Reaction bottle
Titration via
     [Buffer
     ! bottle
      »•«*  i
    i&&2.
                                          Filtering
                                          Column
                                assembly
   A.
                          Micro pipet
JL-at:
 Figure 1.  Components of CHEMetrics Total Chlorine in Waste Oil Test Kit
          (Cat. No. K2610).
                            9077 - 13
                     Revision 0
                     September 1994

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Push plunger
down to
transfer
sample
           Figure 2.1
                                                             Figure 22
                      * Crush
          Figure 23
                                          Buffer Bottle
                 Figure 2.4
              Reaction bottle
              upsidedown in
              component tray
         Figure 2.5
Aqueous
Layer
                                                        Filtering CoJmar
                                                                        Figure 2.6
                                                         Titratioo Vial
         Figure  2.   React ion-Extraction Procedure.
                            9077 -  14
                           Revision  0
                           September 1994

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 Attaching
 the Valve
 Assembly
   Figure 3.1
                    Valve
                    Assembly
                     Titret
         \
                      Lift control bar
 Snapping
 the Tip
    Figure 3.2
 Performing the
 Analysis
    Figure 3.3
  Watch for
  color change
  here

Press control bar

  Sample pipe


   Sample —
Reading
the Result
  Figure 3.4
 Read
 scale units
 when color
 changes
 permanently
        Figure 3.  Titration Procedure
                  9077 - 15
                Revision 0
                SepteAer 1994

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                       METHOD 9077,  METHOD B
REVERSE  TITRATION  QUANTITATIVE  END  POINT  TEST KIT  METHOD
           START
     ? IE Shake glass
      vial;  pour in 1C
      react i an bottle
         1.2S Fill
      mierDpipel with
    oil;  remove excess
     oil, transfer cil
    to reaction bottle
     1  3B  Squeexe air
       f rom  reaction
     bottle, cap;  mi K
     7.4H Crush sodium
         ampoule
     7  SB  - 7 .fcB Shake
    r*actiqn  bottle for
     3D *«cor»d», wait
        ane minute
     ?.?B Pour Suffer
       into  reaction
         b o 111 *
 7 .BB -  1 9B Shake
  gent 1y; release
gaa;  ihak«, r»l*•*•
 ga*;  tu?n foottl*
 upaide  down;  wa i t
    one  BSinutE
   7.10B Prepare
 f11tering column
7.118 Filter lower
   aqueouj layer
 thro ug h f A. 11 * r i j\g
    caiufcn into
  titratien vial
 7.12B Shake vial
  ? . 138 Aartemhl*
 g 1 VB *a»*ip,bly over
     Tilret
7,14B  Insert Titret
  into Titretisr
 7 15B Snap  tip of
      Titr»t
7.16B -  7 _20B Pull
  mm*l 1  BStount ef
•ample  into Titr«t;
   nn;  wait 30
  areconda ; rcpea t
procot  unti 1 color
changes  from purpl«
  to p*l«  yellow
 ? .218 When color
  chango*  to pa 1*
Tit ret;  record t»»t
r«suit  from Titr»t
  7.22B Calculate
 concent ration of
 chlorine in ug/g
       STOP
                              9077  - 16
                                           Revision  0
                                           Septerrber  1994

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                                   METHOD C

             DIRECT TITRATION QUANTITAVE END POINT TEST KIT METHOD

4.0C  APPARATUS AND MATERIALS

      4.1C    The  CHLOR-D-TECT Q40D03  is  a complete  self-contained kit.   It
includes;  a sampling syringe to withdraw a  fixed  sample volume  for  analysis; a
polyethylene test tube #1 into which the sample is introduced for dilution and
reaction  with  metallic sodium;  a  polyethylene  tube #2 containing  a buffered
aqueous extractant and the diphenylcarbazone  indicator; a microburette containing
the mercuric nitrate titrant; and a plastic filtration funnel.  Also included are
instructions to conduct the test.

5.0C  REAGENTS

      5.1C   All necessary reagents are contained within the kit.  The diluent
solvent containing the catalyst,  the metallic sodium, and the diphenylcarbazone
are separately glass-encapsulated in the precise quantity required for analysis.
A predispensed volume  of  buffer  is contained  in the second polyethylene tube.
Mercuric nitrate titrant  is also supplied in a sealed titration  burette.

      5.2C   The  kit  should  be  examined upon  opening  to  see that  all  of the
components are present and that  all ampoules (3) are in place and not leaking.
The liquid in Tube #2  (clear cap) should be approximately 1/2 in.  above the 5-mL
line and the tube should  not  be  leaking.  The  ampoules are not supposed to be
completely full.

6.0C  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1C   See Section  6.0A of Method A.

7.DC  PROCEDURE

      7.1C   Preparation.  Open analysis carton, remove contents, mount plastic
test tubes in the provided holder.

             NOTE:  Perform the  test  in a warm, dry area  with adequate light.
             In cold weather, a truck cab is sufficient.   If a warm  area is not
             available, Step- 7.3C should be performed wh:"!e warning Tube *1 ir
             palm of hand.

      7.2C   Sample introduction.  Unscrew the white dispenser cap from Tube #1.
Slide the plunger  in the empty syringe  a few times to make certain that it slides
easily.   Place the top of the syringe in the oil sample to be tested, and pull
back on  the  plunger until it reaches  the  stop and cannot  be pulled further.
Remove the syringe from the sample container,  and wipe any excess oil from the
outside of the syringe with the enclosed tissue.  Place the tip of the syringe
in Tube il, and dispense the oil sample by depressing the  plunger. Replace the
white cap on the tube.
     Available from Dexsil Corporation,  One Hamden Park Drive,  Hamden, CT 06517.

                                   9077  -  17                       Revision 0
                                                                  September 1994

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      7.3C    Reaction.  Break the lower  (colorless) capsule containing the clear
diluent  solvent  by squeezing the  sides  of the test tube.   Mix thoroughly by
shaking  the  tube  vigorously for  30  seconds.    Crush  the upper  grey  ampoule
containing metallic sodium,  again by squeezing the sides of the test tube.  Shake
vigorously for 20  seconds.   Allow reaction to proceed for 60 seconds,  shaking
intermittently several times while timing  with a watch.

              CAUTION:  Always  crush   the  clear  ampoule  in  each  tube  first.
              Otherwise, stop the test and start over using another complete kit.
              False  (low)  results may occur and allow a contaminated sample to
              pass without detection  if  clear ampoule is  not crushed  first.

      7.4C    Extraction.  Remove caps from both tubes.  Pour the clear buffered
extraction solution from Tube #2  into Tube #1.   Replace the white cap on Tube II,
and shake  vigorously  for 10 seconds.   Vent tube by  partially unscrewing the
dispenser cap. Close cap securely, and shake for an additional  10 seconds.  Vent
again, tighten cap, and stand  tube upside  down on white  cap.   Allow phases to
separate for 2 minutes.

              NOIEi Tip Tube #2  to an  angle  of only about 45°.   This will prevent
              the holder from sliding  out.

      7.5C    Analysis.  Put filtration  funnel  into  Tube  #2.   Position Tube #1
over funnel and open nozzl-e on dispenser cap.  Squeeze the sides  of Tube fl to
dispense the clear  aqueous lower  phase through the filter into Tube 12 to the 5-
rnL line  on Tube  #2.   Remove the  filter  funnel,  and close the  nozzle  on the
dispenser cap.  Place the plunger  rod in the titration burette and press until
it clicks  into place.   Break off (do not pull off) the tip  on the titration
burette.   Insert  the burette  into Tube 12, and  tighten the cap.   Break the
colored ampoule,  and shake gently for 10 seconds.  Dispense titrant dropwise by
pushing down on burette rod in small   increments.  Shake the tube  gently to mix
titrant with solution in Tube #2  after each increment.  Continue adding titrant
until  solution turns from yellow  to red-violet.  An  intermediate pink color may
develop in the solution, but should be disregarded.  Continue  titrating until a
true red-violet color is realized.  The chlorine concentration of the original
oil sample is read directly off  the  titrating  burette  at the tip of the black
plunger.  Record  this  result immediatley as the red-violet color will fade with
time.

8.0C QUALITY CONTROL

      8.1C    Refer to Chapter One  for specific quality control procedures.

