SW846PU31

                  PROPOSED  UPDATE  III
                         Cover  Sheet

      THIS PACKET CONTAINS NEW AND REVISED MATERIAL
              BEING PROPOSED FOR INCLUSION IN:
         TEST METHODS FOR EVALUATING SOLID WASTE
                 PHYSICAL/CHEMICAL METHODS
                     (SW-846) THIRD EDITION
Contents:

1.    Cover sheet.  (What you are currently reading)

2.    Instructions. Read this  section!  It explains how proposed Update III
     relates to the rest of your SW-846.

3.    Proposed Update III Disclaimer. Table of Contents, and Preface.  The
     Table of Contents (dated January 1995) lists all of the methods (Third
     Edition,  Updates I, II, IIA, IIB, and proposed Update III)  in the order
     in which they will appear in the manual when Update III is finalized.

4.    Revised Chapter Two:  Choosing the Right Method

5.    Revised Chapter Three and new/revised methods for inorganic analyses.

6.    Revised Chapter Four and new/revised methods for organic analyses.

7.    Revised  Chapter Five and new/revised methods for  miscellaneous
     analyses.

8.    Revised Chapter Six and new/revised methods for properties analyses.

9.    Revised Chapter Eight (revised section separation sheets only).

10.   Revised Chapter Ten and new/revised  methods for  sampling.
                                           U.S. Environmental Protection Agency
                                           Region 5, Library (PL-12J)
                                           77 West Jackson Boulevard, 12th Ftoor
                                           Chicago, IL  60604-3590

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f

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                             INSTRUCTIONS
SW-846, a methods manual, 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 proposes and finalizes these new
and revised  methods  as updates to the manual.  To  date, the Agency has
issued Final Updates I, II, IIA, IIB, and Proposed Update III.

These instructions include directions on where to find information on getting
your basic manual up-to-date and what to do  with your Proposed Update III
package.  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).
The following definitions are provided to you as a guide:

      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, a copy of Final Update II/IIA, a copy of
      Final Update IIB, and a copy of Proposed Update III.

      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 Proposed Update III package in the mail.
BACKGROUND INFORMATION

A number of SW-846 update packages have been released to the public since the original
Third Edition was released. The dates and labels on these packages can be confusing. The
following is a brief summary of what new subscribers and previous subscribers should check
upon receipt of the Proposed Update III package:
                               Instructions - 1              Proposed Update III
                                                               January 1995

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NEW SUBSCRIBERS - If you are a new subscriber, you should perform the following tasks
before addressing your new Proposed Update III:

     • Place the original Third Edition of SW-846 (September 1986) in the properly labeled
      four 3-ring notebooks according to the instructions in Update IIB.

    •  Incorporate Final Update I (July 1992) into the manual according to the instructions
      in Update IIB.

     • Incorporate Final Updates II (September 1994) and HA (August 1993) into the
      manual according to the instructions in Update IIB.

     • Incorporate  Update IIB (January 1995)  into the  manual  according to the
      instructions in Update IIB.
PREVIOUS SUBSCRIBERS - If you are a previous subscriber, it is important to establish
exactly what is currently contained in your manual before addressing Proposed Update III.
If your manual is properly updated, the ONLY white pages in the document should be
dated September 1986 (Third Edition), July 1992 (Final Update I), August 1993 (Final
Update HA),  September 1994 (Final Update II), and January 1995 (Final Update IIB).
Remove (and  recycle or archive) any white pages from your manual that have any other
dates. There may also be colored pages (e.g., yellow pages for Proposed Update II) inserted
in the manual.  Remove all yellow, blue, or green pages from the manual.  These colored
pages represent proposed  (not promulgated) versions of methods and chapters.  Some
individuals may have chosen to keep their copies of proposed versions in separate binders
and thus removal from SW-846 is not necessary.

The table on the next page (entitled "A Brief History of the SW-846, Third Edition and Its
Updates") can be used as an aid to understanding the update  history of SW-846, Third
Edition.   Finalized (promulgated) updates are printed in bold and underlined.   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 updates.
                                  Instructions - 2               Proposed Update III
                                                                     January 1995

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A BRIEF HISTORY OF THE SW-846, THIRD EDITION AND ITS UPDATES
Package
Third Edition
Proposed Update I
Final Update I
(Accidently Released)
Proposed Update II
(Accidently Released)
Final Update I
Proposed Update II
Proposed Update IIA*
(Available from EPA by
request only.)
Final Update IIA* (Included
with Final Update II.)
Final Update II
Final Update IIB**
Proposed Update III
Date Listed on Methods
September 1986
December 1987
November 1990
November 1990
July 1992
November 1992
October 1992
August 1993
September 1994
January 1995
January 1995
Color of Paper
White
Green
White
Blue
White
Yellow
White
White
White
White
Pink
Status of Package
Finalized (Promulgated)
Obsolete
Obsolete! Never formally
finalized.
Obsolete! Never formally
proposed.
Finalized (Promulgated)
Obsolete
Obsolete
Finalized (Promulgated)
Finalized (Promulgated)
Finalized (Promulgated)
Proposed
           *  Contains only Method 4010.
          **  Contains only a revised Table of Contents, a revised Chapter Six, and revised Methods 9040B
             and 9045C
PROPOSED UPDATE III

Update III has been proposed by the USEPA Office of Solid Waste for official inclusion in
the SW-846 methods manual.  The Proposed Update III package includes 37  revised
methods, six revised chapters, other revised parts (i.e., the Table of Contents, Disclaimer,
and Preface) and 61 new methods.  The  term  "proposed" indicates that the USEPA is
allowing the public the opportunity to comment on the Proposed Update III material (e.g.,
submit suggestions or recommendations regarding the content of the methods).

Regarding one of the revised chapters, the Agency has revised Chapter Eight to reflect the
proposed new location of Method 9040B in that chapter. The Agency wishes to move
Method 9040B from Chapter Six, "Properties", to Chapter Eight, "Methods for Determining
Characteristics".  Chapter Eight is the more appropriate location for Method 9040B since
                                  Instructions - 3
Proposed Update III
       January 1995

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it is the method promulgated for pH measurements in support of determinations for the
Corrosivity Characteristic, see 40 CFR § 261.22(a)(l).  (The method itself has not been
revised and is not open for  comment.)  In addition, the Agency has added  and revised
section numbers and section titles in Chapter Four to accommodate new organic methods.
Specifically, the Agency has added a section 4.3.5, "Miscellaneous Spectrometric Methods",
and moved the "Miscellaneous Screening Methods" from section 4.4 to a new section 4.5.
Section 4.4 will now contain all of the immunoassay methods, most of which will be added
as part of Update III when made final.

In order to distinguish  proposed updates from finalized (promulgated) updates, each
proposed update is printed on colored paper.  (Final updates are printed on white paper.)
The Proposed Update III package  is printed on pink paper.  "January 1995" is  the date
found in the lower right-hand corner of each page in the Proposed Update III package.
(Note: Methods 9040B and 9045C of SW-846 are also dated January 1995, but are printed
on white paper, and are part of the final and promulgated Update IIB package.  These
methods are not open for comment at this time.)

A proposed rule  has been  published  in the  Federal Register in association with this
proposed update package.  It formally announces  the proposed changes to the SW-846
manual  and states that  comments  on  the proposed rule and the Proposed Update  III
package must be submitted within 60 days after the date of publication of the proposed rule.
SW-846 methods not  contained in this package are not open to comment from the public.
In addition, as  explained in  the  proposed rule, only sections 3.2, 6.2,  7.2, 7.3, and 7.4 of
proposed Update III Method 9095A are open to comment.

As explained in the "Addresses" section of the proposed rule, the public should submit an
original  and two copies  of their comments  to  the  Docket  Clerk (OS-305), U.S.
Environmental Protection Agency, 401 M Street, SW, Washington, DC  20460.  EPA is also
asking prospective commenters to voluntarily submit one additional copy of their comments
on labeled personal computer diskettes in ASCII (TEXT)  format or  a word processing
format that can be converted to ASCII  (TEXT).  It is essential to specify on the disk label
the word processing software and version/edition as well  as the commenter's name. This
will allow EPA to convert the comments into one of the word processing formats utilized
by the Agency.  Please use mailing envelopes designed to physically protect the submitted
diskettes.  EPA emphasizes that submission of comments on diskettes is not mandatory, nor
will it result in any  advantage  or disadvantage to any commenter.   Rather,  EPA is
experimenting with this procedure as an attempt to expedite our internal review process and
response to comments.  This expedited procedure is  in conjunction  with the Agency's
"Paperless Office Effort" campaign.

Proposed methods do not become an official part of SW-846 until  after  the Agency
addresses the comments, publishes  a final rule in the Federal Register announcing the
promulgation of the  update, and publishes a final  (promulgated) version of the update

                                  Instructions - 4               Proposed Update III
                                                                     January 1995

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package for distribution. A final update package may be different from the proposed update
package to reflect technical or editorial changes made to the manual in response to public
comment or for other reasons.

In addition to requesting comment on the material in the Proposed Update III package, the
Agency is also requesting comment on the removal of 14 packed column GC and two other
methods from SW-846. The packed column methods have been superseded by capillary
column methods or other techniques that provide better resolution, selectivity and sensitivity.
The table  to follow is a list of the methods being proposed for deletion from the manual.
METHODS BEING PROPOSED FOR REMOVAL FROM SW-846
Method
Number
5040A
8010B
8020A
8030A
8040A
8060
8080A
8090
8110
8120A
8140
8150B
8240B
8250A
9200
9252A
Title
Analysis of Sorbent Cartridges from Volatile Organic Sampling Train
(VOST): Gas Chromatography/Mass Spectrometry Technique
Halogenated Volatile Organics by Gas Chromatography
Aromatic Volatile Organics by Gas Chromatography
Acrolein and Acrylonitrile by Gas Chromatography
Phenols by Gas Chromatography
Phthalate Esters
Organochlorine Pesticides and Polychlorinated Biphenyls by Gas
Chromatography
Nitroaromatics and Cyclic Ketones
Haloethers by Gas Chromatography
Chlorinated Hydrocarbons by Gas Chromatography
Organophosphorus Pesticides
Chlorinated Herbicides by Gas Chromatography
Volatile Organics by Gas Chromatography/Mass Spectrometry
(GC/MS)
Semivolatile Organic Compounds by Gas Chromatography/Mass
Spectrometry (GC/MS)
Nitrate
Chloride (Titrimetric, Mercuric Nitrate)
                                  Instructions - 5
Proposed Update III
       January 1995

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HANDLING OF PROPOSED UPDATE III

Since these are only proposed methods and chapters, the material in Proposed Update III
does not change anything in the official promulgated version of the manual (i.e., SW-846,
Third Edition, as updated by Updates I, II, IIA, and IIB). The user should not remove any
white pages from the manual at this time.  Some subscribers incorporate proposed updates
in their manual, without removing any white pages, e.g.,  they retain the proposed and
previously promulgated versions of methods side-by-side in the manual.  However, this
update  is particularly  large and the four binders  provided with SW-846 may not
accommodate all of the pages, particularly  in Volume IB, which contains the organic
methods.  Therefore, regarding the placement and storage of this proposed update, the
Agency recommends one of the following:

1.    The subscriber may place the pink sheets in the manual (without removing the white
      pages of promulgated methods) in the order that they appear in the new Update III
      Table of Contents.  Due to the volume of material in Proposed Update III, the
      subscriber can split the material in any volume (e.g., Volume IIB) into two parts and
      place one part into an extra binder supplied by the subscriber.

2.    Instead of inserting  the proposed methods into  the manual with the promulgated
      methods, the subscriber may instead simply place the entire Proposed Update III
      package into a separate binder supplied by the subscriber.

IN SUMMARY

To summarize these instructions, please note the following important points:

      This package contains Proposed Update III. The USEPA is proposing these methods
      for inclusion in SW-846.

      The public may  submit comments to  the EPA regarding these methods in paper
      and/or electronic format.  SW-846 methods not contained in this package are not
      open to comment from the public.

      Do not remove any  white pages from your copy of SW-846  at this time. Proposed
      methods do not become an official part of SW-846 until after the Agency addresses
      the comments, publishes a final  rule in the  Federal  Register announcing the
      promulgation of the update, and publishes a final (promulgated)  version of the
      update package for  distribution.

      If you have properly inserted all other updates, PROPOSED UPDATE III WILL
      NOT FIT  IN  THE  EXISTING  FOUR 3-RING  BINDER  NOTEBOOKS
      PROVIDED WITH THE MANUAL.  You may either insert (without replacing any

                                  Instructions - 6              Proposed Update III
                                                                    January 1995

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      white pages) Proposed Update III and split some of a volume into your own separate
      binder, or you may simply not insert the Proposed Update III into the manual and
      instead keep the proposed methods in your own separate binder.
ASSISTANCE

After reading these instructions, if you have any difficulties understanding the status of the
package or have technical questions regarding the methods, you may telephone the Methods
Information Communication Exchange (MICE) at 703-821-4690  for help.  If you have
questions concerning your SW-846 U.S. Government Printing Office (GPO) subscription, you
should telephone the GPO at 202-512-1806.  If you did not purchase your SW-846 from the
GPO, the GPO will not be able to help you.
SW-846 AVAILABILITY ON CD-ROM

A CD-ROM version of Test Methods for Evaluating Solid Waste, Physical/Chemical Methods
(SW-846)  is  being  developed by EPA in cooperation with the National Technical
Information Service (NTIS).  On a single disc, it will include all text and figures found in
the promulgated version of SW-846 as updated by Updates I, II, IIA, and IIB.  It will also
include Proposed Update III to SW-846.  It can be used for word searching (e.g, analytes,
keywords); and to cut and paste or export text and diagrams to update or develop laboratory
standard operating procedures (SOPs).  This SW-846 CD-ROM is scheduled for release in
the Fall of 1995. To order by phone, call NTIS at (703) 487-4650 and request order number
PB95-503249LLC.
                                 Instructions - 7               Proposed Update III
                                                                    January 1995

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                                  DISCLAIMER
      The mention  of trade names  or  commercial  products does  not constitute
endorsement  or  recommendation for  use by  the U.S.  Environmental  Protection
Agency.

      SW-846 methods are designed to be used with equipment from any manufacturer
that results in  suitable method performance (as assessed by accuracy, precision,
detection limits and matrix compatibility).  In several  SW-846 methods, equipment
specifications and settings are given for  the specific  instrument used during
method development,  or subsequently  approved for use  in  the method.   These
references are made to provide the  best possible guidance to laboratories using
this manual.  Equipment not specified  in the method may be used as long as the
laboratory achieves equivalent or  superior method performance,  or performance
appropriate  for  the  intended  testing  application.  If  alternate  equipment is
used,  the  laboratory  must  follow the manufacturer's instructions  for  their
particular instrument.

      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.
                                DISCLAIMER - 1                      Revision 2
                                                                  January 1995

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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     METHODS  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 -- INORGANIC 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 and
                              Extracts
                                    CONTENTS - 1                          Revision 4
                                                                        January 1995

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      Method 3020A:


      Method 3031:

      Method 3040A:
      Method 3050B:
      Method 3051:

      Method 3052:

      Method 3060A:
           Acid Digestion of Aqueous Samples and  Extracts for Total
           Metals  for  Analysis   by  Graphite   Furnace   Atomic
           Absorption (GFAA)  Spectroscopy
           Acid Digestion of Oils for Metals  Analysis  by  FLAA or
           ICP 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
           Microwave  Assisted  Acid  Digestion  of Siliceous  and
           Organically Based Matrices
           Alkaline Digestion for Hexavalent Chromium
3.3   Methods for Determination of Inorganic Analytes
      Method 0060:
      Method 0061:

      Method 6010B:
      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
6020:
7000A:
7020:
7040:
7041:
7060A:
7061A:
7062:
7063:

7080A:
7081:
7090:
7091:
7130:
7131A:
7140:
7190:
7191:
7195:
7196A:
7197:
7198:
7199:
7200:
7201:
7210:
7211:
7380:
7381:
7420:
Determination of Metals in Stack Emissions
Determination  of  Hexavalent  Chromium  Emissions  from
Stationary Sources
Inductively   Coupled   Plasma   -   Atomic   Emission
Spectroscopy
Inductively Coupled Plasma - Mass Spectrometry
Atomic Absorption Methods
Aluminum (AA, Direct Aspiration)
Antimony (AA, Direct Aspiration)
              Furnace Technique)
             Furnace Technique)
             Gaseous Hydride)
             Arsenic (AA, Borohydride Reduction)
             Aqueous  Samples  and  Extracts  by  Anodic
Antimony (AA,
Arsenic (AA,
Arsenic (AA,
Antimony and
Arsenic  in
         (AA,
Stripping Voltammetry (ASV)
Barium (AA, Direct Aspiration)
Barium (AA, Furnace Technique)
Beryllium (AA, Direct Aspiration)
Beryllium (AA, Furnace Technique)
Cadmium (AA, Direct Aspiration)
             Furnace Technique)
             Direct Aspiration)
              Direct Aspiration)
              Furnace Technique)
          Hexavalent (Coprecipitation)
          Hexavalent (Colorimetric)
          Hexavalent (Chelation/Extraction)
          Hexavalent (Differential Pulse Polarography)
Determination of Hexavalent Chromium  in Drinking Water,
Groundwater and Industrial Wastewater Effluents by Ion
Chromatography
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)
Cadmium (AA,
Calcium (AA,
Chromium (AA
Chromium
Chromium,
Chromium,
Chromium,
Chromium,
                               CONTENTS  -  2
                                                       Revision 4
                                                     January  1995

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            Method
            Method
            Method
            Method
            Method
            Method
            Method
7421:
7430:
7450:
7460:
7461:
7470A:
7471A:
            Method 7472:

            Method 7480:
            Method 7481:
            Method 7520:
            Method 7521:
            Method 7550:
            Method 7580:
            Method
            Method
            Method
            Method
            Method
            Method
            Method
            Method
            Method
            Method
            Method
            Method
            Method
            Method
            Method
7610:
7740:
7741A:
7742:
7760A:
7761:
7770:
7780:
7840:
7841:
7870:
7910:
7911:
7950:
7951:
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 Semi sol id Waste (Manual Cold-Vapor
Technique)
Mercury  in  Aqueous  Samples  and
Stripping Voltammetry (ASV)
Molybdenum (AA, Direct Aspiration)
           (AA, Furnace Technique)
            Direct Aspiration)
            Furnace Method)
            Direct Aspiration)
                  (P4)  by  Solvent
                                              Extracts  by  Anodic
Molybdenum
Nickel (AA,
Nickel (AA,
Osmium (AA,
White  Phosphorus
Chromatography
Potassium (AA, Direct Aspiration)
Selenium (AA, Furnace Technique)
Selenium (AA, Gaseous Hydride)
Selenium (AA, Borohydride Reduction)
Silver (AA, Direct Aspiration)
Silver (AA, Furnace Technique)
Sodium (AA, Direct Aspiration)
Strontium (AA, Direct Aspiration)
Thallium (AA, Direct Aspiration)
Thallium (AA, Furnace Technique)
Tin (AA,  Direct Aspiration)
Vanadium (AA, Direct Aspiration)
Vanadium (AA, Furnace Technique)
Zinc (AA, Direct Aspiration)
Zinc (AA, Furnace Technique)
                                              Extraction  and  Gas
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).
        A suffix  of  "C"  in the method number indicates  revision  three (the
        method has been revised three times).  In order to properly document
        the method used for analysis, the entire method number including the
        suffix letter designation (e.g., A, B, or C) 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 4
                                                     January 1995

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                                     VOLUME ONE

                                      SECTION  B
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
METHOD 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

            Method
            Method
            Method
            Method
            Method
            Method
            Method
     Extractions and Preparations
3500B:
3510C:
3520C:
3535:
3540C:
3541:
3542:
            Method 3545:
            Method 3550B:
            Method 3560:

            Method 3561:

            Method 3580A:
            Method 3585:
            Method 5000:
            Method 5021:

            Method 5030B:
Organic Extraction and Sample Preparation
Separatory Funnel Liquid-Liquid Extraction
Continuous Liquid-Liquid Extraction
Solid Phase Extraction (SPE)
Soxhlet Extraction
Automated Soxhlet Extraction
Extraction  of Semivolatile  Analytes Collected  Using
Modified Method 5 (Method 0010) Sampling Train
Accelerated Solvent Extraction
Ultrasonic Extraction
Supercritical  Fluid  Extraction  of  Total  Recoverable
Petroleum Hydrocarbons (TRPH)
Supercritical Fluid Extraction of Polynuclear Aromatic
Hydrocarbons
Waste Dilution
Waste Dilution for Volatile Organics
Sample Preparation for Volatile Organic Compounds
Volatile  Organic  Compounds  in  Soils and  Other  Solid
Matrices Using Equilibrium Headspace
Purge-and-Trap for Aqueous Samples
                                    CONTENTS - 4
                                                       Revision 4
                                                     January 1995

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      Method 5031:

      Method 5032:
      Method 5035:

      Method 5041A:
           Volatile,  Nonpurgeable,  Water-Soluble  Compounds  by
           Azeotropic Distillation
           Volatile Organic Compounds by Vacuum Distillation
           Closed-System Purge-and-Trap and Extraction for Volatile
           Organics in Soil and Waste Samples
           Analysis  for Desorption  of  Sorbent Cartridges  from
           Volatile Organic Sampling Train (VOST):  Capillary GC/MS
           Technique
      4.2.2
     Cleanup
      Method 3600C:
      Method 3610B:
      Method 3611B:
      Method
      Method
      Method
      Method
      Method
      Method
3620B:
3630C:
3640A:
3650B:
3660B:
3665A:
Cleanup
Alumina Cleanup
Alumina    Column
Petroleum Wastes
Florisil 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 8000B:
      Method 8011:

      Method 8015B:
      Method 8021B:
      Method 8031:
      Method 8032A:
      Method 8033:

      Method 8041:

      Method 8061A:

      Method 8070A:
      Method 8081A:

      Method 8082:

      Method 8091:

      Method 8100:
      Method 8111:
           Determinative Chromatographic Separations
           1,2-Dibromoethane  and  l,2-Dibromo-3-chloropropane  by
           Microextraction and Gas Chromatography
           Nonhalogenated Organics Using GC/FID
           Halogenated  Volatiles   by  Gas  Chromatography  Using
           Photoionization and Electrolytic Conductivity Detectors
           in Series:  Capillary Column Technique
           Acrylonitrile by Gas Chromatography
           Acrylamide by Gas Chromatography
           Acetonitrile  by  Gas  Chromatography  with  Nitrogen-
           Phosphorus Detection
           Phenols  by  Gas  Chromatography:     Capillary  Column
           Technique
           Phthalate Esters by  Capillary  Gas  Chromatography with
           Electron Capture Detection (GC/ECD)
           Nitrosamines by Gas Chromatography
           Organochlorine  Pesticides  by  Capillary  Column  Gas
           Chromatography
           Polychlorinated Biphenyls  (PCBs) by Capillary Column Gas
           Chromatography
           Nitroaromatics  and Cyclic  Ketones:  Capillary  Column
           Technique
           Polynuclear Aromatic Hydrocarbons
           Haloethers:  Capillary  Column Technique
                              CONTENTS - 5
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Method 8121:


Method 8131:

Method 8141A:

Method 8151A:
            Chlorinated   Hydrocarbons
            Capillary Column Technique
by   Gas   Chromatography:
            Aniline and  Selected Derivatives  by  GC:    Capillary
            Column Technique
            Organophosphorus  Compounds
            Capillary  Column Technique
            Chlorinated  Herbicides  by  GC  Using
            Pentafluorobenzylation Derivatization:
            Technique
 by  Gas  Chromatography:
           Methylation  or
          Capillary Column
4.3.2

Method 8260B
      Gas Chromatographic/Mass Spectroscopic Methods
Method 8270C
Method 8280A
Method 8290:
            Volatile Organic Compounds by  Gas  Chromatography/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  and
            Polychlorinated Dibenzofurans  by High  Resolution  Gas
            Chromatography/Low   Resolution   Mass    Spectrometry
            (HRGC/LRMS)
                  Signal-to-Noise  Determination  Methods
                  Recommended Safety and  Handling  Procedures  for
                  PCDDs/PCDFs
            Polychlorinated    Dibenzodioxins     (PCDDs)     and
            Polychlorinated Dibenzofurans (PCDFs) by High-Resolution
            Gas  Chromatography/High-Resolution  Mass  Spectrometry
            (HRGC/HRMS)
Attachment A:     Procedures   for   the    Collection,    Handling,
                  Analysis, and Reporting  of Wipe  Tests Performed
                  within the Laboratory
      Appendix A:
      Appendix B:
4.3.3
      High Performance Liquid Chromatographic Methods
Method 8310:
Method 8315A:

      Appendix

Method 8316:

Method 8318:

Method 8321A:


Method 8325:
            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/TS/MS) or Ultraviolet (UV) Detection
            Solvent  Extractable Non-Volatile  Compounds  by  High
            Performance  Liquid  Chromatography/Particle  Beam/Mass
            Spectrometry  (HPLC/PB/MS)
                        CONTENTS - 6
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      Method 8330:      Nitroaromatics and Nitramines by High Performance Liquid
                        Chromatography (HPLC)
      Method 8331:      Tetrazene  by Reverse  Phase  High  Performance  Liquid
                        Chromatography (HPLC)
      Method 8332:      Nitroglycerine by  High Performance Liquid Chromatography


      4.3.4       Infrared Methods

      Method 8410:      Gas Chromatography/Fourier Transform Infrared (GC/FT-IR)
                        Spectrometry  for  Semi volatile  Organics:    Capillary
                        Column
      Method 8430:      Analysis of Bis(2-chloroethyl)ether  Hydrolysis Products
                        by Direct Aqueous  Injection GC/FT-IR
      Method 8440:      Total  Recoverable Petroleum Hydrocarbons  by  Infrared
                        Spectrophotometry


      4.3.5       Miscellaneous Spectrometric Methods

      Method 8520:      Continuous Measurement of Formaldehyde in Ambient Air


4.4   Immunoassay Methods

      Method 4000:      Immunoassay
      Method 4010A:     Screening for Pentachlorophenol by  Immunoassay
      Method 4015:      Screening   for   2,4-Dichlorophenoxyacetic   Acid   by
                        Immunoassay
      Method 4020:      Screening for Polychlorinated Biphenyls by Immunoassay
      Method 4030:      Soil Screening for Petroleum Hydrocarbons  by Immunoassay
      Method 4035:      Soil  Screening  for   Polynuclear  Aromatic Hydrocarbons
                        (PAHs) by Immunoassay
      Method 4040:      Soil Screening for Toxaphene by Immunoassay
      Method 4041:      Soil Screening for Chlordane by Immunoassay
      Method 4042:      Soil Screening for DDT by Immunoassay
      Method 4050:      TNT Explosives in  Water and Soils by Immunoassay
      Method 4051:      Hexahydro-l,3,5-trinitro-l,3,5-triazine  (RDX)  in  Soil
                        and Water by Immunoassay

4.5   Miscellaneous Screening Methods

      Method 3810:      Headspace
      Method 3820:      Hexadecane   Extraction  and   Screening   of  Purgeable
                        Organics
      Method 8275A:     Semi volatile  Organic  Compounds  (PAHs   and  PCBs)  in
                        Soils/Sludges   and    Solid   Wastes   Using   Thermal
                        Extraction/Gas    Chromatography/Mass    Spectrometry
                        (TE/GC/MS)
      Method 8515:      Colorimetric Screening Method for Trinitrotoluene (TNT)
                        in Soil
      Method 9078:      Screening Test Method for Polychlorinated Biphenyls in
                        Soil


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            Method 9079:
Screening Test Method for Polychlorinated Biphenyls in
Transformer Oil
APPENDIX -- COMPANY REFERENCES
                                                         i
        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).
        A suffix  of  "C"  in the method number indicates revision  three  (the
        method has been revised three times).  In order to properly document
        the method used for analysis,  the entire method number including  the
        suffix letter designation (e.g., A, B, or C) 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 - 8
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                                     VOLUME ONE

                                      SECTION  C
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
            Method
            Method
            Method
            Method
            Method
            Method
5050:
9010A:
9012A:
9013:
9020B:
9021:
9022:
            Method 9023:
            Method 9030A:
            Method 9031:
            Method 9035:
            Method 9036:

            Method 9038:
            Method 9056:
            Method 9057:
            Method 9060:
            Method 9065:

            Method 9066:

            Method 9067:
            Method 9070:

            Method 9071A:
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
Extractable Organic Hal ides (EOX) in Solids
Acid-Soluble and Acid-Insoluble Sulfides
Extractable Sulfides
Sulfate (Colorimetric,  Automated, Chloranilate)
Sulfate (Colorimetric, Automated, Methylthymol Blue, AA
ID
Sulfate (Turbidimetric)
Determination of Inorganic Anions by Ion Chromatography
Determination  of   Chloride   from   HC1/HC12  Emission
Sampling  Train  (Methods  0050  and  0051)  by  Anion
Chromatography
Total Organic Carbon
Phenol ics   (Spectrophotometric,   Manual    4-AAP   with
Distillation)
Phenolics    (Colorimetric,   Automated    4-AAP   with
Distillation)
Phenolics (Spectrophotometric,  MBTH with Distillation)
Total Recoverable Oil & Grease  (Gravimetric, Separatory
Funnel  Extraction)
Oil and Grease Extraction Method for Sludge and Sediment
Samples
                                    CONTENTS - 9
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            Method 9075:

            Method 9076:

            Method 9077:

                  Method A:
                  Method B:

                  Method C:
            Method 9131:
            Method 9132:
            Method 9210:

            Method 9211:

            Method 9212:

            Method 9213:

            Method 9214:

            Method 9215:

            Method 9250:
            Method 9251:
            Method 9253:
            Method 9320:
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 Oxidative Combustion and Microcoulometry
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
Potentiometric  Determination  of Nitrate  in  Aqueous
Samples with Ion-Selective Electrode
Potentiometric  Determination  of Bromide  in  Aqueous
Samples with Ion-Selective Electrode
Potentiometric Determination of  Chloride in  Aqueous
Samples with Ion-Selective Electrode
Potentiometric  Determination  of Cyanide  in  Aqueous
Samples and Distillates with Ion-Selective Electrode
Potentiometric Determination of  Fluoride in  Aqueous
Samples with Ion-Selective Electrode
Potentiometric  Determination  of Sulfide  in  Aqueous
Samples and Distillates with Ion-Selective Electrode
Chloride (Colorimetric, Automated Ferricyanide AAI)
Chloride (Colorimetric, Automated Ferricyanide AAII)
Chloride (Titrimetric, Silver Nitrate)
Radium-228
CHAPTER SIX -- PROPERTIES

            Method 1030:
            Method 1120:
            Method 1312:
            Method 1320:
            Method 1330A:
            Method 9041A:
            Method 9045C:
            Method 9050A:
            Method 9080:
            Method 9081:
            Method 9090A:
            Method 9095A:
            Method 9096:
                  Appendix A:
            Method 9100:

            Method 9310:
            Method 9315:
Ignitability of Solids
Dermal Corrosion
Synthetic Precipitation Leaching Procedure
Multiple Extraction Procedure
Extraction Procedure for Oily Wastes
pH Paper Method
Soil and Waste pH
Specific Conductance
Cation-Exchange Capacity of Soils
Cation-Exchange Capacity of Soils
Compatibility Test for Wastes and
Paint Filter Liquids Test
Liquid Release Test (LRT) Procedure
      Liquid Release Test Pre-Test
Saturated  Hydraulic  Conductivity,  Saturated Leachate
Conductivity, and Intrinsic Permeability
Gross Alpha and Gross Beta
Alpha-Emitting Radium Isotopes
(Ammonium Acetate)
(Sodium Acetate)
Membrane Liners
                                    CONTENTS - 10
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                              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
CHAPTER EIGHT -- METHODS FOR DETERMINING CHARACTERISTICS

      8.1   Ignitability

            Method 1010:
                 1
            Method 1020A:
      8.3
      8.4
                  Pensky-Martens   Closed-Cup   Method   for   Determining
                  Ignitability
                  Setaflash Closed-Cup Method for Determining Ignitability
      8.2   Corrosivity

            Method 9040B:
            Method 1110:
Reactivity
Toxicity

Method 1310A:

Method 1311:
                  pH Electrometric Measurement
                  Corrosivity Toward Steel
                              Extraction  Procedure  (EP)  Toxicity  Test  Method  and
                              Structural Integrity Test
                              Toxicity Characteristic Leaching Procedure
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).
        A suffix  of  "C" in the method number indicates  revision  three (the
        method has been revised three times).  In order to properly document
        the method used for analysis, the entire method number including the
        suffix letter designation (e.g., A, B, or C) 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.
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                                     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 METHODS
            Method 0010:
                  Appendix A:
                  Appendix B:
            Method 0011:

            Method 0020:
            Method 0023A:
            Method 0030:
            Method 0031:
            Method 0040:

            Method 0050:
            Method 0051:
            Method 0100:
Modified Method 5 Sampling Train
      Preparation of XAD-2 Sorbent Resin
      Total Chromatographable Organic Material Analysis
Sampling  for  Formaldehyde  Emissions  from  Stationary
Sources
Source Assessment Sampling System (SASS)
Sampling Method  for  Polychlorinated Dibenzo-p-Dioxins
and   Polychlorinated  Dibenzofuran   Emissions   from
Stationary Sources
Volatile Organic Sampling Train
Sampling Method for Volatile Organic Compounds (SMVOC)
Sampling  of  Principal  Organic  Hazardous  Constituents
from Combustion Sources Using Tedlar® Bags
Isokinetic HC1/C12 Emission Sampling Train
Midget Impinger HC1/C12 Emission Sampling  Train
Sampling for Formaldehyde and Other Carbonyl Compounds
in Indoor Air
                                    CONTENTS -  12
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                                PART IV   MONITORING

CHAPTER ELEVEN -- GROUND WATER 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
      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).
        A suffix  of  "C"  in the method number indicates revision  three  (the
        method has been revised three times).   In order to properly document
        the method used for analysis,  the entire method number including  the
        suffix letter designation (e.g., A, B,  or C) 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  -  13                          Revision 4
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                                PREFACE AND OVERVIEW

PURPOSE OF THE MANUAL

      Test Methods for Evaluating Solid IVaste  (SW-846) provides 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
methodologies approved by the Office of Solid Waste for use in implementing the RCRA
regulatory program.   The manual  provides  methodologies for collecting  and  testing
representative  samples  of  waste  and  other  materials to  be  monitored.    Aspects  of
sampling and  testing in 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  in  this  manual  are meant to  be comprehensive  and
detailed, coupled with the  realization that the problems encountered in  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 is possible to  use this  manual in rote fashion.   In other
situations, it 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,  it is unavoidable because of the variety  of  sampling and
analytical conditions found with hazardous wastes.

ORGANIZATION  AND FORMAT

      This manual  is divided  into  two volumes and  thirteen  chapters.  Volume I focuses
on laboratory activities and is divided into three sections:  IA,  IB,  and 1C.   Volume
IA deals with quality control procedures, selection of appropriate test  methods, and
analytical methods for inorganic species.  Volume IB consists  of methods for organic
analytes.  Volume  1C  includes a variety of test methods for miscellaneous  analytes and
properties, including for use  in evaluating whether a waste exhibits certain hazardous
waste characteristics.  Volume II deals with sample acquisition and  includes quality
control,  sampling  plan design  and  implementation,  and  field  sampling  methods.
Discussions  regarding  ground  water   monitoring,   land treatment  monitoring,  and
incineration  are also included in Volume II.

      Volume  I begins with  an overview of the quality control  procedures that should
be adhered to during  application  of the  sampling  and analysis  methods.   The quality
control   chapter (Chapter  One)  and  the  method  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 by  reviewing  Chapter  One and the analytical methods together.   It  is
expected that  individual  laboratories, using SW-846  as the reference  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


                                    PREFACE -  1
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of analytes or  specific  analytes.   It aids the chemist  in  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 and  tables  provide guidance  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 linking  of  the  various  steps in  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.
However, Chapters  Five (Miscellaneous) and Six (Properties) give complete methods which
are not amenable to such segmentation to form discrete procedures.  The introductory
material at the beginning  of  Chapters Three (Inorganic  Analytes)  and  Four  (Organic
Analytes) contains information on sample handling and preservation,  safety, and sample
preparation.

      Part  II,   Characteristics,   of  Volume   I  describes  the   hazardous  waste
characteristics (Chapter Seven) and methods used to determine if the waste is hazardous
because it exhibits a particular characteristic (Chapters Seven  and Eight).

      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.

      Information  regarding the regulatory aspects of several monitoring categories is
also found in Volume II.   These  categories  include  ground water monitoring  (Chapter
Eleven), land treatment  (Chapter Twelve),  and  incineration  (Chapter Thirteen).   The
purpose of this guidance  is to  orient the user to the  analytical  objective,  and to
assist in the development of data quality objectives, sampling plans, and SOPs.

      Significant  interferences,  or  other  problems,  may  be  encountered  with certain
samples.  In these  situations, the  analyst  is  advised  to contact the Chief, Methods
Section (5304),  Technical Assessment Branch, Office of Solid Waste,  US EPA, Washington,
DC  20460 (202-260-4761) for assistance.   The  manual is  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.

SW-846 METHOD NUMBERS

      When published as a new method to SW-846, a method's number does not include a
letter suffix.  However,  each time the method is revised and  promulgated as part of an
SW-846 update, it  receives a new letter suffix,  i.e, a suffix  of "A"  indicates revision
one of that method,  a suffix of "B" indicates revision two, etc.   In order to properly
document the SW-846  method used during analysis, the entire method number including the
suffix letter designation must be identified by the  analyst.   In addition,  a method
reference found within the RCRA regulations and  the text of SW-846 methods and chapters
always refers to  the  latest promulgated revision of the  method,  even  if the method
number at those locations does not include the appropriate letter suffix.


                                     PREFACE -  2
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                                  CHAPTER TWO

                        CHOOSING THE CORRECT PROCEDURE
2.1   PURPOSE

      The  purpose  of  this  chapter is  to aid  the  analyst  in  choosing the
appropriate methods  for  sample  analyses,  based upon the sample matrix and the
analytes to be determined.

      2.1.1 Trace Analysis vs. Macroanalysis

      Through the choice  of sample size  and concentration procedures,  the methods
presented  in  SW-846 were designed 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  ppm)  and "major"
(>10,000 ppm) analyses,  as well, through use of appropriate sample  preparation
techniques that  result in  analyte  concentrations  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,
            and
      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:    Great care should be taken  when  performing trace analyses after the
            analysis  of concentrated  samples,   given  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,  the  apparatus, reagents,  and volumes  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.

      2.1.3 Quality Control  Criteria Precedence

      Chapter One contains general  quality  control  (QC) guidance for analyses
using SW-846  methods.    QC guidance specific  to a  given  analytical technique
(e.g., extraction, cleanup,  sample  introduction, or analysis)  may be found in
Methods 3500, 3600,  5000, 7000, and 8000.   Method-specific QC criteria  may be
found in Sec. 8.0 of each  individual  method (or in  Sec.  11.0 of air sampling
methods).  When inconsistencies exist between the information in these locations,

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method-specific QC criteria take precedence over both technique-specific criteria
and those criteria given  in Chapter One,  and  technique-specific QC criteria take
precedence over the criteria in Chapter One.

2.2   REQUIRED INFORMATION

      In order  to choose the  correct combination  of methods to  comprise  the
appropriate analytical procedure, some basic information is required.

      2.2.1 Physical State(s) of Sample

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

            Aqueous                             Oil  or other Organic Liquid
            Sludge                              TCLP or EP Extract
            Solid                               Stack Sampling (VOST)  Condensate
            Ground Water                        Multiphase Sample

      There may  be  a  substantial degree of overlap  between  the  phases listed
above and it may be  useful  to further divide these phases in certain instances.
A multiphase  sample may  be a combination of aqueous,  organic  liquid,  sludge,
and/or solid phases, and  generally must  undergo  a phase separation as the first
step in the analytical procedure.

      2.2.2 Analytes

      Analytes may be divided  into  various  classes  based  on the  determinative
methods  which  are  used  to  identify  and  quantify  them.   The  most  basic
differentiation  is  between  organic  (e.g., carbon-containing)  analytes  and
inorganic (e.g., metals and anions) analytes.

      Table 2-1 alphabetically lists the analytes SW-846 organic  determinative
methods.  Tables  2-2A and  2-2B  list the organic analytes  that  may be prepared
using Method 3650.  Table 2-3 lists the organic  analytes  that are collected from
stack gas effluents using the volatile organic sampling train (VOST) methodology.
Tables 2-4 through 2-34 list the analytes by organic determinative method.

      Table 2-35  indicates which methods are applicable to inorganic analytes.

      2.2.3 Detection Limits

      Some 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 Primary Drinking
Water Regulations, are desired in the analysis of ground water.
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      2.2.4 Analytical Objective

      Knowledge of  the analytical objective will  be  useful in  the  choice of
sample preparation  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 used during 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 collecting monitoring data.   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 is
often mass spectral  identification.  However, where the sensitivity requirements
exceed those  that  can be  achieved using mass spectral  method  (e.g.,  GC/MS or
HPLC/MS), it may be  necessary to employ a more sensitive  detection method (e.g.,
electron capture).   In these instances, the risk of false positive results may
be  minimized  by  confirming  the   results  through  a  second  analysis with  a
dissimilar detector or chromatographic column.  Thus, the choice of technique for
organic  analytes  may  be  governed by  the detection  limit requirements  and
potential interferents.

      Similarly, the choice  of  technique for metals is governed by the detection
limit requirements  and potential interferents.

      In contrast, monitoring  samples are analyzed to confirm existing and on-
going conditions, tracking the presence or absence of known constituents in an
environmental  or  process  matrix.    In well-defined matrices and  under  stable
analytical conditions, less compound-specific detection modes may be used, as the
risk of false positive results is less.

      2.2.6 Sample Containers, Preservations,  and Holding Times

      Appropriate sample containers,  sample preservation techniques, and sample
holding times for  aqueous matrices are listed in Table 2-36,  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 and 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.
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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 and Sample Preparation Procedures for Organic Analytes

      Methods for preparing samples for organic  analytes are shown  in Table 2-37.
Method 3500 and  associated methods should  be  consulted for further details on
preparing the sample for analysis.

            2.3.1.1     Aqueous Samples

            Methods 3510 and  3520 may be used  for extraction of the semivolatile
      organic compounds  from aqueous  samples.   The  choice  of  a  preparative
      method depends on the  sample.   Method  3510,  a separatory  funnel  liquid-
      liquid extraction technique, is appropriate for samples which will  not
      form a persistent emulsion interface 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 continuous  liquid-liquid extraction technique, may be used
      for any aqueous sample and will  minimize emulsion formation.

            Method 3535  is solid-phase extraction technique that has been tested
      for organochlorine pesticides and phthalate  esters and may be applicable
      to other  semivolatile  and extractable compounds  as well.    The  aqueous
      sample  is  passed  through  a solid  sorbent  material  which  traps  the
      analytes.   They are then  eluted  from  the  solid-phase sorbent with a small
      volume of  organic solvent.   This technique  may  be  used to  minimize the
      volumes of organic solvents  that are  employed, but may not  be appropriate
      for aqueous samples with high suspended solids contents.

                  2.3.1.1.1   Basic  or  Neutral  Extraction  of  Semivolatile
                              Analytes

                  The solvent extract  obtained  by performing Method 3510, 3520,
            or 3535 at a neutral or basic  pH will  contain the neutral  organic
            compounds and the organic bases of  interest.   Refer  to  Table  1 in
            the   extraction  methods  (3510  and/or  3520)   for  guidance  on  the
            requirements for pH adjustment prior to extraction and analysis.

                  2.3.1.1.2   Acidic  Extraction of Phenols and Acid Analytes

                  The solvent extract  obtained  by performing Method 3510, 3520,
            or 3535 at a pH less than or equal  to 2 will contain the phenols and
            acid extractable organics  of interest.


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      2.3.1.2     Solid Samples

      Soxhlet extraction  (Methods  3540  and  3541),  ultrasonic extraction
(Method 3550),  and  accelerated solvent extraction  (Method  3545)  may be
used with  solid samples.   Consolidated samples  should  be ground finely
enough  to  pass  through a  1  mm sieve.   In limited  applications,  waste
dilution  (Methods  3580 and  3585)  may be used  if  the  entire  sample is
soluble in the  specified solvent.

      Methods  3540,  3541,   3545,  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.

      There are two extraction  procedures  for solid samples that employ
supercritical fluid extraction (SFE).  Method  3560 is a  technique for the
extraction of petroleum  hydrocarbons from  various  solid matrices  using
carbon dioxide  at elevated temperature and pressure.  Method 3561 may be
used  to  extract  polynuclear  aromatic  hydrocarbons  (PAHs) from  solid
matrices using  supercritical  carbon dioxide.

      2.3.1.3     Oils and Organic Liquids

      Method 3580,  waste dilution,  may be used to prepare oils and organic
liquid  samples  for analysis  of   semivolatile  and   extractable  organic
analytes by GC or GC/MS.   Method 3585 may be employed  for the preparation
of  these   matrices  for volatiles  analysis  by  GC   or  GC/MS.  To  avoid
overloading the  analytical detection system,  care must  be  exercised to
ensure  that  proper dilutions  are  made.    Methods   3580  and  3585  give
guidance on performing waste  dilutions.

      To remove interferences for semivolatiles and extractables, Method
3611 (Alumina cleanup) 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.
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      2.3.1.4     Sludge Samples

      Determining  the  appropriate methods  for  analysis  of  sludges  is
complicated because  of  the  lack of precise definitions of  sludges  with
respect to the relative  percent  of liquid and solid components.  There is
no set ratio  of  liquid  to solid which enables the  analyst  to determine
which of  the three  extraction  methods cited  is the most  appropriate.
Sludges may be classified into  three  categories:   liquid  sludges,  solid
sludges,  and emulsions,  but  with appreciable overlap.

      If  the  sample is  an  organic sludge  (solid material   and  organic
liquid,  as opposed to an aqueous sludge), the sample should be handled as
a multiphase sample.

            2.3.1.4.1   Liquid Sludges

            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   Solid  Sludges

            Soxhlet  extraction   (Methods  3540  and  3541),   accelerated
      solvent (Method 3545) extraction, 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 semivolatile 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, including:

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

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

      3.     Centrifugation:    Centrifugal  force   may  separate  emulsion
            components by density.
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            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 separating multiphase samples is highly
      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
      no information on the  abundance of the analytes  in the individual phases
      other 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 Table 2-37 for further guidance.

      2.3.2 Cleanup Procedures

      Each  category  in  Table  2-38,  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
instructed  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.
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      2.3.3  Determinative Procedures

      The determinative methods for organic analytes have been divided into three
categories,  as  shown  in Table  2-39:    gas  chromatography/mass  spectrometry
(GC/MS); specific detection methods, i.e., gas chromatography (GC) with specific
non-MS  detectors;  and  high  performance liquid  chromatography  (HPLC).   This
division is intended to help an analyst choose which determinative method will
apply.  Under each  analyte column, SW-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  techniques  of  gas
chromatography and high performance liquid chromatography.  Method 8000 should
be consulted prior to application of any of the gas chromatographic methods.

      Method  8081  (organochlorine  pesticides),  Method  8082 (polychlorinated
biphenyls),  Method  8141   (organophosphorus   pesticides),   and   Method  8151
(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.

      Method  8260  is a  GC/MS  method for  volatile  analytes, which employs a
capillary column.  A variety of  sample  introduction techniques may be used with
Method 8260, including  Methods 5021, 5030, 5031,  and 3585.  A GC with a selective
detector is also useful for the determination of volatile  organic compounds in
a monitoring scenario,  as described in Sec. 2.2.5.

      Method 8270 is a GC/MS method for semivolatile analytes,  which employs a
capillary column.

      Table 2-39 lists  several GC and  HPLC  methods  that apply  to  only a small
number  of   analytes.    Methods  8031  and  8033  are  GC  methods  for  acrolein,
acrylonitrile, and  acetonitrile.   Methods 8315 and 8316  are HPLC  methods  for
these three analytes.    Method  8316 also  addresses  acrlyamide,  which  may be
analyzed by Method 8032.

      HPLC methods have been  developed for other types of analytes, most notably
carbamates (Method 8318), azo dyes and organophosphorus pesticides (Method 8321),
PAHs  (Method  8310), explosives   (Methods  8330  and  8331),  and some  volatile
organics (Methods 8315 and 8316).

      Method 8430  utilizes  a Fourier Transform  Infrared  Spectrometer (FT-IR)
coupled to  a  gas  chromotograph  to determine  bis(2-chloroethyl) ether and  its
hydrolysis  products.   The sample  is  introduced by direct  aqueous  injection.
Method 8440 may  be  employed for the determination of total  recoverable petroleum
hydrocarbons  (TRPH)  in  solid samples  by  infrared  (IR) spectrophotometry.   The
samples may be extracted with supercritical carbon dioxide, using Method 3560.


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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 semivolatile 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.  Method 5031 (Azeotropic Distillation) may be used
as an effective preparative method for pyridine.

      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
inorganic  analytes  should correspond to  the  drinking  water limits which are
avail able.

      2.5.1 Special  Techniques for Inorganic  Analytes

      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

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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.)

            Element(s)           Modifier(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 Analytes 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 cyanide, 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 Water 1984,
     22(1),  18-24.
2.   Riggin,  R.;  et al.  Development  and  Evaluation of Methods for Total Organic
     Halide and  Purgeable Organic  Halide  in  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, G.;  et  al.  Determination  of Inorganic  Anions in  Water by  Ion
     Chromatoqraphy; (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 METHODS FOR ORGANIC ANALYTES
Analyte                                                   Applicable Method(s)


Acenaphthene  	   8100, 8270, 8275, 8310, 8410
Acenaphthylene  	 8100, 8270, 8275, 8310, 8410
Acetaldehyde  	 8315
Acetone 	 8015, 8260, 8315
Acetonitrile  	 8015, 8033, 8260
Acetophenone  	 8270
2-Acetylaminofluorene 	 8270
l-Acetyl-2-thiourea 	 8270
Acifluorfen	8151
Acrolein (Propenal) 	 8015, 8260, 8315, 8316
Acrylamide  	 8032, 8316
Acrylonitrile 	 8015, 8031, 8260, 8316
Alachlor	8081
Aldicarb (Temik)   	 8318, 8321
Aldicarb sulfone   	 8318, 8321
Aldicarb sulfoxide  	 8321
Aldrin  	 8081, 8270
Ally! alcohol	8015, 8260
Ally! chloride	8021, 8260
2-Aminoanthraquinone  	 8270
Aminoazobenzene 	 8270
4-Aminobiphenyl  	 8270
Aminocarb	8321
2-Amino-4,6-dinitrotoluene (2-Am-DNT) 	 8330
4-Amino-2,6-dinitrotoluene (4-Am-DNT) 	 8330
3-Amino-9-ethylcarbazole  	 8270
Anilazine	8270
Aniline 	 8131, 8270
o-Anisidine	8270
Anthracene  	 8100, 8270, 8275, 8310, 8410
Aramite	8270
Aroclor-1016 (PCB-1016)  	 8082, 8270
Aroclor-1221 (PCB-1221)  	 8082, 8270
Aroclor-1232 (PCB-1232)  	 8082, 8270
Aroclor-1242 (PCB-1242)  	 8082, 8270
Aroclor-1248 (PCB-1248)  	 8082, 8270
Aroclor-1254 (PCB-1254)  	 8082, 8270
Aroclor-1260 (PCB-1260)  	 8082, 8270
Aspon	8141
Asulam	8321
Atrazine	8141
Azinphos-ethyl   	 8141
Azinphos-methyl  	 8141, 8270
Barban  	 8270, 8321
Baygon (Propoxur)   	 8318, 8321
Bendiocarb	8321

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                            TABLE  2-1.   (Continued)
Analyte                                                   Applicable Method(s)


Benefin	8091
Benomyl	8321
Bentazon	8151
Benzal chloride 	 8121
Benzaldehyde  	 8315
Benz(a)anthracene 	 8100, 8270, 8275, 8310, 8410
Benzene 	 8021, 8260
Benzenethiol (Thiophenol) 	 8270
Benzidine 	 8270, 8325
Benzo(b)fluoranthene  	 8100, 8270, 8275, 8310
Benzo(j)fluoranthene  	 8100
Benzojkjfluoranthene  	 8100, 8270, 8275, 8310
Benzoic acid	8270, 8410
Benzo(g,h,i)perylene  	 8100, 8270, 8275, 8310
Benzo(a)pyrene  	 8100, 8270, 8275, 8310, 8410
p-Benzoquinone  	 8270
Benzotrichloride  	 8121
Benzoylprop ethyl 	 8325
Benzyl alcohol  	 8270
Benzyl benzoate 	 8061
Benzyl chloride 	 8021, 8121, 8260
a-BHC  (a-Hexachlorocyclohexane)   	 8081, 8121, 8270
(8-BHC  (/3-Hexachlorocyclohexane)   	8081, 8121, 8270
S-BHC  (5-Hexachlorocyclohexane)   	 8081, 8121, 8270
7-BHC  (Lindane, 7-Hexachlorocyclohexane)  	 8081, 8121, 8270
Bis(2-chloroethoxy)methane  	 8111, 8270, 8410
Bis(2-chloroethyl) ether  	 8111, 8270, 8410, 8430
Bis(2-chloroethyl)sulfide 	 8260
Bis(2-chloroisopropyl) ether   	 8021, 8111, 8270, 8410
Bis(2-n-butoxyethyl) phthalate   	 8061
Bis(2-ethoxyethyl) phthalate   	 8061
Bis(2-ethylhexyl) phthalate 	 8061, 8270, 8410
Bis(2-methoxyethyl) phthalate  	 8061
Bis(4-methyl-2-pentyl)-phthalate  	 8061
Bolstar (Sulprofos) 	 8141
Bromacil  	8321
Bromoacetone  	 8021, 8260
4-Bromoaniline   	 8131
Bromobenzene  	 8021, 8260
Bromochloromethane  	 8021, 8260
2-Bromo-6-chloro-4-nitroaniline  	 8131
Bromodichloromethane  	 8021, 8260
2-Bromo-4,6-dinitroanil ine	8131
4-Bromofluorobenzene  	 8260
Bromoform 	 8021, 8260
Bromomethane  	 8021, 8260


                                   TWO  -  12                     Revision 3
                                                              January  1995

-------
                            TABLE 2-1.   (Continued)
Analyte                                                   Applicable Method(s)


4-Bromophenyl phenyl ether  	 8111, 8270, 8275, 8410
Bromoxynil   	8270
Butanal	8315
1-Butanol  (n-Butyl alcohol) 	 8015
n-Butanol	8260
2-Butanone (Methyl ethyl ketone, MEK) 	 8015, 8260
Butralin	8091
n-Butyl alcohol (1-Butanol) 	 8015
t-Butyl alcohol 	 8015
n-Butylbenzene  	 8021, 8260
sec-Butyl benzene	8021, 8260
tert-Butylbenzene 	 8021, 8260
Butyl benzyl  phthalate  	 8061, 8270, 8410
2-sec-Butyl-4,6-dinitrophenol  (DNBP, Dinoseb) 	 8041, 8151, 8270, 8321
Caffeine	8321
Captafol  	 8081, 8270
Captan	8270
Carbaryl (Sevin)  	 8270, 8318, 8321, 8325
Carbendazim	8321
Carbofuran (Furaden)  	 8270, 8318, 8321
Carbon disulfide  	 8260
Carbon tetrachloride  	 8021, 8260
Carbophenothion 	 8141, 8270
Chloral hydrate 	 8260
Chloramben	8151
Chlordane (technical) 	 8270
a-Chlordane   	8081
•y-Chlordane	8081
Chlorfenvinphos 	 8141, 8270
Chloroacetonitrile   	 8260
2-Chloroacrylonitrile 	 8015
2-Chloroaniline 	 8131
3-Chloroaniline 	 8131
4-Chloroaniline 	 8131, 8270, 8410
Chlorobenzene 	 8021, 8260
Chlorobenzilate 	 8081, 8270
2-Chlorobiphenyl  	 8082, 8275
2-Chloro-l,3-butadiene (Chloroprene)  	 8021, 8260
1-Chlorobutane  	 8260
Chlorodibromomethane (Dibromochloromethane) 	 8021, 8260
2-Chloro-4,6-dinitroaniline 	 8131
l-Chloro-2,4-dinitrobenzene 	 8091
l-Chloro-3,4-dinitrobenzene 	 8091
Chloroethane  	 8021, 8260
2-Chloroethanol 	 8021, 8260, 8430
2-(2-Chloroethoxy)ethanol 	 8430


                                   TWO - 13                     Revision 3
                                                              January 1995

-------
                            TABLE  2-1.   (Continued)
Analyte                                                   Applicable Method(s)


2-Chloroethyl vinyl ether 	  8021, 8260
Chloroform  	  8021, 8260
1-Chlorohexane  	 8260
Chloromethane 	  8021, 8260
5-Chloro-2-methylaniline  	 ;  	 8270
Chloromethyl methyl ether 	 8021
2-Chloro-5-methylphenol 	 8041
4-Chloro-2-methylphenol 	 8041
4-Chloro-3-methylphenol 	 8041,  8270, 8410
3-(Chloromethyl)pyridine hydrochloride  	 8270
1-Chloronaphthalene 	   8270, 8275
2-Chloronaphthalene 	 8121,  8270, 8410
Chloroneb	8081
2-Chloro-4-nitroaniline 	 8131
4-Chloro-2-nitroaniline 	 8131
l-Chloro-2-nitrobenzene 	 8091
l-Chloro-4-nitrobenzene 	 8091
2-Chloro-6-nitrotoluene 	 8091
4-Chloro-2-nitrotoluene 	 8091
4-Chloro-3-nitrotoluene 	 8091
2-Chlorophenol  	 8041,  8270, 8410
3-Chlorophenol  	 8041
4-Chlorophenol  	  8041, 8410
4-Chloro-l,2-phenylenediamine 	 8270
4-Chloro-l,3-phenylenediamine 	 8270
4-Chlorophenyl phenyl ether 	 8111,  8270, 8410
2-Chlorophenyl 4-nitrophenyl ether  	 8111
3-Chlorophenyl 4-nitrophenyl ether  	 8111
4-Chlorophenyl 4-nitrophenyl ether  	 8111
o-Chlorophenyl thiourea 	 8325
Chloroprene (2-Chloro-l,3-butadiene)  	  8021, 8260
3-Chloropropionitrile  	 8260
Chloropropham 	 8321
Chloropropylate 	 8081
Chlorothalonil  	 8081
2-Chlorotoluene 	  8021, 8260
4-Chlorotoluene 	  8021, 8260
Chloroxuron	8321
Chlorpyrifos  	 8141
Chlorpyrifos methyl  	 8141
Chrysene  	 8100, 8270, 8275,  8310, 8410
Coumaphos 	  8141, 8270
Coumarin Dyes	8321
p-Cresidine	8270
o-Cresol (2-Methylphenol)	8041,  8270, 8410
m-Cresol (3-Methylphenol)	8041, 8270
p-Cresol (4-Methylphenol) 	 8041, 8270,  8275, 8410

                                   TWO  -  14                      Revision 3
                                                              January 1995

-------
                            TABLE  2-1.   (Continued)
Analyte                                                   Applicable Method(s)


Crotonaldehyde  	 8015, 8260, 8315
Crotoxyphos 	 8141, 8270
Cyclohexanone 	 8315
2-Cyclohexyl-4,6-dinitrophenol  	 8041, 8270
2,4-D	8151, 8321
Dalapon 	 8151, 8321
2,4-DB  	 8151, 8321
DBCP (l,2-Dibromo-3-chloropropane)  	 8011, 8021, 8081, 8260, 8270
2,4-D, butoxyethanol ester  	 8321
DCM (Dichloromethane, Methylene chloride) 	 8021, 8260
DCPA	8081
DCPA diacid	8151
4,4'-DDD  	 8081, 8270
4,4'-DDE  	 8081, 8270
4,4'-DDT  	 8081, 8270
DDVP (Dichlorvos,  Dichlorovos)  	 8141, 8270, 8321
2,2',3,3'4,4'5,5',6,6'-Decachlorobiphenyl 	 8275
Decanal	8315
Demeton-0, and Demeton-S  	 8141, 8270
2,4-D, ethylhexyl  ester 	 8321
Diallate  	 8081, 8270
Diamyl phthalate  	 8061
2,4-Diaminotoluene   	 8270
Diazinon	8141
Dibenz(a,h)acridine  	 8100
Dibenz(a,j)acridine  	 8100, 8270
Dibenz(a,h)anthracene 	 8100, 8270, 8275, 8310
7H-Dibenzo(c,g)carbazole  	 8100
Dibenzofuran  	 8270, 8275, 8410
Dibenzo(a,e)pyrene   	 8100, 8270
Dibenzo(a,h)pyrene   	 8100
Dibenzo(a,i)pyrene   	 8100
Dibenzothiophene  	 8275
Dibromochloromethane (Chlorodibromomethane) 	 8021, 8260
l,2-Dibromo-3-chloropropane (DBCP)  	 8011, 8260, 8270
1,2-Dibromoethane (EDB, Ethylene dibromide) 	 8011, 8021, 8260
Dibromofluoromethane  	 8260
Dibromomethane  	 8021, 8260
2,6-Dibromo-4-nitroaniline  	 8131
2,4-Dibromophenyl  4-nitrophenyl ether 	 8111
Di-n-butyl phthalate  	 8061, 8270, 8410
Dicamba 	 8151, 8321
Dichlone  	 8081, 8270
3,4-Dichloroaniline  	 8131
1,2-Dichlorobenzene  	 8021, 8121, 8260, 8270, 8410
1,3-Dichlorobenzene  	 8021, 8121, 8260, 8270, 8410
1,4-Dichlorobenzene  	 8021, 8121, 8260, 8270, 8410

                                   TWO - 15                     Revision 3
                                                              January 1995

-------
                            TABLE  2-1.   (Continued)
Analyte                                                   Applicable Method(s)


3,3'-Dichlorobenzidine  	  8270,8325
3,5-Dichlorobenzoic acid  	 8151
2,3-Dichlorobiphenyl  	 8082, 8275
3,3'-Dichlorobiphenyl 	 8275
cis-l,4-Dichloro-2-butene 	 8260
trans-l,4-Dichloro-2-butene 	 8260
Dichlorodifluoromethane 	 8021, 8260
1,1-Dichloroethane  	 8021, 8260
1,2-Dichloroethane  	 8021, 8260
1,1-Dichloroethene  (Vinylidene chloride)  	 8021, 8260
cis-l,2-Dichloroethene  	 8021, 8260
trans-l,2-Dichloroethene  	 8021, 8260
Dichlorofenthion  	 8141
Dichloromethane (DCM, Methylene chloride) 	 8021, 8260
2,6-Dichloro-4-nitroaniline 	 8131
2,3-Dichloronitrobenzene  	 8091
2,4-Dichloronitrobenzene  	 8091
3,5-Dichloronitrobenzene  	 8091
3,4-Dichloronitrobenzene  	 8091
2,5-Dichloronitrobenzene  	 8091
2,3-Dichlorophenol  	 8041
2,4-Dichlorophenol  	 8041, 8270, 8410
2,5-Dichlorophenol  	 8041
2,6-Dichlorophenol  	 8041, 8270
3,4-Dichlorophenol  	 8041
3,5-Dichlorophenol  	 8041
2,4-Dichlorophenol  3-methyl-4-nitrophenyl ether 	 8111
2,6-Dichlorophenyl  4-nitrophenyl ether   	 8111
3,5-Dichlorophenyl  4-nitrophenyl ether   	 8111
2,5-Dichlorophenyl  4-nitrophenyl ether   	 8111
2,4-Dichlorophenyl  4-nitrophenyl ether   	 8111
2,3-Dichlorophenyl  4-nitrophenyl ether   	 8111
3,4-Dichlorophenyl  4-nitrophenyl ether   	 8111
Dichloroprop  (Dichlorprop)  	 8151, 8321
1,2-Dichloropropane 	 8021, 8260
1,3-Dichloropropane 	 8021, 8260
2,2-Dichloropropane 	 8021, 8260
l,3-Dichloro-2-propanol  	 8021, 8260
1,1-Dichloropropene 	 8021, 8260
cis-l,3-Dichloropropene  	 8021, 8260
trans-l,3-Dichloropropene 	 8021, 8260
Dichlorovos  (DDVP,  Dichlorvos)   	 8141, 8270, 8321
Dichlorprop  (Dichloroprop)  	 8151, 8321
Dichlorvos  (DDVP, Dichlorovos)   	 8141, 8270, 8321
Dicrotophos  	 8141, 8270
Dicofol	8081
Dicyclohexyl  phthalate   	 8061

                                   TWO  -  16                     Revision 3
                                                              January  1995

-------
                            TABLE  2-1.   (Continued)
Analyte                                                   Applicable Method(s)


Dieldrin  	 8081, 8270
1,2,3,4-Diepoxybutane 	 8260
Diesel range hydrocarbons 	 8015, 8440
Diethylene glycol 	 8430
Diethyl ether 	 8015, 8260
Diethyl phthalate 	 8061, 8270, 8410
Diethylstilbestrol  	 8270
Diethyl sulfate  	 8270
1,4-Difluorobenzene 	 8260
Dihexyl phthalate 	 8061
Dihydrosaffrole  	 8270
Diisobutyl phthalate  	 8061
Dimethoate  	 8141, 8270, 8321
3,3'-Dimethoxybenzidine 	 8270, 8325
Dimethylaminoazobenzene 	 8270
2,5-Dimethylbenzaldehyde  	 8315
7,12-Dimethylbenz(a)anthracene  	 8270
3,3'-Dimethylbenzidine  	 8270, 8325
a,a-Dimethylphenethylamine  	 8270
2,3-Dimethylphenol  	 8041
2,4-Dimethylphenol  	 8041, 8270
2,5-Dimethylphenol  	 8041
2,6-Dimethylphenol  	 8041
3,4-Dimethylphenol  	 8041
Dimethyl phthalate  	 8061, 8270, 8410
Dinitramine	8091
2,4-Dinitroaniline  	 8131
1,2-Dinitrobenzene  	 8091, 8270
1,3-Dinitrobenzene (1,3-DNB)  	 8091, 8270, 8330
1,4-Dinitrobenzene  	 8091, 8270
4,6-Dinitro-2-methylphenol  	 8270, 8410
2,4-Dinitrophenol 	 8041, 8270, 8410
2,5-Dinitrophenol 	 8041
2,4-Dinitrotoluene (2,4-DNT)  	 8091, 8270, 8330, 8410
2,6-Dinitrotoluene (2,6-DNT)  	 8091, 8270, 8330, 8410
Dinocap	8270
Dinonyl phthalate 	 8061
Dinoseb (2-sec-Butyl-4,6-dinitrophenol,  DNBP) 	 8041, 8151, 8270, 8321
Di-n-octyl phthalate  	 8061, 8270, 8410
Dioxacarb	8318
1,4-Dioxane 	 8015, 8260
Dioxathion  	 8141, 8270
Di-n-propyl phthalate 	 8410
Diphenylamine 	 8270
5,5-Diphenylhydantoin 	 8270
1,2-Diphenylhydrazine 	 8270


                                   TWO - 17                     Revision 3
                                                              January 1995

-------
                            TABLE  2-1.   (Continued)
Analyte                                                   Applicable Method(s)


