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  l2-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

-------
                                         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
                                                                     July 1992

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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
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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 0C.

      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
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               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-l2-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(l2,3-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
11,2-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-l3-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 30C.  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 (ghi)perylene
    Benzo(a)pyrene
    Chrysene
    Dibenz(ah)acridine
    D1benz(a,j)acr1dine
    Dibenzo(a,h)anthracene
        7H-Dibenzo(ci)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
l3S-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-l4-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*
aQ!-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*
Phosji=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
                  2,45-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

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                           TABLE 2-29.
           METHOD 8330 - NITROAROHATICS AND NITRAMINES

4-Amino-26-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
46-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
,eC
4C
4C

4C

4C

4"C

4'C
in
4C

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

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            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

-------
                                      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 TCLPLEACHATES





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""  2C 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  100C 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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            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
          50C  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  100C.   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 300C  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,  4C
     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, 4C
                                 container with Teflon
                                 lined lid
    Soil/Sediments  and  Sludges    250 ml widemouth glass      Cool,  4C
                                 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 <  60C  (140F),  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  (70F)  or, regardless of the pressure at
            21 C  (70F), having  an absolute pressure exceeding 104 psi at 54 C
            (130F), or any  liquid flammable  material  having a vapor pressure
            exceeding 40 psi absolute at 38C  (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 55C (130F), 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
                                                                   September 1994

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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 40C.
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*lhn*LiCliy
                               covibin* rvaiui t /
                               rui t of )i t rct
Canbin*
tract /
liquid
ph,***
of wct*


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
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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
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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
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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
4C.  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  4C
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
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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  + 20C
              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.

                                  1312 - 10                      Revision 0
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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 4C 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 4C  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 + 2C 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
                                                                  September 1994

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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  (4C) 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  4C  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  4C  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 4C 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
                                                                  September  1994

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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  +  2C  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 4C


                            1312  -  17                       Revision 0
                                                            September 1994

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      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

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              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

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       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
(302rpm)
Extraction vmael Holder









                                                   n
      Figure 1.   Rotary Agitation Apparatus


                       UqukJ Irtst/Outt* VHv
     TopFlangt.

 Support Screw*

            Fi
     Support Scratn'
 Bottom Rang**
   Prtsurizd 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 80C, but less  than boiling)  for a minimum of two hours followed with hot
(1:1) nitric acid  (greater than 8QC,  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

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 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
                                lntth*
7.3.$ U** M*
       *l
                                7.1.* Ai

                               MNOgt*
                                7.1,1
                               M.l
                               oarvu
                             Mnktt
                                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).
                                   3051 - 1                       Revision 0
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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

                                   3051 - 2                        Revision  0
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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   2C).  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   0.05C.    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 2C.  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 80C, but less than
boiling) for a minimum of two hours followed with hot (1:1) nitric acid (greater
than 80C, 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 175C in  5.5 minutes
      and permits  a  slow  rise  to  175  -  180C 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.


                             3051 -  7                        Revision 0
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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.


                                   3051 - 9                        Revision  0
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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.
                                  3051  -  10                       Revision 0
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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.
                                  3051 - 11                       Revision 0
                                                                  September 1994

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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
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                                   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)**
  2964
  298+5
  29510
  300+4
  297+3
  292+11
  3037
  (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  (5C).   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
400C 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 (15-20C  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 (35C)
            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

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                            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  (+ 5C).  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

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       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
                                                                September 1994

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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 (15-20C 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  (35C)
            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
                                                                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-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 ( 5C).  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
400C 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  105C.  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
(15-20C 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  35C)  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
4QQC 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 105C.   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  140C  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  4C  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 (+ 5C).   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
 400C 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.
                                  3550A - 4                         Revision 1
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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  I05C.  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
  amplf. tpifcet,
    nd blank*
 7.S.3 Add urrogate
   tndrd 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

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                       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
400C 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

-------

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                                 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
         \

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      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 - 160C, 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

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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 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
                              \

-------
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 130C 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  130C  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
400C 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

-------
                                    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

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                                               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 nxan
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-l4-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

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      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

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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 4C, 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 72F.