      8.2C    Each  sample  should  be tested  two times.    If the  results  do not
agree  to within 10%, expressed as  the  relative percent difference of the results,
a third test must be performed.  Report the results of the two that agree,

9.0C METHOD PERFORMANCE

      9,1C    These data are based on  96 data points  obtained by 12 laboratories
who each analyzed six used crankcase oils and two fuel  oil blends with crankcase
in duplicate.  A data point represents one duplicate analysis of  a sample.
                                   9077 -  18                      Revision 0
                                                                  September 1994

-------
      9.2C   Precision.   The  precision  of the  method as  determined  by the
statistical examination of inter!aboratory test results is  as  follows:

             Repeatability - The difference between successive  results obtained
             by  the  same  operator  with  the  same apparatus  under constant
             operating conditions on  identical test material would  exceed,  in
             the  long run,  in  the  normal  and correct  operation  of the test
             method,  the following values only in 1 case in 20 (see Table 4):


                         Repeatability = 0.175 x*
      *where x is the average of two results  in  ^9/9-

             Reproducibil ity - The difference between two single and  independent
             results  obtained  by  different  operators  working  in different
             laboratories on identical test material would  exceed,  in the long
             run, the following values only in 1 case  in  20:


                        Reproducibility =  0.331 x*


      *where x is the average value of two results in  M9/9-

      9.3C   Bias.  The bias of this test method varies with concentration, as
shown in Table 5:

                     Bias = Amount found  - Amount expected

10.0 REFERENCE

1.    Gaskill,  A.; Estes, E.D.;  Hardison, D.L.;  and Myers,  I.E.  Validation of
      Methods for Determining Chlorine in Used Oils and Oil Fuels.  Prepared for
      U.S. Environmental  Protection Agency, Office of Solid Waste.  EPA Contract
      No.  68-01-7075, wA 80.   July  1988.
                                  9077 - 19                      Revision 0
                                                                 September 1994

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                        TABLE 4.
 REPEATABILITY AND REPRQDUCIBILITY FOR CHLORINE IN USED
   OILS BY THE QUANTITATIVE END POINT TEST KIT METHOD
Average value,
    M9/g
Repeatability,
                                         Reproducibility,
500
1,000
1,500
2,000
2,500
3,000
4,000
88
175
263
350
438
525
700
166
331
497
662
828
993
1,324
                        TABLE  5.
RECOVERY AND BIAS DATA FOR CHLORINE IN USED OILS BY THE
         QUANTITATIVE  END POINT TEST KIT  METHOD
Amount
expected,
M9/g
664
964
1,230
1,445
2,014
2,913
3,812
4,190
Amount
found,
Mg/g
695
906
1,116
1,255
1,618
2,119
2,776
3,211

Bias,
Mi/g
31
-58
-114
-190
-396
-794
-1,036
-979

Percent
bias
-5
-6
-9
-13
-20
-27
-27
-23
    9077  - 20
                                                       Revision 0
                                                       Septenter 1994

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                    METHOD 9077,  METHOD C
DIRECT TITRATION  QUANTITAVE  END POINT  TEST KIT METHOD
                        STABT
                 7.1C Open  teat kit
                 1. 2C Draw  oil junto
                   i^nnge;  remove
                     •KCK33  Oil,
                  da*pen*£  oil antD
                       Tube  #1
                     7.3C Break
                 coiorle** capiule;
                   »i«;  crush gre^
                 capsule ;  wix ;  a 11 o
                 reaction to prDcee
                   for 60 **c»nd*
                  ? 4C Pour Tube #2
                 solution into Tube
                   #1;  mii; vent;
                   &!low phases ic
                      separate
                   . 5C Filter aqueous
                   owec phase in Tube
                   ^1 intc Tube #2;
                    remove filter
                       f urm«l
? SC Place p1ung«r
   in titraton
  burette;  pr»» ;
 brwal* off burett*
tip; inser t butet t«
 in Tube #2; break
 eelDred ampoule;
      ahaka
                                            ? SC Di
                                           tit rant ;
                                                   aba k
  •until aoiuticm
 turn* £r DIP y*l 1 e
   to red- violet
 7.5C Record level
  f roiti  ti t rating
     burette
      STOP
                           9077 -  21
                          Revision  0
                          Septaiter 1994

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                                 METHOD 9252A

                    CHLORIDE  fTITRIHETRIC. MERCURIC NITRATE)
 1.0   SCOPE AND APPLICATION

      1.1     This  method  is  applicable to ground water, drinking,  surface,  and
 saline waters, and domestic  and industrial wastes.

      1.2     The  method is  suitable for all  concentration ranges of  chloride
 content;  however,  in  order to avoid large titration  volume,  a sample  aliquot
 containing not more than  10  to 20 rag Cl"  per  50 mL  is  used.

      1.3     Automated  titration may be  used.

 2.0   SUMMARY OF METHOD

      2.1     An  acidified sample  is titrated with  mercuric nitrate  in  the
 presence of mixed diphenylcarbazone-bromophenol blue  indicator.  The end  point
 of the titration is the formation of the blue-violet mercury  diphenylcarbazone
 complex.

 3.0   INTERFERENCES

      3.1     Anions  and cations at  concentrations normally  found in  surface
 waters do not interfere.   However,  at the  higher concentration often found  in
 certain wastes, problems may occur.

      3.2     Sulfite  interference can be eliminated by oxidizing the 50 ml  of
 sample solution with 0.5-1 mL of H202.

      3.3 Bromide and  iodide  are also titrated with mercuric nitrate in  the same
 manner as chloride.

      3.4 Ferric and chromate ions  interfere  when present  in excess of  10 tng/L.


 4.0   APPARATUS AND MATERIALS

      4.1     Standard laboratory titriraetric equipment, including  1 mL  or 5  mL
microburet with 0.01 mL gradations.

      4.2     Class A volumetric flasks:  1 L and 100  mL.

      4.3     pH Indicator  paper.

      4.4     Analytical balance:  capable of weighing  to 0.0001 g.

 5.0   REAGENTS

      5.1     Reagent-grade  chemicals shall  be  used  in   all  tests.    Unless
 otherwise indicated,  it is  intended  that  all  reagents shall conform to  the


                                  9252A - 1                        Revision  1
                                                                   September 1994

-------
 specifications of the Committee on Analytical Reagents of the American Chemical
 Society,  where  such specifications are available.   Other grades may be  used,
 provided  it is first ascertained that the reagent is of sufficiently high purity
 to  permit its use without lessening the accuracy of  the  determination.

      5,2    Reagent  water.   All references  to water in this  method refer to
 reagent water, as defined in Chapter One,

      5.3    Standard  sodium chloride  solution,  0,025 N:  Dissolve 1.4613 g
± 0.0002  g of sodium chloride  (dried at 600°C for  1  hr)  in chloride-free  water
 in a 1 liter Class A volumetric flask and dilute to the mark with  reagent water.

      5.4    Nitric acid  (HN03) solution:  Add 3.0 ml concentrated nitric acid
to 997 ml of reagent water ("3  + 997" solution).

      5.5    Sodium hydroxide  (NaOH) solution (10 g/L):   Dissolve approximately
10 g of NaOH  in reagent water  and dilute to  1 L with  reagent water.

      5.6    Hydrogen peroxide (H202):   30%.

      5.7     Hydroquinone  solution  (10  g/L):     Dissolve  1  g  of  purified
hydroquinone in reagent water in a 100 ml Class A volumetric flask and dilute to
the mark.

      5.8   Mercuric nitrate tltrant (0.141 N):  Dissolve 24.2 g Hg(N03)2 • H20
in 900 ml of reagent water acidified with  5.0 ml concentrated HN03  in a 1  liter
volumetric  flask  and  dilute   to  the  mark  with  reagent  water.    Filter,  if
necessary.   Standardize against standard  sodium chloride solution (Step 5.3)
using the procedures outlined in Sec. 7.0.  Adjust to exactly 0.141  N and check.
Store in a dark  bottle.  A 1.00 ml aliquot is  equivalent to 5.00 mg  of chloride.

      5.9    Mercuric nitrate  titrant  (0.025 N):   Dissolve 4.2830  g Hg(N03)2 »
H20 in 50 ml  of  reagent   water  acidified  with   0.05 ml   of  concentrated
HN03 (sp. gr. 1.42)  in  a 1 liter  volumetric  flask  and dilute  to the mark with
reagent water.   Filter,  if  necessary.   Standardize against  standard  sodium
chloride solution  (Sec.  5.3) using the  procedures outlined in Sec.  7.0.  Adjust
to exactly 0.025 N  and check.   Store in a dark bottle.

      5.10   Mercuric nitrate  titrant (0.0141 N):  Dissolve 2.4200 g Hg(N03)2 •
H20 in 25 ml of reagent water acidified with  0.25 ml  of  concentrated HN03 (sp.
gr. 1.42)  in  a  1  liter Class  A volumetric flask and dilute to  the mark with
reagent water.   Filter,  if  necessary.   Standardize against  standard  sodium
chloride solution  (Sec.  5.3) using the  procedures outlined in Sec.  7.0.  Adjust
to exactly 0.0141 N and check.   Store in a  dark  bottle.  A 1  ml aliquot  is
equivalent to 500  jug of chloride.

      5.11   Mixed  indicator reagent:  Dissolve 0.5 g crystalline diphenylcar-
bazone and 0.05  g bromophenol blue powder in  75 ml 95% ethanol in  a  100 ml  Class
A volumetric  flask  and  dilute  to the mark with 95%  ethanol.   Store  in   brown
bottle and discard after 6 months.
                                  9252A - 2                       Revision 1
                                                                  September 1994

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      5.12   Alphazurine  indicator solution:   Dissolve 0.005 g of alphazurine
blue-green dye in 95% ethanol or isopropanol  in 100 ml  Class A volumetric flask
and dilute to the mark with  95% ethanol or isopropanol,

6.0   SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1    All  samples  must have been collected using  a  sampling  plan that
addresses the considerations discussed in Chapter Nine of this manual.