Disperse Blue 3	8321
Disperse Blue 14	8321
Disperse Brown 1	8321
Disperse Orange 3	8321
Disperse Orange 30	8321
Disperse Red 1	8321
Disperse Red 5	8321
Disperse Red 13	8321
Disperse Red 60	8321
Disperse Yellow 5	8321
Disulfoton  	 8141, 8270, 8321
Diuron  	 8321, 8325
1,3-DNB (1,3-Dinitrobenzene)  	 8091, 8270, 8330
DNBP (2-sec-Butyl-4,6-dinitrophenol, Dinoseb) 	 8151, 8270, 8321
2,4-DNT (2,4-Dinitrotoluene)  	 8091, 8270, 8275, 8330, 8410
2,6-DNT (2,6-Dinitrotoluene)  	 8091, 8270, 8330, 8410
EDB (1,2-Dibromoethane, Ethylene dibromide)  	 8011, 8021, 8260
Endosulfan I  	8081, 8270
Endosulfan II	8081, 8270
Endosulfan sulfate  	 8081, 8270
Endrin  	 8081, 8270
Endrin aldehyde 	 8081, 8270
Endrin ketone 	 8081, 8270
Epichlorohydrin 	 8021, 8260
EPN	8141, 8270
Ethanol 	 8015, 8260
Ethion  	 8141, 8270
Ethoprop	8141
Ethyl acetate	8015, 8260
Ethyl benzene	8021, 8260
Ethyl carbamate	8270
Ethyl cyanide (Propionitrile) 	 8015, 8260
Ethylene dibromide  (EDB,  1,2-Dibromoethane)  	 8011, 8021, 8260
Ethylene glycol 	 8015, 8430
Ethylene oxide  	 8015, 8260
Ethyl methacrylate	8260
Ethyl methanesulfonate   	 8270
Etridiazole	8081
Famphur 	 8141, 8270, 8321
Fenitrothion  	 8141
Fensulfothion 	 8141, 8270, 8321
Fenthion   	 8141, 8270
Fenuron	8321
Fluchloralin  	 8270
Fluometuron	8321
Fluoranthene  	 8100, 8270, 8275, 8310, 8410
Fluorene   	 8100, 8270, 8275, 8310, 8410

                                    TWO  -  18                      Revision 3
                                                              January  1995

-------
                            TABLE 2-1.   (Continued)
Analyte                                                   Applicable Method(s)


Fluorescent Brightener 61 	 8321
Fluorescent Brightener 236   	 8321
Fluorobenzene 	 8260
2-Fluorobiphenyl  	 8270
2-Fluorophenol  	 8270
Fonophos	8141
Formaldehyde  	 8315
Furaden (Carbofuran)  	 8270, 8318, 8321
Gasoline range of hydrocarbons  	 8015
Halowax-1000  	 8081
Halowax-1001  	 8081
Halowax-1013  	 8081
Halowax-1014  	 8081
Halowax-1051  	 8081
Halowax-1099  	 8081
Heptachlor  	 8081, 8270
2,2',3,3',4,4',5-Heptachlorobiphenyl  	 8082, 8275
2,2',3,4,4',5,5'-Heptachlorobiphenyl  	 8082, 8275
2,2',3',4,4/,5',6-Heptachlorobiphenyl 	 8082
2,2',3,4',5,5',6-Heptachlorobiphenyl  	 8082, 8275
Heptachlor epoxide  	 8081, 8270
Heptanal  	8315
Hexachlorobenzene 	 8081, 8121, 8270, 8275, 8410
2,2',3,3,4,4'-Hexachlorobiphenyl  	 8275
2,2',3,4,4',5-Hexachlorobiphenyl  	 8082, 8275
2,2',3,4,5,5'-Hexachlorobiphenyl  	 8082
2,2',3,5,5',6-Hexachlorobiphenyl  	 8082
2,2',4,4,5,5'-Hexachlorobiphenyl  	 8082
Hexachlorobutadiene 	 8021, 8121, 8260, 8270, 8410
a-Hexachlorocyclohexane  (a-BHC)   	 8081, 8121, 8270
0-Hexachlorocyclohexane  (/3-BHC)   	8081, 8121, 8270
5-Hexachlorocyclohexane  (6-BHC)   	 8081, 8121, 8270
7-Hexachlorocyclohexane  (-y-BHC, Lindane)	8081, 8121, 8270
Hexachlorocyclopentadiene 	 8081, 8121, 8270, 8410
Hexachloroethane  	 8121, 8260, 8270, 8410
Hexachlorophene 	 8270
Hexachloropropene 	 8270
Hexafluoro-2-methyl-2-propanol  	 8015
Hexafluoro-2-propanol  	 8015
Hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX) 	 8330
Hexamethylphosphoramide  (HMPA)  	 8141, 8270
Hexanal	8315
2-Hexanone	8260
Hexyl 2-ethylhexyl phthalate  	 8061
HMPA (Hexamethylphosphoramide)  	 8141, 8270
HMX (Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine)  	 8330


                                   TWO - 19                     Revision 3
                                                              January 1995

-------
                            TABLE  2-1.   (Continued)
Analyte                                                   Applicable Method(s)


1,2,3,4,6,7,8-HpCDD 	 8280, 8290
HpCDD, total  	 8280
1,2,3,4,6,7,8-HpCDF 	 8280, 8290
1,2,3,4,7,8,9-HpCDF 	 8280, 8290
HpCDF, total  	 8280
1,2,3,4,7,8-HxCDD 	 8280, 8290
1,2,3,6,7,8-HxCDD 	 8280, 8290
1,2,3,7,8,9-HxCDD 	 8280, 8290
HxCDD, total  	 8280
1,2,3,4,7,8-HxCDF 	 8280, 8290
1,2,3,6,7,8-HxCDF 	 8280, 8290
1,2,3,7,8,9-HxCDF 	 8280, 8290
2,3,4,6,7,8-HxCDF 	 8280, 8290
HxCDF	8280
Hydroquinone  	 8270
3-Hydroxycarbofuran 	 8318, 8321
5-Hydroxydicamba  	 8151
2-Hydroxypropionitrile   	 8260
Indeno(l,2,3-cd)pyrene   	 8100, 8270, 8275, 8310
lodomethane (Methyl iodide)  	 8260
Isobutyl alcohol (2-Methyl-l-propanol)   	 8015, 8260
Isodrin  	 8081, 8270
Isophorone  	 8270, 8410
Isopropalin	8091
Isopropyl alcohol (2-Propanol)   	 8015, 8260
Isopropylbenzene  	 8021, 8260
p-Isopropyltoluene  	 8021, 8260
Isosafrole	8270
Isovaleraldehyde  	 8315
Jet fuel  	8015, 8440
Kepone   	 8081, 8270
Lannate  (Methomyl)  	 8318, 8321
Leptophos 	 8141, 8270
Lindane  (7-Hexachlorocyclohexane, 7-BHC)   	 8081, 8121, 8270
Linuron  (Lorox)  	 8321, 8325
Lorox  (Linuron)	8321, 8325
Malathion 	 8141, 8270
Maleic  anhydride   	 8270
Malononitrile  	 8260
MCPA	8151, 8321
MCPP	8151, 8321
Merphos  	 8141, 8321
Mestranol	8270
Mesurol  (Methiocarb)   	 8318, 8321
Methacrylonitrile  	 8260
Methanol  	 8015, 8260


                                    TWO  - 20                      Revision 3
                                                              January 1995

-------
                            TABLE  2-1.   (Continued)
Analyte                                                   Applicable Method(s)


Methapyrilene 	 8270
Methiocarb (Mesurol)  	 8318, 8321
Methomyl (Lannate)  	 8318, 8321
Methoxychlor  	 8081, 8270
Methyl acrylate 	 8260
2-Methyl-l-propanol (Isobutyl alcohol)  	 8015, 8260
Methyl-t-butyl ether  	 8260
3-Methylcholanthrene  	 8100, 8270
4,4'-Methylenebis(2-chloroaniline)  	 8270
4,4/-Methylenebis(N,N-dimethylaniline)  	 8270
Methyl ethyl  ketone (MEK, 2-Butanone)  	 8015, 8260
Methylene chloride (Dichloromethane, DCM) 	 8021, 8260
Methyl iodide (lodomethane)  	 8260
Methyl isobutyl  ketone (MIBK, 4-Methyl-2-pentanone) 	 8015, 8260
Methyl methacrylate 	 8260
Methyl methanesulfonate  	 8270
2-Methylnaphthalene 	 8270, 8410
Methyl parathion   	 8270, 8321
4-Methyl-2-pentanone (MIBK, Methyl isobutyl  ketone) 	 8015, 8260
2-Methylphenol (o-Cresol) 	 8041, 8270, 8410
3-Methylphenol (m-Cresol) 	 8041, 8270
4-Methylphenol (p-Cresol) 	 8041, 8270, 8410
2-Methylpyridine (2-Picoline) 	 8015, 8260, 8270
Methyl-2,4,6-trinitrophenylnitramine (Tetryl) 	 8330
Mevinphos 	 8141, 8270
Mexacarbate 	 8270, 8321
MIBK  (Methyl  isobutyl  ketone, 4-Methyl-2-pentanone) 	 8015, 8260
Mirex	8081, 8270
Monocrotophos 	 8141, 8270, 8321
Monuron 	 8321, 8325
Naled	8141, 8270, 8321
Naphthalene 	  8021,  8100, 8260, 8270, 8275, 8310, 8410
NB (Nitrobenzene)  	 8091, 8260, 8270, 8330, 8410
1,2-Naphthoquinone  	 8091
1,4-Naphthoquinone  	 8270, 8091
1-Naphthylamine 	 8270
2-Naphthylamine 	 8270
Neburon	8321
Nicotine	8270
5-Nitroacenaphthene 	 8270
2-Nitroaniline  	 8131, 8270, 8410
3-Nitroaniline  	 8131, 8270, 8410
4-Nitroaniline  	 8131, 8270, 8410
5-Nitro-o-anisidine 	 8270
Nitrobenzene (NB)  	 8091, 8260, 8270, 8330, 8410
4-Nitrobiphenyl  	 8270
Nitrofen  	 8081, 8270

                                   TWO - 21                      Revision 3
                                                              January 1995

-------
                            TABLE  2-1.   (Continued)
Analyte                                                   Applicable Method(s)


Nitroglycerin 	 8332
2-Nitrophenol 	 8041, 8270, 8410
3-Nitrophenol 	 8041
4-Nitrophenol 	 8041, 8151, 8270, 8410
4-Nitrophenyl phenyl ether  	 8111
2-Nitropropane  	 8260
Nitroquinoline-1-oxide  	 8270
N-Nitrosodi-n-butylamine  	 8015, 8260, 8270
N-Nitrosodiethylamine 	 8270
N-Nitrosodimethylamine  	 8070, 8270, 8410
N-Nitrosodi-n-butylamine (N-Nitrosodibutylamine)  	 8015, 8260, 8270
N-Nitrosodiphenylamine  	 8070, 8270, 8410
N-Nitrosodi-n-propylamine 	 8070, 8270, 8410
N-Nitrosomethylethylamine 	 8270
N-Nitrosomorpholine 	 8270
N-Nitrosopiperidine 	 8270
N-Nitrosopyrrolidine  	 8270
2-Nitrotoluene (o-Nitrotoluene, 2-NT) 	 8091, 8330
3-Nitrotoluene (m-Nitrotoluene, 3-NT) 	 8091, 8330
4-Nitrotoluene (p-Nitrotoluene, 4-NT) 	 8091, 8330
o-Nitrotoluene (2-Nitrotoluene, 2-NT) 	 8091, 8330
m-Nitrotoluene (3-Nitrotoluene, 3-NT) 	 8091, 8330
p-Nitrotoluene (4-Nitrotoluene, 4-NT) 	 8091, 8330
5-Nitro-o-toluidine 	 8270
trans-Nonachlor 	 8081
2,2'3,3'4,4'5,5'6-Nonachlorobiphenyl  	 8082, 8275
Nonanal	8315
2-NT (2-Nitrotoluene, o-Nitrotoluene) 	 8091, 8330
3-NT (3-Nitrotoluene, m-Nitrotoluene) 	 8091, 8330
4-NT (4-Nitrotoluene, p-Nitrotoluene) 	 8091, 8330
OCDD	8280, 8290
OCDF	8280, 8290
2,2',3,3',4,4'5,5'-Octachlorobiphenyl 	 8275
Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine (HMX)  	 8330
Octamethyl pyrophosphoramide   	 8270
Octanal	8315
Oxamyl  	8321
4,4'-Oxydianiline  	 8270
Paraldehyde  	 8015, 8260
Parathion	8270
Parathion, ethyl   	 8141
Parathion, methyl  	 8141
PCB-1016  (Aroclor-1016) 	 8082, 8270
PCB-1221  (Aroclor-1221) 	 8082, 8270
PCB-1232  (Aroclor-1232) 	 8082, 8270
PCB-1242  (Aroclor-1242) 	 8082, 8270
PCB-1248  (Aroclor-1248) 	 8082, 8270

                                    TWO  -  22                     Revision 3
                                                              January  1995

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                            TABLE 2-1.   (Continued)
Analyte                                                   Applicable Method(s)


PCB-1254 (Aroclor-1254) 	 8082, 8270
PCB-1260 (Aroclor-1260) 	 8082, 8270
PCNB	8081
1,2,3,7,8-PeCDD 	 8280, 8290
PeCDD, total  	 8280
1,2,3,7,8-PeCDF 	 8280, 8290
2,3,4,7,8-PeCDF 	 8280, 8290
PeCDF, total  	 8280
Pendimethaline (Penoxalin)  	 8091
Penoxalin (Pendimethaline 	 8091
Pentachlorobenzene  	 8121, 8270
2,2',3,4,5'-Pentachlorobiphenyl 	 8082
2,2',4,5,5'-Pentachlorobiphenyl 	 8082, 8275
2,3,3',4',6-Pentachlorobiphenyl 	 8082
2,3',4,4',5-Pentachlorobiphenyl 	 8275
Pentachloroethane 	 8260
Pentachloronitrobenzene 	 8091, 8270
Pentachlorophenol  	 8041, 8151, 8270, 8410
Pentafluorobenzene  	 8260
Pentanal (Valeraldehyde)  	 8315
2-Pentanone 	 8015, 8260
Permethrin	8081
Perthane	8081
Phenacetin	8270
Phenanthrene  	 8100, 8270, 8275, 8310, 8410
Phenobarbital  	 8270
Phenol  	 8041, 8270, 8410
1,4-Phenylenediamine  	 8270
Phorate 	 8141, 8270, 8321
Phosalone	8270
Phosmet 	 8141, 8270
Phosphamidon  	 8141, 8270
Phthalic anhydride  	 8270
Picloram	8151
2-Picoline (2-Methylpyridine)  	 8015, 8260, 8270
Piperonyl sulfoxide 	 8270
Profluralin	8091
Promecarb	8318
Pronamide	8270
Propachlor  	 8081, 8321
Propanal (Propionaldehyde)  	 8315, 8321
1-Propanol  	 8015, 8260
2-Propanol (Isopropyl  alcohol)  	 8015, 8260
Propargyl alcohol  	 8260
Propenal (Acrolein) 	 8260, 8315
Propham	8321
B-Propiolactone 	 8260

                                   TWO - 23                     Revision 3
                                                              January 1995

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                            TABLE  2-1.   (Continued)
Analyte                                                   Applicable Method(s)


Propionaldehyde (Propanal)  	 8315
Propionitrile (Ethyl cyanide) 	 8015, 8260
Propoxur (Baygon) 	 8318, 8321
n-Propylamine 	 8260
n-Propylbenzene 	 8021, 8260
Propylthiouracil  	 8270
Prothiophos (Tokuthion)  	 8141
Pyrene  	 8100, 8270, 8275, 8310, 8410
Pyridine  	 8015, 8260, 8270
RDX (Hexahydro-l,3,5-trinitro-l,3,5-triazine) 	 8330
Resorcinol  	8270
Ronnel  	8141
Rotenone	8325
Safrole	8270
Sevin (Carbaryl)  	 8270, 8318, 8321, 8325
Siduron 	 8321, 8325
Simazine	8141
Silvex  (2,4,5-TP) 	 8151, 8321
Solvent Red 3	8321
Solvent Red 23	8321
Stirophos (Tetrachlorvinphos) 	 8141, 8270
Strobane	8081
Strychnine  	 8270, 8321
Styrene 	 8021, 8260
Sul fall ate	8270
Sulfotepp	8141
Sulprofos (Bolstar)  	 8141
2,4,5-T 	 8151, 8321
2,4,5-T, butoxyethanol ester  	 8321
2,4,5-T, butyl  ester   	 8321
2,3,7,8-TCDD  	 8280, 8290
TCDD, total	8280
2,3,7,8-TCDF  	 8280, 8290
TCDF, total	8280
Tebuthiuron	8321
Temik (Aldicarb)  	 8318, 8321
TEPP	8141
Terbufos  	 8141, 8270
Terphenyl	8270
1,2,3,4-Tetrachlorobenzene   	 8121
1,2,3,5-Tetrachlorobenzene   	 8121
1,2,4,5-Tetrachlorobenzene   	 8121, 8270
2,2',3,5'-Tetrachlorobiphenyl 	 8082, 8275
2,2',4,5'-Tetrachlorobiphenyl 	 8275
2,2',5,5'-Tetrachlorobiphenyl 	 8082, 8275
2,3',4,4'-Tetrachlorobiphenyl 	 8082, 8275
1,1,1,2-Tetrachloroethane  	 8021, 8260

                                    TWO  -  24                      Revision  3
                                                              January  1995

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                            TABLE  2-1.   (Continued)
Analyte                                                   Applicable Method(s)


1,1,2,2-Tetrachloroethane 	 8021, 8260
Tetrachloroethene 	 8021, 8260
2,3,4,5-Tetrachlorophenol 	 8041
2,3,4,6-Tetrachlorophenol 	 8041, 8270
2,3,5,6-Tetrachlorophenol 	 8041
2,3,4,5-Tetrachloronitrobenzene 	 8091
2,3,5,6-Tetrachloronitrobenzene 	 8091
Tetrachlorvinphos (Stirophos) 	 8141, 8270
Tetraethyl dithiopyrophosphate  	 8270
Tetraethyl pyrophosphate  	 8270
Tetrazene	8331
Tetryl (Methyl-2,4,6-trinitrophenylnitramine) 	 8330
Thiofanox	8321
Thionazin (Zinophos)  	 8141, 8270
Thiophenol (Benzenethiol) 	 8270
1,3,5-TNB (1,3,5-Trinitrobenzene) 	 8270, 8330
2,4,5-TNT (2,4,6-Trinitrobenzene) 	 8330
TOCP (Tri-o-cresylphosphate)  	 8141
Tokuthion (Prothiophos) 	 8141
m-Tolualdehyde  	 8315
o-Tolualdehyde  	 8315
p-Tolualdehyde  	 8315
Toluene 	 8021, 8260
Toluene diisocyanate  	 8270
o-Toluidine 	 8015, 8270
Toxaphene	8081, 8270
2,4,5-TP (Silvex) 	 8151, 8321
2,4,6-Tribromophenol  	 8270
2,4,6-Trichloroaniline  	 8131
2,4,5-Trichloroaniline  	 8131
1,2,3-Trichlorobenzene  	 8021, 8121, 8260
1,2,4-Trichlorobenzene  	 8021, 8121, 8260, 8270, 8275, 8410
2,2',5-Trichlorobiphenyl  	 8082, 8275
2,3',5-Trichlorobiphenyl  	 8275
2,4',5-Trichlorobiphenyl  	 8082, 8275
1,3,5-Trichlorobenzene  	 8121
1,1,1-Trichloroethane 	 8021, 8260
1,1,2-Trichloroethane 	 8021, 8260
Trichloroethene 	 8021, 8260
Trichlorofluoromethane  	 8021, 8260
Trichlorfon 	 8141, 8321
Trichloronate 	 8141
l,2,3-Trichloro-4-nitrobenzene  	 8091
l,2,4-Trichloro-5-nitrobenzene  	 8091
2,4,6-Trichloronitrobenzene  	 8091
2,3,4-Trichlorophenol 	 8041
2,3,5-Trichlorophenol 	 8041

                                   TWO - 25                     Revision 3
                                                              January 1995

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                            TABLE  2-1.   (Continued)
Analyte                                                   Applicable Method(s)


2,3,6-Trichlorophenol 	 8041
2,4,5-Trichlorophenol 	 8041, 8270, 8410
2,4,6-Trichlorophenol 	 8041, 8270, 8410
2,4,6-Trichlorophenyl 4-nitrophenyl ether 	 8111
2,3,6-Trichlorophenyl 4-nitrophenyl ether 	 8111
2,3,5-Trichlorophenyl 4-nitrophenyl ether 	 8111
2,4,5-Trichlorophenyl 4-nitrophenyl ether 	 8111
3,4,5-Trichlorophenyl 4-nitrophenyl ether 	 8111
2,3,4-Trichlorophenyl 4-nitrophenyl ether 	 8111
1,2,3-Trichloropropane  	 8021, 8260
0,0,0-Triethyl phosphorothioate 	 8270
Trifluralin 	 8091, 8081, 8270
2,4,5-Trimethylaniline  	 8270
1,2,4-Trimethylbenzene  	 8021, 8260
1,3,5-Trimethylbenzene  	 8021, 8260
Trimethyl phosphate  	 8270
1,3,5-Trinitrobenzene (1,3,5-TNB)  	 8270, 8330
2,4,6-Trinitrobenzene (2,4,6-TNT)  	 8330
Tris-BP  (Tris-(2,3-dibromopropyl)  phosphate)  	 8270, 8321
Tri-o-cresylphosphate (TOCP)  	 8141
Tri-p-tolyl phosphate 	 8270
Tris-(2,3-dibromopropyl) phosphate (Tris-BP)  	 8270, 8321
Valeraldehyde  (Pentanal)   	 8315
Vinyl acetate	8260
Vinyl chloride	8021, 8260
Vinylidene chloride  (1,1-Dichloroethene)  	 8021, 8260
o-Xylene   	 8021, 8260
m-Xylene   	 8021, 8260
p-Xylene   	 8021, 8260
Zinophos (Thionazin)  	 8141, 8270
                                   TWO  -  26                     Revision  3
                                                              January  1995

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                            TABLE 2-2A
METHOD  3650  (ACID-BASE  PARTITION CLEANUP)  - BASE/NEUTRAL  FRACTION
Benz{a)anthracene                         Hexachlorobenzene
Benzo(a)pyrene                            Hexachlorobutadiene
Benzo(b)fluoranthene                      Hexachloroethane
Chiordane                                 Hexachlorocyclopentadi ene
Chlorinated dibenzodioxins                Naphthalene
Chrysene                                  Nitrobenzene
Creosote                                  Phorate
Dichlorobenzene(s)                        2-Picoline
Dinitrobenzene                            Pyridine
2,4-Di n i trotoluene                        Tetrachlorobenzene(s)
Heptachlor                                Toxaphene
                            TABLE 2-2B
    METHOD  3650  (ACID-BASE  PARTITION  CLEANUP)  - 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 - 27                     Revision 3
                                                        January 1995

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                                  TABLE 2-3
 METHOD 5041 - SORBENT CARTRIDGES FROM VOLATILE ORGANIC SAMPLING TRAIN (VOST)
  Acetone
  Acrylonitrile
  Benzene
  Bromodichloromethane
  Bromoform3
  Bromomethane
  Carbon disulfide
  Carbon tetrachloride
  Chlorobenzene
  Chiorodi brompmethane
  Chloroethane
  Chloroform
  Chloromethane
  Dibromomethane
  1,1-Dichloroethane
  1,2-Dichloroethane
  1,1-Dichloroethene
  trans-l,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Ethyl benzene3
lodomethane
Methylene chloride
Styrene3
1,1,2,2-Tetrachloroethane3
Tetrachloroethene
Toluene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane3
Vinyl chloride
Xylenes3
3  Boiling point of this compound is above 132°C.  Method 0030 is not
appropriate for quantitative sampling of this analyte.

b  Boiling point of this compound is below 30°C.  Special precautions must be
taken when sampling for this analyte by Method 0030.  Refer to Sec. 1.3 of
Method 5041 for discussion.
                                   TWO - 28
                Revision 3
              January 1995

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                                   TABLE 2-4
             METHOD 8011  (MICROEXTRACTION AND GAS CHROMATOGRAPHY)
                      l,2-Dibromo-3-chloropropane (DBCP)
                            1,2-Dibromoethane (EDB)
                                   TABLE 2-5
                METHOD 8015 (GC/FID)  -  NONHALOGENATED VOLATILES
Acetone
Acetonitrile
Acrolein
Acrylonitrile
Allyl alcohol
1-Butanol (n-Butyl alcohol)
t-Butyl alcohol
2-Chioroacrylonitri1e
Crotonaldehyde
Diethyl ether
1,4-Dioxane
Ethanol
Ethyl acetate
Ethylene glycol
Ethylene oxide
Hexafluoro-2-propanol
Hexafluoro-2-methyl -2-propanol
Isobutyl alcohol
Isopropyl alcohol
Methanol
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
N-Nitroso-di-n-butyl amine
Paraldehyde
2-Pentanone
2-Picoline
1-Propanol
Propionitrile
Pyridine
o-Toluidine
Gasoline range organics
Diesel range organics
Jet Fuel
                                   TWO - 29
                      Revision 3
                    January 1995

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                                 TABLE 2-6
METHOD 8021 (GC, PHOTOIONIZATION AND ELECTROLYTIC CONDUCTIVITY DETECTORS)
                           HALOGENATED VOLATILES
    Ally!  chloride
    Benzene
    Benzyl chloride
    Bis(2-chloroisopropyl)
       ether
    Bromoacetone
    Bromobenzene
    Bromochloromethane
    Bromodi chloromethane
    Bromoform
    Bromomethane
    n-Butylbenzene
    sec-Butyl benzene
    tert-Butylbenzene
    Carbon tetrachloride
    Chlorobenzene
    Chlorodi bromomethane
    Chloroethane
    2-Chloroethanol
    2-Chloroethyl vinyl ether
    Chloroform
    Chloromethyl methyl ether
    Chloroprene
    Chloromethane
    2-Chlorotoluene
    4-Chlorotoluene
    l,2-Dibromo-3-chloropropane
    1,2-Dibromoethane
    Dibromomethane
    1,2-Dichlorobenzene
    1,3-Dichlorobenzene
    1,4-Dichlorobenzene
    Dichlorodifluoromethane
    1,1-Dichloroethane
    1,2-Dichloroethane
    1,1-Dichloroethene   	
 cis-l,2-Dichloroethene
 trans-1,2-Dichloroethene
 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
 Epichlorhydrin
 Ethyl benzene
 Hexachlorobutadiene
 Isopropylbenzene
 p-Isopropyltoluene
 Methylene chloride
 Naphthalene
 n-Propylbenzene
 Styrene
 1,1,1,2-Tetrachloroethane
 1,1,2,2-Tetrachloroethane
 Tetrachloroethene
 Toluene
 1,2,3-Trichlorobenzene
 1,2,4-Trichlorobenzene
 1,1,1-Trichloroethane
 1,1,2-Trichloroethane
 Trichloroethene
 Tri chlorof1uoromethane
 1,2,3-Trichloropropane
 1,2,4-Trimethylbenzene
 1,3,5-Trimethyl benzene
 Vinyl chloride
 o-Xylene
 m-Xylene
 p-Xylene
                                 TABLE 2-7
METHODS 8031 AND 8032 (GC) AND 8033 (GC WITH NITROGEN-PHOSPHORUS DETECTION)
                          Method 8031:
                          Method 8032:
                         Method 8033:
 Acrylonitrile
 Acrylamide
Acetonitrile
                                  TWO - 30
                        Revision  3
                      January  1995

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                             TABLE 2-8
                    METHOD 8041 (GC)  - PHENOLS
2-Chioro-5-methylphenol
4-Chloro-2-methyl phenol
4-Chloro-3-methyl phenol
2-Chlorophenol
3-Chlorophenol
4-Chlorophenol
2-Cyclohexyl-4,6-dinitro-
  phenol
2,3-Dichlorophenol
2,4-Dichlorophenol
2,5-Dichlorophenol
2,6-Dichlorophenol
3,4-Dichlorophenol
3,5-Dichlorophenol
2,3-Dimethylphenol
2,4-Dimethylphenol
2,5-Dimethylphenol
2,6-Dimethylphenol
3,4-Dimethyl phenol
2,4-Dinitrophenol
2,5-Dinitrophenol
Dinoseb
2-Methylphenol (o-Cresol)
3-Methylphenol (m-Cresol)
4-Methylphenol (p-Cresol)
2-Nitrophenol
3-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,3,4,5-Tetrachlorophenol
2,3,4,6-Tetrachlorophenol
2,3,5,6-Tetrachlorophenol
2,3,4-Trichlorophenol
2,3,5-Trichlorophenol
2,3,6-Trichlorophenol
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
                             TABLE 2-9
              METHOD 8061  (GC/ECD) -  PHTHALATE  ESTERS
Benzyl benzoate
Bis(2-n-butoxyethyl) phthalate
Bis(2-ethoxyethyl) phthalate
Bis(2-ethylhexyl) phthalate
Bis(2-methoxyethyl) phthalate
Bis(4-methyl-2-pentyl )-
  phthalate
Butyl benzyl phthalate
Diamyl phthalate
Dicyclohexyl phthalate
Dihexyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dinonyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Hexyl 2-ethylhexyl phthalate
                            TABLE 2-10
                  METHOD 8070  (GC)  -  NITROSAMINES
                      N-Nitrosodimethylamine
                      N-Nitrosodiphenylamine
                     N-Nitrosodi-n-propylamine
                             TWO - 31
                      Revision 3
                    January 1995

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            METHOD  8081  (GC)  -
  TABLE  2-11
ORGANOCHLORINE PESTICIDES AND PCBs
Alachlor
Aldrin
a-BHC
,8-BHC
5-BHC
7-BHC (Lindane)
Captafol
Chlorobenzilate
a-Chlordane
7-Chlordane
Chloroneb
Chloropropylate
Chlorothalonil
DBCP
DC PA
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dial late
Dichlone
Dicofol
Dieldrin
Endosulfan  I
Endosulfan  II
Endosulfan  sulfate
Endrin
Endrin  aldehyde
Endrin  ketone
Etridiazole
Halowax-1000
Halowax-1001
Halowax-1013
Halowax-1014
Halowax-1051
Halowax-1099
Heptachlor
Heptachlor
  epoxide
Hexachlorobenzene
Hexachlorocyclo-
  pentadiene
Isodrin
Kepone
Methoxychlor
Mi rex
Nitrofen
trans-Nonachlor
PCNB
Permethrin
Perthane
Propachlor
Strobane
Toxaphene
Trifluralin
                                  TWO - 32
                                 Revision  3
                               January 1995

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                            TABLE 2-12
           METHOD 8082 (GC) - POLYCHLORINATED BIPHENYLS
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1260
2-Chlorobiphenyl
2,3-Dichlorobiphenyl
2,2',5-Trichlorobiphenyl
2,4',5-Trichlorobiphenyl
2,2',3,5'-Tetrachlorobiphenyl
2,2',5,5'-Tetrachlorobiphenyl
2,3',4,4'-Tetrachlorobiphenyl
2,2',3,4,5'-Pentachlorobiphenyl
2,2',4,5,5'-Pentachlorobiphenyl
2,3,3',4',6-Pentachlorobiphenyl
2,2',3,4,4',5-Hexachlorobiphenyl
2,2',3,4,5,5'-Hexachlorobiphenyl
2,2',3,5,5',6-Hexachlorobiphenyl
2,2',4,4,5,5'-Hexachlorobiphenyl
2,2',3,3',4,4',5-Heptachlorobiphenyl
2,2',3,4,4',5,5'-Heptachlorobiphenyl
2,2',3',4,4',5',6-Heptachloro-
  biphenyl
2,2',3,4',5,5',6-Heptachlorobiphenyl
2,2',3,3',4,4',5,5',6-Nonachloro-
  biphenyl
                            TABLE 2-13
       METHOD 8091 (GC) - NITROAROMATICS AND CYCLIC KETONES
Benefin
Butralin
1-Chioro-2,4-dinitrobenzene
1-Chioro-3,4-dinitrobenzene
1-Chioro-2-nitrobenzene
l-Chloro-4-nitrobenzene
2-Chloro-6-nitrotoluene
4-Chloro-2-nitrotoluene
4-Chloro-3-nitrotoluene
2,3-Dichloronitrobenzene
2,4-Dichloronitrobenzene
3,5-Dichloronitrobenzene
3,4-Dichloronitrobenzene
2,5-Dichloronitrobenzene
Dinitramine
1,2-Dinitrobenzene
1,3-Dinitrobenzene
1,4-Dinitrobenzene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Isopropalin
1,2-Naphthoquinone
1,4-Naphthoquinone
Nitrobenzene
2-Nitrotoluene
3-Nitrotoluene
4-Nitrotoluene
Penoxalin [Pendimethalin]
Pentachloronitrobenzene
Profluralin
2,3,4,5-Tetrachloronitrobenzene
2,3,5,6-Tetrachloronitrobenzene
l,2,3-Trichloro-4-nitrobenzene
l,2,4-Trichloro-5-nitrobenzene
2,4,6-Trichloronitrobenzene
Trifluralin
                             TWO - 33
                      Revision 3
                    January 1995

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                                  TABLE 2-14
               METHODS 8100 - POLYNUCLEAR AROMATIC HYDROCARBONS
      Acenaphthene
      Acenaphthylene
      Anthracene
      Benz(a)anthracene
      Benzo(b)fluoranthene
      Benzo(j)fluoranthene
      Benzo(k)fluoranthene
      Benzo(g,h,i)perylene
      Benzo(a)pyrene
      Chrysene
      Dibenz(a,h)acridine
      Dibenz(a,jjacridine
Dibenz(a,h)anthracene
7H-Dibenzo(c,g)carbazole
Dibenzo(a,e)pyrene
Dibenzo(a,h)pyrene
Dibenzo(a,ijpyrene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
3-Methylcholanthrene
Naphthalene
Phenanthrene
Pyrene
                                  TABLE 2-15
                         METHOD  8111  (GC)  -  HALOETHERS
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
4-Bromophenyl phenyl ether
4-Chlorophenyl phenyl ether
2-Chlorophenyl 4-nitrophenyl ether
3-Chlorophenyl 4-nitrophenyl ether
4-Chlorophenyl 4-nitrophenyl ether
2,4-Dibromophenyl 4-nitrophenyl
  ether
2,4-Dichlorophenyl 3-methyl-4-
  nitrophenyl ether
2,6-Dichlorophenyl 4-nitrophenyl
  ether
3,5-Dichlorophenyl 4-nitrophenyl
  ether
2,5-Dichlorophenyl 4-nitrophenyl
  ether
2,4-Dichlorophenyl 4-nitrophenyl
  ether
2,3-Dichlorophenyl 4-nitrophenyl
  ether
3,4-Dichlorophenyl 4-nitrophenyl
  ether
4-Nitrophenyl phenyl ether
2,4,6-Trichlorophenyl 4-nitrophenyl
  ether
2,3,6-Trichlorophenyl 4-nitrophenyl
  ether
2,3,5-Trichlorophenyl 4-nitrophenyl
  ether
2,4,5-Trichlorophenyl 4-nitrophenyl
  ether
3,4,5-Trichlorophenyl 4-nitrophenyl
  ether
2,3,4-Trichlorophenyl 4-nitrophenyl
ether
                                   TWO - 34
                      Revision 3
                    January  1995

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                            TABLE 2-16
            METHOD  8121  (GC)  -  CHLORINATED HYDROCARBONS
Benzal chloride
Benzotrichloride
Benzyl chloride
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadiene
a-Hexachlorocyclohexane
  [a-BHC]
/3-Hexach"1 orocycl ohexane
  [jg-BHC]	
5-Hexachlorocyclohexane
  [6-BHC]
7-Hexachlorocyclohexane [7-BHC]
Hexachlorocyclopentadi ene
Hexachloroethane
Pentachlorobenzene
1,2,3,4-Tetrachlorobenzene
1,2,3,5-Tetrachlorobenzene
1,2,4,5-Tetrachlorobenzene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,3,5-Trichlorobenzene
                            TABLE 2-17
        METHOD  8131  (GC)  -  ANILINE AND  SELECTED  DERIVATIVES
Aniline
4-Bromoaniline
2-Bromo-6-chloro-4-nitroanilne
2-Bromo-4,6-dintroaniline
2-Chloroaniline
3-Chloroaniline
4-Chloroaniline
2-Chloro-4,6-dinitroaniline
2-Chloro-4-nitroaniline
4-Chloro-2-nitroaniline
2,6-Dibromo-4-nitroanil ine
3,4-Dichloroaniline
2,6-Dichloro-4-nitroaniline
2,4-Dinitroaniline
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
2,4,6-Trichloroaniline
2,4,5-Trichloroaniline
                             TWO - 35
                      Revision 3
                    January 1995

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                                 TABLE 2-18
               METHOD 8141  (GC)  - ORGANOPHOSPHORUS  COMPOUNDS
   Aspon                                   Fenthion
   Atrazine                                Fonophos
   Azinphos-ethyl                          Hexamethylphosphoramide  (HMPA)
   Azinphos-methyl                         Leptophos
   Bolstar (Sulprofos)                     Malathion
   Carbophenothion                         Merphos
   Chlorofenvinphos                        Mevinphos
   Chlorpyrifos                            Monocrotophos
   Chlorpyrifos methyl                     Naled
   Coumaphos                               Parathion, ethyl
   Crotoxyphos                             Parathion, methyl
   Demeton-0, and -S                       Phorate
   Diazinon                                Phosmet
   Dichlorofenthion                        Phosphamidon
   Dichlorvos (DDVP)                       Ronnel
   Dicrotophos                             Simazine
   Dimethoate                              Stirophos  (Tetrachlorvinphos)
   Dioxathion                              Sulfotepp
   Disulfoton                              TEPP
   EPN                                     Terbufos
   Ethion                                  Thionazin  (Zinophos)
   Ethoprop                                Tokuthion  (Prothiophos)
   Famphur                                 Trichlorfon
   Fenitrothion                            Trichloronate
   Fensulfothion                           Tri-o-cresylphosphate  (TOCP)
                                 TABLE 2-19
METHOD 8151 (GC USING METHYLATION OR PENTAFLUOROBENZYLATION DERIVATIZATON)
                           CHLORINATED HERBICIDES
   Acifluorfen          Dicamba                  MCPP
   Bentazon             3,5-Dichlorobenzoic      4-Nitrophenol
   Chloramben              acid                  Pentachlorophenol
   2,4-D                Dichloroprop             Picloram
   Dalapon              Dinoseb                  2,4,5-TP (Silvex)
   2,4-DB               5-Hydroxydicamba         2,4,5-T
   DCPA diacid          MCPA
                                  TWO - 36                     Revision 3
                                                             January 1995

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                                  TABLE 2-20
                METHOD 8260 (GC/MS)-  VOLATILE ORGANIC  COMPOUNDS
Acetone
Acetonitrile
Acrolein (Propenal)
Acrylonitrile
Ally! alcohol
Allyl chloride
Benzene
Benzyl chloride
Bis(2-chloroethyl)-
  sulfide
Bromoacetone
Bromobenzene
Bromochloromethane
Bromodichloromethane
4-Bromofluorobenzene
Bromoform
Bromomethane
n-Butanol
2-Butanone (MEK)
t-Butyl alcohol
n-Butylbenzene
sec-Butyl benzene
tert-Butylbenzene
Carbon disulfide
Carbon tetrachloride
Chloral hydrate
Chloroacetonitrile
Chlorobenzene
1-Chlorobutane
Chi orodi bromomethane
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl
  ether
Chloroform
1-Chlorohexane
Chioromethane
Chloroprene
3-Chloropropionitrile
2-Chlorotoluene
4-Chlorotoluene
Crotonaldehyde
l,2-Dibromo-3-
  chloropropane
1,2-Dibromoethane
Di bromof1uoromethane
Dibromomethane
1,2-Di chlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
cis-l,4-Dichloro-
   2-butene
trans-l,4-Dichloro-2-
   butene
Dichlorodifl uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-1,2-Dichloroethene
trans-l,2-Dichloro-
   ethene
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
l,3-Dichloro-2-propanol
1,1-Dichloropropene
cis-l,3-Dichloropropene
trans-l,3-Dichloro-
   propene
1,2,3,4-Diepoxybutane
Diethyl ether
1,4-Difluorobenzene
1,4-Dioxane
Epichlorohydrin
Ethanol
Ethyl acetate
Ethyl benzene
Ethylene oxide
Ethyl methacrylate
Fluorobenzene
Hexachlorobutadiene
Hexachloroethane
2-Hexanone
2-Hydroxypropionitrile
lodomethane
Isobutyl alcohol
Isopropylbenzene
p-Isopropyltoluene
Malononitrile
Methacrylonitrile
Methanol
Methyl-t-butyl ether
Methylene chloride
Methyl acrylate
Methyl methacrylate
4-Methyl-2-pentanone
  (MIBK)
Naphthalene
Nitrobenzene
2-Nitropropane
N-Nitroso-di-n-
  butylamine
Paraldehyde
Pentachloroethane
Pentafluorobenzene
2-Pentanone
2-Picoline
1-Propanol
2-Propanol
Propargyl alcohol
B-Propiolactone
Propionitrile (Ethyl
  cyanide)
n-Propylamine
n-Propylbenzene
Pyridine
Styrene
1,1,1,2-Tetrachloro-
   ethane
1,1,2,2-Tetrachloro-
  ethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chlorof1uoromethane
1,2,3-Trichloropropane
1,2,4-Trimethyl benzene
1,3,5-Trimethyl benzene
Vinyl acetate
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
                                   TWO - 37
                                     Revision 3
                                   January 1995

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                                  TABLE 2-21
             METHOD 8270 (GC/MS) - SEMIVOLATILE ORGANIC COMPOUNDS
Acenaphthene
Acenaphthylene
Acetophenone
2-Acetylami nof1uorene
l-Acetyl-2-thiourea
Aldrin
2-Aminoanthraquinone
Aminoazobenzene
4-Aminobiphenyl
3-Amino-9-ethyl-
  carbazole
Anilazine
Aniline
o-Anisidine
Anthracene
Aramite
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Azinphos-methyl
Barban
Benz(a)anthracene
Benzidine
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzoic acid
Benzo(g,h,i)perylene
Benzo(a)pyrene
p-Benzoquinone
Benzyl  alcohol
a-BHC
/3-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
Captafol
Captan
Carbaryl
Carbofuran
Carbophenothion
Chlordane (technical)
Chlorfenvinphos
4-Chloroaniline
Chlorobenzilate
5-Chloro-2-methyl-
  aniline
4-Chloro-3-methyl phenol
3-(Chloromethyl)-
  pyridine hydro-
  chloride
1-Chloronaphthalene
2-Chloronaphthalene
2-Chlorophenol
4-Chloro-l,2-phenylene-
  diamine
4-Chloro-l,3-phenylene-
  diamine
4-Chlorophenyl phenyl
  ether
Chrysene
Coumaphos
p-Cresidine
Crotoxyphos
2-Cyclohexyl-4,6-
  dinitrophenol
4,4'-DDD
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-Di chlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos
Dicrotophos
Dieldrin
Diethyl phthalate
Diethylstilbestrol
Diethyl sulfate
Dihydrosaffrole
Dimethoate
3,3'-Dimethoxybenzidine
Dimethyl ami noazobenzene
7,12-Dimethylbenz(a)-
  anthracene
3,3'-Dimethylbenzidine
a,o;-Dimethylphenethyl -
  amine
2,4-Dimethylphenol
Dimethyl phthalate
1,2-Dinitrobenzene
1,3-Dinitrobenzene
1,4-Dinitrobenzene
4,6-Dinitro-2-methyl-
  phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap
Dinoseb
Dioxathion
Diphenylamine
5,5-Di phenylhydantoi 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
Famphur
Fensulfothion
Fenthion
                                   TWO  -  38
                                     Revision 3
                                   January 1995

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                            TABLE 2-21 (CONTINUED)
Fluchloralin
Fluoranthene
Fluorene
2-Fluorobiphenyl
2-Fluorophenol
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclo-
  pentadiene
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-Methylnaphthalene
Methyl parathion
2-Methylphenol
3-Methylphenol
4-Methylphenol
Mevinphos
Mexacarbate
Mi rex
Monocrotophos
Naled
Naphthalene
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
Nicotine
5-Nitroacenaphthene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
5-Nitro-o-anisidine
Nitrobenzene
4-Nitrobiphenyl
Nitrofen
2-Nitrophenol
4-Nitrophenol
Nitroquino!ine-1-oxide
N-Nitrosodi-n-
  butylatnine
N-Nitrosodiethylamine
N-Nitrosodimethyl amine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propyl-
  amine
N-Ni trosomethylethyl -
  amine
N-Nitrosomorpholine
N-Nitrosopiperidine
N-Nitrosopyrrol idine
5-Nitro-o-toluidine
Octamethyl  pyrophos-
  phoramide
4,4'-Oxydianiline
Parathion
Pentachlorobenzene
Pentachloron i trobenzene
Pentachlorophenol
Phenacetin
Phenanthrene
Phenobarbital
Phenol
1,4-Phenylenediamine
Phorate
Phosalone
Phosmet
Phosphamidion
Phthalic anhydride
2-Picoline
Piperonyl sulfoxide
Pronamide
Propylthiouracil
Pyrene
Pyridine
Resorcinol
Safrole
Strychnine
Sulfall ate
Terbufos
Terphenyl
1,2,4,5-Tetrachloro
  benzene
2,3,4,6-Tetrachloro-
  phenol
Tetrachlorvinphos
Tetraethyl dithio-
  pyrophosphate
Tetraethyl
  pyrophosphate
Thionazine
Thiophenol
  (Benzenethiol)
Toluene diisocyanate
o-Toluidine
Toxaphene
2,4,6-Tribromophenol
1,2,4-Trichlorobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
0,0,0-Triethyl
  phosphorothioate
Trifluralin
2,4,5-Trimethylaniline
Trimethyl phosphate
1,3,5-Trinitrobenzene
Tris(2,3-dibromopropyl)
  phosphate
Tri-p-tolyl phosphate
                                   TWO - 39
                                     Revision 3
                                   January 1995

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                                  TABLE 2-22
      METHOD 8275 (TE/GC/MS)  -  SEMIVOLATILE ORGANIC COMPOUNDS (SCREENING)
Acenaphthene
Acenaphthylene
Anthracene
Benz(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
Benzo(k)fluoranthene
4-Bromophenyl phenyl
ether
1-Chioronaphthalene
Chrysene
Dibenxofuran
Dibenz(a,h)anthracene
Dibenzothiophene
Fluoranthene
Fluorene
Hexachlorobenzene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
2-Chlorobiphenyl
3,3'-Dichlorobiphenyl
2,2',5-Trichloro-
  biphenyl
2,3',5-Trichloro-
  biphenyl
2,4',5-Trichloro-
  biphenyl
2,2',5,5'-Tetrachloro-
  biphenyl
2,2'4,5'-Tetrachloro-
  biphenyl
2,2'3,5'-Tetrachloro-
  biphenyl
2,3',4,4'-Tetrachloro-
  biphenyl
2,2',4,5,5'-Penta-
  chl orobiphenyl
2,3',4,4',5-Penta-
  chlorobiphenyl
2,2',3,4,4',5'-
  Hexachlorobiphenyl
22' 33' 44'-
£.,£. 5O>O jtjT1
  Hexachlorobi phenyl
2,2',3,4',5,5',6-
  Heptachlorobiphenyl
2 2' 3 4 4' 5 5'-
£ , C. ,O,t,t ,3,3
  Heptachlorobiphenyl
2 2' 3 3' 4 4' 5-
{-•,(- ,J,O ,^,^ »3
  Heptachlorobiphenyl
2,2',3,3',4,4'5,5'-
  Octachlorobiphenyl
2,2',3,3'4,4'5,5',6-
  Nonachlorobiphenyl
2,2',3,3'4,4'5,5',6,6'
  Decachlorobiphenyl
                                  TABLE  2-23
               METHODS 8280  (HRGC/LRMS)  AND 8290  (HRGC/HRMS)  -
                   POLYCHLORINATED DIBENZO-p-DIOXINS (PCDDs)
                   AND POLYCHLORINATED DIBENZOFURANS (PCDFs)
2,3,7,8-TCDD
TCDD, total*
1,2,3,7,8-PeCDD
PeCDD, total*
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
HxCDD, total*
1,2,3,4,6,7,8-HpCDD
HpCDD, total*
OCDD
2,3,7,8-TCDF
TCDF, total*
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
PeCDF, total*
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
HxCDF, total*
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
HpCDF, total*
OCDF


*  Analyte of  only Method  8280.
                                    TWO  -  40
                                     Revision 3
                                   January 1995

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                       TABLE 2-24
 METHOD 8310 (HPLC) - POLYNUCLEAR AROMATIC HYDROCARBONS
     Acenaphthene
     Acenaphthylene
     Anthracene
     Benzo(a)anthracene
     Benzo(a)pyrene
     Benzo(b)fluoranthene
     Benzo(g,h,i)perylene
     Benzo(k)fluoranthene
    Chrysene
    Dibenzo(a,h)anthracene
    Fluoranthene
    Fluorene
    Indeno(l,2,3-cd)pyrene
    Naphthalene
    Phenanthrene
    Pyrene
                       TABLE 2-25
            METHOD 8315 - CARBONYL COMPOUNDS
Acetaldehyde
Acetone
Acrolein
Benzaldehyde
Butanal (Butyraldehyde)
Crotonaldehyde
Cyclohexanone
Decanal
2,5-Dimethylbenzaldehyde
Formaldehyde
Heptanal
Hexanal (Hexaldehyde)
Isovaleraldehyde
Nonanal
Octanal
Pentanal (Valeraldehyde)
Propanal
  (Propionaldehyde)
m-Tolualdehyde
o-Tolualdehyde
p-Tolualdehyde
                        TWO - 41
                    Revision 3
                  January 1995

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              TABLE  2-26                                        	
          METHOD 8316  (HPLC)                                   M
              Aery!amide
             Acrylonitrile
               Acrolein
              TABLE  2-27
METHOD 8318 (HPLC) - N-METHYLCARBAMATES
           Aldicarb  (Temik)
           Aldicarb  sulfone
           Carbaryl  (Sevin)
          Carbofuran  (Furadan)
               Dioxacarb
          3-Hydroxycarbofuran
          Methiocarb  (Mesurol)
          Methomyl  (Lannate)
               Promecarb
           Propoxur  (Baygon)
                TWO - 42                     Revision 3
                                           January 1995

-------
    TABLE 2-28.  METHOD 8321 (HPLC/TS/MS) - NON-VOLATILE ORGANIC COMPOUNDS
Azo Dyes
Disperse Red 1
Disperse Red 5
Disperse Red 13
Disperse Yellow 5
Disperse Orange 3
Disperse Orange 30
Disperse Brown 1
Solvent Red 3
Solvent Red 23
Anthraquinone Dyes
Disperse Blue 3
Disperse Blue 14
Disperse Red 60
Coumarin Dyes
Fluorescent Briqhteners
Fluorescent Brightener 61
Chlorinated Phenoxyacid Compounds
2,4-D
2,4-D, butoxyethanol ester
2,4-D, ethylhexyl ester
2,4-DB
Dalapon
Dicamba
Dichlorprop
Dinoseb
MCPA
MCPP
Silvex (2,4,5-TP)
2,4,5-T
2,4,5-T,  butyl ester
2,4,5-T,  butoxyethanol ester

Alkaloids
Strychnine
Caffeine

Organophosphorus Compounds
Asulam
Fensulfothion
Dichlorvos
Dimethoate
Disulfoton
Merphos
Methomyl
Methyl parathion
Monocrotophos
Famphur
Naled
Phorate
Trichlorfon
Thiofanox
Tris-(2,3-dibromopropyl) phosphate
   (Tris-BP)
                                          Fluorescent Brightener 236
Carbamates

Aldicarb
Aldicarb sulfone
Aldicarb sulfoxide
Aminocarb
Barban
Benomyl
Bromacil
Bendiocarb
Carbaryl
Carbendazim
Carbofuran
3-Hydroxy-carbofuran
Chloroxuron
Chloropropham
Diuron
Fenuron
Fluometuron
Linuron
Methiocarb
Methomyl
Mexacarbate
Monuron
Neburon
Oxamyl
Propachlor
Propham
Propoxur
Siduron
Tebuthiuron
                                   TWO - 43
                      Revision 3
                    January 1995

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                            TABLE 2-29
     METHOD  8325  (HPLC/PB/MS)  -  NON-VOLATILE ORGANIC  COMPOUNDS
Benzidine
Benzoylprop ethyl
Carbaryl
o-Chlorophenyl thiourea
3,3'-Dichlorobenzidine
3,3'-Dimethoxybenzidine
3,3'-Dimethylbenzidine
Diuron
Linuron (Lorox)
Monuron
Rotenone
Siduron
                            TABLE 2-30
        METHOD 8330 (HPLC) - NITROAROMATICS AND NITRAMINES
4-Amino-2,6-dinitrotoluene
  (4-Am-DNT)
2-Amino-4,6-dinitrotoluene
  (2-Am-DNT)
1,3-Dinitrobenzene (1,3-DNB)
2,4-Dinitrotoluene (2,4-DNT)
2,6-Dinitrotoluene (2,6-DNT)
Hexahydro-l,3,5-trinitro-
  1,3,5-triazine (RDX)
Methyl-2,4,6-trinitrophenyl-
  nitramine (Tetryl)
Nitrobenzene (NB)
2-Nitrotoluene (2-NT)
3-Nitrotoluene (3-NT)
4-Nitrotoluene (4-NT)
Octahydro-1,3,5,7-tetrani tro-
  1,3,5,7-tetrazocine (HMX)
1,3,5-Trinitrobenzene (1,3,5-TNB)
2,4,6-Trinitrotoluene (2,4,6-TNT)
                            TABLE 2-31
                 METHOD 8331 (REVERSE PHASE HPLC)
                             Tetrazene
                            TABLE 2-32
                        METHOD 8332 (HPLC)
                          Nitroglycerine
                             TWO  - 44
                      Revision 3
                    January 1995

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                                 TABLE 2-33
                         METHOD  8410  -  SEMIVOLATILES
   Acenaphthene
   Acenaphthylene
   Anthracene
   Benzo(a)anthracene
   Benzo(a)pyrene
   Benzole acid
   Bis(2-chloroethoxy)methane
   Bis(2-chloroethyl) ether
   Bis(2-chloroisopropyl) ether
   Bis(2-ethylhexyl) phthalate
   4-Bromophenyl phenyl  ether
   Butyl benzyl phthalate
   4-Chloroaniline
   4-Chloro-3-methyl phenol
   2-Chloronaphthalene
   2-Chlorophenol
   4-Chlorophenol
   4-Chlorophenyl phenyl ether
   Chrysene
   Dibenzofuran
   Di-n-butyl phthalate
   1,2-Dichlorobenzene
   1,3-Dichlorobenzene
   1,4-Dichlorobenzene
   2,4-Dichlorophenol
   Diethyl phthalate
   Dimethyl phthalate
   4,6-Dinitro-2-methylphenol
   2,4-Dinitrophenol
   2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Di-n-propyl phthalate
Fluoranthene
Fluorene
Hexachlorobenzene
1,3-Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane
Isophorone
2-Methyl naphthalene
2-Methylphenol
4-Methylphenol
Naphthalene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitroso-di-n-propylamine
Pentachlorophenol
Phenanthrene
Phenol
Pyrene
1,2,4-Trichlorobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
                                 TABLE 2-34
METHOD 8430 (GC/FT-IR) - BIS(2-CHLOROETHYL)ETHER AND ITS HYDROLYSIS PRODUCTS
                           Bis(2-chloroethyl)ether
                               2-Chloroethanol
                          2-(2-Chloroethoxy)ethanol
                              Diethylene  glycol
                               Ethylene glycol
                                  TWO - 45
                          Revision 3
                        January 1995

-------
                                  TABLE 2-35
                    ANALYSIS  METHODS  FOR INORGANIC  ANALYTES
Compound                                                  Applicable Method(s)


Aluminum  	   6010, 6020, 7020
Antimony  	 6010, 6020, 7040, 7041, 7062
Arsenic 	 6010, 6020, 7060, 7061, 7062, 7063
Barium  	 6010, 6020, 7080, 7081
Beryllium 	 6010, 6020, 7090, 7091
Bromide 	 9056, 9211
Cadmium 	 6010, 6020, 7130, 7131
Calcium 	 6010, 7140
Chloride  	 9056, 9057, 9212, 9250, 9251, 9253
Chromium  	 6010, 6020, 7190, 7191
Chromium,  hexavalent  	 7195, 7196, 7197, 7198, 7199
Cobalt  	 ... 6010, 6020, 7200, 7201
Copper  	 6010, 6020, 7210, 7211
Cyanide 	 9010, 9012, 9013, 9213
Fluoride  	 9056, 9214
Iron	6010, 7380, 7381
Lead  	 6010, 6020, 7420, 7421
Lithium 	 6010, 7430
Magnesium 	 6010, 7450
Manganese 	 6010, 6020, 7460, 7461
Mercury 	 7470, 7471, 7472
Molybdenum  	 6010, 7480, 7481
Nickel  	 6010, 6020, 7520, 7521
Nitrate 	 9056, 9210
Nitrite	9056
Osmium	7550
Phosphate	9056
Phosphorus	6010
Phosphorus, white  	 7580
Potassium 	 6010, 7610
Selenium  	 6010, 7740, 7741, 7742
Silver  	 6010, 6020, 7760, 7761
Sodium  	 6010, 7770
Strontium 	 6010, 7780
Sulfate 	 9035, 9036, 9038, 9056
Sulfide 	 9030, 9031, 9215
Thallium  	 6010, 6020, 7840, 7841
Tin	7870
Vanadium  	 6010, 7910, 7911
Zinc  	 6010, 6020, 7950, 7951
                                   TWO  - 46                     Revision 3
                                                              January  1995

-------
                                                TABLE 2-36
                CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING TIMES FOR  AQUEOUS MATRICESA
Name
Bacterial Tests:
Col i form, total
Inorganic Tests:
Chloride
Cyanide, total and amenable
to chlorination





Hydrogen ion (pH)
Nitrate
Sulfate
Sulfide
Metals:
Chromium VI
Mercury
Metals, except chromium VI
and mercury
Organic Tests:
Acrolein and acrylonitri le

Benzi dines

Chlorinated hydrocarbons

Dioxins and Furans

Haloethers

Nitroaromatics and
cyclic ketones
Nitrosamines

Oil and grease
Organic carbon, total (TOO
PCBs

Pesticides

Phenols

Phthalate esters

Polynuclear aromatic
hydrocarbons
Purgeable aromatic
hydrocarbons
Purgeable Halocarbons

Total organic halides (TOX)

Radiological Tests:
Alpha, beta and radium
Container1

P, G

P, G
P, G






P, G
P, G
P, G
P, G

P, G
P, G
P, G


G, Teflon- lined
septum
G, Teflon- lined
cap
G, Teflon- lined
cap
G, Teflon-lined
cap
G, Teflon- lined
cap
G, Teflon- lined
cap
G, Teflon- lined
cap
G
P, G
G, Teflon- lined
cap
G, Teflon- lined
cap
G, Teflon-lined
cap
G, Teflon- lined
cap
G, Teflon- lined
cap
G, Teflon- lined
septum
G, Teflon- lined
septum
G, Teflon-lined
cap

P, G
Preservation

Cool, 4°C, 0.008% Na2S203

None required
Cool, 4°C; if oxidizing
agents present add 5 mL
0.1N NaAs02 per L or 0.06 g
of ascorbic acid per L;
adjust pH>12 with 50% NaOH.
See Method 9010 for other
interferences.
None required
Cool, 4°C
Cool, 4°C
Cool, 4°C, add zinc acetate

Cool, 4°C
HN03 to pH<2
HN03 to pH<2


Cool, 4°C, 0.008% Na2S2033,
Adjust pH to 4-5
Cool, 4°C, 0.008% Na2S2033,

Cool, 4°C, 0.008% Na2S2033

Cool, 4°C, 0.008% Na2S2033

Cool, 4°C, 0.008% Na2S2033

Cool, 4°C, 0.008% Na2S2033
store in dark
Cool, 4°C, 0.008% Na2S2033,
store in dark
Cool, 4°C2
Cool, 4°C2
Cool, 4°C

Cool, 4°C

Cool, 4°C, 0.008% Na2S2033

Cool, 4°C

Cool, 4°C, 0.008% Na2S2033
store in dark
Cool, 4°C, 0.008% Na2S2032'3

Cool, 4°C, 0.008% Na2S2033

Cool, 4°C2


HN03 to pH<2
Maximum holding time

6 hours

28 days
14 days






24 hours
48 hours
28 days
7 days

24 hours
28 days
6 months


14 days

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,
after extraction
7 days until extraction,
after extraction
7 days until extraction,
after extraction
7 days until extraction,
after extraction
14 days

14 days

28 days


6 months
























40 days

40 days

40 days

40 days

40 days

40 days



40 days

40 days

40 days

40 days

40 days









A Table excerpted,  in part, from Table II,  49  FR 209, October 26,  1984,  p 28.
1 Polyethylene  (P) or Glass (G)
2 Adjust to pH«2 with H2S04, HCl or solid NaHS04.   Free chlorine must be removed  prior to adjustment.
3 Free chlorine must be removed by the appropriate addition of Na2S203.
                                               TWO  -  47
   Revision  3
January  1995

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TABLE 2-37.  PREPARATION METHODS FOR ORGANIC ANALYTES

Analyte Type
Acid Extractable
Acrolein, Acrylonitrile,
and Acetonitrile
Acryl amide
Aniline and Selected
Derivatives
Aromatic Volatiles
Base/Neutral Extractable
Carbamates
Chlorinated Herbicides
Chlorinated Hydrocarbons
Dyes
Explosives
Formaldehyde
Haloethers
Halogenated Volatiles
Nitroaromatic and Cyclic
Ketones
Matrix
Aqueous1
3510
3520
(pH < 2)
5031
80324
3510
3520
(pH >11)
503111
5030
5032
3510
3520
(pH >11)
83185
81516
(pH < 2)
3510
3520
(PH 7)
3510
3520
83307
83318
83 159
3510
3520
5030
5032
3510
3520
(pH 5-9)
Solids
3540
3541
3545
3550
5031

3540
3541
3545
3550
5021
5032
5035
3540
3541
3545
3550
83 185
81516
3540
3541
3550
3540
3541
3545
3550
83307
83318
83 159
3540
3541
3545
3550
5021
5032
5035
3540
3541
3545
3550
Sludges and
Emulsions1-2
3520
(pH < 2)
5031

3520
(pH >11)
5030
5032
3520
(pH >11)
83185
81516
(pH<2)
3520
(pH 7)




5030
3520
(pH 5-9)
Organic
Liquids,
Tars, Oils
3650
35803
3585

35803
3585
3650
35803
83185
35803
35803




3585
35803
                       TWO  -  48
  Revision 3
January 1995

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                                        TABLE 2-37
                         PREPARATION METHODS FOR ORGANIC ANALYTES
                                        (continued)

Analyte Type
Nitrosamines
Non-halogenated Volatiles
Organochlorine Pesticides
Organophosphorus Pesticides
Phenols
Phthalate Esters
Polychlorinated Biphenyls
PCDDs and PCDFs
Polynuclear Aromatic
Hydrocarbons
Volatile Organics
Matrix
Aqueous1
3510
3520
5031
5032
3510
3520
3535
(pH 5-9)
3510
3520
(pH 6-8)
3510
3520
(PH < 2)
3510
3520
3535
(PH 7)
3510
3520
3535
(pH 6-8)
828010
829010
3510
3520
(PH 7)
5030
5031
5032
Solids
3540
3541
3545
3550
5021
5031
5032
3540
3541
3545
3550
3540
3541
3545
3540
3541
3545
3550
3540
3541
3545
3550
3540
3541
3545
828010
829010
3540
3541
3545
3550
3561
5021
5031
5032
5035
Sludges and
Emulsions1'2

5021
5031
5032
3520
(pH 5-9)
3520
(pH 6-8)
3520
(PH < 2)
3520
(PH 7)
3520
(pH 6-8)
828010
829010
3520
(PH 7)
5021
5030
5031
5032
Organic
Liquids,
Tars, Oils

5032
3585
35803
35803
3650
35803
35803
35803
828010
829010
35803
3585
Footnotes are on the following page.
                                         TWO - 49
  Revision 3
January 1995

-------
                                        TABLE 2-37
                         PREPARATION METHODS FOR ORGANIC ANALYTES
                                        (continued)
Footnotes for Table 2-37
1   The pH at which extraction should be performed is shown in parentheses.
2   If attempts to break an emulsion are unsuccessful, these methods may be used.
3   Method 3580 is only appropriate if the sample is soluble in the specified solvent.
4   Method 8032 contains the extraction, cleanup, and determinative procedures for this
   analyte.
5   Method 8318 contains the extraction, cleanup, and determinative procedures for these
   analytes.
6   Method 8151 contains the extraction, cleanup, and determinative procedures for these
   analytes.
7   Method 8330 contains the extraction, cleanup, and determinative procedures for these
   analytes.
8   Method 8331 is for Tetrazene only, and contains the extraction, cleanup, and
   determinative procedures for this analyte.
9   Method 8315 contains the extraction, cleanup, and determinative procedures for this
   analyte.
10  Methods 8280 and 8290 contain the extraction, cleanup, and determinative procedures
   for these analytes.
11  Method  5031 may  be used when  only  aniline  is  to  be determined.
                                         TWO - 50                     Revision 3
                                                                    January 1995

-------
           TABLE 2-38.   CLEANUP METHODS FOR ORGANIC ANALYTE EXTRACTS
Analyte Type
Acid Extractable
Base/Neutral Extractable
Carbamates
Chlorinated Herbicides
Chlorinated Hydrocarbons
Haloethers
Nitroaromatics & Cyclic Ketones
Nitrosamines
Organochlorine Pesticides
Organophosphorus Pesticides
Phenols
Phthalate Esters
Polychlorinated Biphenyls
Polychlorinated Dibenzo-p-Dioxins
and Polychlorinated Dibenzofurans
Polynuclear Aromatic Hydrocarbons
Method
3650
3650
83181
81512
3620
3640
3620
3640
3620
3640
3610
3620
3630
3640
3660
3620
3630
3640
3650
3610
3611
3620
3640
3620
3630
3640
3660
3665
82803
82903
3610
3611
3630
3640
3650
1   Method 8318 contains  the  extraction,  cleanup,  and determinative procedures
   for these analytes.
2   Method 8151 contains  the  extraction,  cleanup,  and determinative procedures
   for these analytes.
3   Methods 8280  and 8290 contain  the extraction, cleanup,  and  determinative
   procedures for these analytes.
                                   TWO - 51
  Revision 3
January 1995

-------
           TABLE  2-39.   DETERMINATIVE METHODS ORGANIC ANALYTES
Analyte Type
Acid Extractable
Acrolein, Acrylonitrile,
Acetonitrile
Acryl amide
Aniline and Selected
Derivatives
Aromatic Volatiles
Base/Neutral Extractable
Carbamates
Chlorinated Herbicides
Chlorinated Hydrocarbons
Dyes
Explosives
Formaldehyde
Haloethers
Halogenated Volatiles
Nitroaromatics and Cyclic
Ketones
Nitrosoamines
Non-halogenated Volatiles
Organochlorine Pesticides
Organophosphorus Pesticides
Phenols
Petroleum Hydrocarbons
Phthalate Esters
Polychlorinated Biphenyls
PCDDs and PCDFs
Polynuclear Aromatic
Hydrocarbons
Volatile Organics
GC/MS
Method
8270
8260
8260
8270
8260
8270

82703
8270



8270
8260
8270
8270
8260
82703
82703
8270

8270
82703
8280
8290
8270
8260
Specific GC
Method

8031
80331
8032
8131
8021


8151
8121



8111
8011, 8021
8091
8070
8015
8081
8141
8041
8015
8061
8082

8100
8011, 8015,
8021, 8031,
8032, 8033
HPLC
Method

83 152
8316
8316


83254
8318, 8321
8321

8321
8330,
8331, 8332
8315


83305



8321





8310
8315
8316
Of these analytes, Method 8033 is for acetonitrile only.
Of these analytes, Method 8315 is for acrolein only.
This method is an alternative confirmation method, not the method  of choice.
Benzidines and related compounds.
Nitroaromatics (see "Explosives").
                                TWO - 52
  Revision 3
January 1995

-------
   CO
   a
   I— 4
   =»
   cr
 '  O
CM CO

LU OC.
al O
=) U.
C3
   CL.
   O

   oo
   *—«
   00
   cc
   o

-------
                              FIGURE 2-2
               SCHEMATIC OF SEQUENCE TO  DETERMINE
           IF A WASTE  IS HAZARDOUS BY  CHARACTERISTIC
   What is
physical state
  of waste?
Perform Paint
  Filter Test
(Method 9095)
Nonhazardous
for corrosivity
characteristic
        Methods 1110 and 9040

               Yes	
          Methods 1010 or 1020

               YBS	
                                         DOT(49CFR 173300)
                                                           -^C^~Hazaroous~^)
                                          Generator Knowledge
                                          OT(49CFR173.151)
                              TWO -  54
   Revision  3
January 1995

-------
           FIGURE  2-2
          (Continued)
    Nonnazardous
    for ignitability
    characteristic
              Reactive CN
              and Sulfide Tests
     Does waste
    generate toxic
        gas'
   Nonhazardous
for toxic gas generation
(reactivity) characteristic
      Is total
   concen. of TC
 constituents •*• 20 <
   TC regulatory
       limif
Nonhazardous
  for toxicity
 characteristic
     Is waste
   leachable and
                                    Nonhazardous
                                      for toxiaty
                                     characteristic
            TWO  -  55
                 Revision 3
              January  1995

-------
                                 FIGURE  2-3A
                                     EP
                                  Sample
                                   1310
    3010
  (7760  Ag)
    6010
 Ba--
Cr --
Ag --
       -- As
       -- Cd
       -- Pb
       -- Se
7470
 Hg
 3510
Neutral
   8151
Herbicides
                           8081
                        Pesticides
                                  TWO - 56
                                         Revision 3
                                       January 1995

-------
                                 FIGURE 2-3B
            .COMMENDED SW-846 METHODS OF ANALYSIS FOR TCLP LEACHATES
                              Sample
                               TCLP





3010













7470
Hg










3510
Neutral








8260
Volatile
Organics









3510
(Acidic
and
Basic)






8151
Herbic-
ides


Ba -


Cr -


Ag -
- As


- Cd


- Pb


- Se
                                  TWO - 57
                                                         Revision 3
                                                       January 1995

-------
                                      FIGURE 2-4A.
                        GROUND WATER ANALYSIS:  ORGANIC ANALYTES
      VGA
Semivolatiles
     8260
  3510 or
   3520
                      8270
                                         Organic
                                         Sample
Pesticides
 3510 or
  3520
 Neutral
                   3620, 3640,
                   and/or 3660
Herbicides
Dioxins
  8151
8280 or
 8290
                                          8081
1  - Optional:  Cleanup required only if interferences prevent analysis.
                                        TWO - 58
                                                  Revision  3
                                                January  1995

-------
                                          FIGURE 2-4B.
                         GROUND WATER ANALYSIS:   INDICATOR  ANALYTES
                                         Indicator
                                        Analyte(s)
1 - Barcelona, 1984, (See Reference 1)
2 - Riggin, 1984, (See Reference 2)
                                            TWO  -  59
  Revision 3
January 1995

-------
                                    FIGURE  2-4C.
                 GROUND  WATER ANALYSIS:    INORGANIC ANALYTES
                              (   GROUND WATER
                              V      SAMPLE
            SAMPLE PREPARATION
                3005 OR 3015
  i
                                 SAMPLE PREPARATION
                                     3015 OR 3020
  i
I
Ag, Al, As, Ba, Be,
Cd, Co, Cr. 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
Ag-7760
Ba-7080
Cd-7130
Cr-7190
Fe-7380
Mn-7460
Ni - 7520
Sb-7040
TI-7840
Zn-7950
AI-7020
Be -7090
Co -7200
Cu-7210
Mg - 7450
Mo -7480
Pb-7420
Sn - 7870
V • 7910
Ag-7761'
Ba-7081'
Be -7091
Cd-7131
Co - 7201
Cr-7191
Cu-7211*
Fe-7381"
Mn- 746T
Mo - 7481
Pb - 7421
Tl - 7841
Sb-7041'
7062*
V-7911
Zn-7951*
*  Follow the digestion procedures as detailed in the individual
  determinative methods.