      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

-------
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 80-100C (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(ai)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
24-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
                                   PSTIClOeS/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
  2C.   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
400C 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  (80-90C) 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  (80-90C) 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
             (35C) 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

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         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  35C) 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

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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

-------

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                                  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 (15-20C 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  35C)   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
    Strt
 7.1.1 Carafullv
combtn* hsxane
   with 1:1
  H2SO4/H20
   solution.
    7.1.2
 Tranfr th
  appropriate
  volyntn to
     vial.
 7.1.3 - 7,1.4
  Cap. vortex
   and allow
    phaaa
  ovparetian.
    7.1.8
  Tranifar
 hx*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 dipo
                        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, vortx,
                                                      and  allow
                                                        phase
                                                     separation.
/ 7.2.4 ta \.
f Dh \ to w
t Mpvation ) 	
>. clean? /
JYea
7.
Trai
hxan
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*
layr.
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
>



>




<
>

' -''


<


c
<

>

>
>



>
5
>


>
<
<




<






>







<
>
>

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 200C 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 35C 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 180C  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 180C  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 180C  for desorption.   The  polymer section of the trap should not
be heated higher than  180C, and  the remaining sections should not exceed
220C  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 1C,  over a temperature range from ambient to 100C.


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 90-100C 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 4C 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 180C 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 180C with the  column at 220C.

            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

                                   5030A - 6                        Revision  1
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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  180C
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
      180C for Methods 8010,  8020,  8021,  8240  and 8260 and  210C  for
      Methods  8015 and 8030.    Trap temperatures  up  to  220C 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 40C
            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   105C.    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 40C + 1C (Methods 8010,
      8020 and 8021) or to  85C   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 4C 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
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                                   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
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                        Figure 1
                    Purging Chamber
       OPTIONAL
       FOAM TRAP
Inch O. D. Ixit
                             Into '4 Inch 0. 0.
      Inttt

2-Way Synnot Vl*
17 cm. 20 Gcuot tynng*
6 mm 0. 0. ftubbtr Stptum


  -IflmmO. D.
                                   Inltt
                                   )4 Inch 0. 0.
                      1'16lnct0 D.
                      St*mlu SIM:
                                                    Flow Control
   Midium NMHV
                        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 ppd
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
                                        Stml 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 ;;

Gfi Wool    5 mm

%
I
k
i
   Ttnax   23 cm
i
 fej
                                       Comprtsiion Pining Nut
                                       nd Ferrule*

                                         14 Ft. 7fl/Foot Rtsittanc*
                                         Wirt WnpBtd Solid
                                                             Thrmocoupl/Controllr Senior
                                                                  Eltctronic
                                                                  Temperature
                                                                  Control and
                                                                  Pyromtttr
                                                            Tubing 25 cm
                                                            0.105 In. I.D.
                                                            0,125 In. O.D.
                                                            Stiinlen Stttl
                   Tp 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
             TO0*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 100C.

      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 180C 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 180C, 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   10C  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 <35C.   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  160C.   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 180C 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

-------
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  132C,  Hethod  0030 is not
appropriate for quantitative sampling of this analyte.

      c   Boiling point of  this compound is below  30C.  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  100C,  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 1QOC, but Method  0030 is always inappropriate for collection of compounds
with boiling points above  132C.  All  target analytes with boiling points greater
than 132C  are so  noted  in the target analyte list presented in Sec. 1.1.  Use
of Method 0030 for collection  of  compounds  boiling between 100C and  132C 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 30C may break through the sorbent under the conditions
used for sample collection.   Quantitative  values  obtained for compounds with
boiling  points below  30C 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 132C 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.
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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 180C   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 180C 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 100C.

            4.2.3 The desorber must be capable of rapidly heating the analytical
      trap to.!80C for desorption.  The polymer section  of the trap should  not
      exceed 180C, and the  remaining  sections  should not exceed 220C,  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 180C 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 -10C to -20C,  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 l2-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 -20C  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 0C.  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 4C  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
180C
11 minutes
40 mL/min
Helium, Grade 5.0
2.5 mL/min helium
Ambient
11 minutes
180C
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
200C
240C
5C
2 minutes
6C/min
240C
1 minute, or until  elution  ceases
105C
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  180C 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  18QC, with the  column  at  220C.

      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 180C,  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 180C 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  220C,    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.
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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
                                                          September 1994

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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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                                   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
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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
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                                   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
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                                   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
Sinred Class frit


     Gas Flow
                          Figure 4.   Sample Purge  Vessel
                                     5041  - 33
    Revision  0
September  1994

-------
    Slack
(or lil 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 repone
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

-------
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

      WarningOxygen 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).


                                    6020-1                        Revision  0
                                                                  September 1994

-------
      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.

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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
Miwd 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 95C  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 H0,
mat ease. HHO.,
 7 . 1 Prpmr<
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 5C 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 900C.

      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
                                                                 >_* ORIM
                         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 ncntretd
          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 125C.
            4.2.2    Ashing time  and temp:   30 sec at 500C.
            4.2.3    Atomizing time and temp:  10 sec at 1900C.
            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
10C  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 90-95C.

      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.
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                                                                  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 95C.   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  nL 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 95C,  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
                                     potaaium
                                   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