      6.2    There  are no special  requirements  for preservation.

7.0   PROCEDURE

      7,1    Place  50 mL of sample in  a vessel for titration.   If the concentra-
tion is  greater than 20 mg/L chloride,  use 0,141 N mercuric  nitrate titrant (Sec,
5.8) in Sec.  7.6, or dilute sample with reagent water.  If the concentration is
less than 2.5 mg/L of chloride, use 0.0141 N mercuric nitrate titrant (Sec. 5.10)
in Sec.  7.6.   Using a 1 mL or 5 mL microburet, determine an indicator blank on
50 mL chloride-free water using Sec. 7.6.  If the concentration is less than
0.1 mg/L of chloride, concentrate an appropriate volume to 50 mL.

      7.2    Add 5  to 10 drops of mixed indicator  reagent  (Sec. 5.11); shake or
swirl solution.

      7.3    If a blue-violet or red color appears, add HN03 solution (Sec. 5.4)
dropwise until  the color changes to yellow.   Proceed to Sec.  7.5.

      7.4    If  a yellow  or  orange  color forms immediately  on addition of the
mixed indicator,  add NaOH solution  (Sec.  5.5) dropwise until  the color changes
to blue-violet;  then add  HN03  solution  (Sec.  5.4)  dropwise until the  color
changes  to yellow.

      7.5    Add 1  mL excess HN03 solution  (Sec. 5.4).

      7.6    Titrate with  O.OZ5  N  mercuric nitrate titrant  (Sec.  5.9) until  a
blue-violet color persists throughout the  solution.  If volume  of titrant exceeds
10 mL or is less  than 1  mL,  use  the 0.141 N  or 0.0141 N  mercuric nitrate
solutions, respectively.   If necessary, take a small sample  aliquot.  Alphazurine
indicator solution (Sec. 5.12) may be added with the indicator to sharpen the end
point.   This  will change color shades.  Practice runs should be ;nade.

             Note: The use of indicator modifications and the presence of heavy
             metal  ions  can change  solution  colors  without  affecting  the
             accuracy of  the determination.   For example,  solutions containing
             alphazurine  may be  bright blue  when  neutral,  grayish purple when
             basic, blue-green when acidic, and blue-violet at the chloride end
             point.  Solutions containing about 100 mg/L nickel  ion and normal
             mixed  indicator are purple  when neutral, green  when  acidic,  and
             gray  at  the  chloride  end  point.    When  applying this method  to
             samples  that  contain  colored   ions  or  that  require  modified
             indicator, it is recommended that the operator become familiar with
             the specific color  changes involved by experimenting with solutions
             prepared as  standards  for comparison of color effects.


                                  9252A - 3                        Revision 1
                                                                  September 1994

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              7.6.1    If chromate  is present  at 100  mg/L and  iron  is  not
      present, add 2 ml of fresh hydroquinone solution (Sec. 5.7).

              7.6.3    If ferric ion is present  use a volume containing no more
      than 2.5 mg of ferric ion  or ferric ion plus chromate  ion.  Add 2 ml fresh
      hydroquinone solution (Sec. 5.7).

              7.6.4    If sulfite ion  is  present,  add 0.5  ml  of  H202  solution
      (Sec. 5.6) to a 50 mL sample and mix for 1 min.

      7.7     Calculation:

                                (A - B)N x 35,450
          mg chloride/liter =	
                                  ml of sample

             where:

                      A = ml  titrant for  sample;

                      B = ml  titrant for  blank; and

                      N = normality  of  mercuric nitrate titrant.

8.0   QUALITY CONTROL

      8.1    All quality control  data  should be maintained  and  available for
easy reference or inspection.  Refer to  Chapter One for specific quality control
guidelines.

      8.2    Analyze  a  standard  reference  material  to  ensure  that  correct
procedures are being followed and  that  all standard reagents have been prepared
properly,

      8.3    Employ  a minimum  of one  blank per analytical  batch  or  twenty
samples, whichever  is  more frequent,  to  determine  if contamination has occurred.

      8.4    Run one  matrix  spike and  matrix duplicate every analytical  batch
or twenty samples,  whichever  is more frequent. Hatrix spikes and duplicates are
brought through the whole sample preparation and  analytical  process.

9.0   METHOD PERFORMANCE

      9.1  Water samples—A  total of 42  analysts in 18  laboratories analyzed
synthetic water samples containing exact increments of chloride, with the results
shown in Table 1. In  a  single laboratory,  using surface  water samples  at  an
average  concentration of  34 mg  CV/L,  the  standard  deviation was +1.0.  A


                                  9252A - 4                       Revision 1
                                                                  September 1994

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synthetic unknown sample  containing 241 mg/L chloride, 108 mg/L Ca,  82 mg/L Mg,
3.1 mg/L K,  19.9 mg/L  Na,  1.1 mg/L nitrate N,  0.25  mg/L nitrate N,  259  mg/L
sulfate and 42.5 mg/L total alkalinity (contributed by NaHC03)  in  reagent water
was analyzed in  10  laboratories  by  the  mereuri metric method,  with  a  relative
standard deviation of  3.3% and a  relative  error  of  2.9%.

      9.2  Oil  combustates- -These data are based on 34 data points  obtained by
five laboratories who each analyzed four used crankcase oils  and three fuel  oil
blends with crankcase oil in duplicate.  The samples were combusted using Method
5050.   A data point represents one duplicate  analysis  of a  sample.   One  data
point  was judged to  be  an outlier and was  not  included in  these results.

           9.2.1  Precision and bias.

                  9.2.1.1 Precision. The  precision of the method  as determined
           by the statistical  examination of interlaboratory  test  results is as
           f ol 1 ows :

                  Repeatability  - The  difference between  successive results
           obtained  by the same operator with the same apparatus under constant
           operating conditions on identical test material  would exceed, in the
           long  run, in the normal and correct operation of the  test  method,  the
           following values only  in 1 case  in 20  (see Table 2):
                         Repeatability - 7 .61
           *where  x  is  the average of two results in M9/9-

                  Reproducibility  -  The difference  between  two  single and
           independent  results  obtained by  different  operators  working  in
           different laboratories  on  identical  test material  would exceed,  in
           the  long  run, the following values only  in 1 case in 20:
                       Reproducibility = 20.02
           *where  x  is  the average value of two results in ug/g.

                  9.2.1.2    Bias.    The  bias  of  this  method   varies  with
           concentration, as shown in Table 3:

                    Bias = Amount found -  Amount expected
                                 9252A  - 5
Revision 1
September 1994

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10,0  REFERENCES

1.    Annual Book of ASTM Standards,  Part 31,  "Water,"  Standard D51Z-67,  Method
A, p. 270 (1976).

2.    Standard Methods for the  Examination  of Water and Wastewater,  15th  ed,,
(I960).

3.    U.S.  Environmental  Protection  Agency, Methods for  Chemical  Analysis  of
Water and Wastes, EPA 600/4-71-020 (1983), Method 325.3.
                                  9252A - 6                       Revision  1
                                                                  September 1994

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          TABLE  1.  ANALYSES  OF  SYNTHETIC  WATER  SAMPLES
              FOR CHLORIDE  BY  MERCURIC  NITRATE  METHOD
Increment as         Precision as          Accuracy as
  Chloride        Standard Deviation     Bias      Bias
                                         (%)      (mg/L)
17
18
91
97
382
398
1.54
1,32
2.92
3.16
11.70
11.80
+2.16
+3.50
+0.11
-0.51
-0.61
-1.19
+0.4
+0.6
+0.1
-0.5
-2.3
-4.7
           TABLE 2.  REPEATABILITY AND REPRODUCIBILITY
                FOR CHLORINE IN USED OILS BY BOMB
             OXIDATION  AND MERCURIC NITRATE  TITRATION
   Average  value,       Repeatability,     Reproducibility,
       Mg/9
500
1,000
1,500
2,000
2,500
3,000
170
241
295
340
381
417
448
633
775
895
1,001
1,097
                            9252A -  7                       Revision 1
                                                            September 1994

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    TABLE 3,  RECOVERY AND BIAS DATA FOR CHLORINE  IN
             USED OILS BY BOMB OXIDATION AND
               MERCURIC  NITRATE TITRATION
 Amount          Amount
expected,        found,        Bias,        Percent
  09/9           09/9          09/9          bias
   320             460          140           +44
   480             578           98           +20
   920             968           48           +5
 1,498           1,664          166           +11
 1,527           1,515         - 12           - 1
 3,029           2,809         -220           - 7
 3,045           2,710         -325           -11
                       9252A - 8                       Revision  1
                                                       Septenfcer 1994

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                    METHOD 9252A
  CHLORIDE  (TITRIMETRIC,  MERCURIC NITRATE)
      ST*RT
  7  1 PUe« SO ml
aasipia s.n titrate on
 vftsml;  d«t*rffltn«
 conc€rstralion of

 tiIfant  to u*« in
Step 7 6;  d*l*r«un«
an tndicator blank
                       7 6 Titr*t»
                       se? evtr i,s r.i. Ira e
                       un t i1
                           f p«r*itt
hydr o>id«
biu«- viol*
...Pi. >.
unL il
t ; add
y.llo.
                         7 ? Caicul*t«
                       conc»ntr* tion of
                      chiorid* in *«»pl«
                            STO?
                    9252A  - 9
Revision  1
Septenfcer 1994

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                                  METHOD 9253

                    CHLORIDE  fTITRIMETRIC.  SILVER NITRATE)


 1.0   SCOPE AND APPLICATION

      1.1    This  method  is  intended primarily for oxygen bomb combustates or
 other waters where the chloride content is 5 mg/L or more and where interferences
 such as  color  or  high  concentrations  of heavy metal  ions  render  Method 9252
 impracticable.