1  When analyzing for total dissolved metals, digestion is not
  necessary if the samples are filtered at the time of
  collection, and then acidified to the same concentration as the standards
                                       TWO -  60
                                                       Revision  3
                                                     January 1995

-------
                                 CHAPTER THREE

                               INORGANIC ANALYTES
3.1  SAMPLING CONSIDERATIONS

3.1.1  Introduction

      This manual contains procedures for the analysis  of  inorganic analytes 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 inorganic 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  functnfnal  relationship
between emission intensity and concentration.                .;

      Method detection limit  (MDL):  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 the 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,  3051, or 3052.
                                  THREE  -  1                       Revision 3
                                                                  January 1995

-------
      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  (ICV)   standard:     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).

      Linear dynamic 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 blank:   A  volume  of  reagent  water  acidified  with  the  same
amounts of acids as were the standards and samples.

      Laboratory 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 use of the  unknown and  the  unknown  plus  several  known amounts of
standard.  See 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 3
                                                                  January 1995

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      3.1.3  Sample Handling and Preservation

      Sample holding times, digestion volumes and suggested collection volumes
are listed in Table 3-1.  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 3
                                                                  January 1995

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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.
                                   THREE - 4                       Revision  3
                                                                   January  1995

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                                 TABLE 3-1.

  SAMPLE  HOLDING  TIMES,  REQUIRED DIGESTION  VOLUMES  AND RECOMMENDED COLLECTION
       VOLUMES  FOR INORGANIC DETERMINATIONS IN  AQUEOUS AND SOLID SAMPLES
Measurement
Digestion
Vol. Req.
 (tnL)a
Collection
Volume (mL)J
Treatment/
Preservative
Holding Timeb
Inorganic Analytes (except hexavalent chromium and mercury):
Aqueous
      Total
      Dissolved
      Suspended
Solid
      Total

Chromium VI:

      Aqueous

      Solid


Mercury:

Aqueous
      Total


      Dissolved
Solid
      Total
    100


    100



    100


    2  9



    100

    2.5  g
    100


    100



    0.2 g
  600


  600



  600


  200 g



  400

  100 g
  400


  400



  200 g
HN03 to pH <2
6 months

Filter on  site;
HN03 to pH <2
6 months

Filter on  site
6 months

6 months
24 hours

One month to
extraction, 4 days
after extraction
HN03 to pH <2
28 days

Filter;
HN03 to pH <2
28 days

28 days
aUnless  stated otherwise.
bAll  non-aqueous samples and  all  aqueous  samples that are  to  be analyzed for
hexavalent chromium must be stored at 4°C  ±  2°C until analyzed, either glass or
plastic containers may be used.
                                   THREE  -  5
                                      Revision 3
                                      January 1995

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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  metal determinations by FLAA, ICP-AES,  or ICP-MS.  The
unfiltered or filtered sample is heated with dilute  HC1  and HN03 prior to metal
determination.

          Method 3010  prepares  waste samples for total metal  determinations 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  determinations  by FLAA,
GFAA,  ICP-AES,  or ICP-MS.   Nitric acid  is added  to  the sample  in  a  Teflon
digestion vessel and heated in a microwave  unit prior to metals determination.

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

          Method 3031  prepares waste  oils,  oil  sludges,  tars,  waxes,  paints,
paint sludges  and other  viscous petroleum products for analysis  by  FLAA and ICP-
AES.   The  samples are  vigorously  digested  with nictric  acid,  sulfuric acid,
hydrochloric  acid, and potassium permanganate prior to analysis.

          Method 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.

          Method 3050  prepares  waste  samples for total metals determinations by
FLAA and ICP-AES, or ICP-MS.  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 metal
determinations by FLAA, GFAA,  ICP-AES  or  ICP-MS.   Nitric acid  is  added  to the
representative  sample  in  a fluorocarbon  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.

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          Method 3052 prepares siliceous and organically based matrices including
ash, biological tissue, oil, oil contaminated soil, sediment, sludge, and soil
for  analysis  by  FLAA, CVAA,  GFAA,  ICP-AES,  and  ICP-MS.    Nitric  acid and
hydrofluoric  acid are  added  to  a  representative sample  in  a  fluorocarbon
digestion vessel and heated in a microwave unit prior to analysis.
                                  THREE - 7                       Revision 3
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                                  METHOD 3031

                       ACID DIGESTION OF OILS  FOR METALS
                     ANALYSIS BY FLAA OR ICP SPECTROSCOPY
1.0   SCOPE AND APPLICATION

      1.1     This method  is  an  acid digestion procedure for  analysis  of  oils,
oil sludges,  tars, waxes, paints, paint sludges and other viscous petroleum
products for  the sixteen toxic  elements listed below:

              Antimony         Arsenic           Barium            Beryllium
              Cadmium          Chromium          Cobalt            Copper
              Lead             Molybdenum        Nickel            Selenium
              Silver           Thallium          Vanadium          Zinc

The resulting digestate can be  analyzed by either flame atomic absorption
spectroscopy  (FLAA) or inductively coupled plasma atomic emission spectroscopy
(ICP-AES).

      1.2     The large concentration of manganese present in the digestate of
Method 3031 can interfere with  the determination of low concentrations of
arsenic which is important for  the recycled oil  regulations.  As an optional
step, manganese may be removed  from the digestate by forming a manganese
phosphate precipitate.  The remaining liquid can be analyzed by either flame
atomic absorption spectroscopy  (FAA) or inductively coupled plasma (ICP-AES).
Chlorides can be removed by the use of nitric acid for analysis by graphite
furnace atomic absorption spectroscopy (GFAA) for arsenic.  These clean-up
procedures may be applicable to other elements as can be demonstrated by
appropriate procedures (Sec. 7.11).

2.0   SUMMARY OF METHOD

      2.1     A representative 0.5-gram sample is mixed with 0.5 grams of
finely ground potassium permanganate and heated to 100°C.   After cooling to
room temperature, 1.5 mL of concentrated sulfuric acid is  added while
stirring.  A strong exothermic reaction occurs,  after which the sample is
heated to near dryness.  The digestate is treated with 10  mL of concentrated
nitric acid and 2 mL concentrated hydrochloric acid, heated to 95°C,  and again
brought to near dryness.   After cooling,  5 mL of concentrated HC1 is  added,
the digestate is again heated to 95°C and is then filtered.   The filter is
washed with hot concentrated HC1.  The filter paper is transferred to a
digestion flask,  treated with 5 mL of concentrated hydrochloric acid,  and
heated to 95°C to dissolve the filter.   The digestate is filtered,  and the
filtrates are combined.  The sample is brought to volume and analyzed by ICP-
AES or Flame AAS.

      WARNING;  THIS PROCEDURE SHOULD NOT BE ATTEMPTED BY  INEXPERIENCED
      PERSONNEL.   MANY OF THE REACTIONS ARE STRONGLY EXOTHERMIC AND CAN RESULT
      IN SPLATTERING OR IN THE GENERATION OF GASES.   GLOVES, FACESHIELDS, AND
      LAB COATS MUST BE WORN WHEN WORKING WITH ACIDS.   IT  IS STRONGLY
      RECOMMENDED THAT THE ADDITION OF SULFURIC  ACID BE PERFORMED BEHIND A
      GLASS SHIELD OR SASH.

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      2.2    To remove the manganese, the digestate is neutralized with
concentrated ammonium hydroxide.  Water and ammonium phosphate are added and
the digestate is stirred while a precipitate of manganese ammonium phosphate
is formed.  When the precipitation is complete, the digestate is filtered.
The ammonia is then boiled off.  The sample is brought to volume and analyzed
on either ICP-AES or FAA.  For GFAA analysis, the volume is reduced and
allowed to cool.  Concentrated HN03 is added and the solution is heated.   When
the reaction is complete, bring to volume and analyze by GFAA.

3.0   INTERFERENCES

      3.1    Most grades of potassium permanganate have elemental impurities
that will interfere with the analysis.  It is important that the permanganate
be checked for purity.  Background correction setting on an ICP-AES that are
appropriate to the digestates of other matrices will not be effective for the
digestates of oils.  Background correction settings must be chosen for this
unique digestate.  These digestates can have very high solids, which may
necessitate the use of internal standards, dilutions,  or method of standard
addition,  manganese is a very strong emitter and has many analytical lines.
analytical wavelengths must be chosen with care to avoid or minimize spectral
overlap.  Inter-element correction for manganese can be used for those
instruments with that capability.

      3.2    Excess ammonium hydroxide will result in the solubilization of
some manganese.

4.0   APPARATUS AND MATERIALS

      4.1    Beakers  - 250 ml, or equivalent.

      4.2    Thermometer (0° - 200°C) or other temperature sensing device.

      4.3    Filter paper - Whatman No. 41, or equivalent.

      4.4    Funnels  - polypropylene, or equivalent.

      4.5    Heating device or hot plate.

      4.6    Volumetric flasks, of suitable precision and accuracy.

             NOTE:  All glassware should be acid washed.

5.0   REAGENTS

      5.1    Reagent Water.  Reagent water will be interference free.  All
references to water in the method refer to reagent water unless otherwise
specified.  Refer to Chapter One of SW-846 for a definition of reagent water.

      5.2    Nitric acid, concentrated, reagent grade (cone. HN03).  Acid
should be analyzed to determine level of impurities.  If method blank is
< MDL, then the acid can be used.
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      5.3    Hydrochloric acid, concentrated, reagent grade  (cone. HC1).
Acid should be analyzed to determine level of impurities.  If method blank is
< MDL, then the acid can be used.

      5.4    Sulfuric acid, concentrated, reagent grade  (cone. H2S04).   Acid
should be analyzed to determine level of impurities.  If method blank is
< MDL, then the acid can be used.

      5.5    Potassium permanganate  - Ultra-pure grade.  Reagent should be
analyzed to determine level of impurities.  If method blank is < MDL, then the
reagent can be used.

      5.6    Organometallic standards - scandium and/or yittrium may be used
as internal standards for most samples.   Standards traceable to NIST Standard
No. 1085, for wear metals in oil, may be used.

      5.7    Base oil, analyte-free.  Oil should be analyzed to determine
level of impurities.  If method blank is < MDL,  then the reagent can be used.

      5.8    Ammonium hydroxide, concentrated, reagent grade - Reagent should
be analyzed to determine level of impurities.  If method blank is
< MDL, then the acid can be used.

      5.9    Ammonium phosphate, reagent grade - Reagent should be analyzed
to determine level of impurities.  If method blank is
< MDL, then 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 pre-washed with detergents, acids,
and water.  See Chapter Three, Step 3.1.3, for further information.

      6.3    Samples should be processed and analyzed as soon as possible.

7.0   PROCEDURES

      7.1    Homogenize sample and then take a representative sample of 0.5
grams (± O.Olg) and place in a beaker.  Larger or smaller sample sizes can be
used if needed.

      7.2    Add 0.5 grams of potassium permanganate powder.  If larger
sample sizes are used,  increase the amount of potassium permanganate so that
the ratio of oil to potassium permanganate is still  1:1.   Mix the oil and
permangante thoroughly until homogeneous.   Thick oils and tars that cannot be
mixed should be heated to achieve mixing (the oil  may react mildly).   It is
important to record the amount of potassium permanganate used for each  sample
if analysis is by ICP-AES and correction is to be made for the amount of
manganese.
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      If more than 10% of the sample is aromatic material, such as xylene,
then the reaction will be incomplete.  If this is the case, increase the
amount of potassium permanganate.  If the sample is a mixture of oil and other
non-organic materials, reduce the amount of potassium permanganate.

             NOTE:  All steps requiring the use of acids should be conducted
             under a  fume hood by properly trained personnel using
             appropriate laboratory safety equipment.  This should include
             face shields and latex gloves.

      7.3    Add 1.0  mL of concentrated H2S04,  stir with  glass  rod and place
the beaker down.  If  larger sample sizes are used, increase the volume of
sulfuric acid so that ratio of oil to sulfuric acid is Ig to 2mL.   The H2S04
can be added dropwise or all  at once, depending on analytical  needs.
(Generally, dropwise  is preferred with low reporting limits are needed.)  The
reaction can take several seconds to begin, but when it occurs it will be very
quick, vigorous, and  exothermic.   Generally larger sample sizes will react
faster than smaller.  Likewise, lower average molecular weight materials will
react faster than heavier.   Do not be mislead by an initial lack of
reactivity.  A grey-white vapor will be ejected from the beaker (S03)  and
splatting and bubbling can occur.  The beaker will become very hot.  This step
is complete when no more gases are given and the sample should be a thick
black lumpy past.  Allow the beaker to cool to the degree necessary.

             NOTE:  Care must be taken when working with very light organic
             materials, such as diesel fuels, as they may flash.  Generally,
             the lower the average molecular weight of the material
             correlates to a greater danger of flashing.  The danger of
             flashing is reduced by adding the sulfuric acid dropwise.

             NOTE:  If more than 10% of the sample is aromatic material,  such
             as xylene, only a little grey-white vapor will form,  this will
             reduce accuracy and complicate nebulization.  If there is a
             significant amount of non-hydrocarbon material, a sputtering
             reaction will occur and black Mn02 particulates will  be given
             off.  See Step 7.2.

      7.4  Add 2 ml of concentrated HN03 and stir.   This  reaction  will  be
slightly exothermic.  If larger sample sizes are used, it is not always
necessary to increase the volume of HN03 proportionately,  depending on
analytical needs.  Some reddish-brown vapor (N02)  may be  given  off.   Allow the
reaction to continue  until  complete, that is when the digestate no longer
gives off fumes.  Allow the beaker to cool as needed.

      7.5  Then add 10 ml of concentrated HC1 and stir.  If larger sample
sizes are used, it is not always necessary to increase the volume of HC1
proportionately, depending on analytical needs.  This reaction will be
slightly exothermic and gas formation and foaming will occur.   Lighter oils
will foam more than will heavier oils.  If excess foaming occurs,  add water to
prevent sample loss.  Allow the beaker to cool as needed.

      7.6  Heat the beaker until  there is no further gas evolution.
(temperature should not exceed 150° C to prevent volatilization).   There may


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be additional foaming or other milder reactions on the hot plate which may
result in overflow from the beaker.  If excess foaming occurs, either remove
the beaker from the place until foaming subsides or add sufficient water to
prevent overflow.  The final digestate should be a clear yellow liquid with
black or dark reddish-brown particulates.

      7.7  Filter the digestate through Whatman 41 filter paper and collect
filtrate in a volumetric flask or beaker.

      7.8  Wash the digestion beaker and filter paper, while still in the
funnel, with no more than 5 ml of hot HC1.

             NOTE:  The purpose of  this next step  is  to recover antimony,
             barium, and silver that may not have  been complete solubilized.
             If the sample  is not being prepared for  these analytes, the next
             step may be skipped.

      7.9  (Optional)  After having washed the filter paper, remove the filter
and residue from the funnel and place in back in the  beaker.  Add 5 ml of
cone. HC1 and place the beaker back on the heating source until the filter
paper dissolves (temperature should not exceed 150° C to prevent
volatilization).  Remove the beaker from the heating  source and wash the cover
and sides with reagent grade water and then filter the residue and collect the
filtrate in the same flask or beaker as steps 7.6 and 7.7.  If a volumetric
flask is used,  bring to volume after the filtrate has cooled.

      7.10  (Optional)  If the filtrate is collected  in a beaker, the filtrate
can be heated again on the hot plate to drive off excess HC1.  This can reduce
matrix effects in sample introduction (temperature should not exceed 150° C to
prevent volatilization).  When sufficient HC1 has been removed, remove the
beaker from the hot plate,  allow to cool, and then transfer the contents to a
volumetric flask and bring to volume.  However, if too much HC1 is removed,
barium, silver and antimony can be lost.

      7.11  Analyze the filtrate by either ICP_AES or FAAS.  Depending on the
final volume selected, the total  solids in the digestate may be high enough to
cause nebulization problems.  This can be corrected for by following step 7.9
and/or using internal  standards and/or other matrix correction procedures.

Manganese Removal  Steps

             NOTE:  The purpose of these next steps is to remove the
             manganese in the digest by precipitating it as manganese
             ammonium phosphate under alkaline conditions.  Elements that do
             not form insoluble phosphates, such as arsenic, are filtered out
             and can be analyzed at lower concentrations,

      7.12  Take the digestate,  or portion of digestate and reduce the volume
to remove as much HC1  as possible without going below 10 ml.   Then add cone.
NH4OH until  pH  is  7  or  greater.   For most  matrices,  the  digestate  will  change
colors (often from yellow to brown)  at pH 7.   A mild exothermic reaction will
occur immediately.
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      7.13  Add at least 2 g ammonium phosphate for each 1 g of potassium
permanganate used in the digestion and stir.  An excess of phosphate is needed
for good analyte recovery.  Then add enough water and mix to ensure maximum
precipitation.  A pink or yellow silky amorphous precipitate, manganese
ammonium phosphate, will form.  If too much NH4OH is used some of the
manganese ammonium phosphate can be solubilized.  Stir until precipitation is
complete.  Some ammonium phosphate may remain unreacted at the bottom of the
beaker.

      7.14  Filter the digestate through Whatman 41 filter paper (or
equivalent) and collect filtrate in a volumetric flask or beaker.

      7.15  Heat the filtrate to volatilize the ammonia (temperature should
not exceed 150" C to prevent volatilization),  the volume of filtrate can be
reduced by heating to no less than 10 ml.  IF too much water is removed any
ammonium chloride formed will solidify.  If this occurs, either add enough
water to dissolve the solids or filter out the solids and wash the residue
with deionized water.  A third alternative is to use nitric acid to destroy
the ammonium chloride by using step 7.16.

      7.16  The filtrate can be analyzed by ICP-AES or FAAS.  The chlorides in
the digestate will prevent the analysis by GFAAS.

      7.17  To analyze the digestate by GFAAS, reduce the volume as much as
possible.  Cool and add sufficient cone. HN03 to drive off all  chlorides.
Heat gently and a mild exothermic reaction will occur.  When no more reddish-
brown gas (N02) is given off, the reaction is complete and the digestate can
be cooled and taken to volume.  This liquid can be analyzed by ICP-AES, FAAS,
or GFAAS.

8.0   QUALITY CONTROL

      8.1    All quality control measures described in Chapter One should be
fol1 owed.

      8.2    For each analytical batch of samples processed, method blanks
should be carried throughout the entire sample-preparation and analytical
process.  The blank will be useful in determining if samples are being
contaminated.  Do not subtract measured blank values from sample results.  Use
blanks to determine the source of contamination and eliminate it.

             NOTE: This blank MUST include an analyte-free oil or explosive
             reactions can occur.

      8.3    Duplicate samples should  be processed on a routine basis.  A
duplicate sample is a sample brought through the whole sample preparation and
analytical process.  Refer to Chapter One for the proper protocol.

      8.4    Organometallic  standard reference materials  (SRMs) or laboratory
control samples spiked with organo-metallic standards should be employed to
determine accuracy.  Recoveries of SRMs and/or spikes should be +/- 25% of
their true values.
                                   3031 - 6                       Revision 0
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9.0   METHOD PERFORMANCE

      Refer to Tables 1, 2, 3, and 4.

10.0  REFERENCES

1.    HMU 800, Acid Digestion of Oils  for Metals Analysis by FLAA or ICP
      Spectroscopy, Southern California Laboratories.
                                   3031  -  7                       Revision 0
                                                                 January 1995

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                                   Table  1
                       Performance Data Using SRM 1085"
Element
Silver
Chromium
Copper
Molybdenum
Nickel
Lead
Vanadium
8 n = 5
Analyte
Silver
Silver
Chromium
Chromium
Copper
Copper
Molybdenum
Nickel
Nickel
Lead
Lead
Vanadium
True
Value
306
296
295
303
303
297
292
Percent
Method of
Analysis
ICP-AES
FAAS
ICP-AES
FAAS
ICP-AES
FAAS
ICP-AES
ICP-AES
FAAS
ICP-AES
FAAS
ICP-AES
Mean
Value
283
295
291
283
261
297
393
Tabl
Recoveries and
True
Value
306
306
296
296
295
295
303
303
303
297
297
292
Percent
Recovery SD

e 2
Standard
Mean
Value
302
254
278
240
301
250
282
262
237
246
260
292
92 35
100 14
99 11
93 23
86 8.
100 17
135 12
Deviations86
Percent
Recovery
98
83
94
81
102
85
93
86
78
83
88
100
6

Standard
Deviations
22
6.7
19
16
24
11
12
24
9.3
17
4.2
14
8  Procedures tested using NIST SRM 1085.
b  n = 12
                                   3031 - 8
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                                    Table 3
        Mean Measured Values for Oil Standards by Simultaneous ICP-AESa
Analyte
Silver
Arsenic
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Molybdenum
Nickel
Lead
Antimony
Selenium
Thallium
Vanadium
Zinc
500 jug/g 100 /yg/g
472
146
31.0
575
442
441
487
566
529
458
360
667°
350
NA
512
512
90.2
67.9
26.6
113
83.5
82.3
95.2
114
95.7
86.4
62.0
84.3
93.0
72.2
98.2
93.2
Concentration
50 /yg/g 25 fjg/g
46.2
39.0
8.4
56.6
43.87
42.4
50.5
55.6
48.7
46.4
30.3
68.3
50.1
37.6
49.8
43.8
23.1
18.1
5.8
28.2
21.6
20.7
27.6
25.5
26.1
25.1
16.1
42.3
25.8
28.1
27.6
16.8
5.0/yg/g
5.15 (l)b
1.8 (l)b
4.67
6.26
3.96
3.36
10.1
3.11
6.47
5.19
3.34
20.4
11.8
10.9
13.6
1.6
2.5/yg/g
2.3 (l)b
<1
2.17
3.25
1.67
0.69
7.09
0.50
3.64
4.80
3.05
7.22
11.6
<1
7.88
<1
a  n  =  8
b  Numbers in parenthesis represent the number of "less than" values,
0  The  highest standard for antimony was 1000 //g/g.

NA = Not Analyzed
                                   3031 - 9
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                                       Table  4
            Standard  Deviations  for  Oil  Standards  by Simultaneous  ICP-AES
Analyte 500 /yg/g
Silver
Arsenic
Barium
Beryl 1 i urn
Cadmium
Cobalt
Chromium
Copper
Molybdenum
Nickel
Lead
Antimony
Selenium
Thallium
Vandium
Zinc
14
3.1
0.88
3.4
2.1
2.1
2.6
3.3
3.2
2.3
1.5
34C
5.7
NA
3.8
2.4
100 jug/g
3.6
4.1
9.2
1.5
1.7
1.8
6.5
2.2
1.6
2.6
9.8
2.5
5.4
8.5
4.4
2.8
Concentration
50 fjg/g 25 fjg/g
1.1
1.7
4.0
1.5
0.73
0.69
1.3
1.9
0.62
0.08
5.6
1.6
6.8
13
0.84
3.0
4.1
1.9
5.9
0.41
0.66
1.3
4.0
1.2
1.0
7.5
2.4
2.7
8.0
18
7.2
3.2
5.0//g/g
6.3
1.1
0.30
0.35
0.53
0.24
4.5
1.7
0.69
1.2
1.6
3.7
6.4
8.2
11
4.7
2.5/^/g
0.46
b
0.18
0.46
0.26
0.30
5.1
b
0.36
2.0
3.5
1.7
4.3
b
8.3
b
8  n  -  5
b  The  results were non-detects.
c  The  highest antimony standard  was 1000 //g/g.

NA = Not Analyzed
                                   3031  -  10                      Revision 0
                                                                  January 1995

-------
            METHOD 3031
  ACID  DIGESTION OF OILS
ANALYSIS_BI FLAA OR ICP
 FOR METALS
SPECTROSCOPY
1
r
7.1 Homogenize
sample.
i
r
7.2 Add potasium
permanganate
powder and heat.
1
f
7.3 Add concentrated
H2S04tO
permanganate
mixture.
>
r
7.4 Add
concentration HNOj
i
f
7.5 Add
concentrated HCI.
>
f
7.6 Filter digestate.
i
f
7,7 Rinse filter paper
and containment
vessel into the flask
containing digestate.
^
r
7.8 Add 5 mL
concentrated HCI
and reheat.
>
'
7.9 Analyze by
ICP-AES or
flame.
,
\t
           3031 - 11
                   Revision  0
                   January 1995

-------
                                 METHOD 3040A

               DISSOLUTION  PROCEDURE  FOR  OILS,  GREASES, OR WAXES
1.0  SCOPE AND APPLICATION

      1.1   This method is used for the preparation of samples containing oils,
greases,  or  waxes  for analysis  by atomic  absorption  spectroscopy  (AAS)  or
inductively coupled plasma emission  spectroscopy (ICP)  for the following metals:

                        Antimony                Copper
                        Arsenic                 Iron
                        Barium                  Lead
                        Beryllium               Manganese
                        Cadmium                 Nickel
                        Chromium                Vanadium

      1.2   This method  is a  solvent  dissolution  procedure,  not  a digestion
procedure.  This procedure can be very  useful  in the analysis of crude oil, but
with spent or used oil high in particulate material  it is less effective; most
particulate material  is   not  dissolved,  and therefore  the  analysis  is  not  a
"total"  metal  determination.   Because  the highest  percentage  of  metals  is
expected to be contained  in the particulate  material, oil analysis using Method
3040A will not provide an adequate estimate of the total metals concentration.

            Caution: Overheating of oils and solvents  can result in an
            explosion or  fire, caution should be taken.

      1.3  This method  is  applicable for the  dissolution of multi-phasic aqueous
wastes containing either  oils, greases,  or waxes. If a waste is multi-phasic it
can be determined  by  using Method 3040A in combination with one  of the other
sample preparation methods.

            Caution: The  analysis of solvents in an  ICP should only be conducted
            after consultation with the manufacturer.

      1.4   This method is suitable for conducting analyses in support of TCLP
determinations if the percent solids,  as conducted according to the procedures
specified in the Method 1311, are below 0.5%.

2.0  SUMMARY OF METHOD

      2.1   A representative sample is dissolved in an appropriate solvent (e.g.,
xylene,  kerosene,  or  methyl  isobutyl  ketone).   Organometallic  standards are
prepared using the same solvent, and the samples and standards are analyzed by
AAS or ICP.
                                   3040A  -  1                       Revision 1
                                                                  January 1995

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3.0  INTERFERENCES

      3.1   Diluted  samples  and  diluted organometallic  standards  are  often
unstable.  Once standards and  samples  are diluted,  they should be analyzed as
soon as possible.

      3.2   Solvent  blanks   should  be  used  to  rinse  nebulizers  thoroughly
following aspiration of high concentration standards or samples.

      3.3   Viscosity  differences can  result  in different  rates  of  sample
introduction;  therefore,  all  analyses  shall  be  performed  by the  method of
standard addition  or internal standardization (only for ICP).  Peristaltic pumps
often prove useful when analysis is performed by ICP.  In addition, a mass-flow
controller may also alleviate some viscosity problems.

4.0  APPARATUS AND MATERIALS

      4.1   Volumetric glassware or equivalent.

      4.2   Analytical balance, 300 g capacity, minimum + O.Olg.

      4.3   Atomic absorption spectrometer:   With an auxiliary oxidant control
and a mechanism for background correction.

      4.4   Inductively coupled  plasma emission  spectrometer  system:   With a
mechanism for  background  correction  and interelement interference correction.
A peristaltic pump is optional.

5.0  REAGENTS

      5.1   Methyl isobutyl ketone (MIBK).

      5.2   Xylene.

      5.3   Kerosene.

      5.4   Organometallic  standards  -  scandium  and yittrium may  be  used as
internal standards for most samples.  Standards traceable to NIST Standard  No.
1085, for wear metals  in oil, may be used.   (Two  possible sources are Conostan
Division, Conoco Speciality Products,  Inc.,  P.O. Box 1267, Ponca City, OK 74601,
and  the U.S.  Department  of  Commerce,   National  Institutes  of  Standards  and
Technology, Washington, DC 20234).

      5.5   Base  Oil.

      5.6   Stabilizer.

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.

                                   3040A - 2                      Revision  1
                                                                  January  1995

-------
      6.2   Samples shall be stored in an undiluted state at room temperature.

      6.3   Samples should be processed and analyzed as soon as possible.

7.0  PROCEDURE

      7.1   Weigh out a  2 gram  representative  sample  of the waste or extract.
Separate and weigh the phases if more than one phase is present.

      7.2   Weigh an aliquot of the organic  phase  and dilute  the aliquot  in the
appropriate solvent.  Warming facilitates the subsampling of crude-type oils and
greases  and  wax-type wastes.   Xylene or  kerosene are  usually  the preferred
solvent  for longer-chain hydrocarbons  and  for  most analyses performed by TCP.
The longer-chain hydrocarbons usually require a  minimum of a 1:10  (W/W) dilution,
and lighter oils may require only a 1:5 (W/W) dilution if low detection limits
are required.

      7.3   Prepare a series of  standards using the base oil  and diluting  by the
same factor used for  the samples.   Add the  internal  standard before diluting.
The  concentration  of the  internal  standard should  be  in  the middle  of the
concentration range.

      7.4   If  the  sample  contains particulates,  the result may  be variable
depending on whether the particles are aspirated into the instrument.  Samples
may be  centrifuged  after dilution to remove particulates from the solution prior
to analysis.

      7.5   All  metals must be analyzed by the method of standard additions if
an internal  standard is  not  used.   Because the  method of standard additions can
account only for multiplicative interferences (matrix or physical interferences),
the  analytical  program  must  account  for  additive  interference  (nonspecific
absorption  and  scattering   in  AAS and  nonspecific emission  and  interelement
interference in ICP) by employing background correction when using the ICP.

      7.6   Sample  preparation  for the  method of  standard additions  can  be
performed on a weight  or volume basis.  Sample aliquots  of viscous wastes should
be weighed.   Weigh  identical  amounts of the sample  into three wide-mouth vials.
Dilute the first vial such that the final  concentration falls on the lower end
of the  linear portion of  the calibration  curve  and  significantly  above the
detection limit.  Add sufficient standard  to  the second aliquot to increase the
sample concentration by approximately 50%.  Adjust the third sample concentration
so that  it  is approximately twice  that  of the first.   The  second  and third
aliquots are then diluted to the same final volume as the first aliquot.  Because
of the  wide  variability in waste  samples,  and the problems  encountered with
analyzing them,  the  analyst's best judgement must be used to  permit efficient use
of this method.

      7.7   Set up  and calibrate the analytical  instrumentation according to the
manufacturer's directions for nonaqueous samples.

      7.8   Report data as  the weighted average for all sample phases.

                                   3040A - 3                       Revision 1
                                                                  January 1995

-------
            [(Pi  * C,)  +  (P2 * C2)]/PT = CF

      P,  = weight of the  first phase (Kg)

      P2  = weight of the  second phase (Kg)

      CT  = concentration  of the first phase (mg/Kg)

      C2  = concentration  of the second phase (mg/Kg)

      PT  = weight of both phases (Kg)

      CF  = final  concentration of waste (mg/Kg)

8.0  QUALITY CONTROL

      8.1   Preparation  blanks  (e.g., Conostan  base  oil  or  mineral  oil plus
reagents)  should  be  carried  through  the complete  sample-preparation  and
analytical process on a routine  basis.  These blanks  will  be  useful  in detecting
and determining the magnitude of any sample contamination.  Refer to  Chapter One.

      8.2   Replicate samples should be processed on a routine basis.  Replicate
samples will be used to determine precision.  Refer to Chapter One.

      8.3   Samples and standards should be diluted as closely as possible to the
time of analysis.

      8.4   All analyses must be performed  by the method of standard additions
if an internal  standard is not used.  See Method  7000, Section 8.7, for  further
information.

      8.5   Data must  be  corrected  for background absorption and emission and
interelement interferences.

9.0  METHOD PERFORMANCE

      9.1   Refer  to Tables 1 and 2  for  a  single lab study.

10.0  REFERENCES

1. Used Oil Characterization Sampling and Analysis Program.   Draft Final  Report.
   February 15,  1991.
                                   3040A - 4                       Revision  1
                                                                   January 1995

-------


TABLE 1 - METHOD
PERFORMANCE DATA
SINGLE LAB STUDY: ASSESSMENT OF ACCURACY
ANALYTE
Arsenic
Cadmium
Chromium
Lead
Barium
# ANALYSES
2
20
20
20
20
MEAN PERCENT
SPIKE RECOVERY
76
100.6
107.2
97.4
97.0
STANDARD
DEVIATION OUTLIERSA
39.6 1
16.8 4
13.1 2
20.2 2
30.7 4



TABLE 2 - METHOD
PERFORMANCE DATA
SINGLE LAB STUDY: ASSESSMENT OF PRECISION
ANALYTE
Arsenic
Cadmium
Chromium
Lead
Barium
# REPLICATE
PAIRS
1
10
10
10
10
RELATIVE %
DIFFERENCE
73
1.8
2.8
4.1
5.9
STANDARD
DEVIATION OUTLIERS6
1
1.9 0
1.9 0
6.6 1
12.1 1
B
- Percent  recovery outside of the laboratory's 80 - 120 % acceptance criteria.
  Outliers included  in  statistical  analysis.

- RPD outside of the laboratory's 20 % acceptance  criteria.
  Outliers included  in  statistical  analysis.
                                  3040A - 5
                                                                Revision  1
                                                                January  1995

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                         METHOD  3040A
DISSOLUTION  PROCEDURE FOR  OILS.  GREASES,  OR WAXES
                      i
^
r
7 1 Weigh out 2 grams of sample
                                          7.2 Separate and weigh phases
         7.2 Weigh aliquot of organic phase;
           dilute with appropriate method.
                      I
          7 3 Prepare series of spike sample.
     7.4 If sample contains particulatet centrifuge
        7 5 Analyze metals by standard additions
                     method.
         7.6 Weigh sample into 3 vials; dilute
         1st vial; add standard to 2nd vial to
        increase concentration by 50%; adjust
          3rd vial concentration to twice the
            concentration of the 1st vial.
          7 7 Set up and calibrate analytical
                 instrumentation.
         7 8 Report data as weighted avg.
                             3040A  -  6
Revision  1
January  1995

-------
                                 METHOD 3050B

                ACID DIGESTION OF SEDIMENTS,  SLUDGES,  AND SOILS

1.0   SCOPE AND APPLICATION

      1.1   This  method has  been  written to  provide two  separate digestion
procedures, one for the preparation of sediments,  sludges, and  soil  samples for
analysis by flame atomic absorption spectroscopy  (FLAA) or inductively coupled
plasma atomic  emission spectroscopy (ICP-AES)  and one for  the preparation of
sediments, sludges,  and soil  samples for analysis of samples  by  Graphite Furnace
AA (GFAA) or inductively coupled plasma mass spectrometry (ICP-MS). The extracts
from these two procedures are not  interchangeable and should only be used with
the analytical  determinations outlined in this section.  Samples prepared by this
method may  be  analyzed by  ICP-AES for all  the  listed metals as long  as the
detecion limits are adequate for the required end-use  of  the data.  Alternative
determinative techniques may be used if they are scientifically valid and the QC
criteria  of  the  method,  including those dealing with  interferences,  can be
achieved.  The recommended determinative techniques for each element are listed
below:

            	FLAA	               GFAA/ICP-MS
            Aluminum                Magnesium               Arsenic
            Antimony                Manganese               Beryllium
            Barium                  Molybdenum              Cadmium
            Beryllium               Nickel                  Chromium
            Cadmium                 Potassium               Cobalt
            Calcium                 Silver                  Iron
            Chromium                Sodium                  Lead
            Cobalt                  Thallium                Molybdenum
            Copper                  Vanadium                Selenium
            Iron                    Zinc                    Thallium
            Lead                                            Vanadium
2.0  SUMMARY OF METHOD

      2.1    For  the  digestion of  samples  for GFAA  or  ICP-MS analyses,  a
representative 1-2 gram (wet weight) or 1 gram (dry weight) sample is digested
in repeated additions of nitric acid  and repeated additions of hydrogen peroxide.
The digestate is then reduced in volume or  heated for two hours and analyzed by
GFAA or ICP-MS.  For FLAA/ICP-AES analyses, 10 mL of cone. HC1 is added to the
digestate from the GFAA/ICP-MS digestion.  After refluxing for 15 minutes, the
sample is made to volume  and  is now ready  for analysis  by FLAA/ICP-MS.   In an
optional  step to increase the solubility of  some metals (see Sec. 7.4:NOTE), this
digestate is filtered, and the filter paper and residue are washed,  first with
5 mL of hot  hydrochloric  acid and then  20 mL of hot deionized water.   Filter
paper and  residue are  returned to  the  digestion  flask,  refluxed  with  5  mL
concentrated hydrochloric  acid, and then filtered again.  A separate sample shall
be dried for a total  % solids determination if needed.
                                   3050B  -  1                       Revision 2
                                                                  January 1995

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3.0  INTERFERENCES

      3.1   Sludge samples can contain diverse matrix types, each of which may
present its own analytical  challenge.   Spiked  samples and any relevant standard
reference material should  be  processed  in  accordance with  the quality control
requirements given in Sec. 8.0,  to  aid  in  determining  whether Method 3050B is
applicable to a given waste.


4.0  APPARATUS AND MATERIALS

      4.1   Digestion Vessels - 250-mL.

      4.2   Watch glasses  - ribbed.

      4.3   Drying ovens - able to maintain 30°C + 4°C.

      4.4   Thermometer - 0-200°C.

      4.5   Filter paper - Whatman No. 41 or equivalent.

      4.6   Centrifuge and centrifuge tubes.

      4.7   Analytical balance - able to accurately weigh to 0.01 g.

      4.8   Heating source - Adjustable and able to maintain a temperature of 90-
95°C. (e.g., hot plate,  block digester, microwave, etc.)

      4.9   Funnel or equivalent.

      4.10  Graduated cylinder or equivalent.

      4.11  Volumetric Flasks - 100-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.  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  will  be  interference  free.    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   Nitric  acid  (concentrated),  HN03.    Acid  should  be  analyzed  to
determine level of impurities.  If method blank  is  < MDL, the acid can be used.
                                   3050B  -  2                       Revision 2
                                                                  January 1995

-------
      5.4   Hydrochloric acid  (concentrated), HC1.   Acid should be analyzed to
determine level of impurities.  If method blank is  < MDL, the acid can be used.

      5.5   Hydrogen  peroxide  (30%),  H202.    Oxidant should  be analyzed to
determine level of impurities.  If method blank is  < 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 and glass containers are both suitable.  See  Chapter Three,  Step
3.1.3, for further information.

      6.3   Nonaqueous samples should be  refrigerated  upon receipt and analyzed
as soon as possible.

      6.4   It can be  difficult  to obtain a representative  sample with wet or
damp  materials.    Wet samples  may be dried,  crushed,  and ground  to  reduce
subsample variability  as long  as  drying  does not affect the extraction of the
analytes of interest in the sample. If insoluble compounds are formed by drying,
then the sample must be analyzed as received.


7.0  PROCEDURE

      7.1   Mix  the sample  thoroughly  to  achieve homogeneity  and  sieve if
necessary using a USS  #10 sieve.  All equipment used for homogenization should
be cleaned according to the  guidance  in  Sec. 6.0 to  minimize the potential of
cross-contamination.  For each digestion  procedure, weigh to the nearest 0,01 g
and  transfer  a  1-2  g sample  (wet weight)   or  1 g sample  (dry weight)  to  a
digestion vessel.  For samples with low percent  solids  a larger sample size may
be used as long as digestion is completed.

            NOTE: All steps  requiring  the  use of acids  should be conducted under
            a  fume  hood   by  properly   trained  personnel  using  appropriate
            laboratory safety  equipment.   The  use of an acid  vapor scrubber
            system for waste minimization is encouraged.

      7.2   For the digestion of samples  for analysis  by GFAA or ICP-MS, add 10
mL of 1:1 HN03, mix the slurry, and cover with a watch glass or vapor recovery
device.  Heat  the sample to 95°C and reflux for 10 to 15 minutes without boiling.
Allow the sample to cool,  add 5 mL of  concentrated  HN03, replace the cover, and
reflux for 30  minutes.  If brown fumes  are  generated, indicating oxidation of the
sample by HN03,  repeat this  step  (addition of 5  mL  of  cone.  HN03) over and over
until no brown fumes are given off by the sample indicating the complete reaction
with HN03.  Using a ribbed watch glass or vapor recovery system, either allow the
solution to evaporate  to  approximately  5 mL  without  boiling or heat  at  95°C
without boiling for two hours.  Maintain  a covering of  solution over the bottom
of the vessel  at all times.
                                   3050B  -  3                       Revision 2
                                                                  January 1995

-------
            7.2.1  After Step 7.2 has  been  completed and the sample has cooled,
      add 2 ml of  water  and  3 ml of 30% H202.  Cover the  vessel  with a watch
      glass or vapor recovery device and return the covered vessel to the heat
      source for warming  and  to start the peroxide reaction. Care  must be taken
      to  ensure  that  losses  do  not  occur  due  to  excessively  vigorous
      effervescence.  Heat until  effervescence subsides and cool the vessel.

            7.2.2  Continue to add 30% H202 in 1-mL aliquots with warming until
      the effervescence  is minimal  or until  the  general  sample appearance is
      unchanged.

            NOTE: Do not add more than a total of 10 ml 30% H202.

            7.2.3  Cover the  sample  with  a  ribbed  watch glass or vapor recovery
      device and continue heating the acid-peroxide digestate until the volume
      has been reduced to approximately 5 mL or heat at 95°C without boiling for
      two hours.  Maintain  a  covering  of  solution  over the  bottom  of the vessel
      at all times.

            7.2.4 After cooling,  dilute to 100 ml with water.   Particulates in
      the digestate should  then be removed  by filtration, by centrifugation, or
      by allowing the sample  to settle.  The sample is  now ready  for analysis by
      GFAA or ICP-MS.

                  7.2.4.1    Filtration - Filter through Whatman No.  41 filter
            paper (or equivalent).

                  7.2.4.2    Centrifugation -  Centrifugation at 2,000-3,000 rpm
            for 10 minutes is usually sufficient to clear the supernatant.

                  7.2.4.3    The     diluted    digestate    solution    contains
            approximately 5% (v/v)  HN03.   For analysis, withdraw aliquots of
            appropriate volume and add any  required reagent or matrix modifier.

      7.3   For the analysis  of samples for FLAA or ICP-AES, add  10 mL cone. HC1
to the sample digest from 7.2.3 and cover with a watch glass or vapor recovery
device.  Place  the sample  on/in  the heating  source and  reflux  at 95°C for 15
minutes.

      7.4   Filter  the  digestate  through  Whatman No.  41  filter paper  (or
equivalent) and collect filtrate in a 100-mL volumetric flask. Make to volume and
analyze by FLAA or ICP-AES.

            NOTE;  Sec.  7.5  is only allowed  for  antimony, barium,  lead,  and
            silver, and may  be used to improve the solubilities and recoveries
            of these analytes when necessary. These steps are optional and are
            not required on  a routine basis.

      7.5   Add 2.5  mL  cone. HN03 and  10 mL cone. HC1 to  a  1-2 g sample (wet
weight) or 1 g sample (dry weight) and cover with  a watchglass or vapor recovery
device.  Place the sample on/in the  heating source and reflux for  15 minutes.
                                   3050B -  4                      Revision 2
                                                                  January 1995

-------
            7.5.1 Filter the digestate through Whatman No.  41 filter paper
      (or equivalent) and collect filtrate in a 100-mL volumetric flask.
      Wash the filter paper, while still  in the funnel, with no more than
      5 ml of hot (95°C)  HC1, then with 20 mL  of hot  (95°C) reagent water.
      Collect washings in the same 100-mL volumetric flask.

            7.5.2 Remove the filter and  residue from the funnel, and place them
      back in the vessel.  Add 5 ml of cone.  HC1,  place the vessel back on the
      heating source, and heat at 95°C until  the filter paper dissolves.  Remove
      the vessel  from the  heating  source and wash  the  cover and  sides with
      reagent water.  Filter the  residue  and collect the  filtrate in the same
      100-mL volumetric flask.   Allow filtrate to cool, then dilute to volume.

            NOTE:  High concentrations of metal salts with temperature-sensitive
            solubilities  can result  in  the formation  of  precipitates  upon
            cooling  of primary  and/or  secondary filtrates.   If  precipitation
            occurs in the flask upon cooling, do not dilute to volume.

            7.5.3 If a precipitate forms on the bottom of  a flask, add up to 10
      mL of concentrated  HC1 to  dissolve the  precipitate.  After precipitate is
      dissolved, dilute to volume with reagent water.  Analyze by FLAA or ICP-
      AES.

      7.6   Calculations

            7.6.1    The  concentrations  determined  are  to be reported  on  the
      basis of  the  actual  weight  of the sample.   If a dry  weight analysis is
      desired, then the percent solids of the sample must also be provided.

            7.6.2    If percent  solids  is  desired,  a separate  determination of
      percent solids must be performed on a homogeneous aliquot of the sample.


8.0  QUALITY CONTROL

      8.1   All  quality  control  measures described  in  Chapter One  should  be
followed.

      8.2   For each batch of samples processed, a method blank  should be carried
throughout the entire sample preparation and analytical process according to the
frequency described in Chapter One.   These blanks will be useful in determining
if samples are being  contaminated.  Refer to Chapter  One for the proper protocol
when analyzing method blanks.

      8.3   Spiked replicate samples should  be  processed on  a routine  basis.
Spiked replicate samples  will be used to determine precision.   The criteria of
the determinative method  will dictate frequency,  but 5% is recommended.   Refer
to Chapter One for the proper protocol  when  analyzing spiked replicates.

      8.4   Standard reference materials  (SRM)  must be employed  to  determine
accuracy.  A  SRM should  be included with each batch of samples  processed  and
whenever a new  sample matrix is being analyzed.   Refer to Chapter One for  the
proper protocol when analyzing  SRMs.


                                  3050B - 5                       Revision  2
                                                                  January 1995

-------
      8.5   Limitations for the FLAA and  ICP-AES optional digestion procedure:
The approximate linear upper range for a  2.00-g sample size.

                Ag     2,000 mg/kg
                As 1,000,000 mg/kg
                Ba     2,500 mg/kg
                Be 1,000,000 mg/Kg
                Cd 1,000,000 mg/kg
                Co 1,000,000 mg/kg
                Cr 1,000,000 mg/kg
                Cu 1,000,000 mg/kg
                Mo 1,000,000 mg/kg
                Ni 1,000,000 mg/kg
                Pb   200,000 mg/kg
                Sb   200,000 mg/kg
                Se 1,000,000 mg/kg
                Tl 1,000,000 mg/kg
                V  1,000,000 mg/kg
                Zn 1,000,000 mg/kg

            NOTE:  These  ranges will  vary with sample matrix, molecular form,
            and size.
9.0   METHOD PERFORMANCE

      9.1   In  a  single  laboratory,  the  recoveries  of  the  three  matrices
presented in Table  1  through  Table  3 were obtained using the FLAA and ICP-AES
digestion procedure.  The spiked  samples  were  analyzed  in duplicate.   Table 4
represents results  of analysis  of NIST Standard Reference Materials that were
obtained using both atmospheric  pressure microwave digestion techniques and hot-
plate digestion procedures.


10.0  REFERENCES

1.    Rohrbough,  W.G.;  et  al .  Reagent Chemicals,  American  Chemical  Society
Specifications, 7th ed.; American Chemical Society: Washington, DC, 1986.

2.    1985 Annual  Book of ASTM Standards, Vol. 11.01; "Standard Specification for
Reagent Water"; ASTM: Philadelphia,   PA, 1985; D1193-77.

3.    Edgell, K.; USEPA Method  Study 37 -  SW-846 Method 3050 Acid Digestion of
Sediments. Sludges, and Soils.  EPA  Contract No. 68-03-3254, November 1988.

4.    Kimbrough, David E., and Wakakuwa, Janice R. Acid Digestion for Sediments,
Sludges, Soils, and Solid Wastes.  A Proposed Alternative to EPA SW 846 Method
3050,  Environmental  Science and Technology, Vol. 23, Page 898, July 1989.

5.    Kimbrough, David E.,  and Wakakuwa, Janice  R.  Report of an Inter! aboratory
Study Comparing  EPA  SW  846 Method  3050  and an  Alternative Method  from the
California Department of Health  Services, Fifth Annual Waste Testing and Quality
Assurance Symposium, Volume  I,  July  1989.   Reprinted  in Solid Waste Testing and


                                  3050B -  6                      Revision 2
                                                                  January 1995

-------
Quality Assurance:  Third Volume, ASTM  STP  1075,  Page 231,  C.E.  Tatsch, Ed.,
American Society for Testing and Materials, Philadelphia, 1991.

6.    Kimbrough, David E., and Wakakuwa, Janice R. A  Study of the Linear  Ranges
of Several  Acid Digestion Procedures. Environmental  Science and  Technology, Vol.
26, Page 173,  January  1992.   Presented  Sixth  Annual  Waste  Testing and Quality
Assurance Symposium, July 1990.

7.    Kimbrough, David E., and Wakakuwa, Janice R. A  Study of the Linear  Ranges
of Several Acid Digestion Procedures,  Sixth Annual  Waste Testing  and Quality
Assurance Symposium,  Reprinted in Solid Waste  Testing  and  Quality Assurance:
Fourth Volume, ASTM STP 1076,   Ed.,  American Society  for Testing and Materials,
Philadelphia,  1992.
                                  3050B - 7                       Revision 2
                                                                  January 1995

-------
     TABLE 1

STANDARD RECOVERY8



 Percent Recovery
                 i
Analyte
Ag
As
Ba
Be
Cd
Co
Cr
Cu
Mo
Ni
Pb
Sb
Se
Tl
V
Zn
,11 values are percent
iulti standard; n = 3.
3050A
9.5
86
97
96
101
99
98
87
97
98
97
87
94
96
93
99
recovery.

3050B w/option
98
102
103
102
99
105
94
94
96
92
95
88
91
96
103
95
Samples: 4 ml of 100

                                           mg/mL
     3050B  -  8
Revision 2
January 1995

-------
                                    TABLE  2

                              Percent Recovery"'0
            Sample 4435 Sample 4766 Sample HJ     Average

            3050A 3050B 3050A 3050B 3050A 3050B 3050A 3050B
Ag
As
Ba
Be
Cd
Co
Cr
Cu
Mo
Ni
Pb
Sb
Se
Tl
V
Zn
9.8
70
85
94
92
90
90
81
79
88
82
28
84
88
84
96
103
102
94
102
88
94
95
88
92
93
92
84
89
87
97
106
15
80
78
108
91
87
89
85
83
93
80
23
81
69
86
78
89
95
95
98
95
95
94
87
98
100
91
77
96
95
96
75
56
83
b
99
95
89
72
70
87
87
77
46
99
66
90
b
93
102
b
94
97
93
101
106
103
101
91
76
96
67
88
b
27
77
81
99
93
89
83
77
83
92
81
32
85
74
87
87
95
100
94
97
94
94
97
94
98
98
91
79
94
83
93
99
a - Samples: 4 ml of 100 mg/mL multi-standard in 2 g of sample.   Each value is
percent recovery and is the average of duplicate spikes.

b - Unable to accurately quantitate due to high background values.

c - Method 3050B using optional  section
                                  3050B - 9                       Revision  2
                                                                  January 1995

-------
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                                     METHOD  3050B
           ACID DIGESTION  OF  SEDIMENTS,  SLUDGES,  AND  SOILS
 7.3 Add 10 mL con-
 centrated HCI to the
digest from 7.2.3 and
   cover reflux for
    15 minutes.
                                         7.1  Mix sample
                                         to homogeneity.
                                       7.2 Add 10 mL VI
                                       HNO3and reflux for
                                        s*. 1 0 minutes.
                                        7.2 Add 5 mL cone
                                        HNO3and reflux for
                                         30 mini.; repeat
                                       until dig. is complete
                                           evaporate to
                                           5 mL; cool.
                                        7.2.1 - 7.2.2 Add
                                       2 mL water and 3 mL
                                       30% HjOj continue
                                       to add 1  mL aliquots
                                       of HzO2 until bubbling
                                            subsides.
    7.3.1  Filter,
   lakt to volume.
                                      7.2.4 Filter/centrifuge.
                                        if necessary, dilute
                                      to 100 mL with water.
                                                             Only for Sb, Ba, Pb, and Ag
                                                            	if required	
   7.4 Analyze by
  FLAA or ICP-AES.
                                          7 2.3 Analyze by
                                          GFAA or ICP-MS.
7.8
Calculations.
 7.5 Add 2.5 mL cone.
 NNO and 10 ml cone.
 HCI to sample reflux
   for 1 5 minutes.
 7 5.1 Filter digeltate
    and collect in
   volumetric flask.
7.5.1 Wash filter paper
with 5 mL hot HCI and
 then with 20 ml hot
reagent water. Collect
 in same 1 00 mL flask
     as filtrate
                                                                            7.5.2 Remove filter
                                                                           and residues and place
                                                                            back in vessel. Add
                                                                            5 mL HCL and heat
                                                                           filter; collect in same
                                                                             flask as filtrate.
                                                                             7 5.3 If precipitate
                                                                              forms add up to
                                                                           10 mL HC! to dissolve.
                                                                             Dilute to volume.
   7.5.3 Analyze by
   FLAA or ICP-AES
                                           3050B  -  12
                  Revision  2
                  January  1995

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                                  METHOD 3052

MICROWAVE ASSISTED ACID DIGESTION OF SILICEOUS AND ORGANICALLY BASED MATRICES

1.0   SCOPE AND APPLICATION

      1.1  This method  is applicable to the microwave  assisted  acid digestion of
siliceous  matrices,  organic  matrices  and other  complex  matrices.    Ashes,
biological tissues, oils,  oil  contaminated soils, sediments, sludges, and soils
may be digested using this method for total decomposition (relative to the target
analyte list)  and  if analysis  is  required.  This method is applicable 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
      Beryllium

Other elements  and matrices may be analyzed by this  method if performance is
demonstrated for the analytes of interest, in  the matrices of interest,  at the
concentration levels of interest (see Sec. 8.0).

      1.2  This method  is  provided  as  a  rapid multi-element, microwave assisted
acid digestion prior to analysis protocol so that decisions can be made about the
site or  material.   Digests  and alternative procedures  produced  by the method are
suitable for analysis by flame atomic absorption spectroscopy (FLAAS), cold vapor
atomic  absorption  spectroscopy  (CVAAS),  graphite  furnace atomic  absorption
spectroscopy  (GFAAS),  inductively  coupled  plasma atomic emission spectroscopy
(ICP-AES),  inductively coupled  plasma  mass  spectrometry  (ICP-MS)  and  other
analytical elemental analysis  techniques  where applicable.   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 3052.

      1.3   The goal  of this  method  is  total  sample decomposition  and  with
judicious choice of acid combinations  this  is achievable for most matrices (see
Sec. 3.2).   Selection  of  reagents which  give  the  highest  recoveries  for the
target analytes is considered the optimum method condition.


2.0  SUMMARY OF METHOD

      2.1   A  representative  sample  of up  to  0.5 g is digested  in  9 mL  of
concentrated nitric acid and usually 3 mL hydrofluoric acid  for 15 minutes using
microwave heating with a suitable laboratory microwave system.  The  method has
several   additional  alternative   acid   and   reagent  combinations   including
hydrochloric acid and  hydrogen peroxide.   The method  has provisions for scaling
up the sample  size to  a maximum of 1.0 g.  The sample  and  acid are  placed in
appropriate fluorocarbon microwave vessels. The vessel  is  sealed and heated in

                                   3052 - 1                       Revision 0
                                                                  January 1995

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the microwave system.  The temperature profile is specified to permit specific
reactions and  incorporates  reaching  180 ± 5°C in approximately  less than 5.5
minutes and  remaining at 180 ± 5°C for 9.5 minutes for the completion of specific
reactions (Ref. 1,  2, 3, 4).  After cooling, the vessel contents may be filtered,
centrifuged, or  allowed  to settle and  then  decanted, diluted to  volume, and
analyzed by the appropriate SW-846 method (Ref. 5).


3.0  INTERFERENCES

      3.1   Gaseous  digestion  reaction products, very  reactive,  or volatile
materials may  create high  pressures  when heated and  may  cause venting  of the
vessels with potential loss of sample and  analytes.   The complete decomposition
of either carbonates, or  organic samples,  may  cause enough pressure to vent the
vessel  if the sample size  is greater than  0.25 g.  Variations of the method due
to very reactive materials are specifically addressed  in Sees.  7.3.4 and 7.3.6.1.

      3.2   Most samples will  be totally dissolved by this  method with judicious
choice of the acid  combinations.  A few refractory sample matrix compounds, such
as Ti02,  alumina,  and other oxides may  not be  totally  dissolved.  In some cases
they may contain target analyte elements.


4.0  APPARATUS AND MATERIALS

      4.1  Microwave apparatus  requirements.

            4.1.1  The temperature  performance  requirements necessitate  the
      microwave decomposition system  to sense  the temperature to within ± 2.5°C
      and automatically adjust the microwave field output power within 2 seconds
      of sensing.  Temperature  sensors  should be accurate to ± 2°C (including
      the final reaction temperature of 180°C); verification at  two points  > 50°
      C apart should be determined periodically.   Temperature feedback control
      provides the primary  control performance mechanism for the method.  Due to
      the  flexibility  in  the  reagents  used  to   achieve  total  analysis,
      temperature  feedback control  is necessary  for reproducible  microwave
      heating.

            Alternatively,   for a specific  set  of  reagent(s)  combination(s),
      quantity, and specific vessel type, a calibration control mechanism can be
      developed similar to  previous microwave methods (see  Method  3051  in Ref
      5).   Through calibration  of the  microwave power,   vessel  load  and heat
      loss,   the  reaction  temperature profile  described  in Sec.  7.3.6  can be
      reproduced.  The calibration settings are specific  for the number and type
      of vessel used and for the microwave system in addition to the variation
      in reagent combinations.  Therefore no specific calibration settings are
      provided  in  this  method.   These  settings may be developed  by  using
      temperature  monitoring  equipment  for each  specific  set of  equipment and
      reagent combination.   They may only be used if not altered as previously
      described in other methods  such as 3051 and 3015.    In this circumstance,


                                   3052 - 2                       Revision 0
                                                                  January 1995

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the microwave system provides programmable  power with a minimum of 600 W,
which can be programmed to within ± 12 W of the required power.  Typical
systems  provide  a  nominal  600 W  to  1200 W  of power  (Ref.  1,  2,  6).
Calibration control provides backward  compatibility with older laboratory
microwave systems without temperature monitoring or feedback control and
with lower  cost  microwave systems for some repetitive  analyses.   Older
lower pressure vessels may not be compatible.

      4.1.2  The  microwave  unit cavity is corrosion resistant  and well
ventilated.   All  electronics  are  protected  against corrosion  for safe
operation.

      CAUTION: There  are many safety  and operational  recommendations
      specific to the model  and manufacturer  of  the  microwave equipment
      used  in  individual  laboratories.    A   listing  of these  specific
      suggestions  is  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.

      4.1.3  The  method requires essentially microwave  transparent and
reagent resistant materials  such  as  fluorocarbon  polymers  (examples are
PFA or TFM)  to contain acids and samples. For higher pressure capabilities
the  vessel   may   be  contained within  layers  of  different  microwave
transparent materials  for strength, durability, and safety.   The vessels'
internal  volume   should  be  at least 50  ml, capable  of  withstanding
pressures  of at  least   30  atm  (30   bar  or   435  psi),  and capable  of
controlled  pressure relief.   These  specifications  are  to provide  an
appropriate, safe,  and  durable reaction  vessel  of which there  are many
adequate designs  by many suppliers.

      CAUTION:  The outer layers of vessels are frequently not as acid or
      reagent resistant as the liner material  and must  not  be chemically
      degraded or physically damaged to retain the performance and safety
      required.    Routine examination of  the vessel  materials  may  be
      required to ensure their safe use.

      CAUTION:  The  second  safety  concern relates  to  the use  of  sealed
      containers   without  pressure  relief  devices.  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
      fluorocarbons may  crack,  burst, or explode  in the unit under certain
      pressures.    Only   fluorocarbon  (such as  PFA or  TFM  and  others)
      containers   with  pressure  relief mechanisms  or  containers  with
      fluorocarbon liners and  pressure relief mechanisms are  considered
      acceptable.

      Users  are  therefore advised not  to use  domestic (kitchen)  type
      microwave ovens  or to  use inappropriate sealed containers  without
      pressure  relief  for microwave acid digestions  by  this  method.   Use

                             3052  - 3                        Revision 0
                                                            January 1995

-------
            of  laboratory-grade  microwave  equipment  is  required to  prevent
            safety hazards.  For further details, consult References 3 and 7.

            4.1.4   A  rotating turntable  is employed  to  insure  homogeneous
      distribution of  microwave  radiation  within most systems  (Ref.  1).   The
      speed of the turntable should be a minimum of 3  rpm.

            CAUTION:  Laboratories  should   not   use  domestic   (kitchen)  type
            microwave  ovens  for  this  method.  There  are  several  significant
            safety issues.  First, when an acid such as nitric  is used to effect
            sample digestion  in  microwave  units in open  vessel(s),  or sealed
            vessel equipment,  there is the  potential  for the  acid  gas vapor
            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 system
            with isolated  and corrosion resistant safety devices prevents this
            from occurring.

      4.2  Volumetric ware, volumetric flasks, and graduated cylinders, 50 and
100 ml capacity or equivalent.

      4.3  Filter paper, qualitative or equivalent.

      4.4  Filter funnel,  polypropylene, polyethylene  or equivalent.

      4.5  Analytical  balance,  of appropriate capacity, with a minimum ± 0.0001
g or  appropriate  precision for the weighing of the sample.   Optionally,  the
vessel with  sample and  reagents may  be  weighed  before and  after  microwave
processing to evaluate the seal integrity in some vessel  types.


5.0  REAGENTS

      5.1  All reagents should be of  appropriate purity or high  purity  (acids for
example,  should be sub-boiling distilled where possible)  to minimize the blank
levels due to elemental  contamination.  All  references  to water in  the method
refer to  reagent water (Ref.  8).   Other  reagent  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.


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.

                                   3052 - 4                       Revision 0
                                                                  January 1995

-------
     6.3  Refer to Chapter Three for the appropriate holding times and storage
conditions.
7.0  PROCEDURE

     7.1 Temperature control of closed vessel microwave instruments provides the
main feedback control  performance mechanism for the method.  Control requires a
temperature sensor in  one or more vessels during the entire decomposition.  The
microwave decomposition system should sense the temperature to within ± 2.5°C and
permit adjustment of the microwave output power within 2 seconds.

     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 (fluoropolymer liners only)
should be cleaned  by  leaching  with hot (1:1) hydrochloric  acid  (greater than
80°C, but less  than boiling) for a minimum  of two hours followed with hot (1:1)
nitric acid  (greater than 80°C, but less  than boiling) for a minimum of two hours
and rinsed  with reagent water and dried in a clean environment.  This cleaning
procedure should  also be  used whenever the prior use of the digestion vessels is
unknown or cross contamination  from vessels  is  suspected.   Polymeric  or glass
volumetric  ware (not used with HF) 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  a well-mixed sample to  the  nearest 0.001 g  into  an
      appropriate vessel  equipped with a pressure relief mechanism.   For soils,
      ash,  sediments,  sludges,  and siliceous wastes, initially use no more than
      0.5 g. For oil or oil contaminated soils,  initially use no more than 0.25
      9-

            7.3.2   Add 9  ± 0.1 ml concentrated  nitric acid  and  3 ±  0.1  ml
      concentrated   hydrofluoric  acid  to the vessel  in a fume  hood.    If  the
      approximate silicon dioxide content  of the sample is  known, the  quantity
      of hydrofluoric  acid may  be varied  from 0 to  5 ml  for  stoichiometric
      reasons.   Samples with higher concentrations of silicon  dioxide  (> 70%)
      may require  higher  concentrations  of hydrofluoric  acid  (>  3  ml  HF).
      Alternatively samples with lower concentrations  of silicon dioxide (<  10%
      to 0%) may require much less hydrofluoric acid  (0.5 ml  to 0 ml).  Examples
      are presented in  Table 1,  2, 3,  and  6.

            7.3.3   The  addition  of other reagents with the original  acids prior
      to digestion may  permit  more   complete  oxidation  of  organic  sample
      constituents, address specific decomposition chemistry  requirements,  or
      address specific  elemental stability  and  solubility problems.
                                   3052 -  5                       Revision  0
                                                                  January 1995

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      The addition  of 2  ±  2 ml  concentrated  hydrochloric acid  to  the
nitric and hydrofluoric acids is  appropriate for the stabilization of Ag,
Ba, and Sb and high concentrations of Fe and Al in solution.  The amount
of HC1 needed will vary depending on the matrix and the concentration of
the analytes.  The addition of hydrochloric acid may;  however, limit the
techniques  or  increase  the  difficulties  of  analysis.     Examples  are
presented in Table 4.

      The addition  of  hydrogen  peroxide  (30%)   in  small   or catalytic
quantities  (such  as  0.1  to 2 ml)  may  aid in  the  complete  oxidation of
organic matter.

      The addition of water (double deionized) may (0 to 5 ml)  improve the
solubility of minerals and prevent  temperature spikes  due  to exothermic
reactions.

      CAUTION:  The use of microwave equipment with temperature feedback
      control is required to control the unfamiliar reactions of unique or
      undemonstrated reagent  combinations of unknown samples.  These tests
      may  require  additional  vessel   requirements  such  as  increased
      pressure capabilities.

      CAUTION: Only one acid mixture or quantity may be used  in a single
      batch  in  the microwave to  insure consistent reaction  conditions
      between all vessels and monitored  conditions.   This  limitation is
      due to the  current  practice  of monitoring  a representative vessel
      and applying a uniform microwave  field to reproduce these reaction
      conditions within a group of vessels being simultaneously heated.

      CAUTION:   Toxic nitrogen  oxide(s),  hydrogen fluoride,  and toxic
      chlorine (from the addition of hydrochloric  acid) fumes  are usually
      produced during digestion.   Therefore, all  steps involving open or
      the opening of  microwave  vessels must be performed  in  a properly
      operating fume ventilation system.

      CAUTION:    The  analyst  should   wear  protective gloves and  face
      protection  and  must not  at any  time  permit  a solution containing
      hydrofluoric acid to come in contact with skin or lungs.

      CAUTION:    The  addition   of hydrochloric  acid   must  be  from
      concentrated hydrochloric acid and not from a premixed combination
      of acids as a  buildup  of chlorine gas  will  result  from a premixed
      acid solution.

      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.


                             3052 - 6                       Revision 0
                                                            January 1995

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      CAUTION: The addition of hydrogen  peroxide  should only be done when
      the reactive components of the  sample  are known.  Hydrogen peroxide
      may react rapidly and violently on easily oxidizable materials and
      should not be added  if  the  sample may contain large quantities of
      easily oxidizable organic constituents.

      7.3.4  The analyst should be aware of the potential for a vigorous
reaction.   If a vigorous  reaction  occurs  upon the  initial  addition of
reagent  or  the  sample  is  suspected  of  containing easily  oxidizable
materials, allow the sample to predigest in  the  uncapped digestion vessel.
Heat may be added in this  step for safety considerations  (for example the
rapid release of carbon dioxide from carbonates,  easily oxidized organic
matter,  etc.).   Once  the  initial reaction  has  ceased,   the  sample may
continue through the digestion procedure.

      7.3.5  Seal the vessel  according  to the manufacturer's directions.
Properly  place  the  vessel  in  the  microwave  system  according to  the
manufacturer's   recommended   specifications  and   connect   appropriate
temperature  and pressure  sensors  to  vessels according to manufacturer's
specifications.

      7.3.6   This  method  is  a performance based  method,  designed to
achieve or approach total  decomposition  of  the sample through achieving
specific reaction conditions.  The temperature  of each sample should rise
to 180 ± 5°C in  approximately 5.5  minutes and remain  at 180 + 5°C for 9.5
minutes.  The temperature-time and pressure-time profile are given for a
standard soil sample in Figure  1.   The  number  of samples simultaneously
digested is dependent  on the  analyst.  The number may range from 1 to the
maximum  number  of  vessels that the  microwave  units magnetron  can heat
according to the manufacturer's or literature specifications (the number
will depend  on  the power  of  the  unit,  the quantity  and combination of
reagents,  and the heat loss from the vessels).

      The pressure should peak between 5 and 15 minutes for most samples
(Ref.  2,  3,  6).   If  the  pressure  exceeds  the  pressure limits of the
vessel,  the  pressure   will  be  reduced  by  the relief mechanism of the
vessel.

             7.3.6.1   For  reactive substances,  the heating profile may be
      altered  for   safety  purposes.    The   decomposition  is  primarily
      controlled by maintaining the reagents at 180 ± 5°C  for 9.5 minutes,
      therefore the time it takes to heat the  samples  to 180°C  ± 5°C is
      not critical. The samples may be heated at  a slower rate to prevent
      potential  uncontrollable  exothermic reactions.   The  time  to  reach
      180 ± 5°C  may be  increased to 10 minutes provided that 180 ± 5°C is
      subsequently maintained for  9.5 minutes.  Decomposition profiles are
      presented in Figures 1  & 2.   The extreme difference in pressure is
      due to the gaseous digestion products.

             7.3.6.2 Calibration control is  applicable in  reproducing this
      method  provided  the power  in  watts  versus  time   parameters  are

                             3052 -  7                       Revision 0
                                                            January 1995

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      determined to  reproduce  the specifications listed  in  7.3.6.   The
      calibration  settings  will   be   specific   to   the  quantity  and
      combination  of  reagents,   quantity   of  vessels,   and  heat  loss
      characteristics of the vessels (Ref 1).  If calibration control is
      being  used,  any  vessels  containing  acids  for analytical  blank
      purposes  are  counted as  sample  vessels and  when   fewer  than  the
      recommended number  of samples are  to be digested,  the remaining
      vessels should be filled with the same acid mixture to achieve the
      full complement of vessels.  This  provides an energy balance, since
      the microwave power absorbed is proportional to the total  absorbed
      mass in the cavity (Ref.  1).   Irradiate each group of vessels using
      the predetermined  calibration settings.    (Different  vessel  types
      should not be mixed).

      7.3.7  At  the  end of the  microwave program, allow the vessels to
cool for  a minimum of 5  minutes  before  removing  them from the microwave
system.  When the vessels have  cooled to near room temperature, determine
if the microwave vessels have maintained a seal throughout the digestion.
Due to the wide variability of vessel designs,  a single procedure is not
appropriate.  For vessels that are sealed as discrete separate entities,
the vessel weight may be taken before and after  digestion  to evaluate seal
integrity.  If the weight loss of sample exceeds 1% of the weight of the
sample and  reagents, then  the  sample  is  considered compromised.   For
vessels with  burst  disks, a careful  visual  inspection of  the  disk  may
identify compromised vessels.   For vessels with resealing pressure relief
mechanisms, an auditory  or  sometimes  a  physical  sign indicates  a vessel
has vented.

      7.3.8  Complete the  preparation of the sample by carefully uncapping
and  venting  each vessel  in  a fume  hood.    Vent  the vessels using  the
procedure recommended by the vessel  manufacturer.  Transfer the sample to
an  acid-cleaned  bottle.    If  the digested  sample  contains  particulates
which may clog nebulizers or interfere with injection of the sample into
the  instrument,  the sample may  be  centrifuged,  allowed to  settle,  or
filtered.

            7.3.8.1  Centrifugation:  Centrifugation  at 2,000  - 3,000 rpm
      for 10 minutes is usually  sufficient to clear the supernatant.

            7.3.8.2  Settling:   If  undissolved material  remains such as
      Ti02,  or other refractory  oxides, 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:   If necessary,  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.
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           7.3.9  If the hydrofluoric acid concentration is a consideration in
      the analysis technique such as with ICP methods, boric acid may be added
      to permit the  complexation  of fluoride to protect the  quartz plasma torch.
      The amount of  acid added may be varied, depending on the equipment and the
      analysis  procedure.    If  this   option  is  used,   alterations  in  the
      measurement procedure  to  adjust  for the boric  acid  and  any  bias  it may
      cause are necessary.  This  addition will  prevent the  measurement of boron
      as one  of the elemental constituents  in the sample.   Alternatively,  a
      hydrofluoric  acid resistant  ICP torch  may  be  used  and  the  addition of
      boric acid would  be  unnecessary  for this analytical  configuration.   All
      major manufacturers have hydrofluoric resistant components available for
      the analysis of solutions containing hydrofluoric acid.

           7.3.10  The removal or reduction of the quantity of the hydrochloric
      and hydrofluoric acids prior to analysis may be  desirable.  The chemistry
      and  volatility of  the analytes  of interest  should be  considered  and
      evaluated when using this alternative.  Evaporation  to near dryness in a
      controlled  environment with  controlled pure  gas  and neutralizing  and
      collection of  exhaust  interactions  is  an alternative where appropriate.
      This manipulation may be performed in  the microwave system, if the system
      is capable of this function, or external to the microwave system in more
      common  apparatus(s).    This  option  must  be  tested and validated  to
      determine  analyte  retention   and  loss  and  should  be   accompanied  by
      equipment  validation  possibly  using  the  standard   addition  method  and
      standard  reference  materials.    This  alternative may  be used  to  alter
      either the acid concentration  and/or  acid  composition.   Note: The final
      solution  typically  requires  nitric acid to maintain appropriate  sample
      solution  acidity  and  stability of  the  elements.   Commonly,  a  2% (v/v)
      nitric acid concentration  is desirable.   Examples  of analysis performed
      with and without removal of the hydrofluoric acid are presented in Table
      5.  Waste minimization  techniques should be used to capture reagent fumes.
      This procedure  should  be tested  and  validated  in  the apparatus  and on
      standards before using on unknown samples.

           7.3.11 Transfer or decant the sample into  volumetric  ware and dilute
      the digest to  a known  volume.  The  digest  is now ready  for analysis for
      elements  of  interest  using  appropriate  elemental   analysis  techniques
      and/or SW-846  methods.

           7.3.12   Sample size may be scaled-up from  0.1, 0.25,  or 0.5 g to 1.0
      g through a series of 0.2 g sample size  increments.    Scale-up can produce
      different reaction conditions and/or produce increasing  gaseous reaction
      products.  Increases in sample size may not  require alteration of the acid
      quantity or combination,  but  other reagents may  be added to permit a more
      complete  decomposition  and  oxidation  of  organic   and  other  sample
      constituents where necessary (such as increasing the  HF  for the complete
      destruction of silicates).   Each step of the  scale-up must  demonstrate
      safe operation before continuing.

     7.4  Calculations:  The concentrations determined are to be  reported on the
basis of the actual  weight of the original sample.

                                   3052 - 9                       Revision  0
                                                                  January  1995

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7.5  Calibration of Microwave Equipment

       NOTE: If the  microwave  unit uses temperature feedback  control  to
       follow  performance   specifications   of  the  method,   then   the
       calibration procedure will not be necessary.

       7.5.1  Calibration   is  the  normalization  and  reproduction  of  a
 microwave  field  strength  to  permit  reagent  and energy  coupling in  a
 predictable and reproducible manner.  It balances  reagent heating and heat
 loss from the  vessels and is equipment dependent due to the heat retention
 and loss  characteristics of  the  specific vessel.   Available power  is
 evaluated to permit the microwave  field  output  in watts to be transferred
 from one microwave system to another.

 Use of  calibration  to control  this  reaction  requires balancing  output
 power, coupled energy,  and heat  loss  to  reproduce the temperature heating
 profile in  Sec.  7.3.6.  The  conditions for  each acid mixture  and  each
 batch containing  the same specified number of vessels  must be determined
 individually.     Only   identical  acid  mixtures  and  vessel  models  and
 specified numbers of vessels may be used in a given batch.

       7.5.2  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 system.  The calibration format
 required  for  laboratory  microwave   systems   depends  on  the  type  of
 electronic system used by  the manufacturer to  provide  partial microwave
 power.   Few  systems  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 (7.5.4), otherwise,  the  analyst must  use  the
 multiple point calibration method (7.5.3).

       7.5.3   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 Sec.  7.5.5.
 This  data  is clustered  about   the  customary  working  power  ranges.
 Nonlinearity  has been  commonly  encountered  at the  upper  end  of  the
 calibration.   If the  system'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.

       7.5.4   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  Sec. 7.5.5.    From the 2-
 point line calculate the power setting corresponding to the required power

                             3052  -  10                      Revision 0
                                                             January 1995

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      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 ± 10 W, use the multiple point calibration
      in 7.5.3.   This point  should also  be  used to  periodically  verify the
      integrity of the calibration.

            7.5.5  Equilibrate a large volume of water to room temperature (23
      ± 2°C).  One  kg of reagent water is weighed  (1,000.0  g  +  0.1  g) into a
      fluorocarbon beaker or a beaker made of  some other material that does not
      significantly absorb microwave energy (glass absorbs microwave energy and
      is not recommended).   The initial  temperature  of the water should be 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 system'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:

                                   (K) (Cp) (m) (DT)
         Eq. 1             P =      	
      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 °C-1) of water

m = the mass of the water sample in grams (g)

DT = 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'VT1)  the  calibration  equation
      simplifies to:


         Eq. 2              P = (DT) (34.86)
                                   3052  -  11                       Revision 0
                                                                  January 1995

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            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 ± 5 V.  Electronic components in most
            microwave units are  matched to the system's  function  and output.
            When any part of the  high voltage circuit, power source, or control
            components in the  system have been  serviced or replaced, it will be
            necessary to recheck  the system's calibration.  If the power output
            has  changed  significantly  (± 10 W),  then  the entire  calibration
            should be reevaluated.
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.).  The relative percent
difference between replicate determinations is to be calculated as follows:

                              D  - D

                       RPD =
                             (D  + D
            where:

                  RPD = relative percent difference.
                   D, = first sample value.
                   D2 = second sample value  (replicate).


                  (A control limit of + 20%  RPD  shall be used for sample values
            greater than ten times the instrument detection limit.)


     8.3   Spiked  samples and/or matrix matching  standard  reference materials
(SRMs)  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.  Spike sample recovery
and/or SRMs are to be within ± 20% of the actual value.

     8.4  Blank samples should be prepared using the same reagents and quantities
used in sample  preparation,  placed  in  vessels  of  the same  type,  and processed
with the samples.
                                   3052 -  12                      Revision 0
                                                                  January 1995

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     8.5   Other  alternate method performance quality  control  criteria may be
allowed as long as they meet the data quality objectives of the analysis.

9.0  METHOD PERFORMANCE

     9.1  Precision:  Precision data for Method  3052,  is  presented  in tables at
the end  of the document.   Values  are  given  as concentration  ±  the standard
deviation.

     9.2  The performance criteria are provided  in  an  example  in Figure  1.  The
temperature profile will  be within ± 5°C of the mean of the temperature profile,
but the  pressure  curve  will  vary  depending  on  the acid mixture  and  gaseous
digestion products and the thermal  insulating properties of the vessel.


10.0  REFERENCES

1. Introduction to Microwave  Sample  Preparation:  Theory and Practice, Kingston,
H. M.  and Jassie,  L.  B.,  Eds.;  ACS Professional  Reference Book Series; American
Chemical Society:   Washington, DC,  1988.

2. Kingston, H. M., Walter, P. J.,  Comparison of Microwave Versus Conventional
Dissolution  for  Environmental  Applications,  Spectroscopy,  Vol.  7  No.  9,20-
27,1992.

3. Kingston, H. M., Haswell,  S, Microwave Enhanced Chemistry,  ACS Professional
Reference  Book  Series;  American Chemical  Society: Washington, DC,  1995.  (in
press)

4. Kingston, H.  M.; Walter, P.  0.; Lorentzen,  E.  M.  L.; Lusnak, G. P. Report to
NIST Office of Standard Reference Materials, The  Performance of Leaching Studies
on Soil SRMs 2710 and 2711, Duquesne University, Pittsburgh,  PA, 1994.

5. Test Methods 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.

6. Kingston, H. M.  EPA IAG #DWI-393254-01-0 January 1-March 31, 1988, quarterly
Report.

7. Kingston, H. M. and Jassie, L. B.,  "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.

8. 1985 Annual  Book of ASTM Standards, Vol. 11.01;  "Standard Specification for
Reagent Water"; ASTM, Philadelphia,  PA, 1985,  D1193-77.

9. Kingston, H.  M.; Walter, P. J.; Link, D. D. Validation Study and
Unpublished Data,  Duquesne University, Pittsburgh,  PA, 1995.


                                  3052  -  13                       Revision 0
                                                                  January 1995

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            200
        9  150 -
                        9ml HNO and 3ml HF
                                                    12

                                                    10

                                                    8
                                                       Ul
                                                       Ul

                0        5       10       15
                              time (mln)
Figure 1:   Typical  Reaction Profile  for the  Digestion of a Soil
(Ref 4 and 9)
       £

       u.
200


150


100


 50


  0
                            9ml HNO t and 0.5ml HF

                               ~0.3g Waste Oil
                            t  11  [  i \  ..i.i 1 t  i i
                                                    20
                                                    15
                                                       (Q
                                                       (A
                                                       ift
                                                       m
                                                    5


                                                    0
                                                  20
                0        5     „ 107  , x  15
                               time (mln)
Figure 2:  Typical Reaction Profile for the Digestion of a Oil  (Ref
9)
                             3052 - 14
                                                      Revision 0
                                                      January 1995

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                                TABLE 1.

                       ANALYSIS OF NIST SRM 2704
                   (COMPILATION  OF  REFERENCES  2  AND  9)
NIST SRM 2704 - Buffalo River Sediment
Element
Arsenic
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Phosphorus
Selenium
Sulfur
Thallium
Uranium
Zinc
Analyzed Value
(mg/Kg)
23.4 ± 2.6
3.5 ± 1.2
132.9 ± 1.3
98.0 ± 4.2
155 ± 9.2
1.49 ± 0.14
43.6 ± 3.9
1.016 ± 0.016
(mg/g)
1.13 ± 0.9
3.56 ± 0.16
1.15 ± 0.22
2.97 ± 0.04
441.9 + 0.8
Certified Value
(mg/Kg)
23.4 ± 0.8
3.45 ± 0.22
135 ± 5
98.6 ± 5.0
161 ± 17
1.44 ± 0.07
44.1 ± 3.0
0.998 ± 0.028
(mg/g)
(1.1)


1.2 ± 0.2
3.13 ± 0.13
438 ± 12
Percent Recovery
100
101
98
99
96
103
99
102
103
—
96
95
L 101
Digestion with 9 mL HN03 and 4 mL HF.

Temperature and pressure conditions as described in Sec. 7.3.6 and similar to
Figure 1.
                             3052  -  15
Revision 0
January 1995

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                                TABLE 2.

                       ANALYSIS OF NIST SRM 2710
                   (COMPILATION  OF  REFERENCES  4  AND  9)
NIST SRM 2710 - Montana Soil: Highly Elevated Trace Element Concentrations
Element
Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Zinc
Analyzed Value
(mg/Kg)
39.3 ± 0.9
21.9 ± 0.7
34.0 ± 3.2
2902 ± 83
5425 ± 251
13.5 ± 1.0
36.6 ± 0.5
7007 ± 111
Certified Value
(mg/Kg)
38.4 ± 3.0
21.8 ± 0.2
(39)
2950 ± 130
5532 ± 80
14.3 ± 1.0
35.3 ± 1.5
6952 ± 91
Percent Recovery
102
100
87
98
98
94
104
101
Digestion with either 9 mL HN03 and 4 mL HF or 9 mL HN03,  3  mL  HF,  and  2  mL
HC1.

Temperature and pressure conditions as described in Sec. 7.3.6 and similar to
Figure 1.
                             3052  -  16
Revision 0
January 1995

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                                TABLE 3.

                       ANALYSIS OF NIST SRM 2711
                   (COMPILATION OF REFERENCES  4 AND 9)
NIST SRM 2711 - Montana Soil: Moderately Elevated
Trace Element Concentrations
Element
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Zinc
Analyzed Value
(mg/Kg)
40.5 ± 1.0
45.5 ± 1.0
106.8 ± 3.4
1161 ± 49
19.6 ± 0.9
4.3 + 1.0
342 ± 9.4
Certified Value
(mg/Kg)
41.70 ± 0.25
(47)
114 ± 2
1162 ± 31
20.6 ± 1.1
4.63 ± 0.39
350.4 ± 4.8
Percent Recovery
97
97
94
100
95
93
98
Digestion with 9 mL HN03 and 4 mL HF.

Temperature and pressure conditions as described in Sec. 7.3.6 and similar to
Figure 1.
                            3052  -  17
Revision 0
January 1995

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                                TABLE 4.

            STABLILIZATION AND RECOVERY OF ELEMENTS WITH HC1
                              (REFERENCE 9)
NIST SRM 2710 - Montana Soil: Highly Elevated Trace Element Concentrations
Element
Antimony
Silver
HN03 & HF
Analyzed Value
(mg/Kg)
33.1 ± 2.1
10.6 ± 4.5
Percent
Recovery
86
30
HN03, HF & HC1
Analyzed Value
(mg/Kg)
39.3 ± 0.9
36.6 ± 0.5
Percent
Recovery
102
104
Certified
Value
(mg/Kg)
38.4 ± 3.0
35.3 ± 1.5
HN03 & HF - Digestion used 9 mL & 3 mL respectively.

HN03,  HF, & HC1  - Digestion used 9 mL, 3 mL,  & 2 mL respectively.

Temperature and pressure conditions as described in Sec. 7.3.6 and similar to
Figure 1.
                             3052 -  18
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                                TABLE 5.

     FUMING OFF HYDROFLUORIC ACIT WITH MICROWAVE EVAPORATION SYSTEM
                              (REFERENCE 9)
NIST SRM 2710 - Montana Soil: Highly Elevated Trace Element Concentrations
Element
Antimony
Cadmium
Chromium
Copper
Lead
Nickel
Silver
Zinc
Direct
Analyzed Value
(rag/Kg)
39.3 ± 0.9
21.9 ± 0.7
34.0 ± 3.2
2902 ± 83
5425 ± 251
13.5 ± 1.0
36.6 ± 0.5
7007 ± 111
Percent
Recovery
102
100
87
98
98
106
104
101
Fumed
Analyzed Value
(mg/Kg)
39.4 ± 0.9
23.3 ± 1.6
32.4 ± 0.4
2870 ± 150
5502 ± 106
13.5 ± 0.8
38.9 ± 1.1
6992 ± 132
Percent
Recovery
103
107
83
97
99
106
110
101
Certified
Value
(mg/Kg)
38.4 ± 3.0
21.8 ± 0.2
(39)
2950 ± 130
5532 ± 80
14.3 ± 1.0
35.3 ± 1.5
6952 ± 91
Direct - Digestion used 9 mL HN03 and 3 mL HC1 or 9 mL HN03,  3 mL HF,  and
2 mL HC1.

Fumed - Digestion used 9 mL HN03 & 3 mL HC1  followed by the removal of the HF.

Temperature and pressure conditions as described in Sec. 7.3.6 and similar to
Figure 1.   The digest solution was fumed in a microwave system under vacuum to
-1 mL and 3 mL HC1 added.  The digest solution was fumed to ~1 mL and 3 mL
HN03 added.   The solution was fumed for a final  step to -1 mL and
quantitatively transferred and diluted to final  volume.
                             3052  -  19
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                                TABLE 6.

                       ANALYSIS OF NIST SRM 1084a
                              (REFERENCE 9)
NIST SRM 1084a - Wear Metals in Oil (100 ppm)
Element
Chromium
Copper
Lead
Nickel
Silver
Analyzed Value
(mg/Kg)
98.1 ± 1.1
102.4 ± 2.4
99.2 ± 2.3
99.2 ± 2.4
102.7 ± 2.2
Certified Value
(mg/Kg)
98.3 ± 0.8
100.0 ± 1.9
101.1 ± 1.3
99.7 ± 1.6
101.4 ± 1.5
Percent Recovery
100
102
98
99
101
Digestion with 9 mL HN03 & 0.5 mL  HF.

Temperature and pressure conditions as described in Sec.  7.3.6 and similar to
Figure 2.
                             3052  -  20
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                   METHOD 3052

MICROWAVE  ASSISTED ACID DIGESTION OF SILICEOUS
        AND ORGANICALLY BASED  MATRICES
                    7.1 Establish
                   temp, control of
                  closed microwave
                       vessel.
                 7.2 Wash and rinse
                  digestion vessel.
                 7.3 Perform sample
                     digestion.
                    7.4 Perform
                    calculations.
                    7.5 Perform
                   calibration of
                    microwave
                    equipment.
                      3052  -  21
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                                 METHOD 3060A

                  ALKALINE DIGESTION  FOR HEXAVALENT  CHROMIUM

1.0  SCOPE AND APPLICATION

      1.1   Method  3060A is  an  alkaline  digestion procedure  for  extracting
hexavalent chromium [Cr(VI)] from soluble, adsorbed, and precipitated forms of
chromium  compounds  in  soils,  sludges,   sediments,  and some  industrial  waste
materials.  To quantify total Cr(VI)  in a solid matrix, three criteria must be
satisfied: (a) the extracting solution must solubilize  all forms of Cr(VI), (b)
the conditions of the extraction must not induce reduction of native Cr(VI) to
Cr(III), and (c)  the method must not cause oxidation  of  native Cr(III) contained
in the sample to  Cr(VI).  Method  3060A meets these criteria for a wide spectrum
of solid matrices.  Under the  alkaline  conditions of the extraction,   minimal
reduction of Cr(VI)  or oxidation  of native Cr(III) occurs.  The addition of Mg2+
in a  phosphate  buffer  to the alkaline solution has  been  shown to  suppress
oxidation if  observed.   The accuracy of the  extraction  procedure  is  assessed
using spike  recovery  data  for  soluble   and  insoluble  forms  of  Cr(VI)  (e.g.,
K2Cr207  and  PbCrOJ,  coupled  with measurement  of  ancillary  soil  properties,
indicative of the potential for the soil to  maintain a Cr(VI)  spike  during
digestion,  such  as oxidation-reduction potential   (ORP),  pH,  organic  matter
content, ferrous  iron, and sulfides.  Recovery  of an  insoluble Cr(VI) spike can
be used  to assess the first two criteria, and method-induced oxidation is minimal
except  in soils  high  in Mn and amended with  soluble Cr(III)  salts  or freshly
precipitated Cr(OH)3.

      1.2   The  quantification  of Cr(VI)  in  Method 3060A  digests should  be
performed using  SW-846  Method 7196A  (colorimetric)  or  SW-846  Method 7199 (ion
chromatography).

2.0  SUMMARY OF METHOD

      2.1   This  method  uses  an  alkaline digestion  to  solubilize  both  water-
insoluble and water-soluble Cr(VI)  compounds  in solid waste samples.  The pH of
the digestate must be carefully adjusted  during the digestion procedure.  Failure
to meet the pH specifications will necessitate redigestion of the samples.

      2.2   The  sample  is digested using  0.28M  Na2C0.3/0.5M NaOH  solution and
heating at 90-95°C for 60 minutes  to dissolve the Cr(VI)  and stabilize it against
reduction to Cr(III).

      2.3   The Cr(VI) reaction with diphenylcarbazide is the most common method
for analysis  of  Cr(VI)  solubilized  in  the  alkaline  digestate.   The use  of
diphenylcarbazide has  been well  established  in the colorimetric procedure (SW-846
Method 7196A), in rapid-test field kits and  in the ion chromatographic method for
Cr(VI)  (SW-846 Method  7199).    It  is   highly  selective  for  Cr(VI),  and  few
interferences are encountered when it is used on alkaline digestates.
                                   3060A-1                          Revision 1
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3.0  INTERFERENCES

      3.1   When analyzing a sample digest for total  Cr(VI), it is appropriate
to determine the reducing/oxidizing tendency of each sample matrix.  This can be
accomplished  by characterization  of  each  sample  for additional  analytical
parameters, such as pH (SW-846 Method 9045), ferrous iron (ASTM Method D3872-86),
sulfides  (SW-846  Method 9030) and Oxidation  Reduction Potential  (ORP)  (ASTM
Method D  1498-76).   Other indirect indicators  of  reducing/oxidizing tendency
include Total  Organic Carbon (TOC), Chemical Oxygen Demand (COD), and Biochemical
Oxygen Demand  (BOD).  Analysis of these  additional  parameters  establishes the
tendency  of Cr(VI)  to  exist  in  the  unspiked  sample(s)   and  assists  in  the
interpretation  of  QC  data for matrix  spike recoveries outside conventionally
accepted criteria.

      3.2   Certain substances, not typically found in the alkaline digests of
soils, may  interfere  in the analytical methods for  Cr(VI)  following alkaline
extraction  if the concentration of these interferences are high and the Cr(VI)
concentration is low.  Refer to SW-846 Methods 7196A and 7199 for a discussion
of the specific agents that interfere with Cr(VI)  quantification.

      3.3   For  waste  materials  suspected  of  containing  soluble  Cr(III)
concentrations  greater  than  four times the  laboratory Cr(VI)  reporting limit,
Cr(VI) results  obtained using Method  3060A may be biased high  due  to method
induced oxidation.  The  addition of Mg2+,  in a  phosphate buffer, to the alkaline
extraction solution has  been  shown to suppress oxidation and is  added  (sec. 7.3)
if oxidation is observed or suspected.  The presence of soluble Cr(III) can be
approximated by extracting sample with deionized water (ASTM methods D4646-87,
D5233-92 or D3987-85) and analyzing the resultant leachate for both Cr(VI) and
total Cr.  The  difference between the two values approximates soluble Cr(III).

      3.4   One of the  most  insoluble  forms of  chromate in alkaline solution,
barium  chromate,  may  require  additional  heating  time   to   effect  complete
dissolution in  some soil matrices.

4.0  APPARATUS  AND MATERIALS

      4.1   Beakers or  equivalent: borosilicate glassware,  250-mL,  with watch
            glass covers or equivalent.

      4.2   Graduated Cylinder: 100-mL or equivalent.

      4.3   Volumetric  Flasks:  Class  A  glassware,   1000-mL  and  100-mL  with
            stoppers or equivalent.

      4.4   Filtration Apparatus.

      4.5   Filter membranes (0.45  jum).  Preferably cellulosic  or polycarbonate
membranes.
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      4.6   Heating Device - capable of maintaining the digestion solution at 90
- 95°C with continuous auto  stirring capability or equivalent.

      4.7   Volumetric  pipettes:   Class   A  glassware,   assorted  sizes,  as
            necessary.

      4.8   Calibrated pH meter.

      4.9   Calibrated balance.

      4.10  Thermometer  (NIST-Certified  or  equivalent)  or  other appropriate
            temperature sensing device.

5.0  REAGENTS

      5.1   Nitric  acid:   HN03,   concentrated,  analytical   reagent  grade  or
spectrograde quality.   Store at 20-25'C in the dark.  Discard if the solution has
a yellow tinge; this is indicative  of photoreduction of N03'  to  N02.

      5.2   Sodium carbonate: Na2C03, anhydrous, analytical reagent grade.  Store
at 20-25°C in a tightly sealed container.

      5.3   Sodium hydroxide: NaOH, analytical reagent  grade.  Store at  20-25°C
in tightly sealed container.

      5.4   Magnesium  Chloride:  MgCl2  (anhydrous),  analytical  reagent grade.
392.18 mg MgCl2 is equivalent to  100 mg  Mg2+.    Store  at 20-25°C in a  tightly
sealed container.

      5.5   Phosphate Buffer:

            5.5.1  K2HP04:  analytical reagent grade.

            5.5.2  KH2P04:  analytical reagent grade.

            5.5.3   0.5M K2HP04/0.5M KH2P04 buffer at  pH 7:  Dissolve  87.09  g
      K2HP04  and  68.04 g  KH2P04  into  700  ml of  distilled  deionized  water.
      Transfer to a 1L volumetric flask and dilute to volume.

      5.6   Lead  Chromate:  PbCr04,  analytical reagent  grade.   The  insoluble
matrix spike is prepared by  adding  10-20 mg PbCr04 to  a  separate  aliquot.   Store
under dry conditions at 20-25°C in  a tightly sealed container.

      5.7   Digestion solution: Dissolve 20.0 ± 0.05 g  NaOH and 30.0 ± 0.05 g
Na2C03  in  distilled  deionized water in  a  one-liter volumetric flask and dilute
to the mark.   Store  the solution  in a tightly capped polyethylene  bottle at 20-
25"C and prepare fresh monthly.  The pH of the digestion  solution  must be  checked
before using.  The pH must be 11.5  or greater; if not,  discard.
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      5.8   Potassium Dichromate, K2Cr207, spiking solution (1000 mg/L Cr (VI):
Dissolve 2.829 g of dried  (105°C) K2Cr207 in distilled deionized water in a one-
liter volumetric flask and dilute to the  mark.   Alternatively,  a 1000  mg/L Cr
(VI) certified  primary  standard  solution can be used  (Fisher AAS  standard or
equivalent).   Store at 20-25°C  in  a tightly sealed  container  for up  to  six
months.

            5.8.1 Matrix spiking solution (100 mg/L Cr  (VI)):   Add 10.0 mL of
      the 1000 mg/L K2Cr207 spiking solution (Section 5.8) to a 100 mL volumetric
      flask and dilute to volume with distilled  deionized water.  Mix well.

      5.9   Sulfuric acid (H2S04),  10%  (v/v)  (1.8M):  Add 10 mL  of concentrated
H2S04  to approximately 70 mL  of  distilled deionized water.  Mix well  and  let
cool.   Dilute to a final volume of 100 mL with distilled deionized water.

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   Samples must have been collected using a sampling plan that addresses
the considerations discussed in Chapter Nine of this manual.

      6.2   Samples should be collected using devices and placed in containers
that do not contain stainless steel  (e.g., plastic or glass).

      6.3   Samples should be stored field-moist at 4 ± 2°C until analysis.

      6.4   Hexavalent chromium has been shown (interlaboratory studies) to be
quantitatively stable in field-moist soil samples  for  at  least  one month from
sample collection.  In addition, Cr  (VI) has also been shown  (interlaboratory
studies)  to be  stable  in the  alkaline digestate  for up to  96  hours  after
extraction from soil.

7.0   PROCEDURE

      7.1   Adjust the temperature setting of each  heating device  used in  the
alkaline digestion  by  preparing  and  monitoring  a temperature blank  (a 250 mL
beaker filled with  50 mLs digestion solution (Section 5.7)). Maintain a solution
temperature of  90  - 95 °C  as measured with a  NIST-calibrated  thermometer or
equivalent.

      7.2   Place 2.5 ±  0.10 g of the  as  received sample into a clean and labeled
250 mL  beaker.   The sample  should be  mixed thoroughly before  the  aliquot is
removed.

      7.3   Add 50 mL of digestion solution (Section 5.7) to each sample.  Add
392.18 mg of MgCl2 (Section  5.4)  and  0.5 mL of  1.0 M phosphate buffer (Section
5.5.3).    Cover  all  samples  with watch glasses.   The Mg2+  is  used  to suppress
oxidation  of  certain forms  of Cr(III)  (such  as soluble  forms) that  can be
oxidized to Cr(VI) during the procedure.

      7.4   Stir the samples continuously (unheated) for at least five minutes
using a stirring bar.


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      7.5   Heat the samples and maintain  a  temperature  range of 90 - 95°C with
constant stirring for 60 minutes at temperature.

      7.6   Gradually cool  each  solution  to room temperature  and  transfer it
quantitatively to the filtration apparatus with distilled deionized water rinses
and filter through a 0.45  jum membrane filter.   Rinse the  inside of the filter
flask and filter  pad with distilled deionized water and transfer  the filtrate and
the rinses to a clean 250-mL beaker.

            NOTE:  The remaining sol id after filtration of the matrix spike in
            Section 7.6 should be  saved for possible use  in assessing low Cr(VI)
            matrix spike recoveries.  See Section 8.5.2.  for additional details.
            Store the filtered solid at 4 ± 2°C.

      7.7   Place a magnetic stirring bar into the sample  digest beaker, place
the vessel on a  stirrer,  and,  with constant stirring,  slowly add concentrated
nitric acid solution to the beaker dropwise.  Adjust the pH of the solution to
7.5 ± 0.5 and monitor the  pH  with  a  pH meter.   If the  pH  of the digest should
drop below 7.0, discard  the solution and redigest.  If overshooting pH 7.5 ± 0.5
occurs repeatedly, prepare a diluted nitric acid solution  and repeat digestion
procedure.

            CAUTION: C02 will be evolved.  This  step  should  be performed  in a
            fume hood.

      7.8   Remove the  stirring  bar and  rinse, collecting the  rinsate  in  the
beaker.    Transfer  quantitatively  the  contents  of  the  beaker to  a  100  ml
volumetric flask  and adjust  the  sample  volume to 100 ml  (to the  mark for  the
volumetric flask) with distilled deionized water.  Mix well.

      7.9   The sample digestates are now ready to be analyzed.  Determine  the
Cr(VI) concentration in  mg/kg by SW-846 Method 7196A  (colorimetrically by UV-Vis
spectrometry) or 7199 (colorimetrically by Ion Chromatography).  SW-846 Method
7199 may be preferable for highly colored and/or turbid digests, since organic
acids imparting color to the digest are separated from Cr042" prior to post-column
colorimetric analysis by diphenylcarbazide in SW-846 Method 7199.

7.10   CALCULATIONS

      7.10.1      Sample Concentration
                              „       A x D x E
                              Cone. = 	
                                        B x C
                                    3060A-5                          Revision 1
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            where:       A =  Concentration observed  in  the  digest
                        B =  Initial  moist sample  weight  (g)
                        C =  % Solids/100
                        D =  Dilution factor
                        E =  Final  digest volume  (ml)
      7.10.2      Relative Percent Difference
                          RPD  =   (S ~ D)    x   100
                  where:       S =  Initial  sample result
                              D =  Duplicate sample  result
      7.10.3      Spike Recovery
                   PERCENT RECOVERY = (55J? " SK)  x  100
                                             SA
                  where:      SSR =  Spike sample result
                              SR   =  Sample (unspiked)  result
                              SA   =  Spike added


8.0  QUALITY CONTROL

      8.1   The following Quality Control  (QC) analyses must be  performed  per
digestion batch as discussed in Chapter One.

      8.2   A preparation blank must be prepared and analyzed with each digestion
batch, as discussed in Chapter One, and detected  Cr(VI)  concentrations must be
less than the method detection limit or one-tenth the concentration of the lowest
sample, whichever is greater or the entire batch  must be redigested.

      8.3   Laboratory Control  Sample (LCS):  As an additional  determination of
method performance, utilize  the matrix  spike solution prepared in Section 5.8.1
or the solid matrix  spike  agent,  PbCr04 (Section 5.6)  to spike into  50  mL of
digestion solution (Section 5.7).  Alternatively, the use of a  certified solid
reference material (if available) is recommended.  Recovery  must be within  the
                                   3060A-6                          Revision 1
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certified acceptance range or a  recovery range of 80 to 120% or the sample batch
must be reanalyzed.

      8.4   A separately  prepared duplicate  soil  sample  must  be analyzed at a
frequency of one per batch as discussed  in Chapter One.  Duplicate samples must
have a Relative Percent Difference (RPD)  of < 20%, if  both the original and the
duplicate are > four times the  laboratory reporting limit.  A control limit of
±  the  laboratory  reporting  limit  is  used  when  either  the  original  or  the
duplicate sample is < four times the laboratory reporting limit.

      8.5   Both  soluble  and  insoluble  pre-digestion matrix  spikes must  be
analyzed at a frequency  of one per batch of < 20 field  samples.   The soluble
matrix spike should be spiked with  1.0  ml of the  spiking solution prepared in
Section  5.8.1  (equivalent  to  40   mg/kg  Cr(VI))  or  at  twice  the  sample
concentration, whichever is greater. The insoluble matrix spike is prepared by
adding 10-20 mg  of  PbCr04 (Section 5.6) to a separate sample aliquot.   It is used
to evaluate the  dissolution during the digestion process.  Both matrix  spikes are
then carried  through  the  digestion process  contained  in  Section 7.0.   More
frequent matrix spikes must be analyzed if the soil  characteristics within the
analytical   batch  appear   to  have  significant variability based   on  visual
observation.  An acceptance range for matrix  spike recoveries is 75 - 125%.  If
the matrix  spike  recoveries  are not within  these recovery  limits,  the  entire
batch must  be  redigested/reanalyzed.  If upon  reanalysis the  matrix spike is not
within the  recovery limits, but the  LCS  is within criteria specified  in Section
8.3, information such  as that  specified on Figure 1 and in Section 3.1 should be
carefully  evaluated,  as  the  Cr(VI) data  may be  valid  for  use despite  the
perceived  "QC  failure."   The information on Figure  1 and  discussed below is
provided to interpret  ancillary  parameter data in conjunction with data on spike
recoveries:

            8.5.1 When pre-digestion matrix spike recoveries for  Cr(VI) are less
      than    acceptance range minimum criterion  (75%),  this is  indicative  of
      highly reducing  samples  (e.g.,  anoxic sediments)  with no measurable native
      Cr(VI) in the unspiked  sample  (assuming  the  criteria  in  Section 8.3 are
      met).    Such a  result  indicates  that the  combined  and  interacting
      influences of ORP,  pH and reducing agents (e.g., organic acids, Fe2+ and
      sulfides) caused reduction of Cr(VI)  spikes.

            Oxidation-reduction potentials below the bold diagonal line on
      Fig.  2  indicates a reducing soil  for Cr(VI).   The downward slope to the
      right indicates  that the  Eh  value,  at which Cr(VI)  is  expected  to  be
      reduced,  decreases  with  increasing  pH.  The solubility and  quantity of
      organic constituents will  influence reduction of Cr(VI).  The presence of
      H2S or other  strong  odors  indicate a reducing environment for Cr(VI).  In
      general,  acidic conditions  accelerate  reduction of  Cr(VI)  in  soils,  and
      alkaline conditions tend to stabilize Cr(VI) against reduction.  If spike
      recoveries are not within  the recovery limits,  the reductive nature of the
      sample must be documented.
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            8.5.2 If a low or zero percent pre-digestion matrix spike recovery
      is obtained, an alternate approach  can be used to determine the potential
      contribution of  the sample matrix  to  Cr(VI)  reduction.   This approach
      consists of performing a mass  balance, whereby total chromium is analyzed
      (Method 3050)  for  two samples:  (1)  a  separate unspiked aliquot  of the
      sample previously used for spiking,  and  (2) the digested solids remaining
      after the alkaline  digestion and filtration of the  matrix spike  (i.e., the
      filtered solids from the matrix spike in Section 7.6).

      The  difference  between  the  total  chromium  measurements  should  be
      approximately equal to the amount of the spike added to the matrix spike.
      If the LCS (Section 8.3)  met the  acceptance criteria and the Cr(VI) spike
      is accounted for in the  filtered solids as total  chromium,  it is likely
      that the reduction  of  the  Cr(VI) to insoluble  Cr(III) resulted from the
      reducing matrix of the original sample subjected to Cr(VI)  spiking.

      8.6   A post-digestion Cr(VI)  matrix spike must be analyzed per batch as
discussed in Chapter One. The  post-digestion  matrix spike concentration should
be equivalent  to 40 mg/kg or  twice the  sample concentration observed  in the
unspiked aliquot of the test sample, whichever is greater.

            8.6.1 Dilute the sample aliquot to a minimum extent,  if necessary,
      so that the absorbance  reading for  both the  unspiked  sample aliquot and
      spiked aliquot are within the initial calibration curve.

            8.6.2  A guideline for the post-digestion matrix spike recovery is
      85-115%   recovery.     If  not   achieved,   consider  the   corrective
      actions/guidance on data use specified  in Section 8.5.  These digestates
      may contain soluble reducing agents for Cr(VI), such as fulvic acids.

9.0 METHOD PERFORMANCE

      9.1   A commercial  laboratory analyzed  soil/sediment  samples containing
            Cr(VI) with the following results:

                                        Mean native    Mean  Cr(VI)    Matrix
                                  2"   Cr(VI) Cone.    Spike Cone.  Spike Rec.
                                                         (mq/kq)       Range
  Sample
   Type

   COPR"
Soil  Blends

   Loam


   Clay


   COPR8
Eh (mV)b
500
640
740
510
£H
7.2
6.3
2.9
8.6
  s
(ppm)c
.0


.0


.0


.0
(mq/kq)


  4.1


  ND


  ND


  759
                                                          42.0


                                                          62.5


                                                          63.1


                                                           813
                                      89.8% -
                                       116%

                                      65.0% -
                                       70.3%

                                      37.8% -
                                       71.1%

                                      85.5% -
                                       94.8%
                                    3060A-8
                                                                  Revision 1
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     Sample
      Type        Eh  (mV)b

Anoxic Sediment    330
       s2-
{>H   (ppm)°

6.3   25.0
                      Mean native
                     Cr(VI) Cone.
                        (mq/kq)

                          ND
                            Mean Cr(VI)    Matrix
                            Spike Cone.  Spike Rec.
                              (mq/kq)      Range
                                381
                            0%
  Quartz Sand
 640
5.4  <10.0
ND
                                9.8
75.5% -
 86.3%
Note:
      a
      ND
      b
      c
COPR - Chromite ore processing residue
Not detected
Corrected for the reference electrode
Field measurement
10.0  REFERENCES

      10.1  United States Environmental Protection Agency, 1982.  Test Methods
for Evaluating Solid Wastes, Physical/Chemical Methods.  SW-846,  Second Edition.
Office of Solid Waste and Emergency Response, Washington, D.C.

      10.2  New  Jersey  Department  of  Environmental   Protection   and  Energy
(NJDEPE).  NJDEPE Modified Methods 3060/7196A. 1992.

      10.3  R.  Vitale,  G. Mussoline,  J.  Petura,  B.  James,  1993.    A Method
Evaluation Study  of  an Alkaline Digestion  (Modified  Method  3060)  Followed by
Colorimetric  Determination  (Method  7196A)  for  the  Analysis  for  Hexavalent
Chromium  in  Solid Matrices.  Environmental Standards,  Inc.  Valley  Forge,  PA
19482.

      10.4  Zatka, V.J.,  1985.   Speciation of Hexavalent  Chromium  in Welding
Fumes  Interference  by  Air  Oxidation  of  Chromium.   J.  Ray  Gordon  Research
Laboratory, INCO Limited, Sheridan Park,  Mississauga,  Ontario  L5K 1Z9, Am. Ind.
Hyg. Assoc. J., 46(6):327-331.

      10.5  U.S. EPA  (United States Environmental  Protection Agency), 1982.  Test
Methods for Evaluating Solid Wastes,  Physical/Chemical Methods.  SW-846, Second
Edition.  Office of Solid Waste and Emergency Response,  Washington, D.C.

      10.6  ASTM (American Society for Testing and Materials),  1981.  Standard
Practice for Oxidation Reduction Potential of Water.  ASTM Designation: D1498-76.

      10.7  Vitale,  R.J., Mussoline, G.R., Petura, J.C.  and James,  B.R.  1994.
Hexavalent Chromium Extraction from Soils:   Evaluation of an Alkaline Digestion
Method.  J. Environ.  Qua!. 23: 1249-1256 In Press.
                                    3060A-9
                                                  Revision 1
                                                January 1995

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                                                FIGURE  1

                                  QUALITY  CONTROL  FLOW  CHART
       Field Collection
         of Sample*
    Field Homogenlzatlon
        of Sample*
          I
  Field Characterization of
  Samplea for OR* and pH
 Olgeetlon of Field Samplea
      + QC Samplea
   Optionally, characterize
    •ample for OK*. Fa2*
     pH and  SulfMee to
    detennlne if aample
 exhibit* reducing condition.
    Additional parameter*
   to characterize aample
   include TOC. BOO. and
 COD If reducing conditions
       are auapected.
      Sample Analyal*
      (7198A or 7199)
No
        Waa LCS
      ithin 80-120
    recovery or within
       the certified
       acceptance
         range?
       We* CrIVII
       Matrix Spike
      Sample within
        76-126*
        recovery?
          Waa
     concentration o
   epike added greater
     than four time*
       indigene ue
         level of
          r(VD?
 Report aample
 reoult* without
  qualification.
 Report aampl* reault*.
 Concentration of the
matrix apike added wee
   inelgnlflcant with
 reepect to idlgenoue
    level of Cr(VI).
 Alternately redlgeet
  uaing higher matrix
     aplka level.
             Yea
                                                                   Wee
                                                                Matrix Spike
                                                                 Recovery
                                                                 >126tt?
                                                                    Waa
                                                                Matrix Spike
                                                                  Recovery
                                                                   <76%?
                                Characterize aample for
                               ORP. FE *? pH and aulfMee
                                to determine if aample
                              exhlbtta reducing condition.
                               Additional parameter* to
                                  characterize aampl*
                                include TOC. BOO. and
                               COO if reducing condltlone
                                    are auapected.
                                                  3060A-10
                                                                       Revision  1
                                                                    January  1995

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                                      FIGURE  1
                  QUALITY  CONTROL  FLOW CHART (Continued)
          Doas
      sample contain
    suJfides (rotten egg
         odor or
     measurable Si')?
 Report value and indicate
  sample exhibits highly
    reducing condition.
                                  Report value and indicate
                                    sample exhibit* highly
                                     reducing condition.
            I No
 Plot Eh vs. pH of sample
       on Figure 2.
          Does
      the point fall
      below line A
      on Figure 2?
Report value and indicate
sample exhibits reducing
       condition.
 Report sample results as
qualified due to low matrix
      spike recovery
           OR
  Redigest and reanalyze
samples and QC to confirm
      matrix effect.
                                        3060A-11
                                                   Revision  1
                                                January  1995

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                                          FIGURE 2
                                   Eh/pH Phase  Diagram


The dashed lines define Eh-pH boundaries commonly encountered In soils and sediments.

      2000
>
 £
-C
LJ
      1600  —
      1200
       800  —
       400
          0  I—
      -400  —
                                                           A:  HCr04~/Cr(OH)3
oxidizing |

         J
      -800
                                                       PH

Note the Eh values plotted on this diagram are corrected for the reference electrode voltage:
244 mV  units must be added to the measured value when a separate calomel  electrode is used, or
199 mV  units must be added if a combination platinum electrode is used.
                                                                                     10
                                           3060A-12
         Revision  1
      January 1995

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                    METHOD 3060
ALKALINE  DIGESTION  FOR HEXAVALENT CHROMIUM
                  f    Start    j
^
r
7.1 Equilibrate heating device
temperature to 90-96° C.

                 7.2 Weigh 2.5 +/•
                   0.1 Og cample.
                7.3 - 7.4 Add reagente,
                  stir for 5 minute*.
                 7.5 Heat sample at
               90 - 95°C for 90 mmutee.

              7.6 Cool, filter digestate
               through 0.46 um filter.
            7.7 While atimng, adjust filtrate
            to pH 7.5  +/- 0.6 by dropwise
                 addition of HNO3 .
              7.8 Bring to final volume.
                 Analyze sample by
               SW-846 Methods 7196A
                     or 7199.
                     3060A-13
   Revision  1
January  1995

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3.3  METHODS FOR DETERMINATION OF INORGANIC ANALYTES

          This  section of the manual contains  seven  analytical  techniques for
trace inorganic analyte 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
inorganic analytes  in  the presence of  a large  excess of a single  analyte  is
difficult. Examples would  be  traces  of  inorganic analytes  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   or  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 aspirated
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 dissolution,   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

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sensitive, interferences can be a real  problem; finding the optimum combination
of digestion,  heating  times and  temperatures,  and  matrix modifiers  can  be a
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.
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                                  METHOD 0060

                  DETERMINATION OF METALS IN STACK EMISSIONS
1.0   SCOPE AND APPLICATION

      1.1   This method is used to determine the concentration of metals in stack
emissions from  hazardous  waste  incinerators and  similar combustion processes.
Using the detection limits shown, the following parameters  can  be determined by
this method:

TABLE 1.  ESTIMATED IDLS  FOR METALS DETERMINED BY METHOD 0060
Analyte
Antimony (Sb)
Arsenic (As)
Barium (Ba)
Beryllium (Be)
Cadmium (Cd)
Total chromium (Cr)
Copper (Cu)
Lead (Pb)
Manganese (Mn)
Mercury (Hg)
Nickel (Ni)
Phosphorus (P)
Selenium (Se)
Silver (Ag)
Thallium (Tl)
Zinc (Zn)
ICP-AES3
/vg/L
40e
60
2
0.3
4
7
6
50
2

20
60
80
7
40
2
Flame AASb
A/g/L
200e
2f
100
5
5
50
20
100
10

40

2f
10
100
5
GFAASC
/vg/L
3e
1

0.2
0.1
1

1




2

1

CVAASd
W/L









0.2






 a    Estimated IDLs by ICP-AES, Method 6010.
 b    Estimated IDLs by direct aspiration Flame AAS, Method 7000.
 c    Estimated IDLs by Graphite Furnace AAS, Method 7000.
 d    Estimated IDL by Cold Vapor AAS, Method 7470.
 e    Detection limit for Sb may be higher depending on digestion used.
 f    Estimated IDLs for As & Se by Hydride AAS, Method 7000.
      1.2   This method may also  be  used  for  the determination of particulate
emissions following  the additional  procedures  described in  Section  7.1.5.2.
Modifications to the sample recovery  and  analysis  procedures  described in the
particulate emissions  protocol  may potentially  impact  the  front-half mercury
determination.   Field  tests to date  have shown that  of the  total  amount of
mercury measured by the method, only  0  to  <2% was  measured  in the front half.
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Therefore, it is tentatively concluded, based on the above data, that particulate
emissions may  be  measured by  this  train,  without  significantly  altering the
mercury results.

      1.3   For the  analyses  described  in this  methodology and  for  similar
analyses,  the  response   for   Inductively  Coupled  Plasma  Atomic  Emission
Spectroscopy  (ICP-AES)  is linear over  several  orders of magnitude.   Samples
containing metal  concentrations  in  the micrograms  per milliliter  (/yg/L)  to
milligrams per  liter (mg/L) range  in the analytical  finish solution  can  be
analyzed using this technique.  Samples containing greater than approximately 50
mg/L of chromium,  lead,  or arsenic should be diluted to that  level or lower for
final analysis.  Samples containing greater  than approximately 20  mg/L of cadmium
should be diluted to that level before analysis.

      1.4   The actual method detection limits are sample dependent  and may vary
as the sample matrix affects the limits.  Method detection limits for antimony
can also be dependent on the digestion  method used and may be considerably higher
than the estimated detection limits.  Method detection limits for all  analytes
may differ from the  estimated detection  limits when hydrofluoric acid digestion
is used.  For more information on MDLs, refer to Chapter One.

      1.5   The complexity of this methodology is such that to obtain reliable
results, the  testers (including analysts) should be experienced and knowledgeable
in source sampling,  in  handling and  preparing  (including  mixing)  reagents  as
discussed, and in using adequate safety procedures and protective equipment.

2.0   SUMMARY

      2.1   The  stack   sample  is  withdrawn  isokinetically  from  the  source.
Particulate  emissions are collected  in the  probe  and on a  heated  filter and
gaseous emissions  are collected in a series of chilled  impingers.  Two impingers
are  empty,  two impingers  contain  an  aqueous  solution  of dilute  nitric  acid
combined with  dilute hydrogen  peroxide, two (or  one)  other impingers  contain
acidic  potassium  permanganate  solution,   and   the  last  impinger  contains  a
desiccant.

      2.2   Sampling  train components  are  recovered and digested  in  separate
front-half and back-half  fractions.  Materials collected in the sampling train
are acid digested  to dissolve inorganics and to  remove  organic constituents that
may  create  analytical   interferences.   Acid digestion  is  performed by using
prescribed SW-846 digestion techniques.

      2.3    The   nitric  acid  and  hydrogen  peroxide  impinger   solution,  the
hydrochloric  acid rinse solution, the  acidic  potassium  permanganate  impinger
solution, and  the probe rinse  and digested filter  solutions are analyzed for
mercury  by  Cold  Vapor  Atomic   Absorption  Spectroscopy  (CVAAS).   All   of the
sampling train catches except for the permanganate solution  are analyzed  for Cr,
Cd, Ni, Mn,  Be, Cu,  Zn,  Pb, Se, P, Ti, Ag,  Sb,  Ba, and As by ICP-AES or Atomic
Absorption Spectroscopy (AAS).   If antimony,  arsenic, cadmium, lead, selenium,
and thallium require  greater  analytical sensitivity than can be obtained  by ICP-
AES, then Graphite Furnace Atomic Absorption Spectroscopy  (GFAAS) is  used  for the

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analysis.  Additionally, if desired,  the tester may use AAS for analyses of all
metals if the resulting  in-stack method  detection limits  meet the goal  of the
testing program.

      2.4  For  convenience,  aliquots  of each  digested sample Fraction 1A plus
Fraction 2A can  be combined for a single analytical determination, proportionally
with  respect  to the original  Fractions 1A and 2A.   Fraction 1A  is normally
diluted to 300  ml  following digestion prior  to analysis  and the concentrated
Fraction 2A  is  normally  diluted  to  150 ml  following digestion and  prior to
analysis.

      2.5   The  efficiency  of  the analytical procedure  is  quantified  by the
analysis of spiked  quality control  samples  containing  each of the target metals
and/or other quality assurance measures including  actual  sample matrix effects
checks.

3.0   INTERFERENCES

      3.1   Refer to the  appropriate  determinative method for instructions on
minimization of interferences.

4.0   APPARATUS AND MATERIALS

      4.1   Sampling train -  A schematic of  the sampling train is shown  in Figure
A-l.  It is similar to the EPA Method 5 train.  The  sampling train consists of
the following components.

            4.1.1       Probe nozzle  (probe  tip)  and borosilicate  or  quartz
      glass probe liner  -  Same  as Method 5,  Sections 2.1.1  and  2.1.2,  except
      that glass nozzles are  required unless an alternate probe  tip prevents the
      possibility of  contamination  or  interference  of   the  sample  with  its
      materials of construction.   If  a  probe  tip other than  glass  is used, no
      correction of the  stack  sample  test  results  can be made because  of the
      effect on the results by the probe tip.

            4.1.2       Pitot tube and  differential  pressure gauge  -  Same as
      Method 2,  Sections 2.1 and 2.2,  respectively.

            4.1.3       Filters -  Quartz fiber or glass fiber filters without
      organic binders shall  be used.   The  filters shall contain  less than 1.3
      ug/in.2 of each of the metals to  be measured.  Analytical results provided
      by filter manufacturers are acceptable.   However,  if no such results are
      available, filter blanks  must be analyzed  for  each  target metal prior to
      emission  testing.   The  filters  should exhibit  at  least  99.95 percent
      efficiency (<0.05  percent  penetration)  on  0.3  micron  dioctyl  phthalate
      smoke  particles.    The filter  efficiency  test  shall  be  conducted  in
      accordance with ASTM Standard Method D2986-71 (incorporated by reference).
      For particulate  determination in sources containing S02 or S03, the filter
      material must  be  of a  type that is unreactive  to S02  or  S03,  as described
                                   0060 -  3                       Revision 0
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                                        8
                                        I
                                       JS
                                       to
                                        o
                                        g
                                        w
                                       1
0060 - 4
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in  Method  5.   Quartz  fiber  filters that  meet these  requirements are
recommended.

      4.1.4       Filter holder - Glass,  same  as Method  5, Section 2.1.5,
except  that  a  Teflon  filter  support  or  other  non-metallic,  non-
contaminating support must be used to replace the glass frit.

      4.1.5       Filter heating system - Same as Method  5, Section 2.1.6.

      4.1.6       Condenser

            4.1.6.1     The  following  system  shall  be  used  for  the
      condensation and  collection  of gaseous  metals and for determining
      the moisture content  of the stack gas.  The condensing system should
      consist of three to seven impingers connected in  series with leak-
      free ground  glass fittings  or  other  leak-free,   non-contaminating
      fittings.  The  first  impinger  is optional and is  recommended as a
      moisture knockout trap for use  during  test conditions which require
      such a  trap.   The first  impinger shall  be empty.   The second and
      third   impingers  shall   contain  known   quantities  of  a  nitric
      acid/hydrogen peroxide solution (Section 5.8).  The fourth shall be
      empty.  The fifth  and sixth impingers shall contain a known quantity
      of acidic  potassium  permanganate solution (Section  5.12),  and the
      last  impinger  shall   contain a known quantity of  silica  gel  or
      equivalent desiccant. A  thermometer capable of measuring to within
      1°C  (2°F)  shall  be  placed  at  the outlet  of the last  impinger.

            4.1.6.2  The first impinger shall  be appropriately sized for
      a potentially  large  moisture  catch  and  constructed  generally as
      described for the  first  impinger in Method  5,  Section  2.1.7.   The
      second  impinger (or the first  HN03/H202  impinger)  shall also be as
      described for the  first  impinger in Method  5.   The  third impinger
      (or,  in any case, the impinger used  as  the  second HN03/H202 impinger)
      shall be the same  as  the Greenburg-Smith impinger  with  the standard
      tip described as  the  second impinger in  Method 5,  Section  2.1.7.
      All  other  impingers  used  in  the metals  train are the  same  as the
      first HN03/H202  impinger.

            4.1.6.3 When the moisture knockout impinger  is not needed, it
      is removed from the train and the other impingers  remain the same.
      If  mercury  analysis  is  not  to   be  performed,  the  potassium
      permanganate impingers and  the empty impinger preceding  them are
      removed.

      4.1.7       Metering    system,   barometer,   and   gas   density
determination equipment  - Same as Method  5, Sections  2.1.8 through 2.1.10,
respectively.

      4.1.8       Teflon  tape  -  For   capping  openings   and   sealing
connections,   if necessary,  on  the sampling train.


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      4.2   Sample recovery.   Same  as  Method  5,  Sections 2.2.1 through 2.2.8,
with the following exceptions and additions:

            4.2.1       Non-metallic probe-liner  and probe-nozzle  brushes or
      swabs - For quantitative  recovery of materials collected in the front half
      of the  sampling  train.   Description  of  acceptable all-Teflon component
      brushes or  swabs  to  be  included  in EPA's Emission Measurement Technical
      Information Center (EMTIC) files.

            4.2.2       Sample storage containers - Glass bottles, 1000 mL and
      500  mL,  with  Teflon-lined  caps  which  are  non-reactive   to  oxidizing
      solutions,   shall   be used  for  samples  and  blanks   containing  KMn04.
      Polyethylene bottles may be used for other sample types.

            4.2.3       Polypropylene  tweezers and/or  plastic  gloves  -  For
      recovery of the filter from the sampling train filter holder.

      4.3   Sample preparation and analysis equipment.

            4.3.1       Refer  to  the  appropriate  preparation and analytical
      techniques  for the proper apparatus and materials.  Refer to Section 7.2
      for a description of preparation techniques.

5.0   REAGENTS

      5.1  Reagent grade chemicals shall  be used in  all tests.  Unless otherwise
indicated,   it  is  intended that  all  reagents  conform  to  the  specifications
established by 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.  Refer to Chapter One for a definition of reagent
water.   Analyze  the water for  all  target  metals  prior  to field use.  All target
metals  should be  less than the MDL.

      5.3   Nitric acid, concentrated - Baker Instra-analyzed or equivalent.

      5.4   Nitric acid  (0.1 M) - Add, with  stirring, 6.3 mL of concentrated  HN03
to a flask  containing approximately 900  mL of water.   Dilute  to  1000 mL with
water.   Mix  well.   The  reagent shall contain  less  than 2 jjg/l  of each target
metal.

      5.5   Nitric acid,  10 percent  (V/V).   Add,  with  stirring,  500 mL of
concentrated HN03 to  a flask containing approximately  4000 mL of water.  Dilute
to 5000 mL  with water.  Mix well.   Reagent shall contain  less than  2 /vg/L of each
target  metal.
                                   0060 - 6                       Revision 0
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      5.6   Nitric  acid,  5  percent (V/V).     Add,  with  stirring,  50  ml of
concentrated HN03 to 800 ml  of water.   Dilute  to  a  1000 ml with water.  Reagent
shall contain less than 2 //g/L of each target metal.

      5.7   Nitric  acid,  50  percent  (V/V).   Add, with  stirring,   125  ml of
concentrated HN03 to a flask containing approximately 100 ml of water.  Dilute
to 250 mL with water.  Mix well.  Reagent  shall  contain less  than  2/yg/L of  each
target metal.

      5.8   Nitric  acid  (HN03)/hydrogen  peroxide (H202)  absorbing  solution, 5
percent HN03/10  percent H202  Add carefully, with stirring,  50 ml of concentrated
HN03 to  a 1000-mL volumetric flask containing 500  mL of water.  Carefully add 333
mL of 30% H202 to the flask.   Dilute to  volume with  water.   The reagent shall
contain less than 2/yg/L of each target metal.

      5.9   Hydrochloric acid (8M), HC1  - Carefully add with stirring 690 mL of
concentrated HC1 to a flask containing  250 mL  of  water.  Dilute to 1000 mL  with
water.  Mix well.  The reagent shall contain less than/yg/L of Hg.

      5.10  Hydrogen peroxide, 30 percent  (V/V).

      5.11  Potassium permanganate, 5 percent  (W/V).

      5.12  Acidic potassium permanganate (KMn04) absorbing  solution, 4 percent
KMn04 (W/V),  10  percent  H2S04 (V/V) - Prepare fresh  daily.  Carefully mix 100 mL
of concentrated H2S04 into 800 mL of water.  Add water,  with stirring,  to  make
a volume of  1000 mL.  This solution is  10% H2S04 (V/V).  Dissolve, with stirring,
40 g of  KMn04 into sufficient 10% H2S04 to make a volume of 1  liter.  Prepare and
store in glass bottles to prevent degradation.  The reagent shall contain  less
than 2 //g/L  of Hg.

            CAUTION: To prevent autocatalytic  decomposition  of the permanganate
            solution, filter the solution  through Whatman  541  filter  paper.
            Also, due to reaction of the potassium permanganate with the acid,
            there may be  pressure  buildup  in  the sample  storage bottle;  these
            bottles  should  not be fully  filled  and  should  be  vented  both to
            relieve  excess   pressure  and  prevent  explosion  due to  pressure
            buildup.   Venting  is  highly  recommended,  but should  not  allow
            contamination of the solution;  a No.  70-72  hole drilled  in  the
            container cap and Teflon liner is suggested.

      5.13  Sulfuric acid, concentrated.

      5.14  Silica gel  and crushed ice - Same as EPA Method 5, Sections 3.1.2 and
3.1.4, respectively.

      5.15  Hydrofluoric acid, concentrated.

      5.16  Refer to the  appropriate preparation and  analytical  technique for
reagent  and  standard preparation procedures.

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6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1   Sampling.   The  complexity  of this method is such  that,  to obtain
reliable  results,  testers  should  be  trained  and experienced  with the  test
procedures.

            6.1.1       Pretest preparation.   Follow the same general procedure
      given  in  Method  5,  Section  4.1.1,   except that,  unless  particulate
      emissions  are  to  be  determined,  the  filter need  not  be  desiccated  or
      weighed.  All sampling train glassware should first  be rinsed with hot tap
      water and  then washed in  hot  soapy water.   Next,  glassware  should  be
      rinsed three times  with  tap  water, followed by three  additional  rinses
      with reagent water.    All glassware  should  then be  soaked  in  a 10% (V/V)
      nitric acid solution  for  a minimum of 4 hours, rinsed three  times  with
      reagent water,  rinsed a  final time  with  acetone, and allowed  to air dry.
      All glassware  openings where  contamination can occur  should  be  covered
      until the sampling train is assembled,  prior to sampling.

            6.1.2       Sampling train  calibration.  Maintain a laboratory log
      of all  calibrations.   Calibrate the sampling train components according to
      the indicated  sections of  Method 5:  probe  nozzle  (Section  5.1);  pitot
      tube (Section 5.2);  metering  system (Section 5.3);  probe  heater (Section
      5.4); temperature  gauges  (Section 5.5);  leak-check of the metering system
      (Section 5.6);  and barometer  (Section  5.7).