 2.0   SUMMARY OF METHOD

      2.1    Water adjusted to pH 8.3  is  titrated with silver nitrate solution
 in the presence of potassium chromate indicator.   The end  point  is  indicated by
 persistence of the orange-silver chromate color.

 3.0   INTERFERENCES

      3.1    Bromide, iodide, and sulfide are titrated along with the chloride.
 Orthophosphate and polyphosphate interfere if present in concentrations greater
 than 250 and 25 mg/L,  respectively.  Sulfite  and objectionable color  or turbidity
 must be eliminated.  Compounds that precipitate at pH 8.3 (certain hydroxides)
 may cause error by occlusion,

      3.2    Residual sodium carbonate from the bomb combustion may react with
 silver nitrate to produce the precipitate,  silver carbonate.  This competitive
 reaction may interfere with the  visual detection  of the end point.  To remove
 carbonate from  the test  solution, add small quantities of sulfuric acid followed
 by agitation.

 4.0   APPARATUS AND MATERIALS

      4.1    Standard laboratory titrimetric equipment, including  1 ml or 5 mL
microburet with 0.01  ml gradations,  and 25 mL buret.

      4.2    Analytical balance:  capable of weighing to  0.0001 g.

      4.3    Class A volumetric flask:  1 L.

 5.0   REAGENTS

      5.1    Reagent  grade chemicals  shall  be  used  in  all  tests.    Unless
otherwise indicated,  it is  intended  that  all reagents  shall  conform  to the
 specifications  of the Committee  on Analytical  Reagents of  the American Chemical
 Society, where such  specifications  are available.   Other grades may  be used,
provided it  is  first ascertained that the reagent  is  of sufficiently high purity
to permit its use without lessening the accuracy of the determination.

      5.2    Reagent water.   All  references to water  in  this  method  refer to
reagent water,  as defined in Chapter One.

      5.3    Hydrogen peroxide (30%), H20r

                                   9253 - 1                        Revision 0
                                                                   September 1994

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       5.4     Phenolphthalein indicator solution (10 g/L).

       5.5     Potassium chromate  indicator solution.  Dissolve 50 g  of potassium
 chromate (K2Cr04) in  100 ml of reagent water  and  add silver nitrate (AgN03)  until
 a slightly red precipitate is produced.  Allow the solution  to stand, protected
 from light, for  at least 24  hours after the addition of AgN03.  Then filter  the
 solution to remove the precipitate  and dilute to  1  L with reagent water,

       5.6     Silver  nitrate  solution, standard (0.025N).  Crush approximately
 5 g of silver  nitrate (AgNO,)  crystals and  dry  to constant  weight  at 40°C.
 Dissolve 4.2473  ± 0.0002 g of the crushed,  dried  crystals in  reagent water  and
 dilute  to  1  L  with  reagent water.    Standardize  against  the  standard NaCl
 solution, using  the procedure given  in Section  7.0.

       5.7     Sodium  chloride solution, standard (0.025N).   Dissolve 1.4613 g
 ± 0.0002 g of sodium chloride (dried  at 600°C for 1 hr)  in chloride-free water
 in a 1  liter Class A  volumetric flask and dilute to the mark  with reagent water.

       5.8     Sodium hydroxide solution  (0.25N).  Dissolve approximately 10 g of
 NaOH in reagent  water  and dilute to  1  L with reagent water.

       5.9     Sulfuric  acid (1:19),  HZS04. Carefully add 1 volume of concentrated
 sulfuric acid to  19 volumes  of reagent water, while mixing.

 6.0   SAMPLE COLLECTION, PRESERVATION, AND  HANDLING

      6.1    All  samples  must have been collected  using a  sampling plan that
 addresses the considerations discussed in Chapter Nine of this manual,

      6.2    There are no special requirements  for preservation.

 7.0   PROCEDURE

      7.1    Pour 50 mL or  less  of the sample,  containing  between 0.25 mg  and
 20 mg of chloride ion,  into a  white porcelain container.  Dilute to approximately
 10 ml with reagent water, if necessary.  Adjust the pH to the phenol phthalein end
 point (pH 8.3) using H2S04  (Sec.  5.9)  or NaOH  solution  (Sec.  5.8).

      7.2    Add  approximately 1.0 mL of K.Cr04 indicator solution and mix.  Add
 standard AgN03  solution dropwise from a *25 ml  buret  until  the  orange color
 persists throughout the sample when illuminated with a yellow light or viewed
with yellow goggles.   Be consistent with endpoint recognition.

      7.3    Repeat the procedure described in Sees. 7.1 and  7.2 using exactly
one-half as much  original  sample, diluted to 50 mL with  halide-free water.

      7.4    If  sulfite ion  is  present, add  0.5 mL  of H,02  to  the  samples
described in Sees. 7.2  and 7.3 and mix for 1  minute.  Adjust tne pH, then proceed
as described in Sees.  7.2 and 7.3.
                                   9253 - 2                       Revision 0
                                                                  September 1994

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       7.5     Calculation

              7.5.1    Calculate the chloride ion concentration in the original
       sample,  in  milligrams  per liter,  as follows:

              Chloride (mg/L) = [(V1 - V2) x N x 71,000] / S

              where:

              Vj -     Milliliters of standard AgNO, solution added in titrating
                      the sarple prepared in Sec.  7.1.

              V2 =     Miliniters of standard AgNO, solution added in titrating
                      the sample prepared in Sec.  7.3.

              N =     Normality of standard AgN03  solution.

              S -     Mill inters of original sample in  the  50 ml test sample
                      prepared in Sec.  7.1.

         71,000 =     2 x 35,500 mg Cl"/equivalent, since Vx - 2V2.


8.0   QUALITY CONTROL

      8.1     All  quality control  data  should be  maintained  and  available for
easy reference or inspection.  Refer to Chapter One for  specific quality control
guidelines.

      8.2     Analyze  a  standard  reference  material   to ensure  that  correct
procedures are being followed and that  all standard reagents have been prepared
properly.

      8.3     Employ  a minimum of one  blank per  analytical  batch  or  twenty
samples, whichever is  more frequent, to determine if contamination has occurred.

      8.4     Run  one  matrix  spike and  matrix duplicate every analytical batch
or twenty samples, whichever  is more frequent.  Matrix spikes and duplicates are
brought through the whole sample preparation and analytical process.


9.0   METHOD PERFORMANCE

      9.1    These  data  are  based  on  32  data  points  obtained  by  five
laboratories who each  analyzed  four used crankcase  oils and three fuel oil blends
with crankcase in duplicate.   The samples were combusted using Method 5050.  A
data point represents  one duplicate analysis of a sample.  Three data points were
judged to be outliers and were not included in these results.

             9.1.1    Precision.   The  precision of the  method as determined by
      the  statistical  examination  of  inter-laboratory  test results  is  as
      follows:
                                   9253 - 3                       Revision 0
                                                                  September 1994

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              Repeatability - The difference between successive results obtained
      by  the  same operator with  the  same apparatus under  constant  operating
      conditions on identical test material would exceed,  in  the  long run,  in
      the normal and correct operation  of  the test method, the following values
      only in 1 case in 20 (see Table 1):


                          Repeatability = 0.36 x*
      *where x 1s the average of two results in

             Reproduclbilitv - The difference between two single and independent
      results obtained by different operators working in different laboratories
      on identical test material would exceed, in the  long  run,  the following
      values only in 1 case in 20:
                         Reproducibility = 0.71 x*
       where x is  the  average  of  two  results  in jig/g,


             9.1.2    Bias.  The bias of this method varies with concentration,
      as shown in  Table 2:                                                           \


                    Bias  = Amount found - Amount expected

10,0  REFERENCES

1.    Rohrbough,  W.6.;  et al.  Reagent Chemicals,  AmericanChemical  Society
Specifications. 7th ed.; American Chemical  Society:  Washington, DC,  1986.

2.    1985 Annual  Book of ASTM  Standards, Vol.  li.Oi;  ''Standard Specification for
Reagent Water"; ASTM:  Philadelphia,  PA, 1985; 01193-77.