            6.1.3       Preliminary determinations.  Same as  Method 5,  Section
      4.1.2.

            6.1.4       Preparation of  Sampling Train.

                  6.1.4.1   Follow the same general procedures  given in Method 5,
            Section  4.1.3,  except  place  100 mL  of  the nitric  acid/hydrogen
            peroxide  solution   (Section   5.8)  in  each  of  the  two HN03/H202
            impingers (normally  the  second  and  third  impingers) as shown  in
            Figure A-l.   Place  100  mL  of  the acidic potassium permanganate
            absorbing solution (Section  5.12)  in  each of  the two permanganate
            impingers.  Transfer  approximately 200 to  300 g of preweighed silica
            gel  from  its  container  to  the last  impinger.  Alternatively,  the
            silica gel  may  be  weighed  directly in the impinger  just prior  to
            train assembly.

                  6.1.4.2   Several  options are  available to the tester based on
            the sampling conditions.  The empty first impinger is not needed if
            the  moisture  to be  collected in the  impingers  is  calculated  or
            determined to  be less than  100 mL.  If  necessary,  use as applicable
            to this methodology the procedure  described in Section 7.1.1 of EPA
            Method 101A,  40 CFR  Part  61, Appendix B, to maintain  the  desired
            color in the last permanganate impinger.
                                   0060 - 8                       Revision 0
                                                                  January 1995

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      6.1.4.3   Retain for  reagent  blanks,  volumes  of  the nitric
acid/hydrogen peroxide solution and 100 ml of the acidic potassium
permanganate solution.  These reagent blanks should be labeled and
analyzed as described  in  Section  7.   Set  up the sampling train as
shown  in  Figure A-l.   If necessary to ensure  leak-free sampling
train connections, Teflon tape or other non-contaminating material
should be used instead of silicone grease to prevent contamination.

CAUTION:   Extreme care  should  be taken to  prevent contamination
within the train.   Prevent  the  mercury collection reagent (acidic
potassium permanganate) from contacting any glassware of the train
which  is  washed  and  analyzed  for manganese.    Prevent hydrogen
peroxide from mixing with the acidic potassium permanganate.

      6.1.4.4  Alternatively, mercury emissions can be measured in
a separate train which measures  only mercury emissions by using EPA
Method 101A with  the modifications described below (and with the
further modification  that  the  permanganate  containers  shall  be
processed as described in the Section  5.12  caution comment.   This
alternative method  is applicable  for  measurement  of mercury and
manganese emissions, and  it  may be  of  special  interest  to sources
which must measure both mercury and manganese emissions.  [Section
7.2.1 of Method 101A shall be modified as follows after the 250 to
400-mL KMn04 rinse:   To  remove  any precipitated  material  and any
residual  brown deposits on the glassware following the permanganate
rinse,  rinse  with  approximately  100  ml  of  the  reagent  water.
Carefully  add  this  water  rinse,  assuring  transfer of  all  loose
precipitated materials from  the three  permanganate impingers into
the permanganate  Container  No.  1.  If no visible deposits remain
after this water rinse, do not rinse with  HC1.  However, if deposits
do remain  on the glassware after this water rinse,  wash the impinger
surfaces with 25  ml of 8M  HC1, and  place  the wash  in  a separate
sample container  labeled Container  No.  1A  containing  200  ml  of
water.  Wash the  impinger walls and stem with the  HC'I  by turning the
impinger on its side and  rotating  it so that  the HC1 contacts all
inside surfaces.  Use  a total of  only  25 ml  of  8M HC1  for rinsing
all permanganate impingers combined.  Rinse the first impinger, then
pour the actual  rinse used for the first impinger  into the 25 mL of
8M HC1 rinse carefully  with stirring into  Container No. 1A.  Analyze
the HC1 rinse separately by carefully  diluting,  with stirring, the
contents of Container No. 1A to  500 ml with  reagent water.  Filter
(if necessary) through  Whatman 40 filter paper, and then analyze for
mercury according to  Section  7.4.7, except limit  the  aliquot size to
a maximum of 10 ml.  Prepare and analyze  a blank by using the same
procedure  as that used by Container No. 1A,  except  add  5 ml of 8M
HC1 with stirring  to 40 mL  of  water,  then  dilute  to 100  ml with
reagent water.   Then  analyze the blank as instructed for the sample
from Container No. 1A.   Because  the previous separate permanganate
solution rinse  (Section  7.1.5.5)  and  water rinse  (as modified  in
these  guidelines)  have  the capability  to  recover  a   very  high
                       0060 - 9                       Revision 0
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            percentage  of  the mercury  from the  permanganate  impingers,  the
            amount of mercury in the HC1 rinse  in Container No.  1A may be very
            small, possibly even  insignificantly  small.  However, add the total
            of any  mercury analyzed and calculated  for the HC1  rinse  sample
            Container No.  1A  to  that calculated  from the  mercury  sample from
            (Section 7.1.5.5) which  contains the separate  permanganate rinse
            (and water rinse  as modified herein)  for  calculation  of the total
            sample mercury concentration.]

            6.1.5       Leak-check procedures.  Follow the leak-check procedures
      given in Method 5, Section 4.1.4.1 (Pretest Leak-Check),  Section 4.1.4.2
      (Leak-Checks During the Sample  Run), and Section 4.1.4.3 (Post-Test Leak-
      Checks).

            6.1.6       Sampling train operation.  Follow the procedures given
      in Method 5, Section 4.1.5.   For each  run,  record  the data required on a
      data sheet such as the one shown in Figure  5-2  of  Method 5.

            6.1.7       Calculation of percent isokinetic.   Same  as Method 5,
      Section 4.1.6.

7.0   PROCEDURE

      7.1   Sample recovery.  Begin cleanup  procedures as soon as  the probe is
removed from the stack at the end of a sampling period.

            7.1.1       The probe  should  be allowed  to cool prior  to  sample
      recovery.    When   it  can  be  safely   handled,  wipe   off  all  external
      particulate matter near the  tip of the probe nozzle  and  place a rinsed,
      non-contaminating cap over the probe  nozzle to  prevent losing or gaining
      particulate matter.  Do not cap the probe tip  tightly while  the sampling
      train is cooling.   This normally  causes  a  vacuum to  form in the  filter
      holder,  thus  causing the undesired  result of  drawing liquid  from  the
      impingers into the filter.

            7.1.2       Before moving the sampling train to the cleanup site,
      remove the  umbilical  cord  from the last  impinger and  cap the impinger.
      Cap  off  the  filter  holder  outlet   and   impinger   inlet.     Use  non-
      contaminating caps,  whether  ground-glass stoppers,   plastic  caps,  serum
      caps, or Teflon tape to close these openings.

            7.1.3       Alternatively, the train  can be disassembled before the
      probe and filter holder/oven are completely cooled,  if this  procedure is
      followed:   Initially  disconnect the filter holder outlet/impinger inlet
      and loosely cap the open ends.   Then disconnect the probe from the filter
      holder or cyclone inlet and  loosely cap the  open ends.  Cap the probe tip
      and remove the umbilical cord as previously described.

            7.1.4       Transfer the  probe  and filter-impinger assembly  to a
      cleanup area that  is  clean and protected from the wind  and other potential


                                   0060  - 10                       Revision 0
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causes of contamination or loss of sample.  Inspect the train before and
during disassembly and note any abnormal conditions.

      7.1.5       The  sample  is recovered  and  treated as  follows  (see
schematic in Figure A-2).  Assure that all  items  necessary for recovery of
the sample do not contaminate it.

            7.1.5.1  Container No. 1 (filter).  Carefully remove the filter
      from the  filter  holder  and place it  in its  identified  petri  dish
      container.  Acid-washed polypropylene or Teflon coated tweezers or
      clean disposable surgical  gloves rinsed with water should be used to
      handle the  filters.   If it is necessary  to  fold the filter,  make
      certain the particulate  cake is inside the  fold.   Carefully transfer
      the filter and any particulate matter or filter fibers that adhere
      to the filter holder gasket to the petri dish  by  using a dry (acid-
      cleaned)  nylon bristle brush.    Do  not use  any metal-containing
      materials when recovering this train.  Seal the labeled petri dish.

      NOTE:       Follow  the  procedure  in  Section  7.1.5.2  only  if
                  determination of  particulate  emissions  are  desired in
                  addition to metals emissions.   If  only metals emissions
                  are  to  be  determined, skip Section  7.1.5.2  and  go to
                  Section 7.1.5.3.

            7.1.5.2  Container No. 2 (acetone rinse).

                  7.1.5.2.1  Taking care to see that dust on the outside
            of the probe or other exterior surfaces  does not get into the
            sample,  quantitatively  recover particulate matter  and  any
            condensate from the  probe nozzle, probe fitting  (fittings made
            of plastic such as Teflon, polypropylene, etc. are recommended
            to  prevent contamination  by  metal   fittings.    Further,  if
            desired  a  single  glass  piece may be used, but it  is  not a
            requirement of this methodology),  probe  liner,  and front half
            of the filter holder by washing these components with 100 ml
            of acetone and placing the wash in a  glass container.  The use
            of  exactly 100  mL  is  necessary for  the  subsequent  blank
            correction procedures.  Reagent water may be used instead of
            acetone.   In  these  cases,  save a water blank.   Perform the
            acetone rinses as follows:   Carefully remove the probe nozzle
            and clean  the  inside  surface  by rinsing with  acetone from a
            wash  bottle  and  brushing with a  non-metallic  brush.   Brush
            until  the  acetone  rinse  shows  no  visible  particles,  after
            which make a final rinse of the inside  surface with acetone.
            Brush  and  rinse the sample exposed inside of the  Swagelok
            fitting  with  acetone  in  a  similar way  until  no  visible
            particles remain.
                             0060 -  11                       Revision 0
                                                            January 1995

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               0060 - 12
                             Revision 0

                             January 1995

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                  7.1.5.2.2 Rinse the probe liner with acetone by tilting
            and rotating the probe while squirting acetone into its upper
            end so that all inside  surfaces will  be  wetted with acetone.
            Allow the acetone  to drain from the lower end into the sample
            container.  A funnel may be used to aid in transferring liquid
            washings to the container.  Follow the  acetone  rinse with a
            nonmetallic  probe  brush.   Hold the  probe  in  an  inclined
            position, squirt acetone  into the upper end as the probe brush
            is being pushed with a twisting action through the probe; hold
            a sample container underneath  the lower end of the probe, and
            catch any  acetone and particulate matter  which  is  brushed
            through the probe.  Rinse and  brush three times or more until
            no visible particulate matter is carried  out  with the acetone
            or until none remains in the probe liner on visual inspection.
            Rinse the brush with acetone, and quantitatively collect these
            washings in the sample container.  After the brushing, make a
            final acetone rinse of the probe as described above.

                  7.1.5.2.3  It is  recommended  that  two  people clean the
            probe to minimize  sample  losses.  Between sampling runs, keep
            brushes clean and  protected from contamination.

                  7.1.5.2.4  Clean the  inside  of the front  half of the
            filter  holder  by  rubbing the  surfaces  with  a  nylon  bristle
            brush and  rinsing  with   acetone.   Rinse each  surface three
            times or more  if  needed  to remove visible particulate.  Make
            a final rinse  of the brush  and  filter holder.   Make  a final
            rinse of  the  brush and  filter holder.   After  all  acetone
            washings and particulate matter have been collected  in the
            sample container,  tighten the  lid on  the sample container so
            that  acetone will  not leak out when it  is  shipped  to the
            laboratory.  Mark the height of the  fluid level  to determine
            whether or not  leakage occurred during  transport.  Label the
            container clearly to identify  its contents.

      7.1.5.3   Container No.  3 (probe rinse).   Keep the  probe assembly
clean and free from contamination as described  in Section 7.1.5.2 during
the 0.1M nitric acid rinse  described  below.  Rinse the probe liner, probe
nozzle, and filter, and  front  half of  the filter holder  thoroughly with
100 ml  of  0.1 M  nitric  acid  and place the  wash  into a  sample  storage
container.

      NOTE: The  use of exactly 100  ml  is necessary for  the subsequent
      blank correction procedures.   Perform the  rinses  as applicable and
      generally  as  described  in Method 12,  Section 5.2.2.   Record the
      volume of the combined rinse.  Mark the height  of the fluid level on
      the outside of the storage container and use this mark to determine
      if leakage occurs during transport.   Seal the container and clearly
      label the  contents.   Finally,  rinse the nozzle, probe liner, and
      front half of the filter holder with water  followed by acetone and
      discard these rinses.

                            0060  -  13                       Revision 0
                                                            January 1995

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      7.1.5.4  Container No. 4  (Impingers 1 through 3,  HN03/H202 impingers
and moisture knockout impinger, when used,  contents and rinses).   Due to
the potentially large quantity of liquid involved,  the tester may palace
the  impinger solutions  from  Impingers 1,  2,  and  3   in  more than  one
container.  Measure the liquid in the first three impingers volumetrically
to within 0.5 ml using  a graduated cylinder.  Record the volume of liquid
present.  This information is required to  calculate the moisture content
of the  sampled  flue  gas.   Clean each of the first  three  impingers,  the
filter  support,  the back  half  of  the filter  housing,  and  connecting
glassware by thoroughly rinsing with  100 mL of 0.1  M  nitric acid using the
procedure as applicable and generally as described in  Method 12,  Section
5.2.4.

      NOTE:  The  use  of  exactly  100 ml of  0.1 M nitric  acid rinse is
      necessary for the subsequent blank correction procedures.  Combine
      the rinses and impinger  solutions, measure  and  record the  volume.
      Mark  the  height   of  the fluid  level  on outside of  container to
      determine if leakage occurs during transport.   Seal  the container
      and clearly label the contents.

      7.1.5.5   Containers  No.  5A (0.1M HN03),  5B  (KMn04/H2S04 absorbing
solution),  and 5C (8M HC1  rinse  and  dilution).   If mercury is not being
measured in this train,  then  Impingers  4, 5,  and 6,  as  shown in Figure A-
1, are not  necessary and may be eliminated.

            7.1.5.5.1   Pour  all the  liquid,  if   any,   from  the impinger
      which was empty at the  start  of  the  run  (normally Impinger 4)  and
      which  precedes the  two permanganate  impingers  into  a graduated
      cylinder and measure the volume to within 0.5  ml.  This information
      is required to calculate the  moisture  content of the sampled  flue
      gas.   Place the  liquid in Sample  Container No.  5A.   Rinse  the
      impinger  (No.  4)  with  100 ml  of 0.1M  HN03  and place  this  into
      Container No.  5A.   Pour all the  liquid  from  the two permanganate
      impingers into a  graduated  cylinder and measure the volume to within
      0.5  ml.   This information  is required to  calculate  the moisture
      content  of the  sampled  flue gas.     Place this  KMn04 absorbing
      solution  stack sample  from the  two  permanganate  impingers  into
      Container  No.  5B.   Using  100  ml  total of  the  fresh acidified
      potassium permanganate  solution, rinse the permanganate impinger and
      connecting glass pieces a minimum of three times.  Place  the rinses
      into  Container No. 5B,  carefully assuring  transfer  of all loose
      precipitated materials  from the two impingers into Container No. 5B.
      Using 100 ml total  of  water,  rinse  the permanganate  impingers and
      connecting glass  pieces a minimum  of  three  times,  and place the
      rinses  into  Container  No. 5B, carefully assuring  transfer of all
      loose precipitated material,  if any,   from  the  two  impingers  into
      Container No. 5B.  Mark the height of the fluid level  on  the outside
      of the bottle to determine if  leakage occurs during  transport.  See
      the following note and  properly prepare the bottle and clearly label
      the  contents.


                             0060 -  14                      Revision 0
                                                            January  1995

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      NOTE:  Due to the potential reaction of the  potassium  permanganate
      with the acid,  there may be pressure  buildup in  the sample storage
      bottle.   These  bottles shall not be filled full and shall  be vented
      to relieve excess pressure.  Venting is required.  A No. 70-72 hole
      drilled  in the  container cap and Teflon  liner is suggested.

            7.1.5.5.2   If no  visible  deposits remain  after the  above
      described water rinse, do not rinse with HC1.  However, if deposits
      do remain on the glassware after this water rinse, wash the impinger
      surfaces with  25 ml of  8M HC1, and  place  the wash in a  separate
      sample container labeled Container No. 5C that  contains  200 ml of
      water.  Wash the impinger walls and stem with the HC1 by turning the
      impinger on its side and rotating it  so  that  the  HC1  contacts all
      inside surfaces.  Use a  total  of  only 25 ml of  8M HC1  for rinsing
      both permanganate impingers  combined.   Rinse the  first  impinger,
      then pour  the  actual  rinse used  for  the first  impinger  into the
      second impinger for its  rinse.  Finally, pour the  25  ml  of 8M HC1
      rinse carefully with  stirring  into  Container No.  5C.    Mark the
      height of the fluid  level  on the outside of the bottle to  determine
      if leakage occurs  during transport.

      7.1.5.6    Container  No.   6 (silica gel).    Note  the color  of the
indicating silica gel to  determine whether  it  has been  completely spent
and make a notation  of its condition.   Transfer the silica  gel  from its
impinger to its original container  and seal.  The  tester may use a funnel
to pour the silica gel  and  a  rubber policeman to  remove  the silica gel
from the impinger.   The  small  amount of particles  that may adhere to the
impinger wall  need not be removed.   Do not  use water or other liquids to
transfer the silica gel  since  weight  gained  in the silica gel impinger is
used for moisture calculations.  Alternatively, if a balance is  available
in the  field,   record the  weight of the spent silica gel  (or silica gel
plus impinger) to the nearest  0.5g.

      7.1.5.7   Container No. 7 (acetone  blank).  If particulate  emissions
are to be determined, at least once during  each field  test,  place 100-mL
portion of the acetone used in the sample recovery process into a labeled
container  for use in the front-half  field  reagent  blank.    Seal  the
container.

      7.1.5.8   Container No. 8A (0.1  M nitric acid blank).  At least once
during  each field test, place 300  ml of the 0.1  M  nitric acid  solution
used in the sample recovery process  into a  labeled container for use in
the sample recovery process into a labeled container for  use in the front-
half and back-half field reagent blanks.  Seal  the container.

      7.1.5.9   Container No. 8B (water blank).  At least once during each
field test, place 100 mL of the water used in the sample recovery process
into a labeled Container No.  8B.  Seal  the  container.

      7.1.5.10  Container  No.  9 (5 percent nitric acid/10 percent hydrogen
peroxide blank).  At least once  during  each field test,  place  200 ml of

                            0060 -  15                       Revision 0
                                                            January 1995

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      the 5% nitric acid/10% hydrogen peroxide solution used as the nitric acid
      impinger reagent into a labeled  container  for use in the back-half field
      reagent blank.  Seal  the container.

            7.1.5.11  Container No. 10  (acidified potassium permanganate blank).
      At least  once during  each  field test, place 100  ml  of the  acidified
      potassium permanganate solution  used as the  impinger solution and in the
      sample recovery process into a labeled container for use in the back-half
      field  reagent blank  for  mercury analysis.   Prepare  the container  as
      described in Section 7.2.5.5.1  note.

            7.1.5.12  Container No. 11  (8M HC1  blank).  At  least  once during
      each field test, place 200 mL of water into a  sample container.  Then pour
      25 ml of 8M HC1 carefully with stirring into  the  200 ml of  water in the
      container.  Mix well  and seal the container.

            7.1.5.13  Container No. 12 (filter blank).   Once  during each field
      test, place an unused filter from the same lot as the sampling filters in
      a labeled  petri dish.  Seal the petri  dish.   This will  be  used in the
      front-half field reagent blank.

      7.2   Sample  preparation.   Note  the level  of the liquid  in  each of the
containers and  confirm on  the analysis sheet whether or  not leakage occurred
during transport.  If  a noticeable  amount of leakage has  occurred  either  void the
sample  or  use  approved  methods  to  correct  the  final  results.   A  diagram
illustrating sample preparation and analysis procedures for each of the sample
train components is shown in Figure A-3.

            NOTE:       Follow the appropriate  sample  preparation procedures:

            Method 3010:       Acid   Digestion   of   Aqueous   Samples   and
                              Extracts for Total Metals  for Analysis by FLAA or
                              ICP.
            Method 3015:       Microwave   Assisted   Acid   Digestion  Digestion
                              of Aqueous Samples and Extracts.
            Method 3050:       Acid  Digestion   of  Sediments,  Sludges,   and
                              Soils.
            Method 3051:       Microwave    Assisted    Acid    Digestion    of
                              Sludges, Soils, and Oils.
                                   0060 - 16                      Revision 0
                                                                  January 1995

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         Figure A-3.  Sampling Preparation  and Analysis Scheme
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If the  sampling  train uses an optional  cyclone,  the cyclone catch  should  be
prepared and digested using the same  procedures described  for the filters and
combined with the digested filter samples.

            7.2.1       Container No.  1  (filter).  If particulate emissions are
      being determined,  then desiccate the filter and filter catch without added
      heat and weigh to  a constant weight as described in Section 4.3 of Method
      5.  For analysis of metals,  divide the filter with its filter catch into
      portions containing approximately  0.5 g each and place into the analyst's
      choice of either individual  fluorocarbon based microwave pressure relief
      vessels or Parr® Bombs.   Add 6 ml  of concentrated nitric acid and 4 ml of
      concentrated hydrofluoric acid  to each vessel.   For microwave heating,
      microwave the sample according to the parameters defined in Method 3051.
      For conventional heating, heat the Parr® Bombs in an oven at 140°C  (285°F)
      for 6 hours following the manufacturer's recommendations  for Bomb loading,
      assembly and disassembly, cleaning,  and handling.   Cool  the  samples  to
      room  temperature   and  combine  with  the  acid digested  probe rinse  as
      required in Section 7.3.3.

            NOTE: Hydrofluoric acid (HF) has been identified as an exceptional
            health and contact hazard.   Burns  and  other symptoms can be sever
            and may  not appear immediately.   The  analyst  should  perform all
            operations with HF under appropriate laboratory conditions (i.e., in
            a  fume  hood suitable  for  HF  work),  should  be  fully informed
            regarding the appropriate safety data  (e.g.,  all  hazard warnings,
            storage  and  handling  requirements, spill cleanup  procedures, and
            emergency treatments for exposure),  and  should  wear the appropriate
            laboratory  protective equipment  (e.g.,  goggles,  face  shield, lab
            coat, rubber apron, long rubber gloves)  when preparing and handling
            digestates and other  solutions containing HF.

            7.2.2       Container No.  2  (acetone rinse).  Measure the liquid in
      this container either volumetrically to +1 ml or gravimetrically to ±0.5
      g.   Transfer  the  contents  to  an  acid-cleaned tared 250-mL  beaker and
      evaporate to dryness at ambient  temperature  and pressure.   If particulate
      emissions are being determined,  desiccate for 24 hours without added heat,
      weigh  to a  constant  weight  according  to  the procedures  described  in
      Section  4.3  of Method  5, and report the  results  to  the nearest  0.1 mg.
      Redissolve the residue with 10 ml  concentrated nitric acid and  carefully,
      with stirring, combine  the  resultant sample including all liquid  and any
      particulate  matter with Container No.  3  prior  to beginning the  Section
      7.3.3.

            7.2.3        Container  No. 3  (probe  rinse).   The pH of this sample
      shall be 2 or lower.  If the pH  is higher, the sample should be acidified
      by careful addition, with stirring, with concentrated nitric acid  to  pH 2.
      The sample should be rinsed  into a  beaker with water and  the  beaker should
      be covered with a ribbed watchglass. The sample volume  should  be  reduced
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to approximately 20 ml  by heating on a hot plate  at  a temperature just
below boiling. Then follow one of the digestion procedures listed below.

            7.2.3.1     Digest the  sample  using the  appropriate method
      (Method 3010, 3015,  or Parr Bomb),  using the HF modification and
      then continuing  to follow the procedures  described in Section 7.2.1.

            7.2.3.2     Combine the digestate prepared in Section 7.2.1.
      The resultant combined sample  is a Fraction 1  precursor.  Filter the
      combined  solution of  the   acid  digested filter and probe  rinse
      samples using Whatman  541 filter  paper.   Dilute to 300  ml (or the
      appropriate  volume  for  the  expected  metals concentration)  with
      water.  This dilution is Fraction  1.  Measure and record the volume
      of the Fraction  1  solution to  within 0.1 ml.  Quantitatively remove
      a 50-mL aliquot and label as Fraction IB.  Label the remaining 250
      ml portion as Fraction 1A.   Fraction 1A is used  for ICP-AES or AAS
      analysis.  Fraction IB is used for the determination of front-half
      mercury.

      7.2.4       Container No. 4  (Impingers 1-3).  Measure and record the
total volume of this sample  (Fraction 2) to within 0.5  mL.  Remove a 75-to
100-mL aliquot for mercury analysis and label  as Fraction 2B.   Label the
remaining  portion  of  Container No.  4  as  aliquot  Fraction  2A.   Aliquot
Fraction 2A defines the volume of 2A prior to digestion.  All  of aliquot
Fraction 2A is digested  to produce concentrated Fraction 2A.  Concentrated
Fraction 2A defines the  volume of 2A after digestion which is normally 150
mL.   Concentrated  Fraction  2A is  analyzed  for  all   the  metals except
mercury.   The Fraction 2B  aliquot  should  be prepared and  analyzed for
mercury as described  in  Section  7.4.7.  Fraction 2A shall be  pH  2 or
lower.  If necessary,  use  concentrated nitric acid to lower Fraction 2A to
pH 2.  The sample  should be rinsed into a beaker with water and the beaker
should be  covered with  a ribbed watchglass.  The sample volume should be
reduced to approximately 20 mL by  heating on a hot  plate  at a temperature
just below boiling. Then  follow either of the  digestion procedures below.

            7.2.4.1  Method  3015:    Microwave Assisted Acid Digestion of
      Aqueous Samples and Extracts.  Cool, filter the  sample,  and dilute
      to  150 mL  (or the appropriate  volume  for  the  expected metals
      concentrations) with water.   This  dilution is concentrated  Fraction
      2A.  Measure  and  record  the volume  of the Fraction 2A solution to
      within 0.1 mL.

            7.2.4.2  Method  3010:   Acid Digestion of Aqueous Samples and
      Extracts  for Total  Metals  for Analysis  by  FLAA and ICP.   Cool,
      filter the sample, and dilute to  150 mL  (  or  the  appropriate volume
      for  the expected  metals concentrations) with water.  This dilution
      is concentrated Fraction 2A.  Measure and record the volume of the
      Fraction 2A solution to within 0.1 mL.

      7.2.5  Container Nos. 5A, 5B,  and  5C  (Impingers  4,  5,  and 6).  Keep
these samples separate  from  each  other.

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            7.2.5.1  Measure and record the volumes of 5A and 5B each to
      within 0.5 ml.   Dilute Sample  5C  to 500 ml with water.  The Samples
      5A, 5B,  and 5C are referred to respectively as Fractions 3A, 3B, and
      3C.  Follow the analysis procedures described in Section 7.4.,

            7.2.5.2  Because the permanganate rinse and water rinse have
      the capability  to recover a  high  percentage of the mercury from the
      permanganate  impingers,  the  amount  of mercury  in  the  HC1  rinse
      (Fraction 3C)  may  be very  small,  possibly even  insignificantly
      small.  However, as  instructed in this method, add the total of any
      mercury measured in and calculated for the HC1  rinse (Fraction 3C)
      to that  for  Fractions IB, 2B, 3A,  and 3B for  calculation  of the
      total sample  mercury concentration.

      7.2.6  Container No. 6 (silica gel).  Weigh the spent silica gel (or
silica gel  plus impinger) to the  nearest 0.5 g  using  a  balance.   (This
step may be conducted in the field).
7.3  Calibration

      7.3.1  Refer to the  appropriate  analytical  methods  for the proper
calibration procedures.

7.4   Sample analysis.

      7.4.1    For  each  sampling train,  seven  individual   samples  are
generated  for  analysis.    A schematic  identifying  each sample  and  the
prescribed sample preparation and analysis  scheme  is shown in Figure A-3.
The  first  two  samples,  labeled  Fractions 1A  and  IB,  consist  of  the
digested samples from the  front  half of the train.   Fraction  1A is  for
ICP-AES and AAS  analysis as  described  in Section  7.4.5.   Fraction IB is
for determination of front-half mercury as described in Section 7.4.7.

      7.4.2  The back half  of the  train  was  used to  prepare  the third
through seventh samples.  The third  and  fourth samples, labeled Fractions
2A and  2B,  contain  the  digested samples from the moisture  knockout, if
used, and HN03/H202 Impingers  1 through 3.  Fraction 2A is for ICP-AES or
AAS analysis.  Fraction 2B will be analyzed for mercury.

      7.4.3  Samples 5A,  5B, and  5C  are  labeled  Fractions 3A, 3B,  and 3C,
respectively.  They consist of the impinger contents and rinses from the
empty Impinger 4 and  the permanganate  Impingers 5 and 6.   These  samples
are analyzed for mercury as described in Section  7.4.7.  The total back-
half mercury catch is determined  from the sum of Fraction 2B  and Fraction
3A, 3B, and 3C.

      7.4.4  Initially,  analyze  all  samples for iron, aluminum,  and all
the target metals except mercury .   If iron  and aluminum are present in
the  sample,  the sample  may have to be diluted  so  that each  of these


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elements  is  at  a  concentration  of  less than  50  ppm  to  reduce  their
spectral interferences on arsenic, cadmium,  chromium, and lead.

            NOTE: When analyzing  samples in a hydrofluoric acid matrix, an
            alumina torch should  be  used.   Since  all front-half samples
            will contain hydrofluoric acid,  use an alumina torch.

      7.4.5  ICP-AES analysis.  Fraction 1A and Fraction 2A are analyzed
by ICP-AES using  EPA  SW-846 Method 6010.   Refer  to  method  6010 for the
proper analytical procedures.

      7.4.6   AAS  by   direct  aspiration  and/or  graphite  furnace.    If
analysis of metals in Fraction 1A and Fraction 2A using graphite furnace
or direct aspiration AAS is desired, Table A-2 should also be consulted to
determine  possible  interferences  and  techniques  to  use  for  their
minimization.   Refer  to SW-846  Vol.  1A to  determine  the appropriate
analytical protocol.

      7.4.7  Cold vapor AAS mercury analysis.  Fraction IB,  Fraction 2B,
and Fraction  3A,  3B,  and 3C  should  be analyzed  separately for mercury
using  cold vapor  atomic absorption  spectroscopy following  the method
outlined in EPA SW-846 Method 7470.  Refer to Method 7470 for the proper
analytical protocol.  If no  prior knowledge exists of the expected amount
of mercury in the sample, dilute  a 1-mL to 10-mL aliquot of each original
sample to  100 ml.  Record the amount of the aliquot  used for dilution to
100 ml.  A 5-mL  aliquot  is suggested for the first  dilution to  100 mL.  To
determine the stack emission value for mercury, the  amount of the aliquot
of the sample used  for dilution and analysis is dependent on  the  amount of
mercury in the  aliquot:  the  total  amount  of  mercury in the  aliquot used
for analysis must  be less than 1  ug,  and  within  the range (zero to 1000
ng) of the calibration curve.

7.5  Calculations

      7.5.1   Dry  gas  volume.   Using the data  from  this test, calculate
Vm
-------
                  7.5.4.1    Fraction   1A,  front  half,  metals  (except  Hg).
            Calculate the amount of each metal collected  in  Fraction 1 of the
            sampling train using the following equation:

                  Mfh          = Ca1 Fd VsolnJ                              Eq. I1

            where:

                  Mfh          =     total   mass  of  each  metal  (except  Hg)
                                    collected in  the front half  of the sampling
                                    train  (Fraction 1), ug.
                  Ca1          =     concentration of metal  in  sample Fraction
                                    1A as  read from  the standard curve  (ug/mL).
                  Fd          =     dilution  factor  (Fd =  the  inverse of the
                                    fractional  portion  of  the  concentrated
                                    sample in the solution actually  used in the
                                    instrument to produce the reading Ca1.  For
                                    example, when a 2 mL volume of  Fraction 1A
                                    is diluted to 10 mL, Fd  = 5).
                  Vso,n1        =     total  volume  of digested  sample solution
                                    (Fraction 1), ml.

                  7.5.4.2    Fraction  2A,  back  half,  metals  (except  Hg).
            Calculate the amount of each metal collected  in  Fraction 2 of the
            sampling train using the following equation.

                  Mbh          «     Ca2 Fa Va                            Eq. 21

            where:

                  Mbh          =     total   mass  of  each  metal  (except  Hg)
                                    collected in the back half  of the  sampling
                                    train (Fraction 2), ug.
                  Ca2          =     concentration    of   metal    in   sample
                                    concentrated Fraction 2A, as read  from the
                                    standard  curve  (ug/mL).
                  Fa          =     aliquot   factor,   volume  of   Fraction   2
                                    divided by volume  of aliquot Fraction 2A.
                  Va          =     total  volume of digested  sample  solution
                                    (concentrated   Fraction   2A),   ml.    See
                                    Section 6.1.4.1 or  6.1.4.2  as applicable.

                  7.5.4.3  Total train, metals (except Hg).  Calculate the  total
            amount  of each  of the  quantified metals collected  in the  sampling
            train as follows:
     1If Fractions 1A and 2A are combined, proportional aliquots must  be  used.
Appropriate changes must be made in Equations  1-3 to reflect this  approach.

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                  Mt           =     (M,h  - Mfhb) +  (Mbh -  Mbhb)             Eq. 31

            where:

                  Mt           =     total mass of each metal (separately stated
                                    for  each  metal)  collected in  the  sampling
                                    train, ug.
                  Mfhb         =     bank  correction  value  for  mass of  metal
                                    detected in front-half field reagent blank,
                                    ug.
                  Mbhb         =     blank  correction value  for  mass of  metal
                                    detected  in back-half field  reagent blank,
                                    ug.

            NOTE: If the measured blank value  for  the front  half  (Mfhb) is in the
            range  0.0  to  A ug  [where A  ug  equals the value  determined  by
            multiplying  1.4  ug/in.2 times  the actual area  in  square inches of
            the filter used in the emission sample], Mfhb may be used to  correct
            the emission sample value (Mfh); if Mfhb exceeds A ug,  the greater of
            the two following values may be used:   A ug, or  the lesser value of
            Mfhb or 5 percent of Mfh.

            If the measured blank value for the back half (Mbhb) is in the range
            0.0 to 1 ug, Mbhb may be used to correct  the  emission  sample value
            (Mbh);  if Mbhb exceeds 1  ug,  the greater of the two following values
            may be used:   1  ug or 5 percent of Mbh.

            7.5.5  Mercury  in source sample.

                  7.5.5.1  Fraction IB,  front  half, Hg.  Calculate the amount of
            mercury collected  in the front half,  Fraction  1, of  the  sampling
            train using  the  following equation:

                          Qfh
                  Hgfh =  	 x  Vsolnl                                      Eq. 4
                         M1B

            where:

                  Hgfh         =     total  mass  of  mercury  collected  in  the
                                    front half of the sampling train (Fraction
                                    1),  ug.
                  Qfh          =     quantity of mercury in analyzed sample, ug.
                  Vsoln1        =     total  volume   of digested sample  solution
                                    (Fraction  1),  ml.
     1If Fractions 1A and 2A are combined, proportional  aliquots must be used.
Appropriate changes must be made in  Equations  1-3  to  reflect this approach.

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       'f1B
                  volume of Fraction IB analyzed, mL.
                  following    Note.
                                                             See the
NOTE:  Vf1B is  the  actual  amount  of  Fraction  IB  analyzed.    For
example,  if 1 ml  of Fraction IB were diluted to 100 mL  to  bring it
into the  proper  analytical  range, and  1 ml  of the 100  ml  dilution
was analyzed, Vf1B would  be  0.01.

      7.5.5.2  Fraction  2B and  Fractions 3A,  3B, and 3C, back half,
Hg.  Calculate the  amount of mercury collected in Fraction 2 using
Equation 5 and Fractions 3A, 3B, and 3C using Equation  6. Calculate
the  total amount of mercury collected  in   the  back  half of  the
sampling  train using Equation 7.
               'f2B
where:
        Qbh2
Hgbh2	x  v,





Hgbh2

Qbh2

V2B
                       soln-2
                                                               Eq.  5
                         total  mass of mercury collected in Fraction
                         2,  ug.
                         quantity of mercury in analyzed sample, ug.
                         total  volume of Fraction  2,  ml.
                         volume of Fraction 2B analyzed, ml (see the
                         following note).
NOTE:  Vf2b  is  the  actual  amount of  Fraction  2B  analyzed.    For
example,  if 1  mL of Fraction  2B  were  diluted to  10 mL  to bring it
into the proper analytical range, and 5 mL of the 10-mL dilution was
analyzed,  Vf2b  would be 0.5.Use Equation 6 to calculate separately
the back-half  mercury for Fractions 3A, 3B,  and 3C.
       Hg



where:


H9bh3(A.B,


Qbh3(A,B,C I


"f3|A.B,C)

u
ysoln,3(A,B,C)
                      •
-------
            Hgbh  =  Hgbh2 + Hgbh3A + Hgbh3B + Hgbh3C                     Eq.  7

      where:

            Hgbh         =      total mass of mercury collected in the back
                               half of  the  sampling  train,  ug.

            7.5.5.3   Total  train mercury  catch.    Calculate  the  total
      amount of mercury collected in the sampling train using Equation 8.

            Hgt = (Hgfh - Hgfhb)  + (Hgbh  - Hgbhb)                       Eq.  8

      where:

            Hgt         =      total  mass  of  mercury collected  in  the
                               sampling train,  ug.
            Hgfhb        =      blank correction value for mass of mercury
                               detected in front-half field reagent blank,
                               ug.
            Hgbhb        =      blank correction value for mass of mercury
                               detected in  back-half field reagent blank,
                               ug.

      NOTE: If the total of the measured blank values (Hgfhb + Hgbhb) is in
      the range  of 0  to 6 ug,  then the total  may be  used  to correct the
      emission sample value  (Hgfh  + Hgbh);  if it exceeds 6 ug, the greater
      of the following  two values may  be  used:  6  ug or  5 percent of the
      emission sample value  (Hgfh  +  Hgbh).

      7.5.6   Metal concentration of  stack gas.   Calculate each  metal
separately  for the cadmium,  total chromium, arsenic,  nickel,  manganese,
beryllium,  copper,  lead,  phosphorus,  thallium, silver,  barium,  zinc,
selenium,  antimony,  and  mercury concentrations  in  the  stack gas  (dry
basis, adjusted  to standard  conditions)  as  follows:

      C8 = K4  (Mt/Vm(std))                                              Eq.  9

where:

      Cs                =      concentration of each  metal in the  stack gas,
                               mg/dscm.
      K4                =      10"3 mg/ug.
      Mt                =      total mass  of each metal  collected in the
                               sampling train,  ug;   (substitute  Hgt for  Mt
                               for the  mercury  calculation).
      Vm(std)             =      volume of gas sample  as measured  by the dry
                               gas  meter,   corrected  to   dry   standard
                               conditions,  dscm.
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            7.5.7  Isokinetic variation  and acceptable results.  Same as Method
      5, Sections 6.11 and 6.12, respectively.


8.0   QUALITY CONTROL

      8.1   Sampling Blanks.

            8.1.1       Field Reagent Blanks  (FRBs).   When analyzed, the blank
      samples in Container Nos.  7  through  12  shall be processed, digested, and
      analyzed as follows.   Digest and process one of the filters from Container
      No. 12 contents per Section 7.2.1, 100 mL from Container  No. 7 per Section
      7.2.2, and 100 mL from Container No. 8 per Section 7.2.3.  This produces
      Fraction  Blank 1A and  Fraction Blank  IB  from Fraction  Blank 1.   (If
      desired,  the  other  two filters may be digested separately  according to
      Section 7.2.1, diluted separately  to 300 mL each, and analyzed separately
      to produce a blank value for each of the two additional filters.  If these
      analyses  are performed, they will  produce two additional values for each
      of Fraction Blank 1A  and Fraction Blank IB.  The three Fraction Blank 1A
      values will be calculated  as three values  of Mfhb in Equation 3 of Section
      7.5.4.3,  then the three values shall be totalled and divided by three to
      become the value  Mfhb  to be  used in  the computation of Mt by  Equation 3.
      Similarly,  the  three  Fraction  Blank IB  values  will  be  calculated
      separately as three values,  {.otalled, averaged,  and used  as the value for
      Hgfhb  in  Equation  8  of Section  7.5.5.3.   The analyses  of the two extra
      filters are optional  and are not a requirement of this method, but if the
      analyses  are  performed,  the  results  must  be  considered as described
      above.)  Combine 100  mL of Container No. 8A with 200 mL of the contents of
      Container No.  9 and  digest  and process the resultant volume per Section
      6.1.4.  This produces concentrated Fraction Blank 2A and  Fraction Blank 2B
      from  Fraction  Blank 2.  A 100-mL portion of Container No. 8A is Fraction
      Blank 3A.  Combine 100 mL of the contents of Container No. 10 with 33 mL
      of the  contents  of  Container No.  8B.  This  produces  Fraction Blank 3B.
      (Use 400  mL as the volume  of Fraction Blank 3B when calculating the blank
      value.    Use  the  actual  volumes  when  calculating  all   the  other blank
      values).  Dilute 225 mL of the  contents of Container No.  11 to  500 mL with
      water.   This  produces Fraction Blank 3C.   Analyze Fraction  Blank 1A and
      Fraction  Blank 2A per Section 7.2.4.1 and/or Section  7.2.4.1   Analyze
      Fraction  Blank IB, Fraction  Blank 2B,  and  Fraction Blank 3A,  3B, and 3C
      per  Section  7.2.4.1.   The  analysis of  Fraction  Blank  1A  produces the
      front-half reagent blank correction values  for  the metals except mercury;
      the  analysis  of  Fraction  Blank IB produces the front-half reagent blank
      correction value for mercury.  The analysis of  Fraction  Blank  2A produces
      the  back-half reagent  blank  correction  values  for  the metals  except
      mercury,  while separate analysis  of Fraction Blanks 2B  and 3  produce the
      back-half reagent blank correction  value for mercury.


            8.1.2       Field Sampling  Train Blanks  (FSTBs).  FSTBs  must be
      submitted with the samples collected at each site.  The  FSTBs  include the


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      sample bottles containing  aliquots  of sample recovery  solvents,  unused
      filters,  and resin cartridges.  At aminimum,  one complete sampling train
      will  be assembled in the field staging area,  taken to the sampling area,
      and leak-checked  at the beginning  and  end of the testing  (or for the same
      total number of times as the actual  test train).  The filter housing and
      probe of  the blank train will be heated during  the  sample  test.  The train
      will  be recovered as if it  were  an actual test sample.  No gaseous sample
      will  be passed through the sampling train.

            8.1.3       Laboratory Reagent  Blanks  (LRBs).   An  attempt  may be
      made to determine  if  the laboratory reagents  used in section 7.2 caused
      contamination. They should be analyzed  by the procedures  in section 7.4.
      The  administrator  will  determine whether  the laboratory  blank  reagent
      values can  be used  in the  calculation of the stationary  source  test
      results.

      8.2   Quality Control  Samples.    The  following  quality  control  samples
should be  analyzed.   All  appropriate Chapter One  quality  control  procedures
should be followed.

            8.2.1       ICP-AES analysis.   Follow the  quality control shown in
      Chapter One and Section 8 of Method 6010.

            8.2.2       Direct aspiration and/or graphite furnace AAS analysis
      for antimony, arsenic, barium, beryllium, cadmium,  copper,  chromium, lead,
      nickel, manganese, mercury,  phosphorus, selenium,  silver, thallium, and
      zinc.  All  samples  should  be analyzed in duplicate.    Perform  a post-
      digestion spike on at  least one front-half sample and  one  back-half sample
      or one combined sample.   If recoveries of less than 75 percent or greater
      than 125  percent  are obtained for the post-digestion spike, analyze each
      sample by the method of standard additions.

            8.2.3       Cold vapor AAS analysis for mercury. All  samples should
      be analyzed  in duplicate.   Perform  a  post-digestion  spike on one sample
      from the  nitric acid  impinger portion  ( must  be within 25% or samples must
      be analyzed by the method of standard additions).
9.0  METHOD PERFORMANCE

       9.1  To  ensure  optimum sensitivity in obtaining  the  measurements,  the
concentrations of target metals in the solutions are suggested to be at least ten
times the  analytical  detection  limits.   Under  certain  conditions,  and  with
greater care in the analytical procedure, this concentration can be as low as
approximately three times the analytical  detection limit.  In all cases, on at
least one sample (run) in the source test and for each metal analyzed, repetitive
analyses, method of standard additions (MSA), serial  dilution, or matrix spike
addition, etc., shall  be used to establish the quality of the data.
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      9.2  Actual in-stack method detection limits will  be determined based on
actual source sampling parameters and analytical  results  as described above.  If
required, the method in-stack detection limits can be made more sensitive than
those shown in Table  2 for a specific test by using one or more of the following
options:

      o     A 1-hour sampling run collects  a stack gas sampling volume of about
            1.25 m3.   If the  sampling time  is  increased  and 5 m3 are collected,
            the  in-stack  method  detection  limits  would be  one fourth  of the
            values shown  in  Table  A-l  (i.e., the method  is four  times more
            sensitive than an hour run).  Larger sample  volumes would make the
            method more sensitive again.

      o     The  in-stack  detection limits  assume that  all  of the  sample is
            digested (with exception of the aliquot for  mercury) and the final
            liquid volumes for analysis are 300 ml for the front half (Fraction
            1) and 150 ml  for  the back half  (Fraction  2A).   If the volume  of the
            front half is concentrated  from 300 ml to 30 ml, the front half in-
            stack detection limits would be one tenth of the values shown above
            (ten times more sensitive).  If the back-half volume is concentrated
            from  150 ml  to  25 ml, the  in-stack detection limits  would  be one
            sixth of the above values.   Matrix effects checks are necessary on
            analyses of samples  and typically are of greater significance for
            samples that have been concentrated to less  than the normal   sample
            volume.   Reduction  to a volume  of  less  than 25 mL may not allow
            redissolving of the residue and may increase interference by other
            compounds.

      o     When  both of  the  above  two improvements  are used on one sample at
            the  same time, the resultant improvements are multiplicative.  For
            example, where stack gas volume is increased  by a factor of five and
            the  total liquid sample digested volume of  both the front and back
            halves is reduced by  factor of six,  the  in-stack method detection
            limit is reduced by a factor of thirty (the  method is thirty times
            more  sensitive).

      o     Conversely, reducing stack  gas  sample  volume and increasing  sample
            liquid volume will increase detection limits  (i.e.,  the method would
            be less sensitive).  The front-half and back-half samples (Fractions
            1A plus  2A) can be combined proportionally  prior to analysis.  The
            resultant liquid volume (excluding the mercury fractions, which must
            be  analyzed  separately)  is  recorded.   Combining  the  sample as
            described does not allow determination (whether  front  or back half)
            of where in the train the  sample was  captured.  The  in-stack  method
            detection limit  then  becomes  a single value for all metals  except
            mercury, for which the contribution  of the mercury  fraction must be
            considered.

      o     The  above discussion  assumes no blank correction.
                                   0060 - 28                      Revision 0
                                                                  January 1995

-------
      9.3  Precision.   The  precision measurements (relative standard deviation)
for  each  metal  detected  in  a  method  development  test  at  a  sewage  sludge
incinerator, are as follows:  Sb  (12.7%), As (13.5%),  Ba  (20.6%),  Cd  (11.5%), Cr
(11.2%), Cu  (11.5%),  Pb (11.6%),  P  (14.6%), Se  (15.3%),  Tl  (12.3%),  and Zn
(11.8%).  The  precision for nickel was  7.7% for another test  conducted  at a
source  simulator.   Beryllium,  manganese,  and silver were not  detected  in the
tests;  however,  based  on the analytical sensitivity of the  ICP-AES for these
metals, it  is assumed that  their  precision values should  be similar to those for
the other metals, when detected  at similar levels.

      9.4  Using (1) the  procedures described in this  method,  (2)  the analytical
detection limits listed in  Section 1,  (3)  a volume of 300 ml  for  the front half
and 150 ml  for the back-half samples,  and  (4)  a  stack gas sample  volume of 1.25
m3,  the corresponding in-stack method detection limits are presented  in Table A-2
and calculated as shown:

            A x B = D
              C
      where:

            A =   analytical detection limit, ug/mL.
            B =   volume of sample prior to aliquot  for analysis, ml.
            C =   stack  sample volume, dscm (dsm3).
            D =   in-stack detection limit, ug/m3.

Values  in Table A-2 are calculated for the  front and  back half and/or the total
train.
10.0  REFERENCES

1.    Method 303F in Standard Methods for the Examination of Water Wastewater,
15th Edition, 1980.  Available from the American Public Health Association, 1015
18th Street, N.W., Washington, D.C. 20036.

2.    EPA Methods 6010,  7000,  7041, 7060, 7131, 7421, 7470,  7740,  and 7841, Test
Methods for  Evaluating  Solid  Waste:   Physical/Chemical Methods.   SW-846 Third
Edition.  September 1988.   Office of  Solid  Waste and Emergency Response, U.S.
Environmental Protection Agency,  Washington, D.C. 20460.

3.    EPA Method 200.7,  Code of Federal  Regulations,  Title 40, Part 136, Appendix
C.  July 1,  1987.

4.    EPA Methods 1 through 5, Code of Federal Regulations, Title 40, Part 60,
Appendix A,  July 1, 1987.

5.    EPA Method 12, Code of Federal Regulations, Title 40,  Part 60, Appendix A,
July 1, 1987.
                                   0060 -  29                      Revision 0
                                                                  January 1995

-------
6.    ASTM Standard  Method  D2986-71,  available from  the  American Society for
Testing and Materials, 1916 Race Street, Philadelphia, PA 19103.
                                   0060 - 30                       Revision 0
                                                                   January 1995

-------
Metal
              TABLE 2.   IN-STACK METHOD DETECTION LIMITS  (ug/m3)
                   FOR TRAIN FRACTIONS  USING  ICP-AES  AND AAS
Front Half
Fraction 1
Probe and Filter
BacKHalf
Fraction 2
Impingers 1-3
Back Half
Fraction 3
Impingers 4-5
Total Train
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Lead
Manganese
Mercury
Nickel
Phosphorus
Selenium
Silver
Thallium
Zinc
7.7 (0.7)*
12.7 (0.3)*
0.5
0.07 (0.05)*
1.0 (0.02)*
1.7 (0.2)*
1.4
10.1 (0.2)*
0.5 (0.2)*
0.6**
3.6
18.0
18.0 (0.5)*
1.7
9.6 (0.2)*
0.5
3.8 (0.4)*
6.4 (0.1)*
0.3
0.04 (0.03)*
0.5 (0.01)*
0.8 (0.1)*
0.7
5.0 (0.1)*
0.2 (0.1)*
3.0** 2.0**
1.8
9.0
9.0 (0.3)*
0.9
4.8 (0.1)*
0.3
11.5 (1.1)*
19.1 (0.4)*
0.8
0.11 (0.08)*
1.5 (0.03)*
2.5 (0.3)*
2.1
15.1 (0.3)*
0.7 (0.3)*
5.6**
5.4
27.0
27.0 (0.8)*
2.6
14.4 (0.3)*
0.8
( )* Detection limit when analyzed by GFAAS.
  ** Detection limit when analyzed by CVAAS, estimated for back-half and total
     train.

NOTE:Actual method in-stack detection limits will be determined based on
     actual source sampling parameters and analytical results as described
     earlier in this section.
                                  0060  - 31
                                                     Revision  0
                                                     January 1995

-------
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                                              METHOD  0060
                         DETERMINATION OF METALS  IN  STACK  EMMISIONS
6 1.4.4 Alternatively, Hg can
be measured in seperate train
     by Method 101A.
                                         6.1.1  - 6.1.2 Prepare sampling train
                                           glassware, filter (if requires) and
                                         calibrate sampling train components.
  6.1.3 - 6.1.4.3 Setup sampling train as
    shown in Fig. A-1. Add reagents to
     appropriate impingers and retain
   volumes  of each reagent for reagent
  blands. Omit impingers  No. 4, 5,  and 6
(1  empty impinger and 2 KMNO  impingers)
          if Hg is  not required.
                                      6.1.5 - 6.1 .7 Leak check sampling train,
                                      perform sampling operation and calculate
                                                percent isokenetic.
                                    7.1.1 - 7.1.4 Parti ally disassemble sampling
                                      train, cap-off sample train inlets, transfer
                                             assemble to cleanup area.
                                       7.1.5 Sample Recovery: Recover filter
                                       and place in container No. 1  (7.1.5.1)
                                        if particulate emissions are  required
                                       (7.1.5.2-7.1.5.2.4) rinse probe nozzle
                                        and fittings with acetone or water,
                                       collect rinses, label as container No. 2.
                                       7.1.5.3  If particulate emissions are not
                                       required, rinse probe liner, nozzle, and
                                       filter with 100 ml 0.1 N HN03, collect
                                          rinses, label as container No. 3.
                                                0060  -  35
                                                        Revision  0
                                                     January  1995

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                                        METHOD  0060  (CONT.)
                       DETERMINATION OF  METALS  IN  STACK EMISSIONS
     7.1.5.4 Measure volume of liquid
     in impingers 1-3, rinse impingers,
      combine liquids and rinses into
            container No. 4.
7 1  5.5 -  7  1.5.6 Measure volume of liquid
  in impinger 4, combine with rinses into
 container 5A  Measure volume of KMnO
 impingers (5&6). combine with rinses into
 container  5B. If visible deposits remain,
  (7 1 5.5.2I rinse with 8N HCL, collect
    rinses,  label as container No. 5C.
     7  1.5.6 Transfer silica gel from
     impingr 7, to container No. 6,
            record weight.
     7.2  Sample Preparation: Prepare
    filter (7.2.1). rinses (7 2.2-7.2.3)
      and impinger solutions (7.2.4-
  7.2.5)  for analysis by the appropriate
      sample preparation procedure:
       Method 3010/3015/3050/
            3051/3055 (7.2).
      7 2.6 Weigh spent silica gel
       if not weighed in the field.
 7.3 Instrument Calibration:  Calibrate
appropriate instrumentation  (ICP-AES/
AAS direct aspiration and/or graphite
  furnace/cold  vapor AAS mercury
  analyses prior to sample analysis).
  7.4 Sample Analysis: 7.4.1 - 7.4.7
 Analyze the seven individual samples
  from  each sampling train using the
 appropriate analytical method. Follow
  all QC procedures in Section 8.0.
 7.5 Calculations: Calculate dry gas
 volume, water vapor content, stack
  gas velocity,a  nd metals content
  using equations or references in
           7.5.1 -  7  5.7.
                                              0060  -  36
                                 Revision  0
                              January  1995

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                                 METHOD 0061

                DETERMINATION OF HEXAVALENT CHROMIUM EMISSIONS
                            FROM STATIONARY  SOURCES
1.0   SCOPE AND APPLICATION

      1.1   This method provides procedures  for  the determination of hexavalent
chromium  (Cr+6)  emissions  from hazardous waste  incinerators,  municipal  waste
incinerators, municipal waste combustors,  and  sewage  sludge incinerators.  With
the approval of the Administrator, this method may also be  used  to measure total
chromium.  The sampling train, constructed of Teflon components, has only been
evaluated  at  temperatures  of  less  than 300°F.   Trains  constructed  of  other
materials, for testing at higher temperatures, are currently being evaluated.

      1.2   Range:  If employing a preconcentration procedure,  the lower limit
of the detection range can be  extended  to  16  nanograms per dry standard cubic
meter (ng/dscm)  with  a  3  dscm gas sample (0.1  ppb  in  solution).   With sample
dilution,  there  is no  upper  limit.    Follow  your  manufacturer's  specific
instructions on employing the preconcentration procedure for these analyses.

2.0   SUMMARY OF METHOD

      2.1   For  incinerators and  combustors,  the  Cr+6 emissions are collected
isokinetically from the source:   To eliminate  the  possibility of Cr + 6 reduction
between  the  nozzle and impinger,  the emission  samples  are  collected with a
recirculatory train where the impinger reagent is continuously recirculated to
the nozzle.  Recovery procedures include a post-sampling purge and filtration.
The impinger train  samples are analyzed for Cr+6 by an  ion chromatograph equipped
with  a  post-column reactor  and  a  visible  wavelength  detector.    The  IC/PCR
separates the Cr+6  as chromate  (Cr04=)  from other diphenylcarbazide reactions
that occur in the post-column reactor.  To  increase sensitivity  for trace levels
of chromium, a preconcentration system may also  be used in conjunction with the
IC/PCR.

3.0   INTERFERENCES

      3.1   Components  in  the  sample mat'rix  may  cause  Cr+6  to  convert  to
trivalent chromium  (Cr+3) or  cause  Cr+3 to  convert  to Cr+e.   A post-sampling
nitrogen purge and  sample  filtration are  included to  eliminate many  of  these
interferences.

      3.2   The  chromatographic  separation  of  Cr+6  using ion chromatography
reduces  the  potential  for  other  metals  to  interfere with   the  post-column
reaction.  For the  IC/PCR analysis,  only compounds  that coelute with  Cr+e and
affect the diphenylcarbazide  reaction will  cause interference.

      3.3   Sample cross-contamination that  can  occur when high-level  and low-
level  samples or standards are  analyzed alternately  is eliminated  by  thorough

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purging of the sample loop.   Purging  can  easily  be  obtained  by increasing the
injection volume of the samples to ten times the size of the  sample loop.

4.0   APPARATUS

      4.1   Sampling Train:   Schematics  of the  recirculatory  sampling  trains
employed in this method are shown in Figures 1 and 2.  The recirculatory train
is readily assembled from commercially available components. All  portions of the
train in contact with the sample are either glass,  quartz, Tygon, or Teflon, and
are to be cleaned  as  per Section  6.0.  The metering system is  identical to that
specified by Method 5 (see  section  3.8.1);  the  sampling  train  consists  of the
following components:

            4.1.1   Probe Nozzle:   Glass or Teflon with a sharp,  tapered leading
      edge.  The  angle  of  taper  shall be < 30° and  the  taper  shall  be  on the
      outside to preserve a constant internal  diameter.  The probe nozzle shall
      be of the button-hook or elbow design, unless otherwise specified  by the
      Administrator.   A range of nozzle sizes suitable for isokinetic sampling
      should be available,  e.g.,  0.32 to  1.27  cm  (1/8 to  1/2 in.)  -- or  larger
      if higher volume sample  trains are used --  inside diameter  (ID) nozzles in
      increments  of  0.16  cm   (1/16  in.).   Each nozzle  shall  be  calibrated
      according to the procedures outlined in Section 7.1.1.

            4.1.2  Teflon Aspirator or Pump/Sprayer Assembly:   Teflon aspirator
      capable of recirculating absorbing reagent at 50 mL/min while operating at
      0.75 cfm.  Alternatively, a pump/sprayer assembly may be  used instead of
      the Teflon aspirator. A Teflon union-T  is connected behind the nozzle to
      provide the absorbing reagent/sample gas mix; a peristaltic pump is used
      to recirculate the absorbing reagent at a flow rate of at least 50 mL/min.
      Teflon fittings, Teflon  ferrules,  and Teflon  nuts  are  used  to connect a
      glass or Teflon nozzle,  recirculation  line,  and sample line to the  Teflon
      aspirator or union-T.   Tygon,  C-flex  or other suitable  inert tubing for
      use with peristaltic pump.

            4.1.3  Teflon Sample Line:  Teflon, 3/8" ID, of suitable length to
      connect aspirator  (or T-union) to first Teflon impinger.

            4.1.4  Teflon Recirculation  Line:  Teflon, 1/4" O.D. and 1/8" I.D.,
      of suitable length to connect first impinger to aspirator (or T-union).

            4.1.5  Teflon  Impingers:   Four  Teflon impingers;  Teflon tubes and
      fittings, such as  made by Savillex*, can be used to  construct impingers 2"
      diameter  by 12"  long,  with  vacuum-tight  3/8" O.D. Teflon  compression
      fittings.  Alternatively, standard  glass impingers  that have been Teflon-
      lined, with  Teflon stems and  U-tubes,  may be used.   Inlet  fittings on
      impinger top to be bored through to accept 3/8"  O.D.  tubing as impinger
      stem.  The second  and third  3/8" OD Teflon stem has a  1/4"  OD Teflon tube,
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                            TEFLON IMPINGERS

Figure 1   Schematic  of  recirculatory  impinger train with  aspirator  assembly.
                                  0061  -  3
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                            TEFLON IMPINGERS

Figure 2   Schematic  of  recirculatory  impinger train with  aspirator  assembly.
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2" long, inserted at its impinger stem should extend to 2" from impinger
bottom,  high  enough  in the  impinger reagent  to prevent  air from  entering
recirculating line; the second and third  impinger stems  should extend to 1/2"
from impinger bottom.   The  first impinger should include a  1/4"  O.D.   Teflon
compression fitting for recirculation line.   The fourth  impinger  serves as a
knockout impinger to trap solution carried over from the previous impingers.

            NOTE: Mention of trade names or specific product does not constitute
            endorsement by the Environmental  Protection Agency.

            4.1.6  Glass Impinger:  Silica gel  impinger, Vacuum-tight impingers,
      capable of containing  400 g. of silica gel,  with compatible fittings.  The
      silica gel impinger will have a modified stem (1/2" ID at tip of stem).

            4.1.7  Thermometer, (identical to that specified  by  Method  5)  at the
      outlet of the silica  gel  impinger,  to monitor the exit temperature  of the
      gas.

            4.1.8  Metering System,  Barometer,  and  Gas Density Determinations
      Equipment:   Same as Method  0010,  Section  4.1.3.9  through  4.1.3.11,
      respectively.

      4.2   Sample Recovery: Clean all items for sample handling or storage with
10% nitric acid solution by soaking,  where possible, and rinse thoroughly with
reagent water before use.

            4.2.1  Nitrogen Purge Line:   Inert  tubing  and fittings capable of
      delivering 0 to  1  scf/min (continuously  adjustable)  of nitrogen gas  to the
      impinger train from a  standard gas cylinder (See  Figure  3).  Standard 3/8-
      inch Teflon regulator and needle valve  may be used.

            4.2.2  Wash Bottles:   Two polyethylene wash  bottles,  for reagent
      water-nitric rinse solution.

            4.2.3  Sample Storage Containers:  Polyethylene, with leak-free screw
      cap, 500-mL or 1000-mL.

            4.2.4  1000-mL Graduated Cylinder and Balance.

            4.2.5  Plastic  Storage Containers:   Air tight containers  to store
      silica gel.

            4.2.6  Funnel and Rubber Policeman: To aid in transfer  of silica gel
      from impinger to storage container; not  necessary if silica gel is weighed
      directly in the impinger.
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                TEFLON IMPINGERS

 Figure 3  Schematic  of post test nitrogen purge system
LHTTTTTTO
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      4.3  Sample Preparation for Analysis:  Sample preparation prior to analysis
includes purging  the sample train  immediately  following the  sample  run,  and
filtering the recovered sample to remove particulate matter immediately following
recovery.

            4.3.1  Beakers, Funnels, Volumetric Flasks, Volumetric Pipets,  and
      Graduated Cylinders:  Assorted sizes, Teflon  or glass, for preparation of
      samples,  sample dilution,  and  preparation  of  calibration  standards.
      Prepare initially following procedure described in Section 5.1.3 and rinse
      between use with 0.1 M HN03 and reagent water.

            4.3.2  Filtration Apparatus:  Teflon, or equivalent,  for filtering
      samples, and Teflon filter holder.  Teflon impinger components have been
      found to  be  satisfactory as  a sample  reservoir  for pressure  filtration
      using nitrogen.

      4.4  Ion Chromatograph:  Refer to Section 4.0 of Metttod  7199 for instrument
and equipment specifications.

            4.4.1  Preconcentrator:   System in-line  with the ion chromatorgaph.

                                      OR

      4.5  Sample preconcentration system:  A  high performance  ion chromatograph
(HPIC) non-metallic column with acceptable anion retention characteristics  and
sample loading rates as described in the analytical method.

5.0  REAGENTS

      5.1   All  reagents  should, at a minimum, conform  to  the specifications
established by  the  Committee on Analytical  Reagents of  the American  Chemical
Society, where such specifications  are available.  All prepared reagents should
be checked by IC/PCR analysis for Cr+6 to assure  that contamination is below the
analytical    detection   limit    for   direct    injection   or,   if   selected,
preconcentration.    If total  chromium is  also  to be determined,  the  reagents
should  also  be  checked  by  the  analytical technique  selected to assure  that
contamination is below the analytical detection limit.

      5.2  Sampling.

            5.2.1   Reagent water:  Reagent water shall be  interferences free.
      All  references  to  water  in  the  method  refer to  reagent  water  unless
      otherwise  specified.   A  definition  of  reagent  water  can  be found  in
      Chapter One.

            5.2.2    Potassium  Hydroxide,  0.1  M:    Add  5.6 gm  of  KOH(s)  to
      approximately 900 ml of reagent water and let  dissolve.  Dilute to 1000 ml
      with reagent water.
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            NOTE: At sources with high concentrations of acids and/or S02,  the
            concentration of KOH  should be increased to 0.5 M to insure that the
            pH of the solution is above 8.5 after sampling.

            5.2.3  Silica Gel  and Crushed Ice:  Same  as Method 5, Sections 3.1.2
      and 3.1.4, respectively.

      5.3  Sample Recovery:  The reagents used in sample recovery are as follows:

            5.3.1  Water:  Same as subsection 5.2.1.

            5.3.2   Nitric  Acid,  0.1 M:   Add 6.3 mL of  concentrated  HN03  (70
      percent)  to  a  graduated cylinder  containing approximately  900 ml  of
      reagent water.  Dilute to 1000 ml with reagent water,  and mix well.

            5.3.3  pFMndicator Strip:  pH indicator capable of determining pH
      of solution between the pH  range of 7 and 12,  at 0.5  pH intervals.

      5.4  Sample Preparation

            5.4.1  Reagent water:  Same as subsection 5.2.1.

            5.4.2  Nitric Acid, 0.1 M:  Same as subsection  5.3.2.

            5.4.3  Filters:  Acetate membrane,  or equivalent, filters with 0.45
      micrometer or smaller pore  size to remove insoluble material.

      5.5  Analysis

            5.5.1  Refer  to Section  5.0  of  Method 7199  for instruction  on
      preparation of analytical reagents.

      5.6  Performance Audit Sample:  A performance audit  sample should analyzed
in conjunction  with  the  samples.  The audit  sample should  be  prepared  in  a
suitable sample matrix at a concentration  similar to the  actual field samples.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   Refer to Section 6.0  of Method 7199 for the proper procedures when
collecting, preserving,  and handling samples.

      6.2  If sample preconcentration is used, dropwise  addition of the ammonium
sulfate/ammonium hydroxide buffer may not be appropriate, since the added sulfate
may lead to premature overloading of the column.
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7.0  PROCEDURE

      CAUTION:  Wear Safety Glasses At All  Times During This Test Method.

      7.1   Sampling:   The  complexity  of this method  is  such that  to obtain
reliable results, testers should be trained and experienced with test procedures.

            7.1.1   Sample  Train  Calibration:    Calibrate  the  sample  train
      components according to the indicated  sections of Method 5:  Probe Nozzle
      (Section 5.1); Pitot  Tube  (Section 5.2);  Metering System  (Section 5.3);
      Temperature  Gauges   (Section  5.5);  Leak-Check  of  the Metering  System
      (Section 5.6); and Barometer (Section  5.7).

            7.1.2  Pretest Preparation:  All components shall be maintained and
      calibrated according  to the procedures  described  in  APTD-0576,  unless
      otherwise specified herein.  Rinse all  sample train  components from the
      glass nozzle  up  to the silica gel  impinger and sample containers with hot
      tap water followed by washing with hot  soapy  water.  Next, rinse the train
      components and sample containers  three  times with tap water  followed by
      three rinses  with reagent water.   All  the components and container should
      then be soaked overnight, or a minimum of 4  hours, in a 10 % (v/v) nitric
      acid solution, then  rinsed three times with  reagent water.    Allow the
      components to air dry prior to  covering all openings  with Parafilm,  or
      equivalent.

            7.1.3  Preliminary Determinations:  Same  as Method 5, Section 4.1.2.

            7.1.4  Preparation of Sampling  Train:   Measure 300 ml of 0.1 M KOH
      into  a  graduated  cylinder (or  tare-weighed  precleaned  polyethylene
      container).  Place approximately  140  ml of  the 0.1 M KOH  reagent in the
      first Teflon  impinger.  Split the rest  of the 0.1 M KOH  between the second
      and third Teflon  impingers.   The next  Teflon impinger is left dry.  Place
      a preweighed 200-to 400-g portion of  indicating  silica gel  in the final
      glass impinger.   (For sampling periods in excess of two  hours, or for high
      moisture sites,  400-g of  silica  gel  is  recommended).  Retain  reagent
      blanks of the 0.1 M  KOH  equal to the volumes used with the field samples.

            7.1.5  Leak-Check Procedures: Follow the leak-check procedures given
      in Method 5.  Section 4.1.4.1 (Pretest  Leak-Check), Section 4.1.4.2 (Leak-
      Checks  during  the  Sample Run),  and  Section 4.1.4.3 (Post-Test  Leak-
      Checks).

            7.1.6  Sampling Train Operation:   Follow the  procedures  given  in
      Method 5,  Section  4.1.5.  The sampling train  should be iced  down with
      water and ice to insure heat transfer  with the Teflon impingers.

            NOTE: If the gas to be sampled  is  above  200°F,  it may be necessary
            to wrap three  or four  feet.  If  the Teflon sample and recirculating
            lines  inside  the  ice bath  to keep  the  recirculated reagent cool
            enough  so  it does not turn to steam.


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            For each run, record the data required on a data sheet such as the
      one shown  in  Figure  5-2 of Method 5.   At  the end of  the  sampling run,
      determine the pH of the  reagent in the first impinger using a pH indicator
      strip.  The pH of  the solution shall  be greater  than  8.5.   If the pH is
      not above 8.5, discard  the solution.   Prepare  a  clean sampling train as
      described above using 0.5 M KOH instead of  0.1 M KOH, as noted in Section
      5.2.2.   Leak-check and operate  the  sampling train as  described above.
      Repeat the sampling run.

            7.1.7  Calculation of Percent Isokinetic: Same as Method 5, Section
      4.1.6.

      7.2  Post-test Nitrogen  Purge.  The nitrogen  purge is used as a safeguard
against the conversion of hexavalent chromium to  the trivalent oxidation state.
The purge is effective in the  removal of S02 from  the impinger contents.  Attach
the nitrogen purge  line to the input of the  impinger train.  Check to insure the
output of the impinger train  is  open, and that the recirculating line is capped
off.  Open the nitrogen gas  flow slowly  and adjust the delivery rate to 10 L/min.
Check the recirculating  line  to insure that the pressure is not  forcing the
impinger  reagent out  through  this  line.    Continue  the  purge  under  these
conditions for one-half hour periodically checking the  flow rate.

      7.3   Sample  Recovery:    Begin  cleanup procedures  as  soon  as  the  train
assembly has been purged  at the end of the sampling run.  The probe assembly may
be  disconnected  from  the  sample train prior  to  sample  purging.    The  probe
assembly should  be  allowed to cool  prior to sample recovery.  Disconnect the
umbilical cord from  the  sample  train.   When the probe assembly can  be safely
handled, wipe off all external  particulate matter  near the tip of the nozzle, and
cap the nozzle  prior to transporting the sample train to a clean up area that is
clean and protected from  the wind and other  potential causes of contamination or
loss of sample.  Inspect the  train  before  and during disassembly  and note any
abnormal conditions.

            7.3.1  Container No. 1 (Impingers 1 through 3):  Disconnect the first
      impinger form  the  second  impinger  and disconnect the  recirculation line
      form the aspirator or peristaltic pump.  Drain the  Teflon  impingers into
      a precleaned graduated cylinder or tare-weighted  precleaned  polyethylene
      sample container and  measure  the  volume of  the liquid to within 1 ml or 1
      gm.  Record the volume of liquid  present as this  information is required
      to calculate the moisture content of the flue gas sample.   If necessary,
      transfer  the  sample  from  the   graduated  cylinder  to   a  precleaned
      polyethylene sample container.  With  reagent water,  rinse  four times the
      insides of the glass  nozzle,  the  aspirator, the sample and  recirculation
      lines, the impingers, and  the connecting tubing, and  combine  the rinses
      with the impinger solution in the sample container.

            7.3.2    Container No.  2  (HN03  rinse  optional  for total  chromium):
      With 0.1 M HN03,  rinse  three times the entire train  assembly,  from the
      nozzle to  the fourth impinger,   and  combine  the  rinses into  a separate
      precleaned polyethylene sample  container  for  possible total  chromium


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      analysis.  Repeat the rinse procedure a final  time with reagent water, and
      discard  the  water rinses.   Mark  the Height of the  fluid level  on the
      container or, alternatively if a balance is available, weigh the container
      and  record the  weight  to permit  determination of  any  leakage  during
      transport.  Label the container clearly to identify its contents.

            7.3.3   Container  No.  3  (Silica Gel):   Note  the  color  of the
      indicating  silica gel   to determine  if  it  has  been completely  spent.
      Quantitatively transfer the silica gel from its impinger to the original
      container, and seal  the  container.  A funnel and a rubber policeman may be
      used to  aid  in  the  transfer.  The small  amount of particulate that may
      adhere to  the  impinger  wall  need not  be  removed.   Do not use water or
      other liquids to transfer the silica  gel.  Alternatively,  if a balance is
      available in the field,  record  the weight  of  the spent silica gel (or the
      silica gel plus impinger) to the nearest 0.5 g.

            7.3.4  Container  No 4  (0.1  M KOH Blank):  Once  during  each field
      test, place a volume of reagent equal to the volume placed in  the  sample
      train  into a  precleaned polyethylene  sample  container,  and  seal  the
      container.   Mark the  height of the fluid  level  on  the  container or,
      alternatively if  a  balance is  available,  weigh the container  and  record
      the weight to permit determination of any leakage during transport.   Label
      the container clearly to identify its contents.

            7.3.5  Container No. 5 (reagent  water Blank):   Once during each field
      test, place  a  volume  of  reagent water  equal  to the volume employed to
      rinse the  sample  train  into  a  precleaned  polyethylene  sample  container,
      and  seal  the container.   Mark  the  height  of the fluid level  on the
      container or, alternatively if a balance is available, weigh the container
      and  record the  weight  to permit  determination of  any  leakage  during
      transport.  Label the container clearly to identify its contents.

            7.3.6  Container No. 6 (0.1 M HN03 Blank):   Once  during  each field
      test if total chromium is to be determined, place a volume of 0.1  M HN03
      reagent equal to  the  volume employed to  rinse the sample train  into  a
      precleaned polyethylene sample container,  and  seal the  container.   Mark
      the height  of  the fluid  level on  the container or,  alternatively  if  a
      balance is available, weigh the container  and record the weight to  permit
      determination of any  leakage  during  transport.   Label   the  container
      clearly to identify its contents.

      7.4  Sample Preparation:   For determination of  Cr+6, the sample should be
filtered immediately following recovery to remove any insoluble matter.  Nitrogen
gas may be used as  a pressure assist to  the  filtration process (see Figure Cr  -
4).  Filter the entire impinger  sample through a 0.45 micrometer acetate  filter
(or equivalent),  and collect the filtrate in a 1000-mL  graduated cylinder.   Rinse
the sample container  with reagent water three  separate  times  and  pass  these
rinses through  the filter, and add the rinses to  the sample filtrate.   Rinse the
Teflon reservoir with reagent water three separate times  and  pass these  rinses
through the filter, and  add the rinses to the sample.  Determine the final  volume


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of the filtrate  and  rinses and return them to  the  rinsed polyethylene sample
container.   Label  the  container clearly to identify  its  contents.   Rinse the
Teflon reservoir once  with  0.1  M  HN03  and  once  with reagent water and discard
these rinses.  If total chromium is to be determined, quantitatively recover the
filter and residue  and  place them in a vial.  (The acetate filter may be digested
with 5 ml of 70% nitric acid; this digestion solution may then be diluted with
reagent water for total chromium analysis by inductively coupled plasma atomic
emission or graphite furnace atomic absorption spectrometric methods.)

            NOTE:  If  the  source  has  a large  amount  of particulate  in the
            effluent stream, testing teams  may wish  to filter the sample twice,
            once  through  a 2-5  micrometer  filter,   then  through  the  0.45
            micrometer filter.

            7.4.1  Container No.  2  (HN03 rinse,  optional  for total  chromium):
      This sample  shall  be  analyzed  in accordance with  the selected procedure
      for total chromium analysis.  At a minimum, the sample should be subjected
      to a digestion procedure sufficient to solubilize all chromium present.

            7.4.2  Container 3  (Silica  Gel):  Weigh  the  spent silica gel to the
      nearest 0.5 g using a balance.  (This step may be conducted  in the field.)

      7.5    Sample  Analysis:   The  Cr+6 content  of  the  sample filtrate   is
determined by  ion  chromatography  coupled with  a post  column reactor (IC/PCR).
Method 7199 should be used for this analysis.  To increase  sensitivity for  trace
levels of chromium, a preconcentration system is  also used in conjuction with the
IC/PCR.   Prior to  preconcentration  and/or  analysis,  all field samples will  be
filtered  through  a 0.45  urn filter.   This fitration  should be conducted just
prior to sample  injection/analysis.

            7.5.1       Preconcentration:  The preconcentration is accomplished
      by  selectively retaining  the analyte on  a  solid  absorbent,  followed  by
      removal of the analyte from the  absorbent.

Refer to Section 7.0 of Method 7199 for  the proper sample  analysis protocol.

      7.6  Calculations

            7.6.1   Dry Gas Volume:   Using the data  form the  test,  calculate
      Vm(std),  the dry gas  sample volume  at standard conditions as outlined  in
      Section 6.3 of Method 5.

            7.6.2  Volume  of Water Vapor and Moisture Content:  Using the data
      form the test, calculate Vw(8td) and Bws, the  volume of water vapor and the
      moisture content of the stack gas, respectively,  using Equations 5-2 and
      5-3 of Method  5.

             7.6.3    Stack Gas  Velocity:   Using  the  data  form  the  test and
      Equations  2-9  of Method 2, calculate the  average  stack gas velocity.
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            7.6.4  Total ug Cr+6 Per Sample.  Calculate as described below:

            m = (S-B) x Vls x d


            Where:

            m = Mass of Cr+e in the sample, ug,
            S = Concentration of Sample, ug Cr+6/mL,
            B = Concentration of blank, ug Cr+6/mL,
          V|8  = Volume of sample after filtration, ml, and,
            d = Dilution factor (1 if not diluted).

8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for the appropriate quality control procedures.

9.0   METHOD PERFORMANCE

      9.1   Sensitivity:  A minimum detection limit of 8 ng/dscm with a 3 dscm
gas sample can be achieved by preconcentration (0.05 ppb in solution).  Follow
instrument manufacturers instructions for sample preconcentration.

      9.2   Precision:  The  precision of the IC/PCR with sample preconcentration
is  5  to  10  percent.    The  overall precision  for  sewage  sludge  incinerators
emitting 120 ng/dscm of Cr+e and 3.5 ug/dscm of total chromium is 25% and 9% for
Cr+6 and total chromium, respectively; for hazardous waste incinerators emitting
300 ng/dscm of Cr+e it is 20%.

      9.3   Refer to Section 9.0 of Method 7199 for additional analytical method
performance information.


10.0  REFERENCES

1.    Carver, Anna C.;  Laboratory  and  Field  Evaluation  of the Methodology for
Determining Hexavalent  Chromium  Emissions from  Stationary Sources.    EPA No.
600/3-92/052, February 1992.
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                           METHOD  0061
 DETERMINATION  OF  HEXAVALENT  CHROMIUM  EMISSIONS
                   FROM  STATIONARY  SOURCES
  71.1 Calibrate sample train
  components according to
  Section 5 of Method S.
           I
7. 1 2 Decontaminate all sample
train components and containers.
Allow components to air dry
i
 7 1 4 Set up sample collection
 train, connect Teflon impingers
 and glass impmger in series,
 add reagents.
           i
 Place 200 - 400 grams of
 preweighted silica gel in final
 glass impmger
           I
  7.1 5 Perform teak-chec*
  procedures given m Section 4
  of Method S.
           I
 7 1 .6 Perform sampling run
 following procedures given in
 Mettod 5, Section 4.
At the end of the sampling run
check the pH of the first Impmger
                       Yas
Discard solution, dean sampling
equipment, add 0 SN KOH to
impingers instead of 0 1 N KOH.
Leak check system and repeat
sampling run
                                     7 1 7 Calculate Percent IsoMnedc.
                                      7 2 Attach nitrogen purge to
                                      input of sampling tram, purge
                                      system lor 30 mm at lOL/mm.
I
                                               7 3 Disconnect sample tram and
                                               move to cleanup and sample
                                               recovery area.
                                     7 3 1 Disconnect impingers,
                                     transfer and measure volume of
                                     liquid m impingers 1 - 3, rinse
                                     sampling components and combine
                                     with impmger solutions. Label
                                     as container No.  1
                                     7 3.2 (Optional for total chromium)
                                     Rinse entire sampling tram with
                                     0 1 N HNQ up to fourth impmger,
                                     combine nnses, labiei as
                                     container No. 2.
                                     733 Quantitatively transfer silica
                                     gel from last impinger to original
                                     container  If possible, weigh
                                     assembly
                                                           i
                                      73.4-7 3.6 Collect volumes of
                                      reagents equivalent to volumes
                                      used dunng the sampling for
                                      blank analysis
                                      7 4 Sample preparation' Cr*s
                                      Filter entire impmger sample
                                      through 0 45um acetate filter
                                      Rinse container and filtration unit.
                                      combine with filtrate Determine
                                      final volume
                              0061  -  14
                                                                     Revision  0
                                                                     January   1995

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                    METHOD  0061
DETERMINATION  OF HEXAVALENT CHROMIUM  EMISSIONS
         FROM  STATIONARY SOURCES (Cont.)
                                      Recover filter and residue,
                                      digest with 5 ml 70% HNO3,
                                      analyze by ICP/AA
              7 6 Sample Analysis
              Analyze sample filtrate for
              Cr"6 by Method 7199
              (Ion Chromatography)
                     I
             76.1 - 7 6 4 Calculate total
             ug Cr*6 per sample (7 6.4)
                      0061  -  15
Revision  0
January  1995

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                                 METHOD 6010B

            INDUCTIVELY  COUPLED .PLASMA-ATOMIC  EMISSION  SPECTROSCOPY

1.0  SCOPE AND APPLICATION

      1.1   Inductively coupled  plasma-atomic  emission spectroscopy (ICP-AES)
determines  trace elements,  including metals,  in  solution.    The method  is
applicable to all of the  elements  listed  in  Table 1.   All  matrices, including
ground water,  aqueous  samples,   TCLP  and  EP extracts,  industrial  and  organic
wastes,  soils,  sludges,  sediments, and other  solid wastes,  require digestion
prior  to analysis.   Refer  to   Chapter  Three for  the  appropriate digestion
procedures.

      1.2   Table  1  lists the elements  for  which this  method  is applicable.
Detection limits, sensitivity, and the optimum and linear concentration ranges
of the elements  can vary with the wavelength,  spectrometer, matrix  and operating
conditions.  Table 1  lists the recommended analytical wavelengths  and estimated
instrumental detection  limits  for the elements in  clean  aqueous sample matrices.
The  detection  limit  data  may   be used  to  estimate  instrument  and  method
performance for other sample matrices.

      1.3   Users of the method   should state the data quality objectives prior
to analysis and  must document and have  on file the  required initial demonstration
performance data described in the following sections prior to using the method
for analysis.

      1.4   Use  of  this  method  is  restricted   to  spectroscopists  who  are
knowledgeable in the correction of spectral, chemical, and physical  interferences
described in this method.

2.0   SUMMARY OF METHOD

      2.1   Prior to  analysis,  samples must  be solubilized  or  digested using
appropriate Sample Preparation Methods (e.g.  Chapter Three).

      2.2  This  method  describes  multielemental determinations by  ICP-AES using
sequential or simultaneous instruments.  The instrument measures characteristic
emission  spectra by  optical  spectrometry.    Samples   are  nebulized  and  the
resulting aerosol is  transported  to the plasma torch.  Element-specific emission
spectra  are  produced by  a  radio-frequency inductively  coupled  plasma.   The
spectra  are  dispersed  by  a grating spectrometer,  and the intensities  of  the
emission lines are monitored by  photosensitive devices such  as diode arrays or
photomultiplier tube(s).  Background  correction  is  required  for trace  element
determination.  Background must be measured adjacent to analyte lines on samples
during analysis.  The  position selected for the background-intensity measurement,
on either  or both sides  of the  analytical  line, will  be  determined  by  the
complexity of the spectrum adjacent to  the analyte line. The position  used should
be as free as possible  from spectral  interference  and  should reflect  the same
change in background intensity  as  occurs at the  analyte wavelength measured.
Background  correction  is  not required in  cases  of  line  broadening where  a

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background correction measurement would  actually degrade the analytical result.
The possibility of additional  interferences  named  in Section 3.0 should also be
recognized  and appropriate  corrections made;  tests  for  their presence  are
described in Step 8.5.

3.0  INTERFERENCES

      3.1   Spectral  interferences  are caused  by background  emission  from
continuous or  recombination phenomena, stray light  from the line emission of high
concentration   elements,  overlap  of a spectral  line  from another  element,  or
unresolved overlap of molecular band spectra.

            3.1.1    Background  emission  and  stray   light  can  usually  be
      compensated  for by  subtracting  the  background  emission  determined  by
      measurements adjacent to the analyte wavelength  peak.   Spectral  scans of
      samples  or single  element  solutions  in  the  analyte  regions  may  indicate
      when  alternate wavelengths  are  desirable  because of  severe  spectral
      interference.   These  scans will  also show  whether  the  most  appropriate
      estimate of the background emission is provided  by an  interpolation from
      measurements on both sides  of the  wavelength peak or by measured  emission
      on  only  one   side.    The   locations  selected  for  the  measurement  of
      background intensity will  be determined  by the complexity of the  spectrum
      adjacent  to  the   wavelength  peak.    The   locations  used  for  routine
      measurement must be free of off-line spectral  interference (interelement
      or  molecular)  or  adequately  corrected  to  reflect  the  same change  in
      background intensity as occurs at  the wavelength peak.

            3.1.2   Spectral  overlaps  may  be avoided  by  using an  alternate
      wavelength  or  can   be  compensated  by equations   that  correct  for
      interelement   contributions.     Instruments  that  use   equations   for
      interelement correction require the  interfering elements  be  analyzed at
      the same time as the element of interest. When operative and uncorrected,
      interferences will produce false positive determinations and be  reported
      as  analyte  concentrations.   More extensive information  on  interferant
      effects  at various wavelengths and resolutions is  available in reference
      wavelength tables  and books.   Users  may apply interelement  correction
      factors  determined on their instruments with tested  concentration ranges
      to  compensate   (off  line   or  on   line)  for  the  effects  of  interfering
      elements.    Some   potential   spectral   interferences  observed  for  the
      recommended wavelengths are given  in  Table  2.   The  interferences listed
      are only those that occur  between  method analytes.  Only interferences of
      a direct overlap nature are listed.  These overlaps  were observed with a
      single instrument having a working resolution of 0.035 nm.

            3.1.3  When  using  interelement correction factors,  the interference
      is  expressed  as analyte concentration  equivalents  (i.e.   false analyte
      concentrations) arising from  100  mg/L of the  interference element.   For
      example, assume that As is  to  be  determined (at 193.696 nm)  in  a sample
      containing approximately 10 mg/L of Al.  According  to Table 2, 100 mg/L of
      Al would yield a false signal for As equivalent to  approximately  1.3 mg/L.


                                   6010B -  2                       Revision 2
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Therefore, the  presence  of  10  mg/L  of Al  would result in a false signal
for As equivalent to approximately 0.13 mg/L.   The  user is cautioned that
other  instruments  may  exhibit  somewhat different levels  of interference
than those shown in Table 2.  The interference effects must be evaluated
for each  individual instrument since  the intensities will vary.

       3.1.4  Interelement corrections  will vary for the same emission line
among  instruments  because of differences in resolution, as determined by
the  grating,  the  entrance  and exit  slit  widths,  and  by the  order of
dispersion.   Interelement corrections will  also  vary depending upon the
choice of background correction points.  Selecting a background correction
point where an interfering emission  line may appear should be avoided when
practical.  Interelement corrections that constitute a major portion of an
emission signal may not yield accurate data.  Users should not forget that
some samples may contain uncommon  elements  that could contribute spectral
interferences.

      3.1.5    The  interference   effects   must  be evaluated  for  each
individual instrument whether configured as a  sequential  or simultaneous
instrument.   For each  instrument,  intensities will vary not  only with
optical  resolution but  also with  operating conditions  (such  as  power,
viewing  height  and  argon  flow  rate).    When   using  the  recommended
wavelengths, the analyst is required  to determine and document for each
wavelength the effect from referenced interferences (Table 2) as well as
any other suspected interferences that may be  specific to the instrument
or matrix.   The analyst  is required  to utilize  a  computer  routine  for
automatic correction on  all  analyses.

      3.1.6  To determine the appropriate location for off-line background
correction, the  user  must scan the area on either side  adjacent  to  the
wavelength  and record  the  apparent  emission  intensity  from  all  other
method analytes. This  spectral information must be documented and kept on
file.  The location selected for background correction  must be either free
of off-line interelement spectral  interference  or a computer routine must
be used for automatic correction on all determinations.  If a wavelength
other than the recommended wavelength  is used,  the  analyst must determine
and document both the overlapping and nearby spectral interference effects
from  all  method  analytes  and  common  elements  and  provide  for  their
automatic  correction   on all   analyses.   Tests  to determine  spectral
interference  must  be   done  using   analyte  concentrations  that  will
adequately describe the  interference.   Normally,  100 mg/L single element
solutions are sufficient; however, for analytes such as iron that may be
found  at  high  concentration,  a more  appropriate test would  be  to  use a
concentration near the upper analytical range limit.

      3.1.7  Users  of  sequential  instruments must  verify the absence of
spectral interference by scanning over a range of 0.5 nm centered on  the
wavelength of  interest  for several  samples.   The range for  lead,  for
example, would be from  220.6 to 220.1 nm. This  procedure must be repeated
whenever a new matrix is to  be analyzed and when  a new calibration curve
is to  be  prepared.  Samples  that  show an  elevated  background emission

                            6010B  - 3                      Revision  2
                                                            January 1995

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across  the  range may be  background  corrected by applying  a correction
factor  equal  to  the emission adjacent to  the line  or at two  points  on
either  side  of the line  and  interpolating between  them.   An  alternate
wavelength that does not  exhibit  a background shift  or spectral  overlap
may also be used.

      3.1.8    If  the  correction  routine  is operating  properly,  the
determined  apparent  analyte(s)   concentration  from   analysis  of  each
interference solution should  fall within  a specific  concentration range
around  the calibration blank.  The concentration  range is  calculated  by
multiplying the concentration of the  interfering element by the value  of
the correction  factor being  tested  and divided  by  10.   If  after  the
subtraction of the  calibration blank  the  apparent analyte  concentration
outside of this range in either a positive  or negative direction, a change
in the correction factor  of more  than  10% should be suspected.  The cause
of the change should be determined and corrected and the correction factor
updated.  The  interference  check  solutions should be  analyzed  more than
once  to confirm  a  change  has  occurred.    Adequate  rinse   time  between
solutions and before analysis  of  the calibration blank will  assist in the
confirmation.

      3.1.9   When interelement  corrections are applied, their accuracy
should  be verified,  daily,  by  analyzing  spectral  interference  check
solutions.  If the correction  factors tested on a daily  basis are found  to
be  within  the  10% criteria for  5  consecutive  days,  the  required
verification frequency of those factors in compliance may be extended  to
a weekly basis.  Also,  if the  nature of the  samples analyzed is such they
do not contain concentrations of the  interfering elements at the 10 mg/L
level,  daily  verification is not required.   All interelement spectral
correction factors  must   be verified  every six  months and  updated,  if
necessary.  Standard solution  should be inspected  to ensure that there  is
no contamination that may be perceived as  a spectral  interference.

      3.1.10  When interelement corrections are not used, verification  of
absence of interferences   is required.

            3.1.10.1 One method is to use  a computer software routine for
      comparing the determinative data to  limits files for  notifying the
      analyst when  an interfering element  is detected in the sample at a
      concentration that  will produce  either  an  apparent false positive
      concentration, (i.e.,  greater than) the analyte instrument detection
      limit,  or false negative analyte concentration,  (i.e.,  less than the
      lower  control  limit of the  calibration blank  defined for  a  99%
      confidence  interval).

            3.1.10.2  Another method  is to analyze an Interference Check
      Solution(s)  which   contains similar   concentrations  of  the  major
      components of the samples (>10 mg/L)  on a continuing basis to verify
      the absence of effects at the wavelengths selected.  These data must
      be  kept  on  file  with  the  sample  analysis data.    If  the  check
      solution confirms  an  operative  interference that is   > 10%  of the

                            6010B - 4                       Revision 2
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            analyte  concentration,  the analyte  must  be  determined  using  (1)
            analytical  and  background  correction wavelengths   (or  spectral
            regions) free of the  interference, (2) by an  alternative wavelength,
            or  (3) by another documented test procedure.

      3.2    Physical  interferences  are effects  associated  with  the  sample
nebulization and transport processes.   Changes  in viscosity  and surface tension
can  cause  significant  inaccuracies,   especially  in  samples  containing  high
dissolved  solids  or  high acid concentrations.   If physical interferences  are
present, they must be reduced by diluting the sample or by  using  a peristaltic
pump, by using  an  internal standard or  by using a high solids  nebulizer.  Another
problem that can occur with high  dissolved  solids is salt  buildup  at the tip of
the nebulizer,  affecting aerosol  flow  rate  and  causing instrumental drift.  The
problem can be  controlled by wetting the argon prior to nebulization,  using  a tip
washer, using a high  solids  nebulizer or diluting the sample.  Also,  it has been
reported that better  control of the argon flow rate, especially to the nebulizer,
improves instrument performance;  this  is accomplished with the  use of mass flow
controllers.

      3.3    Chemical  interferences   include  molecular  compound  formation,
ionization effects, and solute vaporization  effects. Normally, these effects are
not significant with  the ICP technique, but if  observed, can  be  minimized by
careful selection  of  operating conditions (incident power,  observation position,
and so forth),  by buffering of the sample,  by matrix matching, and by standard
addition procedures.   Chemical interferences are highly dependent on matrix type
and the specific analyte element.

      3.4   Memory  interferences result when  analytes   in  a  previous  sample
contribute to the signals measured in  a new sample.  Memory effects can result
from sample deposition on the uptake tubing  to  the  nebulizer and from the build
up of sample material  in the plasma torch and spray chamber.   The  site where
these effects occur is dependent  on the element and can be  minimized by flushing
the system with  a  rinse blank  between samples.   The  possibility  of  memory
interferences should be recognized within an analytical  run  and suitable rinse
times should be used  to reduce them.  The rinse  times necessary  for a particular
element must be estimated prior to analysis.  This may be achieved  by aspirating
a standard containing elements at a concentration ten times  the usual amount or
at the top  of  the linear dynamic range.  The  aspiration  time  for this  sample
should be the same as a normal sample analysis period,  followed by analysis of
the rinse blank at designated intervals.  The length of  time required to reduce
analyte signals to within a factor of two of the method  detection  limit should
be noted.   Until the  required rinse time is established,  this method requires a
rinse period of at least  60  seconds between  samples and  standards.   If a memory
interference is suspected,  the sample must be reanalyzed  after a rinse period of
sufficient length.

      3.5   Users  are  advised that high salt concentrations can cause  analyte
signal suppressions and  confuse interference tests.  If  the  instrument does not
display negative  values,  fortify  the  interference check  solution with  the
elements  of  interest at 0.5 to   1  mg/L and  circumscribe the added  standard
concentration accordingly,  with  the appropriate  10%  concentration  range  for

                                  6010B -  5                       Revision 2
                                                                  January  1995

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testing.    In  the  absence  of  measurable  analyte,   overcorrection  could  go
undetected if a negative value is reported as zero.

      3.6  The dashes in Table 2  indicate  that no measurable interferences were
observed even at  higher interferant  concentrations.   Generally,  interferences
were discernible if they produced peaks, or background shifts, corresponding to
2 to 5% of the peaks generated by the analyte concentrations.

4.0  APPARATUS AND MATERIALS

      4.1  Inductively coupled argon plasma emission spectrometer:

            4.1.1  Computer-controlled  emission  spectrometer with  background
      correction.

            4.1.2  Radio-frequency generator compliant with FCC  regulations.

            4.1.3  Optional mass flow controller for argon gas supply.

            4.1.4  Optional peristaltic pump.

            4.1.5  Optional Autosampler.

            4.1.6  Argon gas supply - high purity.

      4.2  Operating conditions  - The  analyst should  follow the instructions
provided by the instrument manufacturer.

            4.2.1  Before using this procedure to analyze  samples, there must be
      data available documenting initial demonstration  of performance.   The
      required data  document  the selection  criteria  of  background  correction
      points; analytical dynamic  ranges, the applicable equations, and the upper
      limits of those ranges; the method  and instrument  detection  limits; and
      the determination and verification of  interelement correction factors or
      other routines for correcting spectral  interferences.  This data must be
      generated using the same instrument, operating conditions and calibration
      routine to  be  used for sample analysis.  These  documented data  must be
      kept on file and be available for review by the data user  or auditor.

            4.2.1    Specific wavelengths  are   listed   in  Table  1.    Other
      wavelengths may be substituted  if they  can provide the needed sensitivity
      and are corrected  for spectral interference. Because of differences among
      various makes  and models of spectrometers, specific instrument operating
      conditions  cannot  be provided.   The instrument  and operating conditions
      utilized for determination  must be capable of providing  data of acceptable
      quality to  the program and  data user.   The  analyst  should  follow the
      instructions   provided  by  the   instrument  manufacturer   unless  other
      conditions  provide  similar  or  better performance  for a task.   Operating
      conditions  for aqueous  solutions usually  vary  from 1100   to  1200 watts
      forward power,  14 to  18  mm viewing height,  15 to  19  liters/min argon
      coolant flow, 0.6 to 1.5 L/min  argon aerosol flow,  1 to 1.8 mL/min sample

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pumping rate with  a  1  minute preflush time and measurement  time near 1
second per wavelength peak for sequential  instruments and 10 seconds per
sample for simultaneous instruments.   Reproduction of the Cu/Mn intensity
ratio at 324.754 nm  and  257.610  nm  respectively,  by adjusting the argon
aerosol  flow  has  been  recommended  as  a way  to  achieve  repeatable
interference correction factors.

      4.2.2  The plasma operating conditions need to  be optimized  prior to
use  of  the instrument.   The following procedure  is recommended.   The
purpose  of  plasma  optimization  is  to  provide  a maximum  signal  to
background  ratio   for  some  of  the  least sensitive  elements  in  the
analytical array.   The  use  of  a mass  flow  controller to  regulate the
nebulizer gas flow rate greatly facilitates the procedure.

            4.2.2.1  Ignite the plasma and  select an appropriate incident
      RF power.  Allow the  instrument to  become thermally  stable before
      beginning,  about  30 to 60 minutes of  operation.  While aspirating a
      1000 ug/L solution  of yttrium, follow the instrument manufacturer's
      instructions and adjust the aerosol  carrier gas  flow rate through
      the nebulizer  so a definitive blue emission  region  of  the plasma
      extends approximately  from  5  to 20  mm  above  the top of  the  load
      coil.  Record  the  nebulizer gas flow rate or  pressure setting for
      future reference.   The yttrium solution can also be used for coarse
      optical alignment of the torch by observing the overlay of the blue
      light over the entrance slit to  the detectors.

            4.2.2.2   After  establishing  the   nebulizer  gas  flow  rate,
      determine the  solution uptake rate  of  the nebulizer  in  mL/min  by
      aspirating a known volume of calibration blank for a period  of  at
      least three  minutes.   Divide  the  volume aspirated by  the  time  in
      minutes and  record the uptake  rate; set the peristaltic  pump  to
      deliver the  rate  in a steady even  flow.

            4.2.2.3  Profile the  instrument to align it  optically  as  it
      will be used during analysis.  The following procedure can be used
      for both horizontal  and vertical optimization, but is  written for
      vertical.     Aspirate  a solution  containing  10  ug/L  of  several
      selected elements.   These elements can be As,  Se,  Tl  or Pb as the
      least sensitive of  the elements  and most needing  to be optimize  or
      others representing analytical judgement (V,  Cr,  Cu,  Li  and Mn are
      also used with  success).   Collect  intensity  data  at the wavelength
      peak for each analyte at  1  mm intervals  from 14 to  18 mm above the
      load  coil.   (This  region  of  the  plasma is  referred  to  as  the
      analytical  zone.)   Repeat  the process using  the calibration blank.
      Determine the net signal  to blank  intensity  ratio for each analyte
      for each viewing  height setting.  Choose the height for viewing the
      plasma that  provides  the best net intensity ratios for the elements
      analyzed or  the  highest  intensity ratio  for  the  least  sensitive
      element.
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            4.2.2.4  The instrument operating condition finally selected
      as  being  optimum  should  provide the  lowest reliable  instrument
      detection limits and method detection limits.

            4.2.2.5  If either the instrument operating conditions,  such
      as incident power or nebulizer gas flow rate are changed, or a new
      torch injector tube with a  different orifice internal  diameter is
      installed, the plasma and viewing height should  be re-optimized.

            4.2.2.6    After  completing  the  initial  optimization  of
      operating conditions,  but before analyzing samples,  the laboratory
      must  establish  and  initially   verify  an  interelement  spectral
      interference correction routine to be used during sample analysis.
      A  general  description  concerning spectral  interference and  the
      analytical requirements for background correction in particular are
      discussed  in  the  section  on   interferences.    To  determine  the
      appropriate location for background correction and to establish the
      interelement  interference  correction  routine,  repeated  spectral
      scans around  the analytical wavelength  and repeated  analyses  of
      single elements solutions may be required.   Criteria for determining
      an  interelement  spectral  interference  is  an apparent  positive  or
      negative concentration for the analyte  that is outside the 3 sigma
      control  limits of the  calibration blank  for the  analyte.  The upper
      control  limit  is the  analyte   instrument  detection  limit.    Once
      established the entire routine must  be  periodically verified every
      six  months.    Only  a   portion  of the  correction  routine must  be
      verified more frequently or on  a daily basis.  Initial and periodic
      verification of the routine should be kept on file.   Special cases
      where continual verification is required are described elsewhere.

            4.2.2.7  Before  daily calibration  and after the  instrument
      warmup period,  the  nebulizer gas flow  rate must be reset  to the
      determined optimized flow.   If a mass  flow  controller is being used,
      it should be set to the recorded optimized flow  rate,   In order to
      maintain  valid  spectral  interelement  correction  routines  the
      nebulizer gas flow rate should be the same (< 2%  change) from day to
      day.

      4.2.3  For  operation  with  organic solvents, use  of  the auxiliary
argon inlet is  recommended,  as are  solvent-resistant tubing,  increased
plasma  (coolant) argon  flow,  decreased  nebulizer flow,  and  increased RF
power to obtain stable operation and precise  measurements.

      4.2.4  Sensitivity,  instrumental  detection  limit, precision,  linear
dynamic  range,  and  interference  effects  must  be established  for  each
individual analyte line on each particular instrument.  All  measurements
must be within  the  instrument  linear  range where the  correction factors
are valid.

            4.2.4.1  Method detection limits  must be established for all
      wavelengths  utilized,  using fortified  matrices.   An MDL must  be

                             6010B -  8                      Revision 2
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      established  by  the  laboratory  for each  type of  matrix commonly
      analyzed.  Refer to Chapter One for guidance on determining MDLs.

            4.2.5.2  Determination of limits using reagent water represent
      a best case situation and do not represent possible matrix effects
      of real world samples.

            4.2.5.3  If additional confirmation  is desired, reanalyze the
      seven replicate aliquots on  two more non consecutive days and again
      calculate  the  method  detection  limit values for  each  day.   An
      average of the three values  for each analyte may provide  for a more
      appropriate estimate.   Successful  analysis of samples  with added
      analytes or using method of standard additions can give confidence
      in the method detection limit values determined in reagent water.

            4.2.5.4  The upper limit of the linear dynamic range must be
      established for each wavelength utilized  by determining the signal
      responses  from  a  minimum  for three,  preferably  five,  different
      concentration standards across the range.   One of these should be
      near the upper limit  of  the range.  The ranges  which may be used for
      the analysis of  samples should  be judged  by  the  analyst from the
      resulting data.   The data, calculations and rationale for  the choice
      of range  made  should be documented and  kept  on   file.   The upper
      range limit should be an observed  signal no more than 10% below the
      level   extrapolated  from lower   standards.    Determined  analyte
      concentrations that are above  the  upper range  limit must be diluted
      and reanalyzed.    The  analyst  should also  be  aware  that  if  an
      interelement  correction from an  analyte  above  the  linear range
      exists, a second  analyte where the  interelement correction has been
      applied may be inaccurately  reported.  New  dynamic  ranges should be
      determined whenever  there  is a  significant change in  instrument
      response.  For those analytes  that periodically approach the upper
      limit, the  range should be checked every six months.   For those
      analytes that are known  interferences, and  are present at above the
      linear  range,  the  analyst  should  ensure  that   the  interelement
      correction has not been inaccurately applied.

            NOTE: Many of the alkali and alkaline earth metals have non-
            linear response curves due  to ionization and self absorption
            effects.   These curves may  be used  if the instrument allows;
            however the  effective range  must  be checked  and  the second
            order curve fit  should have  a correlation coefficient of 0.999
            or better.   Third order  fits are not acceptable.   These non-
            linear response curves should be revalidated and  recalculated
            every six  months.  These  curves are much more  sensitive  to
            changes in  operating  conditions than  the   linear  lines  and
            should  be   checked whenever  there  have  been   a  moderate
            equipment changes.

      4.2.5   The analyst must  (1) verify  that the  instrument configuration
and  operating  conditions  satisfy  the   analytical  requirements  and  (2)

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      maintain  quality  control  data  confirming  instrument  performance  and
      analytical results.

      4.3  Volumetric flasks of suitable precision and accuracy.

      4.4  Volumetric pipets of suitable precision and accuracy.
5.0  REAGENTS

      5.1  Reagent or trace metals 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  in question  analyze  for  contamination.     If  the
concentration of  the contamination is less  than  the  MDL  then the  reagent is
acceptable.

            5.1.1  Hydrochloric acid (cone), HC1.

            5.1.2  Hydrochloric  acid (1:1),  HC1. Add 500 ml concentrated HC1 to
      400 ml water and dilute to  1 liter in an appropriately sized beaker.

            5.1.3  Nitric acid (cone), HN03.

            5.1.4  Nitric  acid  (1:1),  HN03. Add  500  ml  concentrated HN03 to
      400 ml water and dilute to  1 liter in an appropriately sized beaker.

      5.2   Reagent Water.  All references to water  in the method refer  to reagent
water unless  otherwise  specified.  Reagent water will  be  interference free.
Refer to Chapter One for a definition of reagent water.

      5.3   Standard stock  solutions may  be purchased or  prepared from ultra-
high purity grade chemicals or metals  (99.99 to 99.999% pure).  All  salts must
be dried for 1 hour at 105°C, unless otherwise specified.

      Note: This section does not  apply  when  analyzing  samples that  have been
            prepared by Method 3040.

      CAUTION:  Many metal  salts  are  extremely  toxic  if inhaled  or swallowed.
                Wash hands thoroughly after handling.

Typical   stock  solution  preparation  procedures  follow.   Concentrations  are
calculated based upon the  weight  of pure metal  added, or  with the  use of the
element fraction and the weight  of the metal salt  added.
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Metal

          Concentration (pp.) .

Metal salts
          Concentration (pp.) .  «"<"*           '
                                               (L)
            5.3.1  Aluminum  solution,   stock,  1  mL  =  1000  ug  Al :  Dissolve
      1.000 g of aluminum metal, weighed accurately to at least four significant
      figures,  in  an  acid mixture  of 4.0  ml  of   (1:1)  HC1  and  1.0  ml  of
      concentrated HN03 in a beaker. Warm beaker slowly to effect solution. When
      dissolution  is  complete,  transfer solution quantitatively to a 1-liter
      flask, add an additional  10.0 ml  of  (1:1)  HC1  and  dilute  to  volume with
      reagent water.

                  NOTE:  Weight  of  analyte  is  expressed  to  four  significant
figures for consistency with the weights below because rounding to  two decimal
places can contribute up to 4 % error for some of the compounds.

            5.3.2  Antimony  solution,   stock,  1  ml  =  1000  ug  Sb:  Dissolve
      2.6673 g K(SbO)C4H406 (element  fraction  Sb = 0.3749),  weighed accurately
      to at least four significant figures, in water, add 10 ml (1:1) HC1 ,  and
      dilute to volume in  a 1,000 ml volumetric flask with water.

            5.3.3  Arsenic solution, stock,  1  mL = 1000 ug As:  Dissolve 1.3203
      g of As203  (element  fraction As =  0.7574), weighed accurately to at least
      four  significant  figures,  in  100 ml  of water containing  0.4  g  NaOH.
      Acidify the solution with 2 ml concentrated HN03 and dilute  to volume in
      a 1,000 mL volumetric flask with water.

            5.3.4  Barium  solution,  stock,  1 mL =  1000 ug Ba: Dissolve 1.5163 g
      BaCl2 (element  fraction  Ba = 0.6595), dried  at  250°C for 2 hours, weighed
      accurately to at least four significant  figures, in 10 mL water with 1 mL
      (1:1) HC1.  Add  10.0  mL  (1:1)  HC1 and  dilute  to volume  in   a  1,000  mL
      volumetric flask with water.

            5.3.5  Beryllium solution,  stock,  1  mL  = 1000 ug Be:  Do not dry.
      Dissolve  19.6463  g  BeS04 4H20  (element   fraction Be  =  0.0509),  weighed
      accurately to at  least  four significant figures,  in water,  add 10.0  mL
      concentrated HN03, and dilute to volume in a 1,000 mL volumetric flask with
      water.

            5.3.6  Boron  solution,  stock,   1   mL  =  1000  ug  B:  Do  not  dry.
      Dissolve 5.716  g anhydrous H3B03 (B fraction  = 0.1749), weighed accurately
      to at least four significant figures,  in reagent water  and dilute in a 1-L
      volumetric flask with reagent water.   Transfer immediately after mixing in
      a clean Teflon® bottle to minimize any  leaching of  boron from the  glass
      volumetric container.  Use of  a non-glass volumetric flask is  recommended
      to avoid boron  contamination from glassware.
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      5.3.7  Cadmium solution, stock, 1  mL =  1000 ug Cd:  Dissolve 1.1423
g CdO (element fraction Cd = 0.8754),  weighed accurately to at least four
significant figures, in a minimum amount  of (1:1) HN03. Heat to increase
rate of dissolution.  Add 10.0 mL concentrated HN03 and dilute to volume
in a 1,000 mL volumetric flask with water.

      5.3.8  Calcium solution, stock, 1  mL =  1000 ug Ca: Suspend 2.4969 g
CaC03 (element Ca  fraction  = 0.4005), dried  at 180°C  for  1  hour before
weighing, weighed  accurately to at  least four significant  figures,  in
water and dissolve  cautiously with  a minimum  amount  of (1:1) HN03.   Add
10.0 mL concentrated HN03 and dilute  to  volume  in  a  1,000  ml volumetric
flask with water.

      5.3.9  Chromium  solution,  stock,   1 mL  =  1000  ug  Cr:  Dissolve
1.9231 g Cr03 (element  fraction  Cr  = 0.5200), weighed  accurately to  at
least four  significant figures, in  water.   When  solution  is complete,
acidify with 10 mL  concentrated  HN03  and  dilute to volume  in a 1,000  mi-
volumetric flask with water.

      5.3.10  Cobalt solution, stock, 1 mL =  1000 ug  Co: Dissolve 1.00 g
of cobalt metal,  weighed accurately  to at  least four significant figures,
in a minimum  amount of (1:1) HN03.  Add 10.0 mL (1:1)  HC1  and dilute  to
volume in a 1,000 mL volumetric flask with water.

      5.3.11  Copper solution, stock, 1  mL =  1000 ug Cu:  Dissolve 1.2564
g CuO (element fraction Cu = 0.7989),  weighed accurately to at least four
significant figures),  in  a minimum  amount of  (1:1)  HN03.    Add  10.0  mL
concentrated HN03 and dilute  to volume in a 1,000 mL volumetric flask with
water.

      5.3.12  Iron  solution, stock,  1 mL  = 1000 ug Fe: Dissolve 1.4298 g
Fe203 (element fraction Fe =  0.6994),  weighed accurately to at least four
significant figures,  in a warm mixture of 20  mL  (1:1) HC1  and  2 mL  of
concentrated HN03.  Cool,  add an additional 5.0 mL of concentrated HN03,
and dilute to volume in a 1,000 mL volumetric flask with water.

      5.3.13  Lead  solution, stock,  1 mL  = 1000 ug Pb: Dissolve 1.5985 g
Pb(N03)2  (element fraction Pb =  0.6256),  weighed  accurately  to at least
four significant  figures, in  a  minimum  amount  of  (1:1)  HN03.  Add 10  mL
(1:1) HN03  and dilute to volume in a  1,000 mL volumetric flask with water.

      5.3.14   Lithium  solution, stock,  1 mL  =   1000  ug  Li:  Dissolve
5.3248 g  lithium  carbonate  (element  fraction  Li   =  0.1878),  weighed
accurately to at  least  four  significant  figures,  in  a minimum amount of
(1:1) HC1 and dilute to volume in a  1,000  mL volumetric flask with water.

      5.3.15   Magnesium solution,   stock, 1  mL =  1000 ug Mg:  Dissolve
1.6584 g MgO  (element  fraction  Mg  = 0.6030),  weighed  accurately to  at
least four significant  figures,  in  a minimum amount  of (1:1) HN03.   Add


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10.0 ml  (1:1)  concentrated  HN03 and  dilute to  volume  in  a  1,000 mL
volumetric flask with water.

      5.3.16   Manganese  solution,  stock,  1 ml  = 1000  ug  Mn: Dissolve
1.00 g of manganese metal, weighed accurately to at least four significant
figures,  in  acid  mixture (10 ml concentrated HC1  and  1 mL concentrated
HN03) and dilute to volume in a 1,000 ml volumetric flask with water.

      5.3.17   Mercury solution, stock,  1  mL =  1000 ug  Hg:  Do not  dry,
highly toxic element.   Dissolve 1.354 g HgCl2  (Hg fraction = 0.7388) in
reagent water.  Add 50.0 ml concentrated HN03  and dilute to volume in 1 1-L
volumetric flask with reagent water.

      5.3.18   Molybdenum solution,   stock,  1  mL = 1000  ug  Mo: Dissolve
1.7325 g  (NH4)6Mo7024.4H20  (element  fraction  Mo  =  0.5772),  weighed
accurately to  at  least  four  significant figures,  in  water and dilute to
volume in a 1,000 mL volumetric flask with water.

      5.3.19  Nickel solution,  stock, 1 mL  =  1000  ug Ni:  Dissolve   1.00 g
of nickel metal,  weighed accurately  to at least  four significant figures,
in 10.0 mL hot  concentrated HN03, cool, and dilute to  volume  in  a 1,000 mL
volumetric flask with water.

      5.3.20   Phosphate  solution,  stock,   1  mL =  1000 ug  P:  Dissolve
4.3937 g anhydrous KH2P04  (element fraction  P = 0.2276),  weighed accurately
to at least  four  significant figures, in  water.   Dilute to  volume  in a
1,000 mL volumetric flask with water.

      5.3.21   Potassium  solution,  stock,   1  mL =  1000 ug  K:  Dissolve
1.9069 g  KC1   (element  fraction K  =  0.5244)   dried  at  110°C,  weighed
accurately to at least four significant  figures, in water, and dilute to
volume in a 1,000 mL volumetric flask with water.

      5.3.22   Selenium  solution,  stock,  1  mL = 1000 ug  Se:  Do not  dry.
Dissolve 1.6332 g  H2Se03 (element fraction Se = 0.6123),  weighed accurately
to at least four significant figures, in water and dilute to volume  in a
1,000 mL volumetric flask with water.

      5.3.23   Silica  solution,  stock, 1 mL = 1000 ug  Si02:  Do not  dry.
Dissolve 2.964  g NH4SiF6,  weighed accurately to  at least  four significant
figures, in 200 mL (1:20)  HC1 with heating  at 85°C to effect dissolution.
Let  solution cool  and dilute to volume  in a 1-L  volumetric  flask  with
reagent water.

      5.3.24  Silver solution,  stock, 1 mL = 1000 ug Ag: Dissolve
1.5748 g AgN03 (element fraction Ag  = 0.6350),  weighed accurately to at
least four  significant  figures, in  water  and  10  mL  concentrated HN03.
Dilute to volume in a 1,000 mL volumetric flask with water.
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            5.3.25  Sodium solution,  stock,  1  ml = 1000 ug Na:  Dissolve 2.5419
      g NaCl  (element  fraction Na = 0.3934),  weighed  accurately to at least four
      significant figures, in water. Add 10.0 ml concentrated HN03 and dilute to
      volume in a 1,000 ml volumetric flask with water.

            5.3.26   Strontium  solution,  stock,  1  ml =  1000 ug Sr:  Dissolve
      2.4154 g of strontium nitrate (Sr(N03)2) (element  fraction Sr = 0.4140),
      weighed  accurately  to  at  least  four  significant  figures, in  a  1-liter
      flask containing 10  ml of concentrated HC1 and  700  ml of water.  Dilute to
      volume in a 1,000 ml volumetric flask with water.

            5.3.27   Thallium solution,  stock, 1 ml =  1000 ug Tl:  Dissolve
      1.3034 g T1N03 (element fraction Tl = 0.7672),  weighed accurately to at
      least four significant figures, in water. Add 10.0 ml concentrated  HN03 and
      dilute to volume in a 1,000 ml volumetric flask with  water.

            5.3.28  Tin solution,  stock,  1 ml  = 1000  ug Sn:  Dissolve 1.000 g Sn
      shot, weighed  accurately  to at  least 4 significant  figures,  in  200 ml
      (1:1) HC1  with  heating to  effect dissolution.   Let   solution cool  and
      dilute with (1:1) HC1 in  a 1-L volumetric flask.

            5.3.29   Vanadium solution,   stock,  1  ml  = 1000  ug   V:  Dissolve
      2.2957 g NH4V03  (element  fraction V = 0.4356),  weighed accurately to at
      least four significant  figures,  in a minimum amount of  concentrated HN03.
      Heat to  increase rate of dissolution.   Add 10.0 ml concentrated HN03 and
      dilute to volume in a 1,000 ml volumetric flask with  water.

            5.3.30  Zinc solution, stock, 1  ml = 1000 ug Zn: Dissolve 1.2447 g
      ZnO  (element fraction Zn =  0.8034), weighed accurately to at least four
      significant figures, in  a  minimum  amount  of  dilute  HN03.   Add  10.0 ml
      concentrated HN03 and dilute to volume in a 1,000 ml volumetric flask with
      water.

      5.4   Mixed calibration  standard solutions -  Prepare mixed  calibration
standard solutions by  combining appropriate volumes  of  the  stock  solutions in
volumetric flasks (see Table  3).  Add 2 ml (1:1) HN03 and  10 ml of (1:1) HCl and
dilute to 100  ml  with water.  Prior to preparing the mixed standards, each stock
solution   should  be   analyzed  separately  to  determine   possible  spectral
interference or the  presence of impurities.  Care should  be taken when preparing
the mixed  standards  to  ensure  that  the elements  are  compatible  and  stable
together.   Transfer  the  mixed   standard solutions  to FEP fluorocarbon  or
previously unused polyethylene or polypropylene bottles for storage.   Fresh mixed
standards should be  prepared, as needed, with the realization  that concentration
can change on  aging.  Calibration standards must be  initially verified using a
quality control sample (see Step  5.8)  and  monitored weekly for stability.  Some
typical calibration standard  combinations are  listed  in Table 3.  All mixtures
should then be scanned using  a sequential  spectrometer to verify the absence of
interelement spectral  interference in  the  recommended  mixed standard solutions.
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      NOTE:If the addition of silver to the recommended acid combination results
      in an initial precipitation, add 15 mL of water and warm the flask until
      the solution clears.  Cool and  dilute to  100 ml  with water. For this acid
      combination, the silver concentration should be limited to 2 mg/L.  Silver
      under  these conditions  is  stable  in  a  tap-water  matrix for  30  days.
      Higher concentrations of  silver require additional HC1.

      5.5  Two  types of blanks are  required for the analysis for  samples prepared
by any method other than 3040.  The calibration blank is used in  establishing the
analytical curve, and the method blank is used to identify possible contamination
resulting from varying amounts  of the acids used in the sample processing.

            5.5.1  The calibration blank is prepared by acidifying reagent water
      to  the   same  concentrations of  the  acids  found in  the standards  and
      samples.     Prepare  a sufficient  quantity  to flush  the  system  between
      standards and samples.

            5.5.2  The method blank must contain all of the reagents in the same
      volumes  as  used in the processing of the samples.  The method blank must
      be  carried through  the  complete procedure  and  contain the  same  acid
      concentration  in  the  final  solution  as  the sample  solution  used  for
      analysis.

      5.6  The  check standard  is prepared by the analyst  by combining compatible
elements from a standard source different  than that of the calibration standard
and at concentrations within the linear working range of the instrument (see Step
8.6.1.1 for use).

      5.7  Calibration  verification samples should be  prepared  in the same acid
matrix using the  same  standards used for calibration at  10 times  the  lowest
standard.

      5.8   The   interference  check   solution  is  prepared  to contain  known
concentrations  of interfering elements that will  provide an  adequate test of the
correction factors.  Spike the sample with the elements  of interest,  particularly
those with known  interferences at approximate  concentrations  of 10  times  the
instrumental   detection  limits.    In  the  absence  of  measurable  analyte,
overcorrection  could go  undetected because a negative value could be reported as
zero.  If the  particular  instrument will  display  overcorrection as  a negative
number, this  spiking procedure will  not be necessary.

6.0  SAMPLE COLLECTION,  PRESERVATION,  AND  HANDLING

      6.1  See  the introductory material  in Chapter Three,  Inorganic Analytes,
Steps 3.1 through 3.3.


7.0  PROCEDURE

      7.1  Preliminary treatment of most  matrices  is  necessary because  of  the
complexity and  variability of sample  matrices.   Groundwater samples  which  have

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been prefiltered and acidified will  not  need  acid digestion.  Samples which are
not digested must either use an internal  standard or be matrix matched with the
standards.   Solubil ization and digestion  procedures  are presented  in  Sample
Preparation Methods (Chapter Three,  Inorganic Analytes).

      7.2  Set up the instrument with proper operating parameters established in
Step 4.2.   The  instrument  must be  allowed to become thermally  stable  before
beginning  (usually  requiring  at  least  30  minutes  of operation  prior  to
cal ibration).

      7.3   Profile and calibrate the  instrument  according to the  instrument
manufacturer's  recommended procedures,  using the  typical  mixed  calibration
standard solutions described in Step 5.4.  Flush the  system with the calibration
blank (Step 5.5.1)  between each standard  or as the manufacturer recommends.  (Use
the average intensity of multiple exposures for both standardization and sample
analysis  to  reduce random  error.)   The calibration curve  must  consist  of  a
minimum of a blank and a standard.

      7.4  For  all analytes and determinations, the laboratory must  analyze  a
check standard and a  calibration blank immediately following daily calibration,
after every tenth  sample  and  at the end  of  the sample  run.  The  calibration
verification must be analyzed  immediately following daily  calibration.  Analysis
of the  check  standard, calibration  verification,  and  calibration blank  must
verify that the instrument  is within ± 10% of  calibration  with relative standard
deviation < 3% from replicate  (minimum of two) integrations.  If the calibration
cannot be verified  within the specified limits, reanalyze  either the calibration
verification solution or the check standard (or both).   If the  second analysis
confirms  calibration  to be  outside  the limits, the  sample analysis must  be
discontinued,  the cause determined and the instrument recalibrated.  All samples
following the  last acceptable calibration verification solution or check standard
must be reanalyzed. The analysis data of the  calibration  blank,  check standard,
and  calibration verification solution must  be kept  on  file with the  sample
analysis data.

      7.5   Flush the  system with  the calibration  blank  solution for at least
1 minute (Step 5.5.1) before the analysis of each sample (see Note  to Step 7.3).

      7.6  Calculations:  If dilutions were performed,  the appropriate factors
must be  applied  to sample  values.   All  results should be reported with up  to
three significant figures.

      7.7  The MSA  should be used if an interference is suspected or a new matrix
is encountered.  When  the  method of  standard additions is  used,  standards are
added at one or more levels to portions of a prepared  samples.   This  technique
compensates for enhancement or depression  of  an analyte signal  by a matrix.  It
will not correct for additive interferences, such as contamination, interelement
interferences, or baseline  shifts.  This technique is valid  in  the linear range
when the interference  effect  is  constant over the range,  the  added  analyte
responds the  same  as  the  endogenous  analyte, and  the signal is  corrected for
additive interferences.  The  simplest version of this technique  is  the single


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addition method.  This procedure calls  for  two  identical aliquots of the sample
solution to be taken.  To the first aliquot, a small volume  of standard is added;
while  to  the  second  aliquot,  a  volume  of acid  blank  is added equal  to the
standard addition.  The sample concentration is calculated by: multiplying the
intensity  value  for  the   unfortified  aliquot  by  the  volume  (Liters)  and
concentration (mg/L or mg/Kg) of the standard addition to make the numerator; the
difference  in  intensities  for the fortified sample  and unfortified  sample is
multiplied by the volume (Liters) of the sample  aliquot for  the denominator.  The
quotient is the sample concentration.

      For  more  than  one  fortified  portion of  the  prepared sample,  linear
regression  analysis  can  be applied using a computer or calculator program to
obtain the concentration of the sample solution.

      7.8   An alternative  to  using  the method  of standard  additions  is the
internal standard technique.  Add  one  or more  elements  not in the  samples and
verified not  to cause an  interelement spectral  interference  to the  samples,
standards  and  blanks;  yttrium or scandium are  often used.   The  concentration
should be sufficient for optimum precision  but  not so high  as  to alter the salt
concentration of the matrix.  The element intensity is used by  the instrument as
an internal standard to ratio the analyte intensity signals for both calibration
and  quantitation.    This   technique  is   very useful  in  overcoming  matrix
interferences especially in high solids matrices.

8.0  QUALITY CONTROL

      8.1  All quality control  data should  be maintained and available for easy
reference or inspection.  All  quality control measures described in Chapter One
should be followed.

      8.2  Dilute and  reanalyze samples that exceed the linear  calibration limit
or use  an  alternate,  less  sensitive line for which quality  control  data  is
already established.

      8.3  Employ a  minimum  of one method blank  per sample  batch to determine if
contamination or any memory effects are occurring.  A method blank  is  a volume
of reagent water carried through the same preparation process as  a  sample.

      8.4   Analyze  matrix  spiked duplicate samples at  a  frequency of  one per
matrix batch.   A matrix duplicate sample  is a sample brought through the entire
sample preparation and analytical process in duplicate.

                  8.4.1.1   The  relative  percent difference between  matrix
            duplicate determinations is to be calculated as follows:
                       RPD =
                               Dl
„ x 100
                             (D1 + DJ/2
            where:

                  RPD = relative percent difference.
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                   DT = first sample value.
                   D2 = second sample value  (replicate).

                  (A  control  limit  of ±  20%  RPD  or  within the  documented
            historical  acceptance  limits  for  each  matrix  shall  be  used  for
            sample  values  greater  than ten  times  the  instrument  detection
            limit.)

                  8.4.1.2  The spiked sample or spiked duplicate sample recovery
            is to be within ± 25% of the actual value or within the documented
            historical acceptance limits for each matrix.

      8.5   It  is  recommended that  whenever a new or unusual  sample  matrix is
encountered, a series of tests be performed prior to reporting concentration data
for analyte elements.  These tests, as outlined in Steps 8.5.1 and 8.5.2, will
ensure that neither positive  nor negative interferences are operating on any of
the analyte elements to distort the accuracy of the reported values.

            8.5.1  Dilution Test: If the analyte concentration is sufficiently
      high  (minimally,  a  factor of 10 above the  instrumental  detection limit
      after dilution), an analysis  of a 1:4 dilution should agree within ± 10%
      of  the  original  determination.    If  not,   a   chemical   or  physical
      interference effect should be suspected.

            8.5.2  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% of the  known value.  The spike addition should produce
      a minimum level of 10  times  and  a maximum of  100  times  the instrumental
      detection limit.   If  the  spike  is not  recovered  within  the  specified
      limits, a matrix effect should be suspected.

            CAUTION:If  spectral  overlap is  suspected,   use  of  computerized
            compensation,  an  alternate  wavelength,  or  comparison  with  an
            alternate method is recommended.

      8.6   Check  the  instrument standardization  by analyzing appropriate QC
samples as follows.

            8.6.1  Verify calibration with the Calibration Verification Standard
      immediately  following  daily  calibration.   Verify calibration  with  the
      check standard (Step 5.6)  immediately following daily calibration, after
      every 10 samples and  at the end of the analytical  run.  Use a calibration
      blank (Step  5.5.1)  immediately following daily calibration,  after every 10
      samples and at the end of the analytical  run.

                  8.6.1.1  The  results of the  calibration  verification  are to
            agree  within  10% of the  expected  value;  if  not,   terminate  the
            analysis, correct the problem,  and recalibrate the instrument.
                                  6010B - 18                      Revision 2
                                                                  January 1995

-------
                  8.6.1.2  The results of the check standard are to agree within
            10% of the expected value; if not, terminate the analysis, correct
            the problem, and recalibrate the instrument.

                  8.6.1.3   The results  of the calibration  blank  are to agree
            within three standard deviations of the mean blank value.  If not,
            repeat the analysis two more  times  and  average  the  results.  If the
            average is not  within  three  standard  deviations of the background
            mean, terminate the analysis,  correct the problem,  recalibrate, and
            reanalyze the previous 10 samples.  If the blank is less than 1/10
            the concentration  of  the lowest sample, the analysis  need not be
            terminated.

            8.6.2   Verify the interelement and background correction factors at
      the beginning and end  of an  analytical  run  or twice  during  every 8-hour
      work  shift,  whichever   is  more  frequent.    Do  this  by analyzing  the
      interference check sample (Step 5.8).   Results should be within ± 20% of
      the true value.

9.0  METHOD PERFORMANCE

      9.1   In an EPA round-robin  Phase 1  study, seven laboratories  applied the
ICP technique to acid-distilled water matrices that had been spiked with various
metal concentrates.  Table 4 lists  the true values, the mean  reported  values, and
the mean percent relative standard deviations.

      9.2   Performance data  for  aqueous solutions  and solid  samples  from a
multilaboratory study (9) are  provided in Tables 5 and 6.

10.0  REFERENCES

1.    Boumans, P.W.J.M.  Line Coincidence  Tables for Inductively Coupled Plasma
Atomic  Emission  Spectrometry,  2nd  Edition.    Pergamon  Press,  Oxford,  United
Kingdom, 1984.

2.    Sampling  and  Analysis   Methods  for  Hazardous  Waste Combustion;  U.S.
Environmental Protection Agency; Air and Energy Engineering  Research Laboratory,
Office of Research and Development: Research Triangle Park, NC, 1984; Prepared
by Arthur D. Little,  Inc.

3.    Rohrbough, W.G.;  et  al. Reagent Chemicals,  American  Chemical  Society
Specifications, 7th ed.; American  Chemical Society: Washington, DC,  1986.

4.    1985 Annual Book of ASTM Standards, Vol. 11.01; "Standard Specification for
Reagent Water"; ASTM:  Philadelphia, PA,  1985; D1193-77.

5.    Jones, C.L. et al.  An Inter!aboratory  Study of Inductively Coupled Plasma
Atomic Emission Spectroscopy Method 6010 and  Digestion Method 3050.  EPA-600/4-
87-032, U.S. Environmental Protection Agency, LasVegas,  Nevada, 1987.
                                  6010B - 19                      Revision 2
                                                                  January 1995

-------
                                    TABLE  1
RECOMMENDED WAVELENGTHS AND ESTIMATED INSTRUMENTAL DETECTION LIMITS
Detection
Element
Aluminum
Antimony
Arsenic
Barium
Beryl! ium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Lithium
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Phosphorus
Potassium
Selenium
Silica (Si02)
Silver
Sodium
Strontium
Thall ium
Tin
Vanadium
Zinc
Wavelengtha(nm)
308.215
206.833
193.696
455.403
313.042
249.678x2
226.502
317.933
267.716
228.616
324.754
259.940
220.353
670.784
279.079
257.610
194.227x2
202.030
231.604x2
213.618
766.491
196.026
251.611
328.068
588.995
407.771
190.864
189.980x2
292.402
213.856x2
Estimated
Limitb (ug/L)
30
21
35
0.87
0.18
3.8
2.3
6.7
4.7
4.7
3.6
4.1
28
2.8
20
0.93
17
5.3
10
51
See note c
50
17
4.7
19
0.28
27
17
5.0
1.2
      aThe wavelengths listed (where  x2  indicates second order) are recommended
because of their sensitivity  and  overall  acceptance.  Other wavelengths may be
substituted (e.g.  in  the  case  of an interference) if they can provide the needed
sensitivity and are  treated  with  the same corrective  techniques  for spectral
interference  (see  Step  3.1).  In  time,  other  elements may  be added  as  more
information becomes available and as required.
       The estimated  instrumental  detection limits shown are provided  as a guide
for  an  instrumental   limit.   The  actual  method detection  limits are  sample
dependent and may vary as the sample matrix varies.
      GHighly dependent on operating conditions and plasma position.
                                  6010B - 20
Revision 2
January 1995

-------
                       TABLE 2  POTENTIAL SOIL INTERFERENCES

                  ANALYTE  CONCENTRATION  EQUIVALENTS ARISING  FROM
                        INTERFERENCE AT THE 100-mg/L LEVEL0
 Analyte
Wavelength
   (nm)     Al
Ca    Cr
    Interferanta'b

Cu    Fe    Mg    Mn
Ni
Ti
Aluminum
Antimony
Arsenic
308.215
206.833
193.696

0.47 --
1.3 --

2.9 -- 0.08 --
0.44 --
0.21 --
0.25
1.4
0.45
1.1
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
455.403
313.042
226.502
317.933
267.716
228.616
324.754
                                                                         0.04  0.05
 Iron       259.940
 Lead       220.353
 Magnesium  279.079
 Manganese  257.610
                                    0.08

                                    0.03
            0.17  --
                  0.02  0.11
            0.005 --    0.01
                  0.03  --     --    0.02
                  0.01  0.01  0.04  --
                  0.003 --     0.04  --
                  0.005 --     --    0.03
                  0.003 --

                              0.12  --

                  0.13  --     0.25  --
                  0.002 0.002 --
                                                            0.03

                                                            0.15
                                                            0.05
                                    0.03
                                    0.04

                                    0.02
                              0.07  0.12
Molybdenum 202.030 0.05 -- -- -- 0.03 --
Nickel 231.604
Selenium 196.026 0.23 -- -- -- 0.09 --
Sodium 588.995 -- -- -- -- -- -- -- -- 0.08 --
Thallium
Vanadium
Zinc
190.864 0.30 --
292.402 -- -- 0.05 -- 0.005 -- -- -- 0.02 --
213.856 -- -- -- 0.14 -- -- -- 0.29 --
aDashes  indicate  that no  interference was  observed  even when  interferents were
introduced at the following levels:
      Al -  1000 mg/L                  Mg - 1000 mg/L
      Ca -  1000 mg/L                  Mn -  200 mg/L
      Cr -   200 mg/L                  Tl -  200 mg/L
      Cu -   200 mg/L                   V -  200 mg/L
      Fe -  1000 mg/L
 The  figures recorded  as  analyte  concentrations  are  not  the actual  observed
concentrations;   to  obtain  those  figures,  add  the  listed  concentration  to  the
interferant figure.
Interferences will  be affected by background choice and other  interferences may
be present.
                                  6010B - 21
                                                      Revision  2
                                                      January  1995

-------
                              TABLE  3
                     MIXED STANDARD SOLUTIONS
                                                    i
Solution
      Elements
   I
   II
   III
   IV
   V
   VI
Be, Cd, Mn, Pb, Se and Zn
Ba, Co, Cu, Fe, and V
As, Mo
Al, Ca, Cr, K, Na, Ni,Li, and Sr
Ag (see Note to Step 5.4), Mg, Sb, and Tl
P
                            6010B  - 22
                                    Revision  2
                                    January 1995

-------
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                                   TABLE 5

             ICP-AES  PRECISION AND ACCURACY  FOR AQUEOUS SOLUTIONS*
Element
Al
Sb
As
Ba
Be
Cd
Ca
Cr
Co
Cu
Fe
Pb
Mg
Mn
Mo
Ni
K
Se
Ag
Na
Tl
V
Zn
Mean
Cone.
(mg/L)
14.8
15.1
14.7
3.66
3.78
3.61
15.0
3.75
3.52
3.58
14.8
14.4
14.1
3.70
3.70
3.70
14.1
15.3
3.69
14.0
15.1
3.51
3.57
Nb
8
8
7
7
8
8
8
8
8
8
8
7
8
8
8
7
8
8
6
8
7
8
8
RSDb
(%)
6.3
7.7
6.4
3.1
5.8
7.0
7.4
8.2
5.9
5.6
5.9
5.9
6.5
4.3
6.9
5.7
6.6
7.5
9.1
4.2
8.5
6.6
8.3
Accuracy0
(% of nominal)
100
102
99
99
102
97
101
101
95
97
100
97
96
100
100
100
95
104
100
95
102
95
96
AThese performance values  are independent of sample preparation because the labs
analyzed portions of the same solutions

bN = Number of measurements for mean and relative  standard  deviation  (RSD).