3.    Gaskill, A.; Estes,  E. D.; Hardison, D. L.; and Myers, L.  E.  "Validation
of Methods for Determining Chlorine  in Used  Oils and Oil  Fuels," Prepared for
U.S. Environmental Protection  Agency, Office  of  Solid Waste.  EPA Contract No.
68-01-7075, WA 80.  July 1988.
                                   9253 - 4                       Revision 0
                                                                  September 1994

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                                   TABLE 1.
            REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN USED
              OILS  BY  BOMB  OXIDATION  AND SILVER  NITRATE TITRATION
Average value
Repeatability
   (M9/9)
Riproducibility
      (M9/9)
500
1,000
1,500
2,000
2,500
3,000
180
360
540
720
900
1,080
355
710
1,065
1,420
1,775
2,130
                                   TABLE 2.
             RECOVERY AND BIAS DATA  FOR CHLORINE  IN  USED  OILS  BY
                 BOMB OXIDATION AND  SILVER NITRATE TITRATION
Amount
expected
(M9/9)
320
480
920
1,498
1,527
3,029
3,045
Amount
found
(^g/g)
645
665
855
1,515
1,369
2,570
2,683

Bias,
(M9/9)
325
185
-65
17
-158
-460
-362

Percent
bias
+102
+39
~7
+1
-10
-15
-12
                                   9253 -  5
                                     Revision 0
                                     September 1994

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                             METHOD 9253
             CHLORIDE  (TITRJMITRIC,  SILVER NITRATE)
                              START
                          7 i Plac.  SO mi
                        zampi* ±n porc«l*in
                            eonlainar
 "I  4 Add hydre§»«
paramo**; nan lor  1
                         7,1 »djy«l  pH to
                               B 3
  "1  2 *dd 1 0 nL
 otava^un chranat*.
 »tit, add *ilv«r
  nitcat* unt^.1
  or*n§* color
     p*raiala
 7  3 R»p«»t »t«p»
 7.1 aed 7 2 «ilh
1/2 ** Bueh taapl*
 dilut«d to 50 ml
   ' S Caleulat*
  enccctratian  t>{
  ior^dc in 9«(8pi*
                                                       STOP
                             9253  -  6
                    Revision 0
                    Septenfcer 1994

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                                 METHOD 9040A

                         PH ELECTROHETRIC MEASUREMENT


1.0  SCOPE AND APPLICATION

      1.1    Method 9040 is used to measure the pH of aqueous wastes and those
multiphase wastes where the aqueous phase  constitutes at least 20% of the total
volume of the waste.

      1.2    The corrosivity of concentrated acids and bases,  or of concentrated
acids  and  bases  mixed with  inert substances,  cannot  be measured.    The  pH
measurement requires some water content.

2.0   SUMMARY

      2.1    The pH of the sample  is determined electrometrically using either
a glass  electrode  in  combination  with a  reference potential  or  a combination
electrode.    The measuring  device  is  calibrated using a  series of  standard
solutions of known pH.

3.0   INTERFERENCES

      3.1    The  glass  electrode,  in  general,  is  not  subject to  solution
interferences from color, turbidity, colloidal matter, oxidants, reductants, or
moderate (<0.1 molar solution) salinity.

      3.2    Sodium error at pH levels >10 can be reduced or eliminated by using
a low-sodium-error electrode.

      3.3    Coatings  of  oily material   or  particulate  matter  can  impair
electrode response.  These coatings can usually be  removed by gentle wiping or
detergent washing,  followed  by rinsing with  distilled  water.   An  additional
treatment with hydrochloric acid (1:10) may be necessary to remove any remaining
film.

      3.4    Temperature effects on the electrometric determination of pH arise
from two sources.   The first  is  caused  by the change in electrode  output at
various temperatures.   This interference should be  controlled with instruments
having temperature compensation or  by calibrating the electrode-instrument system
at the temperature of  the samples.   The second source of temperature effects is
the change  of pH due to changes in  the sample as the temperature changes.  This
error is sample-dependent and  cannot be controlled.   It should,  therefore, be
noted by reporting both the pH and temperature at the time of analysis.

4.0   APPARATUS AND MATERIALS

      4.1    pH meter;  Laboratory or field model. Many instruments are commer-
cially available with various specifications and optional  equipment.

      4.2    Glass electrode.
                                   9040A  -  1                       Revision 1
                                                                  September 1994

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      4,3     Reference electrode:  A silver-silver chloride or other reference
electrode of  constant potential may be used,

              NOTE:  Combination  electrodes  incorporating  both measuring  and
              referenced functions are convenient to use and are available with
              solid, gel-type filling materials that require minimal maintenance.

      4.4     Magnetic stirrer and Teflon-coated stirring  bar.

      4.5     Thermometer and/or temperature sensor for automatic compensation.

5.0   REAGENTS

      5.]     Reagent  grade  chemicals  shall  be  used  in  all  tests.    Unless
otherwise indicated,  it  is  intended  that all reagents  shall conform  to  the
specifications of the Committee on Analytical  Reagents of  the American Chemical
Society, where  such  specifications  are  available.   Other grades  may  be used,
provided it  is first  ascertained that the reagent  is of sufficiently high purity
to permit its use without lessening the accuracy  of the determination.

      5.2     Primary  standard  buffer salts  are  available  from  the  National
Institute of  Standards and Technology (NIST)  and should  be  used in situations
where extreme accuracy is  necessary.  Preparation  of reference solutions from
these  salts   requires  some  special  precautions  and  handling,  such  as  low-
conductivity  dilution water, drying ovens,  and carbon-dioxide-free purge gas.
These solutions should be replaced at least once  each month.

      5.3     Secondary standard buffers  may  be  prepared  from NIST  salts  or
purchased as  solutions from  commercial vendors.  These  commercially available
solutions have been  validated  by  comparison  with  NIST  standards  and  are
recommended  for routine use.

6.0   SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

      6,1    All samples  must be collected using a sampling plan that addresses
the considerations discussed in Chapter  Nine of this  manual.

      6.2     Samples should be analyzed as soon as  possible.

7.0   PROCEDURE

      7.1     Calibration:

              7.1.1    Because of the wide  variety of pH meters and accessories,
      detailed operating procedures cannot  be incorporated  into  this method.
      Each analyst must  be acquainted with the  operation of  each  system  and
      familiar with all instrument functions.  Special attention to care of the
      electrodes is recommended.

              7.1,2    Each  instrument/electrode system must  be calibrated at a
      minimum of two  points that  bracket the expected pH of the samples and are
      approximately three pH  units or more apart.   (For corrosivity characteri-
      zation,  the calibration of the pH meter should include  a buffer of pH 2
      for acidic  wastes  and  a pH  12  buffer  for  caustic  wastes.)   Various

                                  9040A - 2                       Revision 1
                                                                  September 1994

-------
       instrument   designs  may   involve   use  of  a  dial  (to  "balance"  or
       "standardize")  or  a  slope  adjustment,  as outlined  in the manufacturer's
       instructions.  Repeat adjustments on successive portions of the two buffer
       solutions until readings are within 0.05 pH units of the buffer solution
       value.

       7.2     Place the sample or buffer solution in a clean glass beaker using
a sufficient volume to cover  the  sensing elements of the electrodes  and to give
adequate clearance for  the magnetic stirring bar.   If  field measurements are
being made, the electrodes  may be immersed directly into the sample stream to an
adequate depth and moved  in a manner to ensure sufficient sample movement across
the electrode-sensing element as indicated by drift-free  readings (<0.1 pH).

      7.3     If the sample temperature differs by more than  2"C from the buffer
solution, the measured pH  values must be  corrected,   Instruments are equipped
with automatic or  manual  compensators that electronically adjust for  temperature
differences.  Refer to manufacturer's instructions.

      7.4    Thoroughly  rinse and gently wipe the electrodes prior to measuring
pH of samples.  Immerse  the electrodes into the sample beaker or sample stream
and gently  stir  at a constant rate  to  provide homogeneity  and  suspension of
solids.   Note and  record  sample pH and  temperature.   Repeat  measurement on
successive aliquots of sample until values  differ by <0,1 pH units. Two or three
volume changes are usually sufficient.

8.0   QUALITY CONTROL

      8.1    Refer  to Chapter One for the appropriate QC  protocols.

      8.2    Electrodes  must be thoroughly rinsed between samples.

9.0   METHOD PERFORMANCE

      9.1    Forty-four  analysts in twenty laboratories analyzed six synthetic
water samples containing exact increments of hydrogen-hydroxyl  ions, with the
following results:
                                                      	Accuracy as	
                      Standard Deviation                Bias             Bias
pH Units                   pH  Units                      %            pH Units

   3.5                       0.10                     -0.29             -0.01
   3.5                       0.11                     -0.00
   7.1                       0.20                     +1.01            +0.07
   7.2                       0.18                     -0.03             -0.002
   8.0                       0.13                     -0.12             -0.01
   8.0                       0.12                     +0.16            +0.01
10.0 REFERENCES

1.    National Bureau of Standards, Standard Reference Material Catalog 1986-87,
      Special Publication 260.
                                   9040A  - 3                       Revision 1
                                                                  September 1994

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          METHOD  9040A
pH  ELECTROMETRIC MEASUREMENT
               Stan
           7.1 Calibrate pH
               meter.
           7.2 Place sample
           or buffer solution
           in glass beaker.
              7.3 Does
             temperature
            differ by more
            than 2C from
               buffer?
 7,3 Corrsct
measured pH
   values.
             7.4 Immerce
             electrodes and
             measure pH of
               sample.
          7.4 Note and record
          pH and temperature;
          repeat 2 or 3 times
             with different
               aliquots.
                 Stop
            9040A  -  4
           Revision 1
           September 1994

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                                 METHOD 90458

                               SOIL AND WASTE pH
1.0   SCOPE AND APPLICATION
      1.1     Method  9045  is  an  electrometric procedure for measuring pH  in
soils and waste samples.  Wastes may be solids, sludges, or non-aqueous
liquids.  If water is present,  it must constitute less than 20% of the total
volume of the sample.