°Accuracy is expressed  as  a percentage of the nominal value for each analyte in
acidified, multi-element solutions.
                                  6010B - 24
Revision 2
January 1995

-------
                                    TABLE  6

              ICP-AES PRECISION AND BIAS FOR SOLID WASTE  DIGESTSA
Element
Al
Sb
As
Ba
Be
Cd
Ca
Cr
Co
Cu
Fe
Pb
Mg
Mn
Mo
Ni
K
Se
Ag
Na
Tl
V
Zn
Spiked Coal Fly Ash
(NIST-SRM 1633a)
Mean
Cone. RSDb
(mg/L) Nb (%)
330
3.4
21
133
4.0
0.97
87
2.1
1.2
1.9
602
4.6
15
1.8
891
1.6
46
6.4
1.4
20
6.7
1010
2.2
8
6
8
8
8
6
6
7
6
6
8
7
8
7
8
6
8
5
3
8
4
5
6
16
73
83
8.7
57
5.7
5.6
36
21
9.7
8.8
22
15
14
19
8.1
4.2
16
17
49
22
7.5
7.6
Bias0
(%AAS)
104
96
270
101
460
101
208
106
94
118
102
94
110
104
105
91
98
73
140
130
260
100
93
Spiked Electroplating Sludge
Mean
Cone. RSDb Biasc
(mg/L) Nb (%) (%AAS)
127
5.3
5.2
1.6
0.9
2.9
954
154
1.0
156
603
25
35
5.9
1.4
9.5
51
8.7
0.75
1380
5.0
1.2
266
8
7
7
8
7
7
7
7
7
8
7
7
8
7
7
7
8
7
7
8
7
6
7
13
24
8.6
20
9.9
9.9
7.0
7.8
11
7.8
5.6
5.6
20
9.6
36
9.6
5.8
13
19
9.8
20
11
2.5
110
120
87
58
110
90
97
93
85
97
98
98
84
95
110
90
82
101
270
95
180
80
101
AThese performance values  are independent of sample preparation because the labs
analyzed portions of the same digests.

bN =  Number of measurements for  mean  and relative  standard  deviation  (RSD).

cBias  for the  ICP-AES data is  expressed as a percentage of  atomic absorption
spectroscopy (AAS) data for the same digests.
                                  6010B - 25
Revision 2
January 1995

-------
                       METHOD 6010B

INDUCTIVELY COUPLED  PLASMA-ATOMIC  EMISSION SPECTROSCOPY
                    Q   Start  J

                        IT
                   7.1 Pretreatment
                    of the sample.
                   7.2 Instrument
                       setup.
                   7.3 Instrument
                     calibration.
                  7.4 Run calibration
                   verification and
                calibration blank and
                analyze to determine
                    if calibration
                     acceptable.
                  7.5 Flush system
                   with calibration
                blank before analysis
                   of each sample.
                        I
                    7.6 Perform
                    calculations.
                7.7 - 7.8 Perform any
                 corrective measures
                     necessary fo
                  accurate analysis.
                 i
                        6010B  -  26
Revision  2
January 1995

-------
                                  METHOD 7063

                    ARSENIC IN AQUEOUS  SAMPLES  AND EXTRACTS
                     BY  ANODIC STRIPPING VOLTAMMETRY  (ASV)
1.0   SCOPE AND APPLICATION

      1.1   This method  is applicable  for  laboratory determinations  of free
dissolved arsenic  in  drinking water,  natural surface water,  seawater,  and in
domestic and industrial wastewater, and in soil  extracts.

      1.2   Arsenic concentrations in  the linear calibration range of 0.3  to 300
/ig/L may be quantified. The upper concentration range may be extended by sample
dilution,  by  decreasing  the  analyte  deposition  time,   or  by  increasing  the
stripping current.

      1.3   The method detection limit for free arsenic is about 0.1 jug/L.

      1.4   The method is equally sensitive for As(III)  and As(V).


2.0   SUMMARY OF METHOD

      Standards and samples are made acidic and rendered electrically conductive
by adding hydrochloric acid.   Free dissolved arsenic is  quantified by anodic
stripping,  at  a potential of +145 mV with  respect  to the  saturated  calomel
electrode (SCE), from  a conditioned gold metal film deposited on  a glassy carbon
electrode (GCE).


3.0   INTERFERENCES

      3.1   Dissolved antimony and bismuth are positive interferences. Dissolved
copper,  at concentrations  greater than 1 mg/L, is also a positive interference.

      3.2   Turbid samples must be filtered through a borosilicate glass filter
with 0.45-^m pores  to  preclude physical erosion of the GCE gold film.

      3.3   Some  wet   deposition  samples  may  have  insufficient  electrical
conductivity for proper operation of the ASV  instrumentation.   This problem is
obviated hy making  the solutions 2 M in HCL.

      3.4   When the analysis is performed according  to  the instructions given
below,  the  following  ions, compounds,  and sample conditions  are  known  not to
interfere with the quantitation of arsenic; seawater salts, water-soluble organic
compounds such  as sugars and tannic acid,  and  dissolved copper at concentrations
less than 100 times the arsenic concentration.
                                   7063 -  1                        Revision 0
                                                                  January 1995

-------
4.0.  APPARATUS AND MATERIALS

      4.1   ASV instrumentation (Radiometer TraceLab, or equivalent),  including
potentiostat, electrodes, stirrer, sample stand,  polyethylene sample  cups,  and
GCE polishing powder.

      4.2   Computer, as recommended by ASV  instrumentation manufacturer.

      4.3   Plastic syringe and a nylon syringe filter with 0.45-^m pores.

      4.4   Adjustable pipetters with polyethylene tips.

      4.5   pH meter or pH indicator paper.

      4.6   General laboratory glassware, including beakers,  graduated cyl inders,
volumetric flasks, etc.


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 interference free.  All references
to water in the method refer to reagent water unless otherwise specified.

      5.3   Hydrochloric acid,  (concentrated  12 M).

            5.3.1 Hydrochloric  acid (2 M),   dilute  167   ml  of  concentrated
      hydrochloric acid to 1 liter with reagent water.

            5.3.2 Hydrochloric acid  (0.1 M), dilute 50 mL of the 2M hydrochloric
      acid solution to 1 liter with  reagent  water.

      5.4   Gold Stock Standard (1000 mg/L Au):  Stock solutions are commercially
available as spectrophotometric standards.

            5.4.1 Gold-plating solution, (50 mg/L Au  dissolved  in  0.1  M HCL):
      prepare by diluting 2.5 mL of  a 1,000 mg/L Au spectrophotometric standard
      solution to 50 mL with 0.1 M HCL.

      5.5   Arsenic Stock Standard (1000 mg/L of arsenic):  Stock solutions are
commercially available as spectrophotometric  standards.
                                   7063 - 2                       Revision 0
                                                                  January 1995

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            5.5.1 Arsenic  intermediate  standard  solution,  1,000  jug/L arsenic:
      Dilute  100  juL  of  the stock standard  to  100 ml with  2% HN03.   Prepare
      weekly.

            5.5.2 Arsenic Working Standards:  These standards  should be prepared
      from the arsenic intermediate standard to be used as calibration standards
      at the time of analysis.  Prepare at least five working  standards over the
      linear calibration range of 0.3 jug/L to 300 /j,g/L by diluting appropriate
      aliquots  of  the intermediate  arsenic  stock solution  with  2% HN03.  The
      actual concentration of the working standards should cover the anticipated
      range of  sample concentrations.


6.0   SAMPLE HANDLING, PRESERVATION,  AND HANDLING

      6.1   All samples must be collected using a sampling plan that addresses
the considerations discussed in Chapter Nine of this manual.

      6.2   All sample containers must be  prewashed  with detergents, acids, and
reagent water.  Plastic and glass containers are both suitable.

      6.3   At the time of  sampling, the sample must  be acidified to a pH <2 with
nitric acid.

      6.4   While  samples  to be  analyzed for  free  dissolved arsenic  do  not
require refrigeration, they should be stored out of direct sunlight in an area
no warmer than  room temperature.


7.0   PROCEDURE

      7.1   Analysis  of  an aqueous  sample for  free dissolved arsenic  by  ASV
involves three major steps.  First, the GCE electrode must be prepared for use
by  plating  on  a  thin   film  of  gold;  the  gold  working  electrode  is  then
conditioned, and finally, the concentration of free arsenic in the samples are
determined.

      7.2   Set up ASV instrumentation, electrodes, and computer according to the
manufacturer's  recommended procedures.    Enter  the  appropriate  program  and
required  data   parameters  into  the  computer  as  directed  by the  instrument
software.

      7.3   Before  applying  a gold  film  to  the  GCE, the  electrode must  be
thoroughly cleaned.   Electrode cleanliness is  checked  by  rinsing  the  GCE with
water.  After gently  shaking  off excess water,  the  entire  electrode  should be
coated with a thin, flat, unbroken water film.  If necessary, clean the GCE by
wiping it with a wet,  soft  paper towel,  polishing  it with polishing powder,  and
rinsing it thoroughly with  water.   Keep  the cleaned electrode immersed in water
or in air saturated with water vapor.
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      7.4   Place  50 mL  of  the gold-plating  solution  (Sec.   5.4.1)  or  an
appropriate volume as recommended by the instrument manufacturer,  into a beaker.
Immerse the electrodes in the gold-plating solution  and initiate the GCE gold-
plating program as instructed by the instrument manufacturer.

      7.5   Following deposition of  GCE  gold  film,  the  electrode  must  be
conditioned prior to actual  sample analysis.   Unconditioned  electrodes  may
produce irreproducible arsenic peak  areas.  Condition  electrodes  by analyzing an
arsenic-free 2  M HCL reagent  solution (see 5.3.1)   or by  analyzing  a  sample
adjusted to contain 2 M HCL (to a 25  ml  sample, add 5 ml  of concentrated HCL, mix
well), according to manufacture's recommended procedures.

      7.6   When the  conditioning procedure  is  complete,  rinse  the electrodes
with  reagent water and  store the electrodes  in reagent water  until  ready  to
analyze the calibration  standards or samples.

      7.7   Following the  instrument  manufacturer's  recommended  calibration
procedures, construct a  calibration  curve  by  analyzing  five working calibration
standards (Sec. 5.5.2);

            7.7.1  To 25 mL working standard, add 5  mL concentrated HCL, mix.

            7.7.2  Immerse the electrodes into the working standard and record
      instrument response.  Rinse the electrodes thoroughly with reagent water
      between each standard.   Construct a calibration  curve  by recording the
      instrument  response  (peak  area  or peak  height)  versus the  standard
      concentration.

      7.8   Analyze  the  samples  by  aliquoting  25 mL of sample  into a beaker.
Allow the temperature of the sample to equilibrate to room temperature (within
the range of 20 °C to 30  °C) if necessary.  Add 5 mL  of concentrated HCL to the
sample and mix.   Immerse the  electrodes  into the  sample and record instrument
response.  Determine  sample concentration from the calibration curve.

      Note: Depending on the composition of the samples, a single  application of
      the gold film may suffice for analysis of up to a dozen or more samples.
      Highly corrosive  and oxidizing  samples  may corrode  the   gold  film and
      degrade the instrument  response,  requiring the  re-application of the gold
      film.  The analyst must  monitor performance of  the electrode by analyzing
      a mid-range  check standard every ten  samples.   A low  recovery  for the
      check standard  indicates that the electrode must be renewed.  Follow the
      procedures  in  Sec.  7.3  through  7.5  to  renew  the gold  film  on  the GCE.
      Following the renewal of the electrode, the instrument  calibration must be
      verified  by analyzing  a  mid-range  standard.   If the  recovery  of  the
      standard is within 10% of the  true value,  a new  calibration  curve need not
      be run.
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8.0   QUALITY CONTROL

      8.1   Initial Calibration Verification standard (ICV):  The ICV contains
a known arsenic concentration and is obtained from an independent source.  The
ICV recovery must be within the range 90% to  110%.   If it is not, the source of
error must be found and corrected.   An  acceptable  ICV must be analyzed prior to
analyzing samples.  The ICV also serves as a laboratory control sample.

      8.2   Continuing Calibration Verification standard (CCV):  After a set of
10 or  fewer samples has  been  analyzed,  and  after  the  final  sample  has been
analyzed, a CCV containing a known  arsenic concentration must be analyzed.  The
CCV recovery must be within the range 90% to  110%.   If it is not, the source of
error must  be found and  corrected  (see  the  note  in Sec.  7.9)   All  samples
analyzed since the last acceptable CCV must be re-analyzed.

      8.3   Reagent blank: A reagent blank must be analyzed with  each analytical
batch or 20  samples, whichever is  more frequent.   A reagent  blank is reagent
water treated as  a sample.  The  indicated concentration of the reagent blank must
not be more  than 0.1 jug/L of  arsenic.  If more  than  0.1  jug/L  of arsenic is
detected in the blank,  sample carryover or reagent contamination is indicated.
The problem must be corrected before analyzing more samples.

      8.4   At least one matrix spike (MS) and  one matrix spike duplicate (MSD)
shall  be included in  each  analytical batch or 20 samples: A matrix duplicate may
be substituted for  the  MSD provided that the  concentration  of  arsenic  in the
sample selected for duplicate analysis is greater than  the  limit of detection.
The spike should  increase  the concentration of free arsenic in the spiked sample
by 50% to 200%.  The volume of the spike must be no more than 1% of the sample
volume.

            8.4.1 The spike recovery should within  the  range  75% to  125%.   If
      the  recovery  of  the spike  is  outside  ±  25%,   the  problem should  be
      identified and corrected.   If a matrix  interference is  suspected, a second
      sample aliquot should be  spiked  to confirm the spike  recovery.   If the
      spike recovery is  still  outside the range of ± 25%,  all  samples must be
      quantified by the method  of standard additions.  Refer to Method 7000 for
      information on the method of standard additions.

            8.4.2 The duplicate samples (MS/MSD and/or Sample/Sample duplicate)
      must give results having  a difference not greater  than 20% of the mean of
      the duplicate results.  If the difference is greater than  20% of the mean,
      the source of error must be found and  corrected.
9.0   METHOD PERFORMANCE

      9.1   In a  single-laboratory evaluation,  standards  with  known  arsenic
concentrations were analyzed  according  to  the instructions given  above.   The
results are listed in  Tables A-l and A-2.
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      9.2   In a  single-laboratory  evaluation,  known amounts  of  arsenic were
added to environmental  water samples and  soil extracts.  The results are listed
in Table A-3.

      9.3   In a  single-laboratory  evaluation,  known amounts  of  arsenic were
added to environmental  water samples and soil  extracts.  The resulting solutions
were analyzed according to the instruction given above and by graphite furnace
atomic absorption  spectrophotometry  (GFAA). The  results are listed  in Table A-4.


10.0  REFERENCES

1.    Pyle, Steven;  Miller,  Eric Leroy; Quantifying Arsenic In Aqueous Solutions
      By Anodic Stripping Voltametry, Contract EMSL-LV/ORD/USEPA.
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TABLE A-l.  ACCURACY AND PRECISION OF ARSENIC (III) DETERMINATIONS
Arsenic (III)
Concentration (jug/L)
0.700
7.00
70.0
Arsenic (III) Recovery
i°/\
(/o)
102
98
100
Relative Standard
Deviation (%)
14
2
5
 TABLE A-2.  ACCURACY AND PRECISION OF ARSENIC (V) DETERMINATIONS
Arsenic (V)
Concentration (M9/L)
0.700
7.00
70.0
Arsenic (V) Recovery
t°/\
\'°)
99
100
99
Relative Standard
Deviation (%)
10
1
2
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TABLE A-3.  QUANTIFYING ARSENIC IN ENVIRONMENTAL SAMPLES BY ASV
Sample
Identification
Tap Water
Tap Water + 1 g/L
Ascorbic Acid
A12544
(Water
A12545
(Water)
A12582
(Water)
A12582
(Water)
A24228
(Water)
A24228
(Water)
A22949
(Water)
A22949
(Water)
A22949
(Water)
A23274
(Soil Extract)
A23274
(Soil Extract)
A23275
(Soil Extract)
A23275
(Soil Extract)
Arsenic Added
(M9/L)
20.0
20.0
10.0
5.00
10.0
20.0
10.0
20.0
10.0
20.0
50.0
10.0
20.0
10.0
30.0
Arsenic Found
(M9/L)
Not Detected
20.2
9.3
5.11
10.0
19.8
10.6
20.5
9.9
20.2
48.2
12.3
22.1
10.5
31.6
Recovery
0%
101%
93%
102%
100%
99%
106%
103%
99%
101%
96%
101%
99%
105%
105%
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             TABLE A-4.  COMPARISON OF ASV AND GFAA RESULTS
                  FOR ARSENIC IN ENVIRONMENTAL SAMPLES
    Sample
Identification
    A12545
    (Water)

    A12582
    (Water)

    A22949
    (Water)

    A23274
(Soil  Extract)

    A23275
(Soil  Extract)
Arsenic Added
Arsenic Found,
       5.00


      10.0


      50.0


      10.0


      30.0
        5.11


       10.0


       48.2


       12.3


       31.6
Arsenic Found,
 GFAA
        5.08


        9.91


       54.0


       12.9


       31.5
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                                   METHOD 7063
                    ARSENIC  IN  AQUEOUS SAMPLES  AND EXTRACTS
                     BY ANODIC  STRIPPING VOLTAMMETRY (ASV)
  7.2 Set up ASV
  instrumentation
    according to
   manufacturer's
   recommended
     procedures.
   7.3 Clean GCE.
7.4 - 7.5 Deposit gold
  film on  the GCE,
 condition electrode.
  7.7.1 - 7.7.2 Add
 5 mL HCI to 25 mL
  working standard;
  immerse electrode
and record  response.
Construct calibration
       curve.
7.3 - 7.4 Clean GCE,
  renew gold film.
7.8 Verify calibration
   with mid-range
     standard.
                               No
                             7.8 Add 5 mL HCI
                             to 25 ml aliquot of
                              samples, analyze.
                                    I
                             7.8 Calculate sample
                              concentration by
                              comparing sample
                                 response to
                              calibration curve.
                             7.8 Verify operation
                             of GCE by analyzing
                                a mid-range
                               check standard.
   Is
recovery
 within
+ /- 10%?
                                                             7.8 Continue analysis
                                                                 of samples.
                                   7063  -  10
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                                  METHOD  7199

    DETERMINATION  OF  HEXAVALENT  CHROMIUM  IN  DRINKING WATER,  GROUNDWATER AND
             INDUSTRIAL  WASTEWATER EFFLUENTS BY  ION CHROMATOGRAPHY
1.0   SCOPE AND APPLICATION

      1.1   This method provides procedures  for the determination of hexavalent
chromium in drinking water, groundwater, and industrial  wastewater effluents.

      1.2   The method  detection  limits for the above matrices  are  listed in
Table 1.  The MDL obtained by an individual  laboratory for a specific matrix may
differ  from those  listed  depending  on  the nature of  the  sample  and  the
instrumentation used.

      1.3   Samples containing  high levels of anionic species such as sulfate and
chloride may cause  column overload.  Samples  containing high levels of organics
or sulfides cause rapid  reduction of soluble Cr(VI)  to Cr(III).  Samples must be
stored at 4°C and analyzed within twenty-four hours of collection.

      1.4   This method should  be used by analysts experienced in  the use of ion
chromatography and  in the interpretation of ion  chromatograms.

2.0   SUMMARY OF METHOD

      2.1   An aqueous  sample  is filtered  through  a 0.45  /zm filter and  the
filtrate is adjusted to  a  pH  of 9 to 9.5 with a buffer solution.   A measured
volume of the sample (50-250 juL)  is  introduced  into  the  ion  chromatograph.  A
guard column removes  organics  from the  sample  before the Cr(VI) as  Cr042" is
separated on an anion exchange  separator column.   Post-column derivatization of
the Cr(VI)  with diphenylcarbazide is followed  by detection of the colored complex
at 530 nm.

3.0   INTERFERENCES

      3.1   Interferences which affect the accurate determination of Cr(VI)  may
come from several  sources.

            3.1.1  Contamination - A trace  amount of Cr is sometimes  found in
      reagent grade salts.  Since a concentrated  buffer solution  is used in this
      method to adjust the pH of samples, reagent blanks  should be analyzed to
      assess for potential  Cr(VI) contamination.   Contamination  can also come
      from improperly cleaned glassware or contact or  caustic or acidic reagents
      of samples with stainless steel  or pigmented material.

            3.1.2  Reduction of Cr(VI)  to Cr(III) can  occur  in  the  presence of
      reducing species in an acidic medium.      However,  at  a  pH of  6.5  or
      greater,  Cr042"which  is less reactive  than  the  HCr04",  is the  predominant
      species.


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            3.1.3 Overloading  of the  analytical  column  capacity  with  high
      concentrations of anionic species,  especially chloride and sulfate, will
      cause a loss of Cr(VI).  The column  specified  in  this method  can handle
      samples containing  up  to 5% sodium  sulfate  or 2% sodium  chloride (1).
      Poor recoveries  from fortified  samples  and tailing  peaks are  typical
      manifestations of column overload.

4.0   APPARATUS AND MATERIALS

      4.1   Ion Chromatograph.

            4.1.1 Instrument  equipped  with a pump  capable  of  withstanding  a
      minimum backpressure of 2000 psi  and  of delivering a constant flow in the
      range of 1-5 mL/min  and  containing no metal  parts  in the sample, eluant or
      reagent flow path.

            4.1.2 Helium gas supply (High purity, 99.995%).

            4.1.3 Pressurized eluant  container, plastic, one or two liter size.

            4.1.4 Sample loops of various sizes  (50 - 250
            4.1.5 A pressurized reagent delivery module with  a  mixing  tee and
      beaded mixing coil .

            4.1.6 Guard Column  -  A column placed before  the  separator column
      containing a sorbent capable of removing strongly absorbing organics and
      particles that would otherwise  damage the separator column (Dionex lonPac
      NG1 or equivalent) .

            4.1.7 Analytical Column - A column packed with  a high capacity anion
      exchange resin capable of resolving Cr04  from other sample constituents
      (Dionex lonPack AS7 or equivalent).

            4.1.8 Postcolumn reactor -  Mixing tee,  or membrane  reactor,  with
      reaction coil.  Must be compatible with flows from 0 to 2 mL/min.

            4.1.9 A low- volume flow- through cell visible lamp detector containing
      no metal parts in contact with the eluant flow  path.  Detection wavelength
      is at 530 nm.

            4.1.10  Recorder,  integrator,  or computer for receiving  analog or
      digital signals for recording detector response (peak height or area) as
      a function of time.

      4.2   Labware  -   All  reusable  glassware  (glass,  quartz,  polyethylene,
Teflon, etc.)  including the sample  containers  should be soaked  overnight in
laboratory grade  detergent  and  water,  rinsed with  water, and soaked for four
hours in a mixture  of  dilute nitric  and hydrochloric acid (1+2+9) followed by
rinsing with tap water  and Reagent water.


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            NOTE: Chromic acid must not be used for the cleaning of glassware.

            4.2.1 Volumetric flasks  and  a graduated cylinder  -  of acceptable
      precision and accuracy.

            4.2.2 Assorted calibrated  pipettes - of acceptable  precision and
      accuracy.

            4.2.3 Disposable syringes - 10-mL, with male luer-lock fittings.

            4.2.4 Syringe filters - 0.45-jum.

            4.2.5 Storage bottle - high density polyproplene, 1-L capacity.

            4.2.6 pH meter - to read pH range 0-14 with accuracy ± 0.03 pH.

            4.2.7 Filter discs  - 0.45-jum pore, 7.3-cm diameter (Gelman Aero BOA,
      Mfr.  No. 4262, or equivalent).

            4.2.8 Plastic syringe filtration unit (Baxter Scientific,  Cat. No.
      1240 IN, 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  conform to  the  specifications
established by 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.

            5.1.1 Ammonium hydroxide, NH4OH,  (sp.gr. 0.902)  (CAS RN 1336-21-6).

            5.1.2 Ammonium sulfate,  (NH4)2 S04  (CAS  RN  7783-20-2).

            5.1.3 1,5 Diphenylcarbazide (CAS RN 140-22-7).

            5.1.4 Methanol,  HPLC grade.

            5.1.5 Sulfuric acid, concentrated (sp.gr. 1.84).

      5.2   Reagent water.  Reagent  water  shall  be interference-free and should
conform to  the performance specifications  of ASTM  Type  I water.  All references
to water in the  method  refer to reagent water  unless  otherwise  specified.   A
definition of reagent water  can be found in Chapter One.

      5.3   Cr(VI)  Stock Solution  (1000 mg/L).   Dissolve 4.501 g of Na2Cr04*4H20
in reagent water and dilute  to one liter.   Transfer to a polypropylene storage
container.
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      5.4   Quality  control  sample  (QCS).   Obtained  and  prepared  from  an
independent source (EPA, MIST or from a commercial  source).  Dilute an aliquot
according to  the instructions and  analyze with samples.   If an  EPA or  NIST
reference sample is  not  available, a  mid-range standard,  prepared from  an
independent commercial source,  may be used.

      5.5   Eluant.  Dissolve 33 g of ammonium sulfate in 500 mL of reagent water
and add 6.5 ml of ammonium hydroxide.  Dilute to one liter with  reagent  water.

      5.6   Post-column reagent.  Dissolve  0.5 g of 1,5 diphenylcarbazide in 100
ml of HPLC grade methanol.   Add to about 500 ml of  Reagent water containing 28
ml of 98% sulfuric acid while  stirring.  Dilute with reagent water to one liter
in a volumetric flask.   Reagent is stable for four or five days, but should only
be prepared in one liter quantities as  needed.

      5.7   Buffer Solution.   Dissolve  33 g of  ammonium sulfate  in  75 ml  of
reagent water  and add 6.5 mL  of ammonium hydroxide.   Dilute to  100 ml  with
reagent water.

6.0   SAMPLE COLLECTION, PRESERVATION AND HANDLING

      6.1   Prior to the collection of the sample, consideration should be given
to the type of data required so that appropriate preservation and pretreatment
steps can be taken.  Filtration and  pH adjustment should be performed at the time
of sample collection or as soon thereafter as practically possible.

      6.2   For  the  determination  of dissolved  Cr(VI),  the  sample  should  be
filtered through  a 0.45-/im filter.  Use a portion  of the  sample  to  rinse the
syringe  filtration  unit and filter  and then  collect  the  required  volume  of
filtrate.  Adjust the pH of the sample  to 9-9.5 by  dropwise addition of buffer
solution (Section 5.7), periodically checking the pH with the pH meter or narrow
pH-range pH paper.   Approximately  10 mL  of sample are  sufficient  for three 1C
analyses.

      6.3   Ship  and  store the samples  at 4°C  in   125-mL  narrow-mouth,  high-
density polypropylene containers, or equivalent.  Bring to ambient temperature
prior to analysis.  Samples should  be analyzed within 24 hours of collection.

7.0   PROCEDURE

      7.1   Sample preparation.   Allow pH-adjusted samples  to  equilibrate to
ambient temperature prior to analysis.   Samples that have not been pH adjusted
should be adjusted as described in Section 6.2.

      7.2   Calibration.    Calibrate the  instrument  using  a  minimum  of  a
calibration blank and three calibration standards  bracketing the anticipated
concentration  range  of  the  samples.  The  calibration  range must cover no more
than two orders of magnitude.  Calibration standards  should be prepared from the
Cr(VI) stock standard  (Section 5.3)  by appropriate  dilution with reagent water
                                    7199 -  4                      Revision 0
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in volumetric flasks.  The standards should be adjusted to a pH of 9-9.5 with the
buffer solution prior to final dilution.

            7.2.1 Establish   ion   chromatographic   operating  conditions   as
      indicated in Table 2 or as instructed by the instrument manufacturer.  The
      flow rate of the eluant  pump  is  set  at 1.5 mL/min and the pressure of the
      reagent delivery  module  adjusted  so that the  final  flow rate  from  the
      detector is 2.0 mL/min.   This requires  manual  adjustment and measurement
      of the fi.nal flow using  a  graduated  cylinder and a stop watch.  A warm-up
      period of approximately 30 minutes  after  the  flow rate has  been adjusted
      is recommended and the  flow  rate should  be checked  prior to calibration
      and sample analysis.

            7.2.2 Injection loop size is  chosen  based on  standard  and  sample
      concentrations and the  selected attenuator setting.   A 250-juL  loop  was
      used to establish the method detection limits in Table  1.  A  50-juL loop
      is normally sufficient for higher concentrations.  The sample volume used
      to load the injection loop should be at  least  10  times  the  loop size so
      that all  tubing  in contact with sample  is  thoroughly  flushed  with  new
      sample to prevent cross contamination.

            7.2.3 A calibration curve  of analyte response (peak height or area)
      versus analyte concentration should  be constructed.   The coefficient of
      correlation for the curve should be  0.999 or  greater.

      7.3   Instrument performance.  Check the performance  of the instrument and
verify the calibration using data gathered from analyses of laboratory blanks,
calibration standards and the quality control  sample.

            7.3.1 After  the  calibration  has  been  established,   it  must  be
      verified by analyzing a QCS.   If the measured concentration  exceeds ± 5%
      of the established value, a second  analysis  should be performed.  If the
      measured  concentration  still exceeds ±  5%  the  established  value,  the
      analysis  should  be   terminated  until   the   source   of  the  problem  is
      identified and corrected.

            7.3.2 To verify  that the instrument is  properly calibrated on  a
      continuing basis, run  a  laboratory blank  and a calibration check standard
      every ten analyses.  If the measured  concentration  of  the analyte deviates
      from the true concentration by more  than  ± 5%, re-analyze the calibration
      check standard.   If this  check  standard  deviates  by  more than ± 5%,  the
      instrument must be recalibrated  and  the previous ten samples re-analyzed.
      The  instrument  response  from  the  calibration check may  be  used  for
      recalibration purposes.   Refer to  Section 7.2 for instrument calibration
      procedures.

      7.4   Sample Analysis.  Draw into a new, unused syringe approximately 3 ml
of sample and attach a syringe filter to the syringe.  Discard 0.5 mL through the
filter and  load  the remaining sample (equal to at least  10X the  sample loop
volume)  into sample  loop.    Samples having  concentrations  higher  than  the


                                   7199 -  5                       Revision  0
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established calibration range must be diluted into the calibration range and re-
analyzed.   Each sample  should be  injected twice  and  the  Relative  Standard
Deviation of the duplicates should be less than 20% or the sample data must be
qualified.

      7.5   Calculations.

            7.5.1 From the calibration curve the concentration of the sample can
      be determined.   For the above procedure,  if there is  no.  dilution,  the
      concentration of the sample should be reported as
            7.5.2 The QC data obtained during the analyses provide an indication
      of the quality of the sample data and should be provided with the sample
      results.

8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for the appropriate quality control procedures.

      8.2   All quality control data should be maintained and available for easy
reference or inspection.

      8.3   Calibration curves should be composed of  a  minimum of a blank and
three standards.

      8.4   Samples exceeding the highest calibration standard must be diluted
and re-analyzed.

      8.5   A  minimum of  one  method blank  sample  per sample batch  must  be
analyzed to check for contamination.  A method blank is reagent water prepared
by adjusting the pH to between  9  and  9.5 with  the same volume of buffer as used
for the samples.

      8.6   A minimum of one duplicate  sample and one matrix  spike sample per
sample batch must be analyzed for each analytical batch to check for duplicate
precision and matrix-spike recovery.

      8.7   A quality control  sample (QCS)  must be analyzed at the beginning of
each analytical run to validate the instrument calibration.

9.0   METHOD PERFORMANCE

      9.1   Instrument operating conditions used for single laboratory testing
of the  method are summarized  in  Table  2.   Dissolved  Cr(VI)  method detection
limits are listed in Table  1.

      9.2   Data  obtained  from  single  laboratory testing  of the  method are
summarized  in Table  3  for  five water  samples representing  drinking water,
deionized water, groundwater, treated municipal sewage wastewater, and treated
                                    7199 -  6                       Revision 0
                                                                  January 1995

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electroplating wastewater.   Samples  were  fortified  with 100 and 1000  p.g/1 of
Cr(VI), and recoveries were determined.

      9.3   Pooled  Precision and  Accuracy:    This  method  was  tested  by  21
volunteer laboratories in  a  joint  study by USEPA  and the American  Society for
Testing and Materials (ASTM). Mean recovery  and accuracy for Cr(VI) (as Cr042")
was determined  from the  retained  data of 13  laboratories  in  reagent water,
drinking water, groundwater,  and various  industrial  wastewaters.   For reagent
water, the mean recovery and the overall,  and single-analyst relative standard
deviations were 105%, 7.8%, and 3.9%, respectively.  Table 4 contains the linear
equations that describe the single-analyst standard deviation and mean recovery
of Cr(VI) in reagent water.

10.0  REFERENCES
      1.    Dionex Technical Note No. 26, May 1990.

      2.    Glaser, J.A.,  Foerst,  D.L.,  McKee,  G.D., Quave,  S.A.,  and Budde,
            W.L.,  "Trace Analyses  for Wastewaters",  Environmental  Science and
            Technology, Vol. 15, No. 12,  1981, pp. 1426-1435.

      3.    Edgell,  K.,   Longbottom,  J.,  and  Joyce,   R.,   "Determination  of
            Dissolved Hexavalent Chromium  in  Drinking Water, Groundwater, and
            Industrial Wastewater Effluents by Ion Chromatography: Collaborative
            Study", (Internal EPA report, 1992).

      4.    Arar, Elizabeth J.,  and Pfaff,  John  D., "Determination of Dissolved
            Hexavalent  Chromium in  Industrial   Wastewater  Effluents  by  Ion
            Chromatography     and    Post-Column    Derivatization     with
            Diphenylcarbazide",  Journal  of Chromatography, 546 (1991) 335-340.
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                 Table  1.  Method Detection Limit for Cr(VI)
Matrix Type
Reagent Water
Drinking Water
Ground Water
Primary Sewage
Wastewater
Electroplating
Wastewater
Retention Time
(min)
3.8
3.8
3.8

3.8

3.8
Method Detection Limit18'
wq/L
0.4
0.3
0.3

0.3

0.3
(a)
  MDL concentrations  are  computed  for  final  analysis  solution  (Section  8.2.2)
                   Table 2.  Ion Chromatographic Conditions
Columns:    Guard Column - Dionex lonpac NGI
            Separator Column - Dionex lonPac AS7

Eluant:     250 mM (NHJ2S04
            100 mM NH4
            Flow Rate =1.5 mL/min

Post-Column Reagent:    2mM Diphenylcarbohydrazide
                        10% v/v CH3OH
                        1 N H2S04
                        Flow rate =0.5 mL/min

Detector:   Visible 530 nm
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               Table  3.  Single-laboratory Precision and Accuracy
Sample Type
Reagent Water

Drinking Water

Ground Water

Primary Sewage
Wastewater
Effluent

Electroplating
Wastewater
Effluent

Cr(VI)
(/vg/L)(a)
100
1000
100
1000
100
1000


100
1000


100
1000
Percent
Mean Recovery
100
100
105
98
98
96


100
104


99
101
RpD(bi
0.8
0.0
6.7
1.5
0.0
0.8


0.7
2.7


0.4
0.4
(al  Sample  fortified  at  this  concentration  level.

(b>  RPD  - relative  percent difference between duplicates.
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       Table  4.  Single-Analyst Precision,  Overall  Precision and Recovery
                          From Multilaboratory Study
                        Reagent Water                 Matrix  Water
                        (6-960 fjg/l)                  (6-960//g/L)
Mean Recovery           X = 1.020C + 0.592             X  =  0.989C  -  0.411

Overall Standard        SR= 0.035X + 0.893             SR=  0.059X  +  1.055
Deviation

Single-Analyst          SR= 0.021X + 0.375             SR=  0.041X  +  0.393
Standard-Devi ation
X = Mean concentration; //g/L, exclusive of outliers.
C = True value, /yg/L.
SR= Overall standard deviation.
SR= Single-Analyst standard deviation.
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                                           METHOD  7199
DETERMINATION  OF  HEXAVALENT  CHROMIUM  IN  DRINKING WATER.  GROUNDWATER AND
             INDUSTRIAL WASTEWATER EFFLUENTS  BY  ION  CHROMATOGRAPHY
                                   7.1 Sample Preparation: Adjust sample pH
                                   to 9 - 9.5, allow sample to equiliberat* to
                                           ambient temperature.
                                  7 2.1 - 7.2 2 Establish instrument operating
                                 conditions and flow rate; select sampling loop.
                                  7.2.3 - 7.3 Calibrate with a minimum of three
                                    standards, verify instrument performance
                                      and calibration with blank analyses,
                                            standards and QCS.
                                                                          Repeat analysis of QCS,
                                                                          if not within +/- 5% T.V.
                                      7.3.2 Verify continuing instrument
                                     calibration every 10 analytical samples
                                   with calibration check standard and blank.
                Recalibrate and reanalyze
                  previous tan samples.
                                                     Yes
                                             Continue analysis.
                                     7.5 Calculate sample concentration frort
                                        calibration curve, report as ug/L.
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                                  METHOD  7472

                    MERCURY IN AQUEOUS  SAMPLES  AND  EXTRACTS
                     BY  ANODIC STRIPPING  VOLTAMMETRY  (ASV)
1.0   SCOPE AND APPLICATION

      1.1   This method is applicable for laboratory determinations of
dissolved organic and inorganic divalent mercury ions and compounds (Hg(IIJ)
in drinking water, natural surface water, seawater, in domestic and industrial
wastewater, and in aqueous soil extracts.  Solid matrices must be solubilized
by acid digested prior to quantitation by ASV.

      1.2   Dissolved Hg(II) in the form of mercury ions and un- ionized
organic and inorganic mercury compounds may be quantified in the concentration
range 0.1 to 10,000 p.g/1  Hg.   The  upper  concentration range  may be  extended
by sample dilution, increasing the stripping current and/or by decreasing the
analyte deposition time.

      1.3   This method cannot be used for direct determination of water-
insoluble mercury compounds.  Analytes containing mercury in this form must be
chemically processed to liberate Hg(II) before the determination.
      1.4   The method detection limit for Hg(II) is 0.1 jug/L  using  a  10-
minute plating time and 3 /^g/L  using  a  1-minute  plating  time.

2.0   SUMMARY OF METHOD

      2.1   Standards and samples are made 0.1 M in CV  and  are rendered
electrically conductive by adding concentrated hydrochloric acid (HCL) or
solid sodium chloride (NaCl).  Hg(II) is quantified by anodic  stripping, at a
potential of +500 mV with respect to an saturated calomel electrode  (SCE),
from a gold metal film deposited on a glassy carbon electrode  (GCE).

3.0   INTERFERENCES

      3.1   ASV cannot distinguish between organic and inorganic divalent
mercury compounds.

      3.2   Turbid samples should be filtered through a borosilicate glass
fiber filter with 0.45-jLim pores  to preclude  physical  erosion of the  GCE  film.

      3.3   Highly corrosive and oxidizing samples may corrode the gold film
on the GCE and degrade the instrument response.  The performance of  the GCE
electrode must be monitored by analysis of a mid-range calibration standard.
Low recovery on the calibration standard may require re-cleaning and re-
application of the gold film.
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      3.4   Samples containing tannic acid in concentrations greater than 100
mg/L cannot be analyzed for mercury by ASV.

      3.5   Some wet deposition samples may have insufficient electrical
conductivity for proper operation of the ASV instrumentation.  This problem is
obviated by making the samples 0.1 M in HCL.

4.0.  APPARATUS AND MATERIALS

      4.1   ASV instrumentation (Radiometer TraceLab, or equivalent),
including potentiostat, electrodes, stirrer, sample stand, polyethylene sample
cups, and GCE polishing powder.

      4.2   Computer, as recommended by ASV instrumentation manufacturer.

      4.3   Plastic syringe and a nylon syringe filter with 0.2-fjm pores.

      4.4   Polyethylene graduated cylinder, 50-mL, Class B, TC/TD.

      4.5   Adjustable pipetters with polyethylene tips.

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 interference free.  All
references to water in the method refer to reagent water unless otherwise
specified.

      5.3   Hydrochloric acid, (concentrated 12 M)

            5.3.1 Hydrochloric acid (0.1 M),  dilute 8.3 ml concentrated HCL
      to 1 liter with reagent water.

      5.4   Sodium Chloride, fine crystals.

      5.5   Gold Stock Standard (1000 mg/L), stock solutions are commercially
available as spectrophotometric standards.

            5.5.1 Gold-plating solution, (50 mg/L Au in 0.1 M HCL), or  as
      recommended by the GCE manufacturer: prepare by diluting 2.5 mL of a
      1000 mg/L gold spectrophotometric standard to 50 mL with 0.1 M HCL.

      5.6   Mercury Stock Standard  (1000 mg/L), stock solutions are
commercially available as spectrophotometric standards.

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            5.6.1 Mercury intermediate standard solution, 1,000/yg/L mercury:
      dilute 100//L of the stock standard to 100 mL with 2% HN03.   Prepare
      weekly.

            5.6.2 Mercury Working Standards: These standards should be
      prepared from the mercury intermediate standard to be used as
      calibration standards at the time of analysis.  Prepare at least five
      working standards over the expected sample concentration range.  Prepare
      working standards by diluting an appropriate aliquot of the intermediate
      mercury stock solution with 2% HN03.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All samples must be collected using a sampling plan that addresses
the considerations discussed in Chapter Nine of this manual.

      6.2   All sample containers must be prewashed with detergents, acids,
and reagent water.  Plastic and glass containers are both suitable.

      6.3   At the time of sampling, the sample must be acidified to a pH <2
with nitric acid.

      6.4   While samples to be analyzed for free dissolved mercury do not
require refrigeration, they should be stored out of direct sunlight in an area
no warmer than room temperature.

7.0   PROCEDURE

      7.1   Analysis of aqueous samples for free dissolved mercury by ASV
involves two major steps.  First, the GCE electrode is cleaned and prepared
for use by plating on a thin film of gold.   The gold-plated electrode is then
used to analyze calibration standards and samples.

      7.2   Set up ASV instrumentation, electrodes, and computer according to
the manufacturer's recommended procedures.   Enter the appropriate program and
required data parameters into the computer as directed by the instrument
software.

      7.3   Before applying a gold film to the GCE, the electrode must be
thoroughly cleaned.  Electrode cleanliness is checked by rinsing the GCE with
water.  After gently shaking off excess water, the electrode should be coated
with a thin, flat, continuous water film.  If necessary, clean the GCE by
wiping it with a wet, soft paper towel, polish it with polishing powder, and
rinse it thoroughly with water.  Keep the cleaned electrode immersed in water.

      7.4   Place 50 mL of the gold-plating solution (Sec. 5.5.1) or an
appropriate volume as recommended by the instrument manufacturer, into a
beaker. Immerse the electrodes in the gold-plating solution and initiate the
GCE gold-plating program as instructed by the instrument manufacturer.
                                   7472 - 3                       Revision 0
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      7.5   Remove the electrodes from the plating solution and rinse well
with water.  Keep the electrodes immersed in reagent water until  ready to
analyze samples.

      7.6   The instrument response is calibrated by preparing a calibration
curve with mercury standards (Sec 5.6.2).  The same stripping current and
plating time settings that are used for analyzing samples must be used for
preparing the calibration curve.

      7.7   Prior to instrument calibration, all calibration standards and
samples must be made 0.1 M in Cl".   Using  a  graduated cylinder, measure 30 ml
of each calibration standard and sample into a sample cup.  Add 0.25 mL of 12
M HCL (Sec 5.3) or 0.18 g of solid NaCl (Sec 5.4) to the standard or sample
and mix.  Samples must be allowed to equilibrate to room temperature (within
the range 20 "C to 30 °C) if necessary.

      7.8   Following the instrument manufacturer's recommended calibration
procedures, construct a calibration curve by analyzing five working
calibration standards.  Immerse the electrodes into 30 ml of the prepared
working standard (Sec 7.7) and record instrument response.  Rinse the
electrodes thoroughly with reagent water between each standard.  Construct a
calibration curve by recording the instrument response (peak area) versus the
standard concentration.

      7.9   Store the electrodes in reagent water until ready to analyze
another sample.

      7.10  Analyze the samples for Hg (II) by aliquoting 30 ml of the
prepared sample (Sec. 7.7) into a sample cup. Immerse the electrodes into the
sample and record instrument response.  Determine the sample concentration
from the calibration curve.

            Note: Depending on the composition of the samples, a single
            application of the gold film may suffice for analysis of up to a
            dozen or more samples.  Highly  corrosive and oxidizing samples may
            corrode the gold film and degrade the instrument response,
            requiring the re-application of the gold film.  The analyst must
            monitor performance of the electrode by analyzing a mid-range
            check standard every ten samples.  A low recovery for the check
            standard indicates that the electrode must be renewed.  Follow the
            procedures in Sec. 7.3 through  7.5 to renew the gold film on  the
            GCE.  Following the renewal of  the electrode, the instrument
            calibration must be verified by analyzing a mid-range standard. If
            the recovery of the standard is within 10% of the true value, a
            new calibration curve need not  be run and the analyst may continue
            with the analysis.
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8.0   QUALITY CONTROL

      8.1   Initial Calibration Verification standard (ICV):  The ICV contains
a known Hg(II) concentration and is obtained from an independent source.  The
ICV recovery must be within the range 90% to 110%.  If it is not, the source
of error must be found and corrected.  An acceptable ICV must be analyzed
prior to analyzing samples.  The ICV also serves as a laboratory control
sample.

      8.2   Continuing Calibration Verification standard (CCV):  After a set
of not more than 10 samples has been analyzed, and after the final sample has
been analyzed, a CCV containing a known mercury concentration must be
analyzed.  The CCV recovery must be within the range 90% to 110%.  If it is
not, the source of error must be found and corrected (See the note in Sec.
7.10)  All samples analyzed since the last acceptable CCV must be re-analyzed.

      8.3   Reagent blank: A reagent blank must be analyzed with each
analytical batch or 20 samples, whichever is more frequent.  A reagent blank
is reagent water treated as a sample.  The indicated concentration of the
reagent blank must be less than the lower detection limit of Hg(II).  If it is
not, sample carryover or reagent contamination is indicated.  The problem must
be corrected before analyzing more samples.

      8.4   At least one matrix spike (MS) and one matrix spike duplicate
(MSD) shall be included in each analytical batch or 20 samples: A matrix
duplicate may be substituted for the MSD provided that the concentration of
mercury in the sample selected for duplicate analysis is greater than the
limit of detection.  The spike should increase the concentration of free
Hg(II) in the spiked sample by 50% to 200%.  The volume of the spike must be
no more than 1% of the sample volume.

            8.4.1  The spike recovery must be within the range 75% to 125%.
      If it is not, the source of error must be found and corrected.  If a
      matrix interference is suspected, a second sample aliquot should be
      spiked to confirm the spike recovery.  If the spike recovery is  still
      outside the range of ± 25%, all samples must be quantified by the method
      of standard additions.  Refer to Method 7000 for information on the
      method of standard additions.

            8.4.2  The duplicate samples (MS/MSD and/or Sample/Sample
      duplicate) should give results having a difference not greater than 20%
      of the mean of the duplicate results.  If the difference is greater than
      20% of the mean, the source of error must be found and corrected.

9.0   METHOD PERFORMANCE

      9.1   In a single-laboratory evaluation, standards with known Hg(II)
concentrations were analyzed in quintuplicate according to the instructions
given above.  The results are listed in Table 1.
                                   7472 - 5                       Revision 0
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TABLE 1. ACCURACY AND PRECISION OF MERCURY ANALYSIS
Mercury Concentration
(M9/L)
5.00
15.0
50.0
Mercury Recovery
(%)
97
101
97
Relative Standard
Deviation (%)
3.8
0.9
1.2
      9.2   In a single laboratory evaluation, the precision and accuracy of
ASV was compared to an EPA-approved spectrophotometric method by analyzing a 1
fj.g/1 and 5  /*g/L  standard  of mercury  (II)  ten times  each.   The  results of this
comparison are listed in Table 2.
TABLE 2. COMPARISON OF ASV AND SPECTROPHOTOMETRIC METHOD FOR QUANTIFYING
DISSOLVED MERCURY
Analytical Method:
Response in yug/L and
(RSD,%) for a 1 /xg/L Hg
(II) standard
Response in yug/L and
(RSD, %) for a 5 ^g/L
Hg (II) standard
Voltammetry 1.0 5.1
(5.2) (2.1)
Spectrophotometric 1.1 5.0
(6.2) (5.7)
10.0  REFERENCES

1.    Pyle, Steven; Miller, Eric Leroy; Quantifying Mercury In Aqueous
      Solutions By Anodic Stripping Voltammetry, EMSL-LV/ORD/USEPA.
                                   7472  - 6
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January 1995

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                                METHOD 7472

                 MERCURY  IN AQUEOUS SAMPLES  AND EXTRACTS
                  BY ANODIC STRIPPING VQLTAMMETRY (ASV)
   7.2 Set up ASV
   instrumentation
    according to
   manufacturer's
     procedures.
                        7.10 Analyze a 30 ml_
                          aliquot of sample,
                          calculate sample
                             cone, from
                          calibration  curve.
7.3 Clean GCE.
i
7
r
4 Apply gold film
to GCE.
                                                       7.10 Verify operation
                                                        of GCE by analyzing
                                                         a mid-range check
                                                          standard  every
                                                            1 0 samples.
 7.7 Add 0.25 mL of
 12 M HCI or 0.18 g
NaCL to all standards
   and samples.
7,3 - 7.4 Clean GCE,
  renew gold film.
    7.8 Analyze 5
calibration standards,
     construct a
   calibration curve.
                               7.10 Verify calibration
                                   with mid-range
                                     standard.
    Is
 recovery
within  + /
   10%?
                           7.10 Continue
                              analysis.
                                  7472  -  7
                                   Revision  0
                                   January  1995

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                                  METHOD 7521

                  NICKEL (ATOMIC ABSORPTION, FURNACE METHOD)


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   If interferences are suspected, see Section 3.0 of Method 7000.

      3.2   In addition to the  normal  interferences experienced during graphite
furnace analysis,  nickel  analysis can  suffer from severe nonspecific absorption
and light scattering caused by matrix components during  atomization.  Background
correction is strongly recommended.

      3.3   Severe memory effects for  nickel may occur in graphite furnace tubes
used for arsenic or selenium analysis by Methods 7060 and 7740, resulting from
the use of a nickel nitrate matrix modifier in those methods.  Use of graphite
furnace tubes and  contact rings for nickel analysis  that are  separate from those
used for arsenic and selenium analyses is strongly recommended.

4.0   APPARATUS AND MATERIALS

      4.1   For basic  apparatus,  see  Section  4.0 of Method  7000.   Due to the
widespread use of  a  nickel-nitrate modifier for atomic absorption analyses, a
dedicated instrument is recommended when conducting analyses by this method.  If
a dedicated  instrument  is  not  available, the  furnace  tubes  and  contact rings
should be changed prior to using this methodology.

      4.2   Instrument parameters (general):

            4.2.1  Drying time and temp.:  30 sec at 125°C.

            4.2.2  Ashing time and temp.:  30 sec at 800°C.

            4.2.3  Atomizing time and temp.:  10 sec at 2700°C.

            4.2.4  Purge gas:  Argon or nitrogen.

            4.2.5  Wavelength:   232.0 nm.

            4.2.6  Background correction:  Recommended.
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            4.2.7  Other operating parameters  should  be set as specified by the
      particular instrument manufacturer.

            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 size
            furnace devices or those employing faster rates of atomization can
            be operated using  lower  atomization temperatures  for shorter time
            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 -  Do not  dry reagent.   Dissolve  4.953 g of
      nickel nitrate  hexahydrate,  Ni(N03)2»6H20 (analytical reagent  grade) in
      reagent water and dilute  to  1.000 L in  a  volumetric flask.  Alternatively,
      procure a certified standard from a supplier and verify concentration 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
      should be  prepared  using  the  same type  of  acid and  at the  same acid
      concentration as in the prepared samples to be analyzed (0.5% v/v HN03).

6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1   See Chapter Three, Step 3.1.3,  "Sample Handling and Preparation."

7.0   PROCEDURE

      7.1   Sample preparation - The procedures for preparation of the sample are
given in Chapter Three, Step 3.2.

      7.2   See Method 7000, Step 7.3,  "Furnace Technique."

8.0   QUALITY CONTROL

      8.1   See Section 8.0 of Method 7000.

9.0   METHOD PERFORMANCE

      9.1   Precision and accuracy data are not available at this time.
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      9.2   The  performance characteristics  for an  aqueous  sample  free  of
interferences are as follows:

      Optimum concentration range:  5-50 ug/L.
      Estimated detection limit:  1 ug/L.

10.0  REFERENCES

1.    Methods for the Chemical  Analysis  of Water and Wastes, U.S. Environmental
Protection Agency, Office of Research and Development, Environmental Monitoring
and Support Laboratory,  ORD Publication  Offices of the Center for Environmental
Research Information, Cincinnati, OH,  1983;  EPA-600/4-79-020.
                                   7521 - 3                       Revision 0
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                METHOD 7521

NICKEL (ATOMIC ABSORPTION.  FURNACE METHOD)
>
5.0
r
Prepare sample.
                See Section 3.2
                of Chapter 3 for
               sample preparation.
               See Section 7.3 of
               Method 7000 for
             'Furnance Technique"
                   7521 - 4
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                                  METHOD  7580

      WHITE PHOSPHORUS (P,) BY SOLVENT EXTRACTION AND GAS CHROMATOGRAPHY


1.0  SCOPE AND APPLICATION

     1.1   Method 7580 may  be used  to  determine the concentration  of white
phosphorus (P4)  (CAS  Registry  No.  7723-14-0)  in  soil,  sediment,  and water
samples.

     1.2   This  method includes two different extraction procedures for water
samples.  The first  procedure  provides sensitivity  on  the  order of 0.01 /Ltg/L,
and may be used to assess  compliance with Federal water quality criteria.  The
second  procedure  provides  sensitivity on the  order of 0.1 /xg/L.   The method
includes one procedure for the extraction of soil/sediment samples which provides
sensitivity on the order of 1 jiig/kg.

     1.3   White phosphorus  is a  toxic,  synthetic substance that has been used
in poisons, smoke-screens, matches,  and  fireworks,  and has been used as a raw
material  in the  production of  phosphoric  acid.    It  has been  used  in smoke-
producing munitions  since  World War I.   White phosphorus is thermodynamically
unstable in the presence of atmospheric oxygen.  As a result, until recently, the
prospect  of  long-term environmental  contamination  from smoke munitions  was
considered unlikely.   However, a catastrophic die-off  of waterfowl  at  a  US
military facility has been  traced  to the presence of P4  in salt marsh sediments,
and  lead  to  the realization  that  P4   can   persist  in  anoxic  sedimentary
environments.

     1.4   While this  method is included in Chapter Three, Metallic Analytes,
the  sample  preparation,   extraction,  and  analytical  techniques employed  are
closely  related   to  those described  in  Chapter Four  for organic  analytes.
Therefore, this method has been written as a stand-alone procedure, describing
both the extraction and analytical techniques.  Analysts  should  refer to Method
8000 for additional  information on gas chromatographic procedures.

     1.5   This  method is restricted to use  by,  or under  the supervision of,
analysts experienced  in solvent extraction and gas chromatography.   Each analyst
must demonstrate the ability to generate acceptable results using this method.

     1.6   Because P4 will spontaneously combust in  air,  the procedures  for the
preparation of standards described  in Section 5 require the use of a glove box
or other suitable enclosed area purged with nitrogen.


2.0  SUMMARY OF  METHOD

     2.1   Water samples  are extracted by one of two procedures,  depending on
the sensitivity required.

           2.1.1   For the more sensitive procedure,  a 500 ml water sample is
     extracted with  50 ml  of  diethyl ether.  The extract is  concentrated  by back
     extraction   with  reagent  water, yielding  a   final  extract  volume  of


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      approximately  1.0 ml.   A  1.0  ,uL aliquot of this extract is injected into
      a  gas chromatograph  (GC) equipped  with  a  nitrogen-phosphorus  detector
      (NPD).  This procedure provides sensitivity on the order of 0.01 ^g/L, and
      may  be used  to  assess compliance with Federal water quality criteria.

            2.1.2    When  a  less sensitive  method  is required for water samples,
      a 30 ml water sample is  extracted once with  3.0  ml of isooctane.  A 1.0 nl
      aliquot  of the extract is  analyzed  by  GC/NPD.   This  procedure  provides
      sensitivity  on  the  order  of 0.1 jitg/L.

      2.2    Wet soil  or sediment samples are  analyzed by extracting a 40 g wet-
weight aliquot of the sample  with a mixture of 10.0 ml of degassed reagent water
and 10.0  ml  of isooctane.    The  extraction   is performed  in a glass jar  on a
platform shaker for  18 hours.  A 1.0 jj.1  aliquot  of the  extract is  analyzed by
GC/NPD.  This procedure provides sensitivity on the  order of 1 M9/kg.

      2.3    The concentration of P4 in the  extract is  calculated using peak area
(or  height)   and  an  external   standard   calibration  procedure.   The  sample
concentration is determined from the extract concentration using the final volume
of  the  sample  extract,  sample   volume  (water samples)  or  sample  weight
(soils/sediments).  Results for soils and  sediments are reported on a wet-weight
basis.

      2.4    Separate calibrations  are required  for  water  and  soil/sediment
samples because the sample  extracts are prepared  in different solvents (diethyl
ether and isooctane).


3.0   INTERFERENCES

      To date, no chromatographic interferences with this  determination have been
reported, in  part due to the selectivity  of  the nitrogen-phosphorus detector.
This procedure offers several advantages compared to  other procedures described
in the  literature which determine  P4  by  converting  it  to  phosphate,  in that
background  concentrations  of  phosphate   are  quite  common  in  many water  and
sediment samples.


4.0   APPARATUS AND  MATERIALS

      4.1    500-mL separatory  funnels  with  PTFE stopcocks, for water sample
extraction  (larger separatory  funnels may be employed).

      4.2    125-mL separatory funnels with PTFE  stopcocks,  for back extraction
of water samples.

      4.3    40-mL amber glass vials (for less sensitive  water method).

      4.4    120-mL glass vials or jars with  PTFE-lined screw caps.

      4.5    500-mL graduated  cylinder.

      4.6    10-mL graduated cylinder.

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     4.7    4-L  (or larger) amber glass bottle with  PTFE-lined  screw cap (for
preparation of the aqueous spiking solution).

     4.8    250-mL  and 50-mL glass volumetric flasks, with ground-glass stoppers.

     4.9    Disposable  pasteur pipets.

     4.10   Vortex  mixer.

     4.11   Platform  shaker,  with table to hold 120-mL vials  or jars used for
soil extractions.

     4.12   Glove box or  other  suitable  system to handle  P4  under  a nitrogen
atmosphere, complete with purified nitrogen source,  gas regulator, and tubing.

     4.13   Analytical  balance,  capable of weighing 0.1 mg.

     4.14   Forceps,  for handling  P4.

     4.15   Gas-tight syringe, 10  /xL.

     4.16   Razor blades or scalpels,  for  cutting  P4.

     4.17   Gas chromatograph, capable of isothermal operation  at 80°C, equipped
with a nitrogen-phosphorus detector, data  system,  and all relevant accessories.

     4.18   GC column,   15  m  wide-bore  capillary  column,  1% methyl  silicone,
 3.0 jim film  thickness  (DB-1, or equivalent).

     4.19   Glass  vacuum   filtration  apparatus  for  degassing  reagent  water
(Supelco 5-8062,  or equivalent).


5.0  REAGENTS

     Unless  otherwise  specified,  all  reagents will  be  at least  ACS reagent
grade.   All  reagents must be checked  for  purity  and contaminants through the
analysis of method blanks  (see Sec. 8.2).

     5.1    White phosphorus,  (99% purity), Aldrich Chemical,  or equivalent.

     5.2    Isooctane (2,2,4-trimethylpentane), ACS spectrophotometric grade.

     5.3    Diethyl ether, pesticide grade.

     5.4    Water,  ASTM regent grade.   The reagent water must be degassed in a
glass vacuum filtration apparatus  or other suitable device to  remove any traces
of oxygen.   Oxygen may also be removed from the  reagent water  by heating the
water to  90"C and purging  it with clean  helium  or  nitrogen, as  is  done for
reagent water used in the  analysis of volatile organics (see Chapter One).

     5.5    Nitrogen, prepurified,  for  glove  box.
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     5.6    Nitrogen,  zero grade,  for GC carrier gas.

     5.7    Hydrogen,  zero grade,  for NPD detector.

     5.8    Preparation   of   calibration  stock  standard   in  isooctane:   The
instrument calibration standards for soil/sediment samples  and for water samples
extracted with isooctane (Sec. 7.6) are prepared in isooctane.   A separate set
of calibration standards is  required for water samples  extracted with diethyl
ether (see Sec. 5.9).

            5.8.1    Cut   several  pieces of  P4  to  the  appropriate  size  under
     degassed  water in  a nitrogen atmosphere.   Care  should be  taken to ensure
     that each piece of  freshly cut P4  is lustrous  on all surfaces.  Each piece
     should  be dried  under a  gentle stream of  nitrogen.

            5.8.2    Place a  small  freshly  cut piece of P4  (approx.  90 mg)  into
     a  preweighed  250-mL  volumetric   flask  containing   a  small  amount  of
     isooctane.

            5.8.3    Weigh the flask containing  the  isooctane  and  piece  of  P4 to
     determine the mass  of P4 by  difference.

            5.8.4    Bring the flask to volume with  isooctane and shake until the
     P4 dissolves.    Protect  the flask from light by  wrapping  the  flask in
     aluminum  foil.

            5.8.5    Calculate the concentration of P4  in the  volumetric flask.

            5.8.6    Using the calibration stock standard, prepare 5 calibration
     standards in isooctane over the linear range of the calibration  curve.  The
     lowest  concentration  standard  should  be  set   at   or below  a  sample
     concentration  of 1 M9A9-   For  a 40  g  (wet weight)  sample and a  1 nl
     injection volume,  the  concentration   of the  lowest  standard   will  be
     approximately 4 /zg/L in isooctane.  To demonstrate the  0.1 /ig/L sensitivity
     for the water sample procedure in Sec. 7.6, the concentration of the lowest
     standard  must  be   approximately  1 jug/L  in  isooctane.    The  remaining
     standards should  span  the  linear working  range of  the  chromatographic
     system (see Method  8000 for a discussion of five-point initial calibration
     standards).

            5.8.7    Store any working stock solutions and calibration standards
     in the  dark  at 4°C.

     5.9    Preparation  of calibration  stock standard  in diethyl  ether

     Because of the volatility  of diethyl ether, it is likely that calibration
standards and  stock standards for the water  samples  extracted  by the diethyl
ether procedure in Sec.   7.3 will have to be  prepared more frequently than  those
standards in isooctane  for the soil/sediment samples procedure.

            5.9.1    Using the isooctane calibration stock standard prepared in
     Sections  5.8.1 - 5.8.5, prepare  5 calibration standards in diethyl  ether
     over  the  linear  range of the calibration  curve.  Since  the  stock  standard

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     is diluted by a factor of approximately 5000,  the small amount of isooctane
     is insignificant.   The  lowest  concentration  standard should be set at or
     below  a  sample  concentration of  0.01  jug/L.   For a 500-mL water sample, a
     1.0 ml final  extract volume, and a 1 /itL injection volume, the concentration
     of  the  standard  will  be  approximately  5 M9/L in  diethyl  ether.   The
     remaining  standards  should   span  the   linear  working  range  of  the
     chromatographic  system  (see Method  8000  for a  discussion  of five-point
     initial  calibration  standards).

            5.9.2    Store any working  stock solutions  and calibration standards
     in the dark  at  -20°C.

     5.10   Preparation of the aqueous  stock solution  of P4 - The solubility of
P4 in water is  approximately 3  mg/L.    The  following  instructions  involve the
preparation of a stock solution  from an excess  of  P4  (i.e., this should produce
a saturated solution of P4 in water).

            5.10.1  Cut a piece of  P4 weighing at least  15  mg,  under degassed
     water  in a nitrogen atmosphere such as a glove box.  Care should be taken
     to ensure  that the piece of freshly  cut  P4  is  lustrous  on  all surfaces.
     The piece  should  be dried  under  a  gentle  stream  of nitrogen.

            5.10.2  Maintaining  the  nitrogen atmosphere,  place the freshly cut
     piece  of P4  into an amber glass  container  with a PTFE-lined  cap  and at
     least  a  4  L  capacity.

            5.10.3  Fill  the container with Type I, degassed reagent grade water,
     leaving  no headspace.

            5.10.4  Seal  the  container,  remove  it  from the nitrogen atmosphere,
     and constantly  agitate  the mixture for at least  60 days.

            5.10.5  As noted  above,  this procedure involves the use of an excess
     of  P4.   After 60 days,  the concentration of the P4  in  the  aqueous stock
     solution must be determined by  extraction with isooctane  and analysis using
     the procedures  in Sec.  7.6.

     5.11   Preparation of the aqueous spiking  solutions  -  Two different aqueous
spiking solutions  are required for preparation  of matrix  spike/matrix spike
duplicate aliquots.  One solution  is used for spiking  water samples.  The other
solution is used for spiking soil/sediment samples.

            5.11.1  Based on  the concentration  of  the  stock solution determined
     in Sec.  7.6,  prepare an aqueous  spiking  solution at a concentration of 5
     /ng/L  by  diluting  the  stock  solution.  A 1.0  ml volume of  this spiking
     solution  added  to  a  500  ml  sample will  produce  a   concentration  of
     approximately  0.01  jug/L of P4.