2.0   SUMMARY OF METHOD

      2.1     The sample is mixed with reagent water, and the pH of the
resulting aqueous solution is measured.

3.0   INTERFERENCES

      3.1     Samples with very  low or very high pH may give incorrect
readings on the meter.  For samples with a true pH of >10, the measured pH may
be incorrectly low.  This error can be minimized by using a low-sodiurn-error
electrode.  Strong acid solutions, with a true pH of <1, may give incorrectly
high pH measurements.

      3.2     Temperature fluctuations will cause measurement errors.

      3.3     Errors will occur  when the electrodes become coated.  If an
electrode becomes coated with an oily material  that will not rinse free, the
electrode can (1) be cleaned with an ultrasonic bath, or (2) be washed with
detergent, rinsed several  times with water, placed in 1:10 HC1  so that the
lower third of the electrode is submerged, and then thoroughly rinsed with
water, or (3) be cleaned per the manufacturer's instructions.

4.0   APPARATUS AND MATERIALS

      4.1     pH Meter with means for temperature compensation.

      4.2    Glass Electrode.

      4.3     Reference electrode:  A silver-silver chloride or other
reference electrode of constant potential  may be used.

             NOTE:  Combination electrodes incorporating both measuring and
              referenced functions are convenient to use and are available
             with solid, gel-type filling materials that require minimal
             maintenance.

      4.4    Beaker:  50-ml,

      4.5    Thermometer and/or temperature sensor for automatic
compensation.

      4.6    Analytical balance:  capable of weighing 0.1 g.

                                  9045B -  1                     Revision 2
                                                                September 1994

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5.0   REAGENTS

      5.1    Reagent grade chemicals shall be used in all tests.  Unless
otherwise indicated, it is intended that all  reagents shall  conform to the
specifications of the Committee on Analytical Reagents of the American
Chemical Society, where such specifications are available.  Other grades may
be used, provided it is first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening the accuracy of the
determination.

      5.2    Reagent water.  All references to water in this method refer to
reagent water, as defined in Chapter One.

      5.3    Primary standard buffer salts are available from the National
Institute of Standards and Technology (NIST)  and should be used in situations
where extreme accuracy is necessary.  Preparation of reference solutions from
these salts requires some special precautions and handling,  such as low-
conductivity dilution water, drying ovens, and carbon-dioxide-free purge gas.
These solutions should be replaced at least once each month.

      5.4    Secondary standard buffers may be prepared from NIST salts or
purchased as solutions from commercial  vendors.   These commercially available
solutions, which have been validated by comparison with NIST standards, are
recommended for routine use,

6.0   SAMPLE PRESERVATION AND HANDLING

      6.1    All samples must be collected using a sampling plan that
addresses the considerations discussed  in Chapter Nine of this manual.

      6.2    Samples should be analyzed as soon as possible.

7.0   PROCEDURE

      7.1    Calibration:

             7.1.1    Because of  the wide  variety  of  pH meters  and
      accessories, detailed operating procedures cannot be incorporated into
      this method.  Each analyst must be acquainted with  the operation of each
      system and <3mi;iar with  &•..  instrument funct'or.s.   ipecac..  etwen'C'or, to
      care of the electrodes is recommended.

             7.1.2    Each  instrument/electrode  system must be  calibrated  at a
      minimum of two points that bracket the  expected pH  of the samples and
      are approximately three pH units  or more apart.  Repeat adjustments on
      successive portions of the two buffer solutions until  readings are
      within 0.05 pH units of the buffer solution value.

      7.2    Sample preparation and pH measurement of soils:

             7.2.1    To  20  g of  soil in  a  50-mL  beaker,  add  20  mL  of  reagent
      water, cover,  and continuously stir the suspension  for 5 minutes. .
                                       9045B  -  2                 Revision 2
                                                                September 1994

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Additional dilutions are allowed if working with hygroscopic soils and
salts or other problematic matrices.

        7.2.2    Let the soil  suspension  stand  for about 1  hour  to allow
most of the suspended clay to settle out from the suspension or filter
or centrifuge off the aqueous phase for pH measurement.

        7.2.3    Adjust  the  electrodes  in the clamps  of the electrode
holder so that, upon lowering the electrodes into the beaker, the glass
electrode will be immersed just deep enough into the clear supernatant
solution to establish a good electrical  contact through the ground-glass
joint or the fiber-capillary hole.   Insert the electrodes into the
sample solution in this manner.  For combination electrodes, immerse
just below the suspension.

       7.2.4    If the  sample  temperature differs by more  than  2°C from
the buffer solution, the measured pH values must be corrected.

       7.2.5    Report  the  results  as  "soil pH  measured in water  at 	
°C" where "	°C" is the temperature at which the test was conducted.

7.3    Sample preparation and pH measurement of waste materials;

       7.3.1    To 20 g  of  waste  sample  in  a 50-mL beaker,  add  20 ml  of
reagent water, cover,  and continuously stir the suspension for 5
minutes. .   Additional  dilutions are allowed if working with hygroscopic
wastes and salts or other problematic matrices.

       7.3.2    Let  the  waste  suspension stand  for about  15 minutes to
allow most of the suspended waste to settle out from the suspension or
filter or centrifuge off aqueous phase for pH  measurement.

       NOTE:  If the waste is hygroscopic and  absorbs all the reagent
       water, begin the experiment again using 20 g of waste and 40 ml
       of reagent water.

       NOTE:  If the supernatant is multiphasic, decant the oily phase
       and measure the pH of the aqueous phase.  The electrode may need
       to be cleaned (Step 3.3} if it becomes  coated with an oily
       material.

       7.3.3   Adjust  the  electrodes  in the clamps  of  the  electrode
holder so that,  upon lowering the electrodes  into the beaker, the glass
electrode will be immersed  just deep enough into the clear supernatant
to establish good electrical  contact through the ground-glass joint or
the fiber-capillary hole.   Insert the electrode into the sample solution
in this manner.   For combination  electrodes, immerse just below the
suspension.

       7.3.4    If the  sample  temperature differs by more  than  2"C from
the buffer solution, the measured pH values must be  corrected.

       7.3.5   .Report  the  results  as  "waste pH measured  in  water  at  _
°C" where "	°C"  is the temperature at which the test was conducted.

                            9045B  - 3                 Revision  2
                                                      September 1994

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8.0   QUALITY CONTROL

      8.1    Refer to Chapter One for the appropriate QC protocols,

      8.2    Electrodes must be thoroughly rinsed between samples.

9.0   METHOD PERFORMANCE

      9.1    No data provided.

10.0  REFERENCES

1.    Black, Charles Allen;  Methods of Soil  Analysis;  American Society of
      Agronomy:   Madison,  WI, 1973.

2,    National  Bureau of Standards,  Standard Reference Material  Catalog, 1986-
      87, Special  Publication 260.
                                   9045B  - 4                 Revision 2
                                                            September 1994

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                                              METHOD  9045B

                                           SOIL AND WASTE  pH
                                  Start
                               7.1 Calibrate
                              each instrument/
                                 electrode
                                 system.
 7.2.1 Add 20 ml
water to 20 g soil;
 stif  continuously
  for 5 minutes.
                                                     7.3.1 Add 20 ml
                                                   water to 20 g waste;
                                                     stir continuously
                                                      for 5 minutss.
  7.2.2 Lst soil
   suspension
   stand for 1
  hour or filter.
                                                      7.3.2 Let waste
                                                        suspension
                                                        stand for 15
                                                      minutes or filter.
                                       Insert
                                     electrodes
                                    into sample
                                      solution.
                                         Do
                                       sample
                                     and buffer
                                     sol'n temps
                                       vary by
                                        2C?
  Correct
measured pH
  values.
                                       Report
                                     results and
                                     temperature
                                                            IS
                                                        supernatant
                                                        multiphasic?
                                                                                      Repeat experiment
                                                                                      with 20 g waste
                                                                                      • nd 40  mi water.
  Decant oily
    phase;
measure pH of
aqueous phase.
                                                                                              Aqueous
                                                                                                Phase
                                                9045B  -  5
                                                                          Revision  2
                                                                          September 1994

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                                  METHOD 9096

                      LIQUID RELEASE TEST (LRT)  PROCEDURE


1.0   SCOPE AND APPLICATION

      1.1    The  Liquid  Release Test  (LRT)  is  a laboratory  test designed to
determine whether or not  liquids  will  be released from sorbents when they are
subjected to overburden pressures in a landfill.

      1.2    Any  liquid-loaded  sorbent  that  fails  the  EPA  Paint Filter Free
Liquids Test (PFT)  (SW-846  Method 9095),  may be assumed to release liquids in
this test.  Analysts should ensure that the material in question will pass the
PFT before performing the LRT.

2.0   SUMMARY OF METHOD

      2.1    A representative sample of the liquid-loaded sorbent, standing 10
cm high in the device, is placed  between twin stainless steel screens and two
stainless-steel grids, in a device  capable  of  simulating  landfill overburden
pressures.  An  absorptive filter paper  is placed on the  side of each stainless-
steel grid opposite the sample (i. e., the stainless-steel screen separates the
sample and the  filter paper, while the stainless-steel  grid  provides a  small air
gap to  prevent wicking of liquid from  the  sample onto the  filter paper).   A
compressive force of 50  psi  is  applied to the  top of  the  sample.  Release of
liquid is indicated when  a visible wet  spot  is observed  on either filter paper.

3.0   INTERFERENCES

      3.1    When  testing sorbents   are loaded with  volatile  liquids  (e.g..
solvents),  any released  liquid migrating  to  the  filter  paper  may rapidly
evaporate.  For this reason,  filter  papers should be examined  immediately after
the test has been conducted.

      3.2    It  is  necessary to thoroughly clean and  dry  the stainless-steel
screens prior to testing to  prevent  false  positive  or false negative results,
Material caught in screen holes may impede liquid transmission through the screen
causing false negative results.  A stiff bristled brush, like those used to clean
testing sieves, may be  used to dislodge material  from holes  in  the  screens.  The
screens should  be ultrasonically cleaned with a laboratory detergent, rinsed with
deionized water,  rinsed with acetone, and thoroughly dried.

      When sorbents containing oily  substances are tested,  it may  be necessary
to use solvents (e.g., methanol or methylene chloride) to remove any oily residue
from the screens  and from the sample holder surfaces.

      3.3    When placing the 76  mm screen on top of  the  loaded sample it is
important to ensure that no  sorbent  is present on top of the screen to contact
the filter paper and cause  false  positive results.   In addition,  some sorbent
residue may adhere to container sidewalls and contact the filter as the sample

                                   9096 - 1                        Revision 0
                                                                   September 1994

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compresses under load, causing wet spots on the edges  of the filter.  This type
of false positive may be avoided by carefully  centering the 76 mm filter paper
in the device prior to initiating the test.

      3,4    Visual examination  of the sample may  indicate that  a release is
certain  (e.g..  free standing  liquid  or a  sample  that flows  like  a liquid),
raising  concern  over  unnecessary clean-up  of  the  LRT device.  An  optional  5
minute Pre-Test,  described in Appendix A  of  this  procedure, may  be  used to
determine whether or not an LRT must be performed.

4.0   APPARATUS AND MATERIALS

      4.1    LRT Device (LRTD):  A device capable of applying 50 psi  of pressure
continuously to the top of a confined, cylindrical sample {see Figure 1).  The
pressure is applied by a  piston on the top of the sample.  All  device components
contacting  the  sample (i.e.,  sample-holder,  screens,  and  piston)  should be
resistant to attack by substances being  tested.  The LRTD consists of two basic
components, described below.

             4.1.1    Sample holder:  A rigid-wall cyl inder, with a bottom plate,
      capable of holding a 10  cm high by 76 mm diameter sample.

             4.1.2    Pressure Application  Device:    In  the  LRTD  (Figure 1),
      pressure is  applied  to   the sample  by a pressure rod pushing against  a
      piston that lies directly over the sample.  The  rod may  be pushed against
      the piston  at  a set pressure using  pneumatic,  mechanical,  or hydraulic
      pressure.   Pneumatic pressure application devices should be equipped with
      a pressure gauge accurate to within  + 1 psi, to  indicate when  the desired
      pressure has been attained and whether or not  it  is adequately maintained
      during the  test.   Other types of  pressure application devices  (e.g.,
      mechanical   or  hydraulic) may  be  used if  they  can apply the specified
      pressure continuously over the ten  minute testing time.   The pressure
      application device must  be  calibrated by the  manufacturer,  using  a load
      cell or similar device placed under the piston,  to ensure that 50+1 psi
      is applied  to  the  top  of  the sample.   The pressure  application  device
      should be  sufficiently rugged  to deliver consistent pressure to the sample
      with repeated use.

      4.2    Stainless-Steel  Screens:   To  separate the sample  from  the filter,
thereby preventing false positive results from particles falling on the filter
paper. The screens  are made of stainless steel  and have hole diameters of 0.012
inches with 2025 holes per square inch.   Two diameters of screens are used;  a
larger (90 mm) screen beneath  the  sample  and a smaller (76  mm) screen that is
placed on top of the sample in the sample-holding cylinder.

      4.3    Stainless-Steel •  Grids:    To  provide  an  air   gap  between  the
stainless-steel  screen and filter paper, preventing  false positive results from
capillary action.  The grids are  made  of 1/32"  diameter, woven, stainless steel
wire cut to two diameters, 90  mm and 76 mm.
                                   9096 - 2                       Revision 0
                                                                  September 1994

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      4.4     Filter Papers:   To detect released liquid.  Two sizes, one 90 mm
 and  one  76  mm,  are  placed on the side of the screen opposite the sample.  The
 76 mm diameter filter paper has the outer 6 mm cut away except 3  conical points
 used for centering the paper (see Figure 2).  Blue, seed-germination filter paper
 manufactured by Schleicher and Schuell (Catalog Number 33900) is suitable. Other
 colored, absorptive papers may be used as long  as they provide sufficient wet/dry
 contrast for the  operator  to  clearly  see a wet spot.

      4.5    Spatula:   To  assist  in  loading and  removing  the sample.

      4.6    Rubber or  wooden mallet:  To tap the sides of the device to settle
 and level the sample.

 5.0   REAGENTS

      5.1    Reagent grade  chemicals shall  be   used  in  all  tests.   Unless
 otherwise  indicated, it  is  intended that all  reagents  shall  conform to the
 specifications of the Committee on Analytical  Reagents  of  the American  Chemical
 Society, where  such specifications are available.   Other grades may  be used,
 provided it is first ascertained that  the reagent is of  sufficiently  high purity
 to permit its use without  lessening the accuracy of the determination.

      5.2    Reagent water.   All  references  to  water  in  this  method  refer to
 reagent water, as defined  in Chapter  One.

      5.3    Acetone.

 6.0   SAMPLE COLLECTION, PRESERVATION AND HANDLING

      6.1    All  samples  should  be collected  using  a  sampling  plan  that
 addresses the considerations  discussed in "Test  Methods  for Evaluating Solid
Wastes (SW-846)." The sampling  plan should be designed  to detect  and sample any
 pockets of liquids that  may be present in a container  (i.e^, in the bottom or top
of the container).

      6.2    Preservatives should not be added to  samples.

      6.3    Samples should be tested as soon  as  possible  after collection, but
 in no case  after more  than three  days  after collection.   If  samples  must be
 stored,  they can be  stored in sealed  containers and maintained under dark, cool
 conditions  (temperature ranging between 35° and 72° F).  Samples should not be
 frozen.

7.0   PROCEDURE

      The procedure  below  was developed for the original LRTD,  manufactured by
Associated Design and Manufacturing Company  (ADM).  Procedures for other LRTDs,
along with evidence  for  equivalency to the ADM device, should be supplied by the
manufacturer.
                                   9096 - 3                       Revision 0
                                                                  September 1994

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      7.1     Disassemble  the  LRTD and make sure that  all  parts  are clean and
dry.

      7.2     Invert the sample-holding cylinder and place the large stainless-
steel screen, the large stainless-steel grid, then a 90 mm filter paper on the
cylinder base (bottom-plate side).

      7.3     Secure the bottom plate  (plate with a hole in the center and four
holes located on  the  outer circumference)  to the flange  on  the  bottom of the
sample-holding cylinder using four knob screws.

      7.4     Turn  the sample  holder assembly  to  the  right-side-up  position
(bottom-plate-side down).  Fill the sample holder with a representative sample
until the sample height measures  10 cm (up  to the etched line in the cylinder).

      7.5     Tap the  sides of the  sample holder with a rubber or wooden mallet
to remove air pockets and to settle and level the sample.

      7.6     Repeat  filling,  and  tapping  until  a sample  height  of  10  cm is
maintained after tapping.

      7.7     Smooth the top of the sample with  a spatula to create a horizontal
surface.

      7.8     Place the small stainless-steel screen,  then the small stainless-
steel grid on top of the sample.

              NOTE:  Prior  to placing  the  stainless-steel   grid  on top  of the
              screen, make sure that no sorbent material is on the grid side of
             the stainless-steel  screen.

      7.9     Place the 76 mm filter  paper  on  top  of  the small  stainless-steel
grid, making sure the filter paper is centered in the device.

      7.10   Using the piston handle (screwed into the  top of the piston) lower
the piston  into  the  sample holder until it  sits  on  top of  the  filter paper.
Unscrew and remove the handle.

      7.11    Place the loaded sample holder into position on the baseplate and
lock into place with two toggle clamps.

      7.12    Place the pressure application device on top of the sample-holder.
Rotate the device to lock it into place and insert the safety key,

      7.13   Connect air lines.

      7.14    Initiate rod movement and pressure  application by pulling the air-
valve lever toward the operator and note time on data sheet.  The pressure gauge
at the top of the pressure  application device  should  read as specified in the
factory calibration  record for  the  particular device.   If not, adjust regulator
to attain the specified pressure.

                                   9096 -  4                       Revision 0
                                                                  September 1994

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      NOTE: After pressure application, the air lines can be disconnected,  the
      toggle  clamps can  be  released,  and  the  LRTD can  be set  aside for  10
      minutes  while other LRTDs  are pressurized.   LRTD pressures  should  be
      checked  every 3  minutes to ensure that the  specified pressure  is  being
      maintained.   If the specified pressure is not being maintained to within
      +  5  psi,  the LRTD must  be  reconnected to  the  air  lines  and  pressure
      applied  throughout the  10 minute test.

      7.15   After  10  minutes place the LRTD on  the  baseplate, reconnect  air
lines and toggle clamps, and  turn off pressure  (retract the  rod) by pushing  the
air-valve lever  away from the operator.  Note time on data  sheet.

      7.16   When  the  air gauge reaches 0  psi,  disconnect the  air  lines  and
remove the pressure-application device  by removing  the safety key, rotating  the
device, and lifting it away from the sample holder.

      7.17   Screw  the piston handle into the top  of the piston,

      7.18   Lift out the piston.

      7.19   Remove the  filter  paper and immediately  examine  it for wet  spots
(wet area  on  the filter  paper).   The presence of a wet spot(s)  indicates a
positive test  (j_.._e.., liquid release).  Note results on data sheet.

      7.20   Release toggle  clamps and  remove  sample holder  from baseplate.
Invert sample holder onto suitable surface and remove the knob screws holding  the
bottom plate.

      7.21   Remove the  bottom  plate and immediately  examine  the filter  paper
for wet  spots  as described  in  Step 7.19.   Note  results  on data  sheet.    Wet
spot(s) on either filter indicates a positive test.

8.0   QUALITY CONTROL

      8,1    Duplicate samples should be  analyzed every twenty samples  or  every
analytical   batch,   whichever  is more  frequent.   Refer  to  Chapter  One  for
additional  QC protocols.

9.0   METHOD PERFORMANCE

      9.1    Precision and accuracy data are not available  at this time.

10.0  REFERENCES

1.    Hoffman,  P.,  G. Kingsbury,  B.  Lesnik, M. Meyers, "Background Document  for
the Liquid Release Test (LRT)  Procedure"; document submitted to the Environmental
Protection Agency by Research Triangle Institute:   Research Triangle  Park,  NC
under Contract No.  68-01-7075, Work Assignment 76  and Contract No. 68-WO-0032,
Work Assignment  12.
                                   9096 - 5                       Revision 0
                                                                  September 1994

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 FIGURE  1.
LRT DEVICE
     Pressure
    Application
      Device
      50  psi
                          Sample-Hoi ding Cylinder

                             Filter

                              Separator  Plate
 9096  - 6
Separator Plate

Filter

Bottom  Plate

    Revision 0
    Septate- 1994

-------
         FIGURE 2.
76 MM DIAMETER FILTER  PAPER
       9096 - 7
Revision 0
Septenter 1994

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                            FIGURE  3.
                   GLASS GRID SPECIFICATIONS.
0.25 inchf
glass rod I.
                         1,7cm
                                                  4.0 cm
                             9.7 cm
                            9096  - 8
Revision 0
Septenfcer 1994

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            FIGURE 4.
POSITIONING OF DYE ON GLASS  PLATE
         Methylene Blue
         Anthraquinone
                                            7.1 on
                 7,5  cm
            9096  -  9
Revision 0
Septaiter 1994

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             METHOD 9096
 LIQUID RELEASE TEST (LET)  PROCEDURE
C   ST»RT    J


drynass

7 2 Plae*
»er»«n , gr id
and f j.1 ter
paper on
cylinder ba»t
I
7.3 Secure
saispl* holder

7.4 - 7.5
Fill cjrl inder
with sample;
tap to remove
ai r
/'VlLder^
X. full? V^
7.7 SwootK
•ample
surface






?,8 Place
v tairtlei* - a t ••!
of aampls


? 9 Place
f il ter pap«r
on gr±d and
center in the
device


7.10 Lower
piston into
•ample holder


7 ,11 Plac*
•ample holder
on baae plate
and * »eu re

7 12

Lock
device on top
of trample
holder


7,13 Connect
air lines *






LRTD and
preBiur c for ID

7. IS - 7 .16
and rttmove
UTD fret*
»ampl« holder

7 .18 Hewov*
pi* ton

7. 19 - 7 21
Di*a**entble and
check filter
paper for vel
»pDt(«)

C STOP J

             9096  -  10
Revision 0
Septarber 1994

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                                  APPENDIX A

                         LIQUID RELEASE TEST PRE-TEST

1.0   SCOPE AND APPLICATION

      1.1    The LRT Pre-Test is an optional, 5 minute laboratory test designed
to determine whether or  not  liquids  will  be definitely  released from sorbents
before applying the LRT.   This test  is  performed to prevent unnecessary cleanup
and possible damage to the LRT device.

      1,2    This  test is  purely  optional  and  completely up to the discretion
of the operator as to when it should be used.

2.0   SUMMARY OF METHOD

      A representative sample will be loaded into a glass grid  that  is placed on
a  glass  plate  already  stained with  2 dyes  (one water  soluble  and  one oil
soluble).  A second glass plate will  be placed on  top and a 2 Ib. weight placed
on top for 5 minutes.  At the end of  5 minutes the base  of the glass grid is
examined for  any  dye running  along  the edges, this  would indicate  a liquid
release.

3.0   INTERFERENCES

      A  liquid  release  can  be  detected at  lower Liquid Loading  Levels  with
extremely clean glassware.   The glass  plates and  glass  grid should be cleaned
with a laboratory detergent,  rinsed with Deionized water, rinsed with acetone,
and thoroughly dried.

4.0   APPARATUS AND MATERIALS

      4.1    Glass Plate:  2 glass plates measuring 7.5 cm x 7.5 cm,

      4.2    Glass Grid:   See Figure 3.

      4.3    Paint Brush:  Two small paint brushes for applying dyes.

      4,4    Spatula:  To assist in loading the sample.

      4.5    Weight:  2.7 kg weight to apply pressure to the sample.

5.0   REAGENTS

      5,1    Reagent  grade  chemicals  shall be  used in  all  tests.    Unless
otherwise indicated,  it  is  intended  that  all  reagents  shall  conform  to the
specifications of  the Committee on Analytical Reagents of the American Chemical
Society,  where  such  specifications  are available.  Other grades may  be used,
provided it  is first ascertained that the reagent is of sufficiently high purity
to permit its use  without lessening the accuracy  of the  determination.

      5.2    Methylene Blue dye in methanol.
                                  9096  -  11
Revision 0
September 1994

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      5.3    Anthraquinone dye in toluene.


6.0   SAMPLE COLLECTION, PRESERVATION AND HANDLING

      See LRT Procedure.

7.0   PROCEDURE

      7.1    Paint one  strip,  approximately 1 cm wide,  of  methylene blue dye
across the center of  a  clean  and dry glass plate (see  Figure  4).   The dye is
allowed to dry.

      7.2    Paint one  strip,  approximately  1  cm wide, of anthraquinone dye
across the center of  the same glass  plate  (see Figure 4).  This strip should be
adjacent to and parallel with the methylene blue strip.  The dye is allowed to
dry,

      7.3    Place the glass grid in the center of the dye-painted glass plate.

      7.4    Place a small  amount of sample  into the glass-grid holes, pressing
down gently until the holes are filled to slightly above the grid top.

      7.5    Place a  second,  clean and dry, glass plate on top of the sample and
grid.

      7.6    Place a 2.7 kg weight on top of the glass  for  5 minutes.

      7.7    After 5  minutes remove  the weight and examine the  base of the grid
extending beyond the  sample holes for any indication  of dyed  liquid.  The entire
assembly may be turned  upside down  for observation.   Any indication of liquid
constitutes a release and the LRT does not need to be performed.

8.0   QUALITY CONTROL

      8.1    Refer to Chapter One for specific quality  control  procedures.

9.0   METHOD PERFORMANCE

      9.1    Precision  and accuracy data are not available  at this time.

10.0  REFERENCES

1.    Research Triangle Institute.   "Background Document for the Liquid Release
      Test:     Single  Laboratory  Evaluation  and  1988   Collaborative  Study".
      Submitted to the Environmental  Protection Agency under  Contract No. 68-01-
      7075,  Work Assignment 76  and Contract No. 68-WO-QQ32,  Work Assignment 12.
      September 18,  1991.
                                  9096  -  12                       Revision 0
                                                                  September 1994

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          METHOD 9096
          APPENDIX A
      STfcRT
 .1  Paint methylene
   blue itrip on
    glass.  dry
     1 2 Paint
anthraquinon* strip
 on glass para11 el
to fir * I »Irip; dry
     Place grid ir
    nler of gl**»
      plat*
1 4 Fill
holes D!
gr^d with a amp! e


7 5 Place second
9 la** plate on tep
of i.
imp 1 e
glmm* for
 1  1 Remove weight
 and check for w«t
     • pot (m }
      STOP
         9096 - 13
                        Revision 0
                        Septenter 1994

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