            5.11.2  Based on  the concentration  of  the  stock solution determined
     in Sec. 7.6, prepare a  soil  spiking solution  at  a concentration of 40 /xg/L
     by diluting  the  stock solution.  A  1.0 ml volume of this spiking solution
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      added  to  a  40  g  wet  soil  sample  will   produce  a  concentration  of
      approximately  1 M9/kg of P4.


6.0   SAMPLE COLLECTION,  PRESERVATION, AND  HANDLING

      6.1    White phosphorus  is  released  into   the  environment  from  smoke
munitions in the form of  small,  discrete  particles.  These particles persist in
soils, sediments, and  may  occur as  suspended  or  colloidal  particles  in anoxic
waters.  Therefore,  some samples  or sample aliquots  from  a  given location may
contain P4 particles while others do not.   The  nature  and  distribution of P4
contamination from other, non-military, sources has not been  studied, but sample
collection  procedures  should  address  the  likelihood that  P4  is present  in
discrete particles,  and must be  designed  to ensure that multiple representative
samples of the matrix of  interest  are collected.  In addition, soil and sediment
samples must be carefully  homogenized and  subsampled.

      6.2    Because  P4  will oxidize  on  contact with  oxygen,  care must be taken
to  limit  the  contact  of the  sample with  the atmosphere  and to  minimize any
introduction of  air into the  samples.    In  addition,  work by  Walsh  and Nadeau
(Ref.  1) and  others indicate  that P4 may be  subject  to losses  as  a  result of
volatilization from the sample.

            6.2.1   Aqueous samples  should be poured gently into the sample
      container to minimize agitation which might drive off the volatile P4.  If
      bubbling  does  occur  while transferring  the  sample to  the  container, the
      sample  should  be  discarded and another sample collected.   Each container
      should be filled  with sample until  it overflows.  Each  container should be
      tightly   sealed with   a  PTFE-lined  cap.   The  container  should  then  be
      inverted  to check for air  bubbles.  If any air bubbles are present, a new
      sample must be collected.

            6.2.2   Containers for soil  samples should be filled as completely
      as  possible,  eliminating as much free air space  as practical.

      6.3    Samples are preserved  by cooling to approximately 4°C.  Do NOT adjust
the pH of water samples or  add chemical preservatives, as these may oxidize the
P4.

      6.4    EPA has  not established  formal  holding times for samples containing
P4.   However,  preliminary  data  suggest that water samples  should be  stored at
approximately  4°C  in  the  dark,  and  should   be  extracted  within  5  days  of
collection.  Soil/sediment  samples should be stored at approximately 4°C, in the
dark,  and kept tightly sealed to prevent  loss  of  moisture.   When  stored  in this
manner,  preliminary data   indicate  that  soil/sediment  samples  may  be  held
indefinitely.

      6.5    Due  to  the  volatility   of  diethyl  ether,  water sample  extracts
prepared with  diethyl  ether  (Sec.  7.3)  should be analyzed within 8 hours of
extraction,  and  extracts  should  be stored in tightly capped containers  in  a
refrigerator until  analysis.
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     6.6    Isooctane extracts  of  soil/sediment samples  (Sec. 7.4) and of water
samples (using the less sensitive  alternative  extraction procedure in Sec. 7.6)
should be  stored  in  tightly capped containers in  a  refrigerator and analyzed
within 30 days of extraction.


7.0  PROCEDURE

     7.1    Establish the instrument operation  conditions,  using the information
below as guidance.

     Column:  DB-1,  15  m by  0.53  mm  ID with 3.0 urn film thickness
     Oven  Temp:   80°C (isothermal)
     Carrier  Gas:  Nitrogen
     Flow  Rate:   30  mL/min

Using these conditions,  P4 will  elute  between 2.5 and 3.0 minutes,  and the entire
chromatographic  run   will  typically  be  less  than  5 minutes.   Optimize  the
performance to minimize interferences and maximize sensitivity.    Document the
operating conditions  used.

     7.2    Initial  calibration

     Because  of the different solvents  used for soil/sediment samples and water
samples (by the more  sensitive method),  separate initial five-point calibrations
are required for each  solvent.  In  addition, the nitrogen-phosphorus detector may
present  problems  with  long-term  stability.    Therefore,  a  5-point  initial
calibration must be performed at the  beginning of each 12-hour analytical shift
during which samples  are to be analyzed.  The calibration procedures are the same
for  both  solvents,  and only  the  calibration associated  with  samples  to  be
analyzed that day must  be run on that day (i.e.,  if only water samples will  be
analyzed, only the calibration  standards  in diethyl  ether need  to  be analyzed
that day).

     As  a  practical  matter,  if  both water and soil/sediment analyses are to be
performed,  the water sample extracts  in diethyl ether should be analyzed first,
to avoid evaporation  of the solvent.   If water samples are extracted using the
less sensitive procedure involving isooctane,  then  both water and soil/sediment
extracts may be analyzed using the same initial  calibration in isooctane.

     Perform  either  of the initial  calibrations  each day, using the procedure
outlined below.    See Method  8000  for further  details of external  standard
calibration procedures.

            7.2.1    The instrument is calibrated by injecting 1.0 /xL aliquots of
     each  calibration standard.   To  avoid "memory effects," vary the order of
     the five standards, or  analyze  from  lowest concentration to highest.

            7.2.2    Calculate  the calibration  factor  (CF) for  the  initial
     calibration  curve  as  follows:
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                                 Area of the peak
                   (Standard concentration in ng/uL)(uL injected)


     Peak height may be used for calculating  the calibration factor, but may not
     be as representative to small, broad, or oddly shaped peaks.

           7.2.3    The linearity  of the  calibration  is  evaluated on  the  basis
     of the  relative standard deviation  of  the  five calibration factors,  in
     accordance with Method 8000.  Calculate the mean CF, the standard  deviation
     (SD) of the CFs, and the relative standard deviation (RSD),  as follows.
                             mean  CF = CF =
                                    I (CF-CF):
                             SD =
                                        n-1
                                RSD =  — x 100
                                      CF


     where n is the number of initial calibration standards analyzed.

           The  calculation  of  a  calibration  factor  is  analogous  to  the
     calculation  of the  slope  of a regression line forced  through  the origin
     (0,0).  Data from the U. S.  Army  Corps of  Engineers indicates that the NPD
     response is linear over a range of at least 20-fold, and passes through the
     origin.  In  order to  be used  for sample  analyses,  the  RSD of the initial
     calibration must be less than  or  equal to 15%.  As noted above, the initial
     calibration  must  be performed at the beginning of each  analytical  shift
     during which samples will be  analyzed.

     7.3   Water  sample extraction  -  diethyl  ether  extraction  procedure
providing sensitivity of approximately  0.01 M9/L-   See Sec.  7.6  for the less
sensitive isooctane alternative extraction procedure.

           7.3.1    Carefully transfer a 500-mL aliquot  of the water sample to
     a  500-mL separatory funnel  (a larger  separatory  funnel  may be employed).
     Add 50 mL of diethyl ether, and  shake the separatory funnel for 5 minutes
     with periodic venting.  Allow the sample  to  stand for 15 minutes, or until
     phase separation occurs.
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      Optional  Step:   Add  16 g  of sodium  chloride  to  the  mixture  of
      liquids in the separatory funnel to increase and stabilize the ionic
      strength of the water sample and  aid  in the phase  separation  during
      the extraction.  If the sample is seawater, addition of  the  sodium
      chloride is not necessary.

      7.3.2   Diethyl  ether  is   relatively   soluble  in  water  and  the
solubility is greatly  affected by temperature.   After  phase  separation,
collect the diethyl  ether (usually 3-10 ml) in a 10-mL graduated cylinder,
and record the exact volume.  Note:   The  volume of the ether  layer will
depend on the temperature and the ionic strength of the water sample.

      7.3.3   For   ease   of  application   in  a  production   laboratory
environment, adjust the volume of the diethyl ether  extract to  a constant
volume of 10.0 ml at this point.  The extract is then concentrated by back
extraction with  reagent water in  Sec. 7.3.4.   The advantage of  the  use of
a constant extract volume here is  that it minimizes the need to recalculate
the volume of reagent water  required for each sample  extract, although the
latter  approach  may  be  employed.   See  Sec.  7.7  for details  of  the
calculation of the volume of reagent water required.

      7.3.4   The  volume of  the  diethyl  ether  extract  is  reduced  to
approximately 1.0 ml by back-extraction with  reagent water.  Transfer the
diethyl ether extract  to a 125-mL separatory  funnel  and  add  99.2  ml  of
reagent water.  Shake for 1 minute.

      7.3.5   After phase separation, collect the remaining diethyl ether
phase in  a  10-mL   (or smaller)  graduated  cylinder  and record  the exact
volume.  Tightly cap the  graduated cylinder until the extract  is analyzed.
See Sec. 6.4 for a discussion of  holding times for these sample extracts.

      7.3.6   If no diethyl ether phase separates,  check  the  temperature
of the solution.   If the  temperature  is significantly below 25eC, then all
of the  diethyl  ether may remain  in solution.  There  are  three  practical
solutions to this problem.

              7.3.6.1  Warm  the solution in the separatory  funnel to 25°C,
      and allow  the phases  to separate.

              7.3.6.2  Add small  volumes (0.5 ml or less) of fresh diethyl
      ether  to  the  solution,  shake the separatory  funnel, and  allow the
      phases  to  separate.    Continue  adding  fresh  ether   until  the
      solubility of the  ether in the  reagent water is exceeded and the
      extract has been concentrated to approximately  1.0 ml.

              7.3.6.3  If this problem persists, calculate the  volume of
      reagent water required at the temperature of the solution (i.e., the
      ambient laboratory temperature), using  Sec. 7.7 and the  solubility
      and  density  of diethyl  ether  at  the  new temperature,  and extract
      another aliquot of the sample and use the newly calculated volume of
      reagent water for  back extraction.

      7.3.7   Prepare  the  water  matrix  spike/matrix spike   duplicate
(MS/MSD) aliquots by adding  500 ml of the water sample selected for spiking

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      7.4.1   Carefully homogenize the soil/sediment sample in its original
container using a spatula.  Weigh  out 40 g of the  homogenized  wet  sample
into a pre-weighed 120-mL glass jar.

      7.4.2   Weigh  out  a separate 5-10 g aliquot  of  each sample for  use
in determining the percent moisture.  Air-dry each  sample in a fume hood
for  at  least a  day, then dry  this aliquot at  105°C for  24   hours  and
reweigh.  The percent moisture is calculated as:


      n      4.    . 4.       wet weight  (g) -dry weight (g)   -..
      Percent moisture =	2	IZi	£	±	i±ix 100
                                  wet weight  (g)


As noted  in  Sec.  2.3,  soil/sediment P4 concentrations are reported on  a
wet-weight basis  using this method.   However,   the percent moisture  is
reported  separately  so that  the data  user  can  make  comparisons between
samples and perform dry weight calculations as  necessary.

      7.4.3   Add 10.0 ml (9.0 ml  for  spiked soil  samples)  of  degassed
Type I reagent water and 10.0 ml of isooctane the sample  in  the glass  jar
from Sec. 7.4.1, and seal the jar with the PTFE-lined cap.

      7.4.4   Vortex the jar for 1 minute.

      7.4.5   Place  the jars on a platform shaker, and shake for 18 hours
(or overnight) at 2500 rpm.

      7.4.6   After  removing the samples from the platform shaker, let  the
samples stand for about 15 minutes to allow phase separation.   If a clear
isooctane layer does  not  form, centrifuge a portion of  the sample for 5  min
at 2500 rpm.

      7.4.7   Using  a disposable Pasteur pipet, transfer an aliquot  of  the
isooctane layer to a suitable labeled storage vial  with a PTFE-lined cap.
See Sec. 6.4 for a discussion of holding times for these  sample extracts.

      7.4.8   Prepare  the MS/MSD aliquots by weighing out two  additional
40-g aliquots of  the soil/sediment sample chosen for  spiking  into clean
120-mL  glass jars.    Add 1.0 ml  of the  aqueous  spiking solution  (Sec.
5.11.2) to each  jar.   Seal  each jar immediately, and  swirl  it until  the
contents  are mixed  (approximately five  times).    Allow  the  samples  to
equilibrate  for 24 hours before extraction.  After  24 hours, extract  the
samples, beginning at Sec. 7.4.3.
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      7.5    Sample analysis

            7.5.1    Allow the  sample  extract to warm  to  room temperature and
      inject  1.0 /zL of the extract (water or soil/sediment) into the GC, using
      a  10 /nL gas  tight  syringe.   Record  the  retention  time and peak area (peak
      height  optional) of P4  in the sample extract.

            7.5.2    Calculate the concentration of  P4  in  the  water samples as
      follows:

                            C  (ng/L)  =
                                        CF x V8 x Vf

        where:       As  =  Area of the sample peak
                    Vf  =  Final  extract volume in L
                    Vs  =  Volume of sample extracted in L
                    Vi  =  Volume injected in L
        and         	
                    CF  =  Average   calibration   factor   from   the   initial
                           calibration in diethyl  ether

            7.5.3    Calculate  the concentration  of  P4  in  the   soil/sediment
      samples as follows:

                                          A  x  V.
                            C  (ng/g)  =     •   f
                                        CF x Mg x Vj


        where:       As  =  Area of the sample  peak
                    Vf  =  Final  extract volume in L
                    Ms  =  Mass of sample extracted in g
                    V|  =  Volume injected in  L
        and         	
                    CF  =  Average  calibration   factor   from   the   initial
                           calibration in isooctane

     Using  the  units above,  the  concentration  will  be in  ng/g,  which  is
     equivalent  to /zg/kg.

            For water  samples extracted with the isooctane  procedure  (Sec. 7.6),
     perform the calculation as  described in  Sec.  7.6.5.

     7.6    Alternative water sample extraction procedure  providing sensitivity
of  approximately  0.1  fj.g/1.    This procedure  must be  used  to  determine  the
concentration of the aqueous stock  solution in Sec. 5.10.

            7.6.1    Add 30 ml of the water sample (or the aqueous stock solution)
     to a 40-mL vial with a PTFE-lined cap.  Add 3.0 ml of  isooctane  to the vial
     and cap it  tightly.

            7.6.2    Shake the vial  for  5 minutes, and  let stand  to allow the
     phases to separate.

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            7.6.3    Remove the  isooctane  layer with a disposable Pasteur pipet.

            7.6.4    Analyze  a  1.0  /xL  aliquot  of  the  isooctane  using  the
     procedure  in Sec. 7.5.1.

            7.6.5    Calculate the concentration of P4  using the equation in Sec.
     7.5.3, using 0.0030 L (3.0 ml)  as the  final  extract volume and 0.030 L (30
     mL) as the sample volume.  Substituting the sample volume for the mass  (Ms)
     in Sec.  7.5.3  will result in a concentration  in units of ng/L.

     7.7    Calculation of  the volume of reagent water needed to concentrate the
diethyl ether extract to 1.0 mL.

     Diethyl  ether  is  very soluble  in water,  and given the  solubility  and the
density of  diethyl  ether,  the  volume  of ether that  will  dissolve  in  a  known
volume of reagent  grade water can be calculated.  By reversing the calculation,
the volume  of reagent water that  would be  necessary  to  dissolve  a  specific
portion of a diethyl ether extract  can be determined.   Since the  P4 will remain
in the free ether  phase, the diethyl ether extract can be safely and effectively
be concentrated by back extraction with reagent water.

            7.7.1    Both the solubility and density of diethyl  ether vary with
     temperature.   At 25°C, the solubility  of ether in water is  6.05%,  on a
     weight/weight  basis.  The density of diethyl ether is 0.7076 g/mL at 25eC.
     The density  of reagent  water  at  25°C  is 0.997 g/mL.   Reducing the volume
     of ether in Sec.  7.3.3, 10 mL,  to 1.0  mL will  require dissolving 9.0 mL of
     ether in reagent  water.

            7.7.2    The volume  of "excess"  ether  is 9.0 mL.

            7.7.3    The mass of this ether  is (9.0 mL x 0.7076  g/mL) =  6.37 g.

            7.7.4    The mass of  an  aqueous solution  saturated with 6.37  g of
     ether is (6.37 g)/(0.0605)  =  105.3  g.

            7.7.5    The mass  of water in that  aqueous solution is (105.3  - 6.37),
     or 98.9  g.

            7.7.6    The volume  of water required  to dissolve 9.0  mL of  ether
            is (98.9 g)/(0.997  g/mL) = 99.2 mL.  Therefore,  99.2 mL of reagent
            water  are added to  the  diethyl  ether  extract in  Sec.  7.3.4.

            7.7.7    Using these relationships, the volume of reagent water needed
     to  concentrate other volumes  of diethyl  ether can also  be calculated.
     Also,  similar  calculations  can be made for temperatures other than 25°C.
      For instance,  at  20°C, the solubility of diethyl ether  in  reagent water is
     6.89% (w/w), the  density  of diethyl ether is  0.7133 g/mL, and the density
     of water is  0.9982 g/mL.  Substituting  these  values into the calculations
      shown above,  the volume of reagent water required to concentrate 10.0 mL
     of diethyl ether to  1.0 mL  at  20°C  is 91.7  mL.
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            7.7.8    Table  1  lists  the  volumes  of  reagent  water  needed  to
     concentrate diethyl ether extracts of various  volumes  less than 10.0 ml to
     a final volume of  1.0 ml, for  both  20  and 25°C.

     7.8    Solid-phase  micro-extraction  (SPME)

     Data  from the U. S. Army Corps  of  Engineers  suggest  that  SPME  may  be a
useful  technique for the analysis of P4.   It may be used to screen samples for
P4,  by  simply  exposing  the  SPME  fiber to the water  sample,  or  adding reagent
water to a  soil/sediment sample  and exposing  the fiber  to  the headspace.   The
fiber is then  thermally  desorbed in a heated injection port  of  the  GC.   Such
screening results may be used to differentiate between water  samples that require
the added  sensitivity  of the diethyl  ether extraction  and those that  may be
adequately treated with the isooctance procedure.

     Additionally,  SPME  may  offer an  alternative to the use of either solvent
in the  determination of P4  in environmental  samples.  Further work in this area
is on-going  at the U.  S. Army Corps  of  Engineers, and may  be  added  to later
revisions of this method.
8.0   QUALITY  CONTROL

      8.1    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 an ongoing analysis of spiked
samples to  evaluate  and  document data quality.   The laboratory must maintain
records to  document  the  quality of the  data generated.   Ongoing data quality
checks are  compared with  established  performance  criteria to determine if the
results of  analyses meet  the  performance characteristics of the method.   When
results of sample spikes  indicate atypical method performance,  a  quality control
reference sample must be analyzed to  confirm that the measurements were performed
in an in-control mode of operation.

      8.2    Before processing  any samples, and with each batch of samples (up to
a maximum of 20 environmental samples of a similar matrix), the  analyst should
demonstrate, through the  analysis of a method blank, that interferences from the
analytical  system, glassware, and reagents are under control.

            8.2.1   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.

            8.2.2   The method  blank  should  be carried  through all stages of
      sample preparation  and  measurement.

            8.2.3   For water samples,  the  method blank consists of  a  500 mL
      volume of reagent water  carried through the  entire  analytical  procedure.

            8.2.4   For soil/sediment samples,  the method blank  may  be prepared
      from  a  20-g aliquot  of  a  dry soil/sediment  sample  from an  area  not
      contaminated with P4, or 20-g of clean dry sand.  The 20-g aliquot is mixed
      with 20  mL of reagent water and  allowed to  stand  for one hour.


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     NOTE:  In  order to be acceptable, neither the water method  blank nor the
            soil/sediment  method blank may  contain  any P4 detectable  by this
            method.   All  samples  associated with a contaminated  method blank
            should  be re-extracted  and reanalyzed.

     8.3    Prior to  the  analysis of any  sample extracts,  the  analyst must
perform  an  initial   five-point   calibration  that  meets   the  performance
specifications  in Sec. 7.2.3.   This initial  calibration must be repeated at the
beginning of each 12-hour  analytical  shift  during which  samples  are analyzed.
The initial  calibration must be performed using the  same solvent as the sample
extracts to be analyzed,  i.e.,  separate  initial  calibrations  are required for
diethyl ether and isooctane.

     8.4    The analyst must verify the initial calibration periodically during
the course  of  sample  analyses  to  ensure  that the response of  the NPD has not
drifted.  The calibration  is verified  using  the mid-point (i.e., third of five)
standard from the initial  calibration, as described  below.

            8.4.1   A total of 10 extracts, including blanks, samples, and MS/MSD
     aliquots  may be  analyzed  following  an  initial  calibration that meets the
     specifications  in Sec. 7.2.3. After the injection  of  the tenth extract,
     the  mid-point  calibration  standard  must  be   injected  to  verify  the
     calibration.

            8.4.2   Based   on   the  response  of  the  calibration  verification
     standard, calculate  the calibration  factor  according to Sec.  7.2.2.

            8.4.3   Calculate the percent  difference (%D) between the calibration
     factor calculated  from the calibration verification  standard (CFJ and the
     mean calibration factor from  the initial  calibration at  the beginning of
     the analytical  shift, as  follows.

                                        CT -CF
                        % Difference  =	*  x 100
                                          CF

            8.4.4   In order for analysis of samples  to continue,  the %D must be
     within ±  15%.   Otherwise, analysis must be halted  until  a  new initial
     calibration is  performed.

            8.4.5   If the calibration verification meets the  ±  15% QC limit,
     then sample analyses  may  continue, continuing to use the mean CF from the
     initial calibration  for calculating  sample  concentrations.

            8.4.6   The calibration must  be  verified after the analysis of each
     set  of 10  extracts   of  sample,  blanks,  MS/MSD.   The  injection  of the
     calibration verification  standard itself  is not counted as part of the 10
     injections.    Analyses  may continue   in  this  fashion,  with  calibration
     verification  standards analyzed  after  each  10  sample extracts, until the
     end  of the  12-hour analytical shift,  or  until the  verification standard
     fails  to  meet  the ±  15% QC limit.
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     8.5    Initial  demonstration of capability

     The  ability  of the analyst to generate acceptable accuracy and precision
using this method  is demonstrated through the analysis  of  spiked  aliquots of
reagent water, as described below.

            8.5.1    Four 500-mL aliquots of reagent water  are  spiked with the
     aqueous  spiking  solution  (Sec.  5.11.1)  to produce  a concentration of
     approximately  0.01  ^tg/L  of P4.

            8.5.2    The four aliquots  are analyzed  according to the procedure
     used for water samples,  beginning in Sec. 7.3.

            8.5.3    Calculate  the  recovery  of P4 in  each  aliquot,  using the
     formula  below.

                                           C
                           Recovery = %R = — x 100
                                           Cn

            where:

          C8  =  Measured concentration of the spiked sample aliquot

          Cn  =  Nominal  (or  theoretical) concentration  of the  spiked  sample
                aliquot

            8.5.4    Calculate  the mean recovery and the standard  deviation of the
     four recoveries.

            8.5.5    The mean recovery must be within the  range 30-130%, and the
     standard deviation of the recoveries must be  less  than or equal  to 30%.
     These  specifications  were  developed from data  provided by the U.  S. Army
     Corps  of  Engineers,  and  represent a  95%  confidence  interval for the
     recovery of  P4 spiked into  four aliquots  at approximately 0.01 /xg/L  (See
     Table  3).   Data  from the  Corps of Engineers  suggest  that recoveries in
     water other than  reagent water  (i.e., pond water, tap water, etc.)  may be
     higher  than  in reagent  water,  perhaps  because  of  the effects  of   ionic
     strength or dissolved constituents  on the solubility of P4.

            8.5.6    If  the  mean  recovery  or  the   standard  deviation of the
     recoveries falls outside of these limits, then the analyst  must  examine the
     entire analytical process, correct problems or  inconsistencies, and repeat
     this test, beginning  at  Sec.  8.5.1.

     8.6    The  laboratory must, on an ongoing basis, prepare and analyze matrix
spike and matrix spike  duplicate samples to assess the  precision  and  accuracy of
the procedure.  The  MS/MSD aliquots  are  prepared and  analyzed  as described in
Sees. 7.3.6  and  7.4.8.  MS/MSD aliquots should be prepared each batch of samples
(up  to  a maximum  of  20 environmental  samples  of  a similar  matrix).    For
laboratories analyzing one  to  ten samples per month,  at least one pair of MS/MSD
must be analyzed each month.
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     The laboratory should develop QC limits for MS/MSD recoveries and precision
(RPD),  using  the procedures  in  Method 8000.   In  the absence  of  laboratory-
specific QC limits, the MS/MSD aliquots  must have recoveries in the range 75-125%
and an RPD less than or equal to 25%.


9.0  METHOD PERFORMANCE

     9.1    The Method Detection  Limit  (MDL)  is defined  in Sec.  5.0 of Chapter
One. MDL values were determined in reagent water, well  water, and surface (pond)
water,  spiked  at approximately 0.01  ^9/L,  and are shown in Table 4.   These MDL
values were calculated from the results of 10 spiked aliquots  of each matrix.

     9.2    MDLs were  determined  for three soil types by spiking the soils with
an aqueous  solution containing P4. The  MDL values are shown in Table 5, and were
determined in clean sand,  a  sandy loam soil  (Lebanon  soil), and soil  from the
Rocky Mountain Arsenal (USAEC Soil). None of these soils were taken from areas
where smoke munitions  have been  employed,  and therefore were not  expected to
contain any P4.   These soil  samples were spiked with P4  at concentrations of
approximately 1-2 M9Ag.

     9.3    To date, only single laboratory performance data have been generated.
Those data  indicate that there may be problems with the recovery of P4 from soils
containing high concentrations of metals.  Therefore,  laboratories employing this
method are encouraged  to  develop  in-house performance data including MDLs and
accuracy and  precision data  for  routinely  encountered  matrices.   These data
should be developed in accordance with the procedures outlined in Method 8000.


10.0 REFERENCES

1.   Walsh,  M.E. and  B.  Nadeau,   "Preliminary Evaluation  of  the  Analytical
     Holding Time for White Phosphorus  in Surface Water," U.S. Army Cold Regions
     Research  and Engineering Laboratory, Hanover, NH, CRREL Report 94-13.

2.   Taylor,  S.  and  M.E. Walsh,  "Optimization of  an  Analytical  Method  for
     Determining White Phosphorus  in  Contaminated Sediments,"  U.S.  Army Cold
     Regions Research and Engineering Laboratory, Hanover,  NH, CRREL Report 92-
     21.

3.   Walsh, M.  E., and S. Taylor, 1993, "Analytical Method for White Phosphorus
     in Munitions-Contaminated Sediments," Analytica Chimica Acta,  282: 55-61.

4.   Walsh,  M.E., 1995,  "Analytical  Method  for White  Phosphorus  in Water,"
     Bulletin  of Environmental Contamination and Toxicology, 54(3).

5.   Budavari,  S., et a/., eds.,  1989,  The Merck Index, Merck & Co., Rahway, NJ.
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                                   TABLE  1
 VOLUME OF  REAGENT WATER  REQUIRED TO CONCENTRATE DIETHYL  ETHER  EXTRACTS TO A
                     1.0 ml FINAL VOLUME AT 20'C AND 25°C
   Volume of  Diethyl
         Ether
Volume of Reagent Water
    Required  at  20°C
Volume of Reagent Water
    Required  at  25°C
10.00
9.75
9.50
9.25
9.00
8.75
8.50
8.25
8.00
7.75
7.50
7.25
7.00
6.75
6.50
6.25
6.00
5.75
5.50
5.25
5.00
4.75
4.50
4.25
4.00
3.75
3.50
3.25
3.00
2.75
2.50
2.25
2.00
1.75
1.50
1.25
91.7
89.3
86.9
84.5
82.1
79.7
77.3
74.8
72.4
70.0
67.6
65.2
62.8
60.4
57.9
55.5
53.1
50.7
48.3
45.9
43.5
41.0
38.6
36.2
33.8
31.4
29.0
26.6
24.1
21.7
19.3
16.9
14.5
12.1
9.7
7.2
99.2
96.4
93.7
90.9
88.2
85.4
82.7
79.9
77.1
74.4
71.6
68.9
66.1
63.4
60.6
57.9
55.1
52.4
49.6
46.8
44.1
41.3
38.6
35.8
33.1
30.3
27.6
24.8
22.0
19.3
16.5
13.8
11.0
8.3
5.5
2.8
Solubility of diethyl ether in water is 6.05% (w/w) at 25°C and 6.89% at 20°C.

Density of diethyl ether is 0.7076 g/mL at 25°C and 0.7133 g/mL at 20°C.

Density of water is 0.997 g/mL at 5°C and 0.9982 g/mL at 20°C.
                                   7580  -  17
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                                   TABLE 2
                   RECOVERY OF P4 FROM SPIKED WATER SAMPLES
                    (ALL VALUES GIVEN AS PERCENT RECOVERY)
          Reagent Water          Well  Water          Pond Water
52
77
44
68
69
68
57
64
56
66
46
94
87
124
74
91
91
99
91
90
92
86
99
82
80
83
84
68
56
68
Mean
Recovery        62.1                 88.7                79.8

Standard
Deviation        9.7                 19.6                12.6

Spike Level      0.012                0.0097              0.0101
The concentration results for these replicate samples were used to calculate the
MDL values in Table 4.

The two lowest and two highest  concentration  values  from  each set of replicates
were used to establish the recovery and precision specifications in Sec. 8.5.
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Mean
Recovery

Standard
Deviation

Spike Level
                                    TABLE  3
                    RECOVERY  OF  P4  FROM  SPIKED SOIL SAMPLES
                    (ALL VALUES GIVEN AS PERCENT RECOVERY)
               Sand
92.5


 4.1

 1.99
                Lebanon Soil
85.9


12.4

 1.24
                USAEC Soil
90
90
97
94
96
85
89
94
92
98
98
66
86
87
93
82
86
66
102
94
76
68
73
74
76
74
74
71
74
70
73.0


 2.5

 0.97
The concentration results  for these replicate samples were used to calculate the
MDL values in Table 5.

The two lowest and two highest  concentration values  from each set of replicates
were used to establish the recovery and precision specifications in Sec. 8.5.
                                   7580  -  19
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                                    TABLE  4
           METHOD DETECTION LIMITS CALCULATED FOR THREE WATER TYPES
           Reagent  Water          Well Water          Pond Water

MDL (M9/L)     0.008               0.009                0.008
     These  MDLs  were  calculated  from the analyses of 10 replicate aliquots of
each water type spiked with P4 at  0.0097 to 0.012 M9/L.  The MDLs were calculated
as the Student's  t  value  for 10  replicates  (2.821)  multiplied by the standard
deviation of the results for each water type.
                                    TABLE 5
            METHOD DETECTION LIMITS CALCULATED FOR THREE SOIL TYPES
               Sand             Lebanon Soil         USAEC Soil

MDL (/ig/kg)    0.02                0.43                 0.07
      These MDLs were calculated from the analyses of 10 replicate aliquots of
each  soil  type  spiked with  P4 at 0.97 to 1.99 Atg/kg.  The MDLs were calculated
as the  Student's  t  value for 10 replicates (2.821) multiplied by the  standard
deviation  of the  results  for each soil type.

      As can  be  seen,  the  MDL  values  vary  significantly.   However,  if one
compares the spiked concentration for each matrix with  the MDL value, it is  clear
that  both the Sand and USAEC Soil were not spiked within 3-5  times  the  estimated
detection  limit (as required, see Chapter One).   The ratio of  the  spiking  level
to the MDL for Sand was 9.7, and 14 for the USAEC Soil.   In  contrast,  the  ratio
for  the Lebanon  Soil is  2.9.   Therefore,  the MDL  for  Lebanon  Soil  should be
considered as more  representative of the method  performance than  either of the
other values because it is closer to the 3-5 times the  estimated detection  limit
range.


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                              METHOD 7580

WHITE  PHOSPHORUS  (P.)  BY SOLVENT  EXTRACTION AND  GAS CHRQMATOGRAPHY
                                  7.1 - 7.2 Establish
                                 instrument operating
                               conditions and perform
                                the initial calibration.
           Soil/Sediment
      Is it a
  water sampl
or a soil/sedimen
     sample?
                                          Water
 7.4 Perform soil/
     sediment
 sample extraction.
7.3 Perform water
sample extraction.
                                 7.6 Perform spike
                                   concentration
                                   determination.
                              7.7 Determine volume of
                              reagent water necessary
                                 for concentration.
                                7.8  Perform the solid-
                               phase micro-extraction.
                               7580 - 21
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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 Handling 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 Orqanics

      Standard 40 ml  glass screw-cap  VOA vials with Teflon lined silicone septa
may be used for liquid  matrices.  Special  40  ml  VOA vials for purge-and-trap of
solid samples are described  in Method 5035.  VOA vials for headspace analysis of
solid samples  are  described in  Method  5021.  Standard  125  ml  widemouth glass
containers may be used  for Methods 5031 and 5032. The vials and septa should be
washed with  soap and water and  rinsed  with  distilled  deionized  water.   After
thoroughly cleaning the vials and septa,  they  should  be  placed  in  an oven and
dried at 100°C for approximately one hour.

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

      When collecting the samples, liquids  and solids should be introduced into
the vials gently to reduce agitation  which might drive off volatile compounds.

      In  general,  liquid  samples  should  be  poured  into   the  vial  without
introducing  any  air  bubbles within  the  vial as it  is being filled.   Should
bubbling occur  as a result of violent pouring, the sample  must be poured out and
the  vial  refilled.   The vials  should be  completely  filled at  the time  of
sampling,   so  that  when  the septum  cap is  fitted  and  sealed,  and the  vial
inverted,  no headspace  is visible. The  sample should be hermetically sealed in

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the vial at the time of sampling, and must not  be  opened  prior  to  analysis  to
preserve their integrity.

            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.

      Immediately prior to analysis of  liquid samples, the aliquot to be analyzed
should be taken from the vial using the instructions from the appropriate sample
introduction technique:

            For smaller analysis volumes, a gas-tight  syringe may  be inserted
            directly through the  septum  of the  vial to withdraw  the sample.

            For larger  analysis  volumes,  (e.g.  purge-and-trap  analyses)  the
            sample may be carefully poured into the syringe barrel.   Opening a
            volatile  sample   to  pour  a  sample into  a  syringe destroys  the
            validity of the sample for future analysis.  Therefore,  if there is
            only one VOA vial, it is strongly recommended that the analyst fill
            a second syringe  at  this time to protect  against  possible loss  of
            sample integrity.   This second sample is maintained only until such
            time as the analyst  has determined  that the  first sample has been
            analyzed properly.

If these guidelines are not followed, the  validity of the data generated from the
samples may be suspect.

      VOA vials for samples with solid  or  semi-solid  matrices (e.g., sludges)
should be filled according to  the guidance given in  the appropriate 5000 series
sample introduction method (see  Table 4-1) to  be used.   When  125-mL widemouth
glass continers  are used, the containers  should  be  filled as  completely  as
possible.  The 125-mL  vials should be  tapped slightly as they are filled to try
and eliminate as much  free air space as possible. A minimum  of 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

                                   FOUR  - 2                         Revision 3
                                                                  January 1995

-------
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.

      Semivolatile 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
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 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;


                                   FOUR - 3                         Revision 3
                                                                  January 1995

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

      3.  Hot water rinse to flush away floated participates;

      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.

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

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

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

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

      3.  No comments required.

      4.  The most  common  and  highly  effective  oxidizing  agent for removal of
          traces of organic compounds is the traditional chromic acid solution
          made  up  of concentrated sulfuric  acid   and  potassium  or  sodium
          dichromate.   For maximum efficiency, the soak solution should be hot
          (40-50°C).    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


                                   FOUR - 4                         Revision 3
                                                                  January 1995

-------
          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.

      5, 6, and 7.  No comments required.

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

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

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

      4.1.5  High Concentration Samples

            Cross contamination of trace  concentration samples may occur  when
      prepared in the same laboratory with high concentration  samples.  Ideally,
      if  both  type  samples are  being  handled,  a  laboratory  and  glassware
      dedicated solely to the preparation of high concentration samples would be
      available  for this purpose.  If this is not feasible,  as a  minimum  when
      preparing high concentration samples, disposable glassware should be  used
      or,  at  least,  glassware dedicated entirely to  the high  concentration
      samples.     Avoid  cleaning  glassware   used  for  both  trace  and  high
      concentration samples in  the same area.
                                   FOUR -  5                          Revision  3
                                                                  January 1995

-------
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4.2  SAMPLE PREPARATION METHODS

     4.2.1  EXTRACTIONS AND PREPARATIONS

         The following methods are included in this section:
         Method
         Method
         Method
         Method
         Method
         Method
         Method
3500B:
3510C:
3520C:
3535:
3540C:
3541:
3542:
         Method 3545:
         Method 3550B:
         Method 3560:

         Method 3561:

         Method 3580A:
         Method 3585:
         Method 5000:
         Method 5021:
         Method 5030B:
         Method 5031:

         Method 5032:
         Method 5035:

         Method 5041A:
Organic Extraction and Sample Preparation
Separatory Funnel Liquid-Liquid Extraction
Continuous Liquid-Liquid Extraction
Solid Phase Extraction (SPE)
Soxhlet Extraction
Automated Soxhlet Extraction
Extraction  of  Semivolatile  Analytes  Collected
Using Modified  Method 5  (Method  0010)  Sampling
Train
Accelerated Solvent Extraction
Ultrasonic Extraction
Supercritical    Fluid    Extraction    of   Total
Recoverable Petroleum Hydrocarbons (TRPH)
Supercritical  Fluid   Extraction  of  Polynuclear
Aromatic Hydrocarbons
Waste Dilution
Waste Dilution for Volatile Organics
Sample Preparation for Volatile Organic Compounds
Volatile  Organic Compounds  in  Soils and  Other
Solid   Matrices   Using   Equilibrium  Headspace
Apparatus
Purge-and-Trap for Aqueous Samples
Volatile, Nonpurgeable,  Water-Soluble Compounds
by Azeotropic Distillation
Volatile Organic Compounds  by Vacuum Distillation
Closed-System Purge-and-Trap  and  Extraction for
Volatile Organics in  Soil and Waste Samples
Analysis  of  Sorbent  Cartridges  from  Volatile
Organic Sampling  Train  (VOST):   Capillary GC/MS
Technique
                                  FOUR  - 8
                                                 Revision 3
                                               January 1995

-------
                                 METHOD 3500B

                  ORGANIC  EXTRACTION AND SAMPLE PREPARATION
1.0  SCOPE AND APPLICATION

     1.1  Method 3500 provides general guidance on the selection of methods used
in the  quantitative extraction (or dilution)  of samples for analysis by one of
the semivolatile or nonvolatile determinative methods.  Cleanup and/or analysis
of the  resultant extracts  are described in Chapter Two as well as in Method 3600
(Cleanup) and Method 8000 (Analysis).

     1.2  The following table  lists the extraction methods, the matrix and the
analyte category.
         SAMPLE EXTRACTION METHODS FOR SEMIVOLATILES AND NONVOLATILES
Method #
3510
3520
3535
3540
3541
3542
3545
3550
3560/
3561
3580
Matrix
Aqueous
Aqueous
Aqueous
Solids
Solids
Air Sampling Train
Solids
Solids
Solids
Non-aqueous Solvent
Soluble Waste
Extraction Type
Separatory Funnel
Liquid-Liquid
Extraction
Continuous Liquid-
Liquid Extraction
Solid-Phase
Extraction (SPE)
Soxhlet Extraction
Automated Soxhlet
Extraction
Separatory Funnel &
Soxhlet Extraction
Accelerated Solvent
Extraction (ASE)
(Heat & Pressure)
Ultrasonic
Extraction
Supercritical Fluid
Extraction (SFE)
Solvent Dilution
Analytes
Semivolatile &
Nonvolatile Organics
Semivolatile &
Nonvolatile Organics
Semivolatile &
Nonvolatile Organics
Semivolatile &
Nonvolatile Organics
Polychlorinated
Biphenyls,
Organochlorine
Pesticides, &
Semivolatiles
Semivolatile Organics
Semivolatile &
Nonvolatile Organics
Semivolatile &
Nonvolatile Orgajiics
Semivolatile Petroleum
Hydrocarbons &
Polynuclear Aromatic
Hydrocarbons
Semivolatile &
Nonvolatile Organics
                                  3500B - 1
  Revision 2
January 1995

-------
      1.3  Method  3580 may  be used  for the  solvent  dilution of  non-aqueous
semivolatile and nonvolatile organic samples prior to cleanup and/or analysis.

      1.4  Methods  3545, 3560, and 3561  are techniques that utilize pressurized
solvent extraction  to reduce the amount  of solvent needed to extract  target
analytes  and  reduce  the  extraction  time  when  compared  to more  traditional
techniques such as Soxhlet extraction.


2.0   SUMMARY OF METHOD

      2.1  A  sample of a  known volume  or  weight is extracted with  solvent or
diluted with solvent.  Method choices  for aqueous samples include liquid-liquid
extraction  by  separatory funnel  or by continuous  extractor and  solid-phase
extraction  (SPE).   Method choices  for  soil/sediment  and solid  waste  samples
include standard solvent  extraction  methods  utilizing either Soxhlet, automated
Soxhlet,  or  ultrasonic   extraction.    Solids  may  also  be  extracted  using
pressurized extraction  techniques such as  supercritical  fluid  extraction or
heated accelerated solvent extraction.

      2.2  The  resultant  extract  is  dried  and concentrated in a  Kuderna-Danish
(K-D) apparatus.  Other concentration devices or techniques may be used in place
of the Kuderna-Danish concentrator  if the  quality control  requirements  of the
determinative methods are met (Method 8000, Sec. 8.0).

NOTE:  Solvent recovery apparatus  is recommended for  use  in methods that require
       the use  of Kuderna-Danish evaporative  concentrators.  EPA recommends the
       incorporation of this  type of reclamation system as  a method to implement
       an  emissions reduction program.

      2.3  See  Sec.  7.0  for additional guidance  to  assist in  selection  of the
appropriate method.


3.0  INTERFERENCES

      3.1  Solvents,  reagents,  glassware,  and other  sample processing hardware
may yield  artifacts  and/or interferences to  sample analysis. All these materials
must be demonstrated to be free from interferences under the conditions of the
analysis  by analyzing  method blanks.    Specific   selection  of  reagents  and
purification of solvents  by distillation in  all-glass systems may be necessary.
Refer to each method for  specific  guidance  on quality control procedures and to
Chapter Four for guidance on the cleaning of glassware.

      3.2   Interferences coextracted from the samples will vary considerably  from
source  to source.    If  analysis  of  an  extracted sample  is prevented  due to
interferences, further cleanup of  the sample extract may  be necessary.  Refer to
Method 3600 for guidance on cleanup procedures.

      3.3  Phthalate esters contaminate many types of products commonly found in
the laboratory. Plastics,  in particular, must be avoided because phthalates are
commonly  used as plasticizers and are easily extracted from plastic materials.
Serious phthalate  contamination  may result  at  any  time if  consistent  quality
control is not practiced.

                                  3500B -  2                        Revision 2
                                                                  January  1995

-------
     3.4   Soap residue  (e.g. sodium dodecyl sulfate), which results in a basic
pH  on  glassware  surfaces,  may  cause   degradation   of  certain  analytes.
Specifically, Aldrin,  Heptachlor,  and  most  organophosphorus  pesticides  will
degrade in this situation.  This problem is  especially pronounced with glassware
that may be difficult to rinse  (e.g.,  500-mL K-D flask).  These items should be
hand-rinsed very carefully to avoid this problem.


4.0  APPARATUS AND MATERIALS

     4.1   Refer  to  the specific method of interest for a  description  of the
apparatus and materials needed.

     4.2   Solvent  recovery apparatus  is recommended  for use  in  methods  that
require the use of Kuderna-Danish evaporative concentrators.  Incorporation of
this apparatus may be required by State or local  municipality regulations  that
govern air emissions  of volatile  organics.  EPA recommends the incorporation of
this type of reclamation system as  a method to implement an emissions reduction
program.   Solvent recovery is  a  means to  conform with  waste minimization and
pollution prevention initiatives.


5.0  REAGENTS

     5.1   Refer  to  the specific method of interest for a  description  of the
solvents needed.

     5.2   Organic-free  reagent water.   All  references  to water in this method
refer to organic-free reagent water as defined in Chapter One.

     5.3   Stock  standards  for   spiking  solutions  -  Stock  solutions may  be
prepared from pure standard materials  or purchased as certified solutions.   The
stock solutions used for the calibration standards are acceptable (dilutions must
be made in a water miscible solvent) except  for the quality control check sample
stock concentrate which  must be prepared independently to serve as  a check on the
accuracy of the calibration solution.

           5.3.1   Prepare  stock  standard solutions by accurately weighing about
     0.0100 g  of pure  compound.  Dissolve the  compound in  a water  miscible
     solvent (i.e. methanol, acetone,  isopropanol  etc.)  and  dilute to volume in
     a  10-mL volumetric flask.  If  compound purity is 96  percent or greater, the
     weight can be used without correction to calculate  the concentration of the
     stock standard  solution.  Commercially-prepared  stock  standard solutions
     can  be used at any concentration  if they  are certified  by the manufacturer
     or by an independent  source.

           5.3.2   Stock standard solutions should be stored in Teflon®-sealed
     containers at 4'C or below.  The solutions should be checked frequently for
     stability.   Refer to the determinative  method for holding  times  of the
     stock solutions.

     5.4   Surrogate standards - A surrogate (i.e., a  compound that is chemically
similar to  the analyte  group but is not expected  to occur in an  environmental
sample) should be added to  each sample, blank, laboratory control  sample (LCS),

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and matrix spike sample just prior to extraction or processing.    The recovery
of the surrogate standard is used to monitor for unusual  matrix  effects, gross
sample processing errors, etc.  Surrogate recovery is evaluated  for acceptance
by determining whether the  measured  concentration  falls  within  the acceptance
limits.

           5.4.1    Recommended surrogates  for certain analyte groups are listed
      in Table  1.   For  methods where  no recommended surrogates  are listed,  the
      lab  is  free  to  select  compounds that fall  within  the definition provided
      above.  Even  compounds that  are on the method target analyte list may be
      used  as a surrogate as  long  as historical data are  available  to ensure
      their absence at  a  given site.   Normally  one or more standards  are added
      for  each  analyte  group.

           5.4.2    Prepare   a  surrogate  spiking concentrate by mixing  stock
      standards  prepared above  and  diluting  with  a  water miscible  solvent.
      Commercially prepared spiking solutions are acceptable.  The concentration
      for semivolatile/nonvolatile organic and pesticide analyses should be such
      that  a  1-mL  aliquot into 1000 mL of a sample provides the  concentrations
      listed  in Table  1.   Where volumes  of  less than  1000 mL  are extracted,
      adjust  the  volume  of  surrogate standard  proportionately.    For matrices
      other than water,  1 mL of surrogate standard is still the  normal spiking
      volume.  However, if gel permeation chromatography will be used for sample
      cleanup,  2 mL should be  added to the sample.  See Table 1  for recommended
      surrogates and concentrations (in an aqueous sample).  The spiking volumes
      are  normally  listed in each  extraction method.   Where concentrations  are
      not  listed,  a   concentration  of  10  times  the  quantitation   limit  is
      recommended.  If  the surrogate  quantitation limit is unknown, the average
      quantitation  limit  of  method  target analytes may  be utilized to estimate
      a surrogate  quantitation limit.

      5.5   Matrix  spike standards  - The following are recommended  matrix spike
standard mixtures for a few  analyte groups.  Prepare a matrix spike concentrate
by mixing  stock  standards  prepared  above  and  diluting with a  water miscible
solvent.   Commercially-prepared spiking  solutions  are  acceptable.   The matrix
spike standards should  be independent of the calibration standard.  A few methods
provide guidance  on  concentrations and the selection of  compounds for matrix
spikes (see Table 2).

           5.5.1    Base/neutral  and  acid  matrix spiking  solution  -  Prepare a
      spiking  solution  in   methanol  that  contains  each  of  the  following
      base/neutral  compounds at  100 mg/L and the  acid compounds at  200 mg/L for
      water  and sediment/soil  samples.   The concentration of these  compounds
      should  be five  times higher for waste  samples.

             Base/neutrals                 Acids

             1,2,4-Trichlorobenzene       Pentachlorophenol
             Acenaphthene                 Phenol
             2,4-Dinitrotoluene           2-Chlorophenol
             Pyrene                       4-Chloro-3-methylphenol
             N-Nitroso-di-n-propylamine    4-Nitrophenol
             1,4-Di chlorobenzene


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           5.5.2    Organochlorine pesticide matrix spiking solution - Prepare a
      spiking  solution  in acetone  or  methanol  that  contains the  following
      pesticides  in the concentrations listed for water and sediment/soil.  The
      concentration should be  five times higher for waste samples.

            Pesticide                     Concentration (mq/L)

            Lindane                               0.2
            Heptachlor                            0.2
            Aldrin                                0.2
            Dieldrin                              0.5
            Endrin                                0.5
            4,4'-DDT                              0.5

           5.5.3    For  methods with no guidance, select five  or more analytes
      (select all analytes for methods with five or less)  from each analyte group
      for  use in  a  spiking solution.   Where  matrix  spike concentrations in the
      sample are not listed it  should be at or below the regulatory concentration
      or,  1 to  5 times higher  than  the background  concentration,  whichever,
      concentration would  be larger.

      5.6   Laboratory  control  spike standard  -  Use  the matrix spike standard
prepared  in Sec. 5.5  as  the spike standard  for  the  laboratory control sample
(LCS).  The LCS should  be  spiked at the  same  concentration as the matrix spike.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      See  Chapters Two  and Four  for guidance  on sample collection.


7.0   PROCEDURE

      7.1   Water, soil/sediment, sludge,  and waste samples requiring analysis for
semivolatile and nonvolatile organic compounds (within this broad category are
special  subsets  of   analytes,   i.e.,   the   different  groups  of  pesticides,
explosives, PCBs etc.), must undergo solvent extraction prior to analysis.  This
manual contains method choices  that are dependent on  the matrix,  the physical
properties of the analytes, the sophistication and  cost of equipment available
to a given laboratory, and the turn-around time required for sample preparation.

           7.1.1    The  laboratory should be  responsible for ensuring that the
      method chosen will provide acceptable extraction  efficiency for the target
      analytes in a given matrix.  In general,  Method 3520 - Continuous Extractor
      for  aqueous samples and Method 3540 - Soxhlet Extraction for solid samples
      are  considered the standard for a broad range of  those matrices.  Depending
      on the requirements  of the QA Project Plan, it may be necessary to verify
      that any  other SW-846  method (or non-SW-846 method)  chosen  for sample
      extraction does provide appropriate extraction efficiency  for the analytes
      of concern  from  matrices at a given  RCRA  site.  When performing method
      comparisons, they must be  performed  on  a site sample  expected  to contain
      some of the target analytes  rather than on  spiked  samples.  Analyze four
      portions  of the  well  homogenized sample  using the  standard  extraction
      method and  four  portions  by  the extraction method  of  interest.   For  a

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     method to be acceptable when comparing the means of the two sets of data,
     the RSD must be < 20% for aqueous samples and < 30% for solid samples.

          7.1.2   Each  method has QC  requirements  that normally  include  the
     addition of surrogates to each sample and  QC samples plus the inclusion of
     a  matrix  spike/ matrix  spike duplicate  (or matrix spike  and  duplicate
     samples), a laboratory control sample, and a reagent blank, in each sample
     extraction batch.  The decision on whether to prepare and analyze duplicate
     samples  or a  matrix spike/matrix  spike duplicate  must  be  based on  a
     knowledge of the samples in the extraction batch.  If the  sample selected
     for duplicate analysis is known to contain target analytes, then precision
     data will result.   However,  if the  samples are  unknown or expected to be
     free  of  target  analytes,  then  the  batch  should  include  the  matrix
     spike/matrix  spike  duplicate to ensure  that   precision data  will   be
     generated within that extraction  batch.

     7.2  Method  3510  -  Applicable to  the extraction  and concentration  of
water-insoluble and  slightly  water-soluble organics  from aqueous  samples.   A
measured volume of sample is solvent extracted using  a separatory funnel.  The
extract is  dried,  concentrated  and,  if  necessary,  exchanged  into  a  solvent
compatible  with  further analysis.    Separatory  funnel  extraction  utilizes
relatively inexpensive glassware and is  fairly rapid  (three, 2-minute extractions
followed by filtration)  but  is  labor   intensive,  uses fairly large volumes of
solvent and is subject to emulsion problems.  Method  3520 should be used if an
emulsion forms  between  the solvent-sample  phases, which  cannot be  broken by
mechanical  techniques.

     7.3  Method  3520  -  Applicable to  the extraction  and concentration  of
water-insoluble and  slightly  water-soluble organics  from aqueous  samples.   A
measured volume of sample is extracted with an organic solvent  in a continuous
liquid-liquid extractor.  The solvent  must have a  density greater than that of
the sample.  The extract is dried, concentrated and,  if necessary, exchanged into
a solvent  compatible  with  further analysis.  Continuous extractors are excellent
for samples with particulates  (of up to 1% solids) that cause emulsions, provide
more efficient  extraction of analytes that are more difficult  to  extract and once
loaded, require no  hands-on  manipulation.   However, they require more expensive
glassware,  use fairly  large  volumes  of solvent and  extraction  time  is rather
lengthy (6 to 24 hours).

     7.4  Method  3535  -  Applicable to  the extraction  and concentration  of
water-insoluble and  slightly  water-soluble organics  from aqueous  samples.   A
measured volume of water is  pumped  through an appropriate medium (e.g., disk or
cartridge) containing a solid  phase that effects the extraction  of organics from
water.   A  small  volume of extraction   solvent  is passed  through  the  medium to
elute the  compounds  of interest.  The eluant is  dried, concentrated  and, if
necessary,   exchanged   into   a   solvent   compatible   with   further  analysis.
Appropriate solid-phase  extraction media  allow extraction of water containing
particulates, are relatively  fast  and  use small volumes  of  solvent.   However,
they do require some specialized pieces of equipment.

     7.5  Method  3540  -  This   method  is  applicable  to   the  extraction  of
nonvolatile  and  semivolatile  organic  compounds  from solids  such  as  soils,
relatively dry sludges,  and solid wastes.   A solid sample is mixed with anhydrous
sodium sulfate, placed into an extraction thimble or  between two plugs of glass

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wool, and extracted using  an  appropriate  solvent  in  a Soxhlet extractor.   The
extract is concentrated and, if necessary, exchanged into a solvent compatible
with further analysis.  Soxhlet extraction uses relatively inexpensive glassware,
once loaded  requires no hands-on manipulation, provides efficient extraction, but
is rather lengthy (16  to 24 hours) and uses fairly  large volumes of solvent.  It
is considered a  rugged extraction method  because  there are very  few variables
that can adversely affect  extraction efficiency.

      7.6  Method 3541  - This  method utilizes a modified Soxhlet  extractor and
is applicable to the  extraction  of  semivolatile/nonvolatile organic compounds
from solids  such  as soils,  relatively  dry  sludges,  and solid  wastes.   A solid
sample is mixed with anhydrous  sodium sulfate, placed  into an extraction thimble
or between two plugs of glass wool,  and extracted  using an appropriate solvent
in an automated Soxhlet extractor.  This device allows the extraction thimble to
be lowered into  the boiling liquid for  the  first hour  and then  extracted in the
normal thimble position for one additional hour.  The automated Soxhlet allows
equivalent  extraction efficiency  in 2  hours,  combines  the concentration  step
within the same device but requires a rather expensive device.

      7.7  Method 3542  -   This method is  applicable  to   the extraction  of
semivolatile organic  compounds from the  Method 0010  air sampling  train.   The
solid trapping material (i.e.,  glass or quartz fiber  filter  and  porous polymeric
adsorbent resin)  are extracted using Soxhlet extraction and the condensate and
impinger fluid are extracted using separatory funnel  extraction.

      7.8  Method 3545  -   This method is  applicable  to   the extraction  of
nonvolatile/semivolatile  organic compounds  from solids such  as soils, relatively
dry sludges, and  solid wastes.  A solid  sample is mixed with  anhydrous sodium
sulfate, placed  into an extraction cell and extracted  under pressure with small
volumes of  solvent.   The  extract  is concentrated  and, if necessary, exchanged
into  a  solvent   compatible with  further  analysis.    The  method  is rapid  and
efficient, in that it  uses  small volumes of solvent,  but does require the use of
an expensive extraction device.

      7.9  Method 3550  -   This method is  applicable  to   the extraction  of
nonvolatile  and  semivolatile  organic  compounds  from  solids  such as  soils,
sludges, and wastes using the technique  of ultrasonic  extraction. Two procedures
are detailed depending upon the expected concentration of organics  in the sample;
a low concentration and a high  concentration method.   In both,  a known weight of
sample  is  mixed  with  anhydrous  sodium  sulfate  and  solvent   extracted  using
ultrasonic extraction.  The extract  is dried,  concentrated and,  if necessary,
exchanged into a  solvent compatible with further analysis. Ultrasonic extraction
is fairly rapid  (three, 3-minute extractions  followed by filtration)  but  uses
relatively large volumes of solvent, requires  a somewhat expensive device and
requires following the details of the method very closely to achieve acceptable
extraction efficiency  (proper  tuning of the ultrasonic device is very critical).
This  technique  is much less  efficient than  the  other  extraction  techniques
described in this  section.  This  is most  evident with  very non-polar organic
compounds (e.g.   PCBs,  etc.) that are  normally strongly adsorbed to  the  soil
matrix.  It  is not appropriate  for use with organophosphorus compounds, because
it may cause the destruction of some  of the target analytes during the extraction
procedure.
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     7.10 Methods 3560 and 3561  - These methods are applicable to the extraction
of total  petroleum hydrocarbons  and PAHs from solids such as soils, sludges, and
wastes using the technique of supercritical fluid extraction (SFE).  SFE normally
uses C02  (which may contain very  small volumes of solvent modifiers).  Therefore,
there is no  solvent waste  for disposal,  may be automated,  provides relatively
rapid extraction,  but,  is currently limited  to  total petroleum hydrocarbons and
PAHs.   It  also requires a  rather expensive device and  sample  size  is  more
limited.  Research on SFE is currently focusing on optimizing supercritical fluid
conditions to allow efficient extraction  of  a broader range of RCRA analytes in
a broad range of environmental matrices.

     7.11 Method 3580 - This method describes the  technique of solvent dilution
of non-aqueous waste samples.  It is designed  for wastes  that may contain organic
chemicals at  a level  greater than  20,000 mg/kg  and that  are soluble  in the
dilution solvent.   When using this method, the analyst  must use caution in the
addition of surrogate  compounds, so as  not to dilute out the surrogate response
when diluting the sample.

     7.12 Sample  analysis - Following preparation  of  a  sample by  one  of the
methods  described  above,  the sample is  ready  for further analysis.   Samples
prepared for semivolatile/nonvolatile analysis may, if necessary, undergo cleanup
(See Method 3600)  prior to application of a specific determinative method.


8.0  QUALITY CONTROL

     8.1  Refer  to  Chapter  One  for  specific guidance  on  quality  control
procedures.    Each laboratory using  SW-846  methods  should  maintain  a  formal
quality assurance program.   Each extraction batch  of 20 or less samples should
contain:  a  reagent blank; either a  matrix  spike/matrix  spike duplicate  or a
matrix spike and duplicate samples; and a  laboratory control sample, unless the
determinative method provides other guidance.

     8.2 Initial   Demonstration   of  Proficiency  -  Each   laboratory  must
demonstrate  initial proficiency with each sample preparation  and  determinative
method combination it utilizes, by generating  data of  acceptable accuracy and
precision for target analytes in a clean  reference matrix.  This will include a
combination  of the sample  extraction method  (usually a 3500  series method for
extractable organics)  and the determinative method  (an 8000 series method).  The
laboratory should  also  repeat the following operations whenever  new staff are
trained or significant changes  in instrumentation  are made.

          8.2.1    The  reference samples are prepared from a  spiking solution
     containing  each  analyte of  interest.   The  reference sample concentrate
      (spiking solution)  may be  prepared  from  pure  standard materials,  or
     purchased as certified  solutions.   If  prepared  by the  laboratory, the
     reference sample concentrate should be  made using stock standards prepared
      independently from those used for calibration.

          8.2.2    The   procedure  for  preparation  of  the  reference  sample
     concentrate  is  dependent upon  the method  being evaluated.   Guidance for
     reference sample concentrations for certain  methods are listed below.  In
     other  cases,  the  determinative  methods contain guidance  on  preparing the


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reference sample concentrate and the reference sample.   If no guidance  is
provided, prepare  a reference sample  concentrate  in  methanol  (or  other
water miscible solvent).  Spike at the concentration the method performance
data are based  on.   The  spike volume  added to water should  not  exceed  1
mL/L so  that  the  spike solvent will not decrease extraction efficiency.
If  the  method  lacks  performance  data,   prepare  a  reference  standard
concentrate  at  such  a  concentration  that  the  spike  will  provide   a
concentration in the clean matrix that is  10  - 50 times  the  MDL  for each
analyte in that matrix.

     The concentration of the target analytes in  the  reference sample may
need to be adjusted  to more accurately reflect  the concentrations that will
be analyzed  in the laboratory.  If the concentration of an analyte is  being
evaluated relative  to  a regulatory  limit,  see  Sec. 8.3.3 for information
on selecting an appropriate spiking level.

     8.2.3   To evaluate the performance of the total  analytical  process,
the reference samples must be  handled in exactly the same manner as actual
samples.  Therefore, 1  ml  (unless the method specifies a different volume)
of the reference sample concentrate is spiked  into each  of four  (minimum
number  of  replicates)  1-L  aliquots of organic-free  reagent water  (now
called the reference sample), extracted as  per the method.   For  matrices
other  than water  or for  determinative methods that  specify  a  different
volume of water,  add 1.0 ml of the reference sample concentrate to at  least
four replicates of the  volume  or weight of sample specified in the method.
Use a clean matrix for  spiking purposes (one that does not have any target
or interference compounds) e.g.,  organic-free reagent  water for the  water
matrix  or  sand or  soil   (free of  organic   interferences)  for the  solid
matrix.

     8.2.4    Preparation  of reference samples

             8.2.4.1   Method  8041   - Phenols:   The  QC  reference sample
     concentrate should contain each analyte at 100 mg/L in 2-propanol.

             8.2.4.2   Method  8061  - Phthalate esters:    The  QC  reference
     sample  concentrate   should  contain  the  following  analytes  at the
     following concentrations  in acetone: butyl benzyl phthalate, 10  mg/L;
     bis(2-ethylhexyl)phthalate,  50 mg/L;  di-n-octyl phthalate,  50  mg/L;
     and any other  phthalate at 25 mg/L.

             8.2.4.3   Method 8070 - Nitrosamines:  The QC reference sample
     concentrate should contain each analyte at 20 mg/L  in isooctane.

             8.2.4.4   Method  8081  - Organochlorine  pesticides:   The  QC
     reference  sample  concentrate  should  contain  each  single-component
     analyte  at  the following concentrations  in  acetone:    4,4'-DDD,  10
     mg/L;  4,4'-DDT, 10 mg/L;  endosulfan  II, 10 mg/L;  endosulfan  sulfate,
     10 mg/L; and any other single-component pesticide  at 2 mg/L.  If the
     method is only to be used to analyze  chlordane or toxaphene, the  QC
     reference sample  concentrate should contain the most  representative
     multicomponent parameter at a concentration  of 50 mg/L in acetone.
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        8.2.4.5  Method  8082  -  PCBs:    The  QC  reference  sample
concentrate should  contain the  most  representative multicomponent
parameter at a concentration of 50 mg/L in acetone.

        8.2.4.6  Method  8091  -  Nitroaromatics  and Cyclic  Ketones:
The QC reference sample concentrate should  contain each analyte at the
following concentrations  in acetone:  each dinitrotoluene at  20 mg/L;
and isophorone and nitrobenzene at 100 mg/L.

        8.2.4.7  Method  8100 -  Polynuclear  aromatic  hydrocarbons:
The QC reference sample concentrate should  contain each analyte at the
following concentrations  in acetonitrile:   naphthalene,  100 mg/L;
acenaphthylene, 100 mg/L;  acenaphthene, 100 mg/L; fluorene,  100 mg/L;
phenanthrene,  100 mg/L;  anthracene,  100 mg/L; benzo(k)fluoranthene  5
mg/L; and any other PAH at 10 mg/L.

        8.2.4.8  Method 8111  -  Haloethers:  The  QC reference  sample
concentrate should contain each  analyte at a concentration of 20  mg/L
in isooctane.

        8.2.4.9  Method  8121  -  Chlorinated  hydrocarbons:   The  QC
reference  sample  concentrate  should  contain  each analyte at  the
following   concentrations   in   acetone:     hexachloro-substituted
hydrocarbons,   10  mg/L;  and any  other  chlorinated  hydrocarbon,  100
mg/L.

        8.2.4.10 Method 8131 - Aniline  and selected derivatives:   The
QC reference  sample  concentrate should  contain each analyte  at  the
following concentrations  in  acetone  at  a concentration 1,000 times
more concentrated than the selected spike concentration.

        8.2.4.11 Method  8141  -  Organophosphorus compounds:    The QC
reference sample concentrate  should contain each  analyte  in acetone
at a  concentration  1,000  times  more concentrated  than  the  selected
spike concentration.

        8.2.4.12 Method  8151  -  Chlorinated   herbicides:    The  QC
reference sample concentrate  should contain each  analyte  in acetone
at a  concentration  1,000  times  more concentrated  than  the  selected
spike concentration.

        8.2.4.13 Method 8260  -  Volatile organics:   The QC reference
sample  concentrate  should  contain  each  analyte   in methanol  at  a
concentration of 10 mg/L.   This concentrate  is  spiked  into  100 mL of
organic-free reagent water, producing enough reference sample for four
aliquots of up to 25 mL each.

        8.2.4.14 Method  8270   -  Semivolatile  organics:     The  QC
reference sample concentrate  should contain each  analyte  in acetone
at a concentration of 100 mg/L.

        8.2.4.15 Method  8310 -  Polynuclear  aromatic  hydrocarbons:
The QC reference sample concentrate should  contain each analyte at the
following  concentrations  in acetonitrile:   naphthalene,  100 mg/L;

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     acenaphthylene, 100 mg/L;  acenaphthene, 100 mg/L; fluorene, 100 mg/L;
     phenanthrene, 100 mg/L; anthracene,  100 mg/L;  benzo(k)fluoranthene,
     5 mg/L; and any other PAH at 10 mg/L.

     8.2.5   Analyze at  least  four replicate aliquots of  the  well-mixed
reference samples by the same  procedures used to analyze  actual  samples
(Sec. 7.0 of each of the  methods).  This will include a combination of the
sample preparation method  (usually  a 3500 series method for  extractable
organics) and the determinative method (an 8000  series method).  Follow the
guidance on data calculation and interpretation presented in Method 8000,
Sec. 8.0.

     8.2.6   The following methods contain specific  extraction and sample
preparation requirements applicable only to that method.   Refer  to these
individual methods for extraction and preparation procedures required prior
to  instrumental  analysis,  and  for  information  on  the preparation  of  QC
reference samples.

             8.2.6.1  Method    8275   -   Thermal    Chromatography/Mass
     Spectrometry (TC/MS) for Screening Semivolatile Organic Compounds.

             8.2.6.2  Method 8280 - Polychlorinated  Dibenzo-p-Dioxins and
     Polychlorinated Dibenzofurans.

             8.2.6.3  Method 8290 - Polychlorinated  Dibenzo-p-dioxins and
     Polychlorinated Dibenzofurans.

             8.2.6.4  Method 8318 - N-Methylcarbamates by High Performance
     Liquid Chromatography (HPLC).

             8.2.6.5  Method  8321  -  Solvent   Extractable  Non-Volatile
     Compounds by High  Performance Liquid Chromatography/Thermospray/Mass
     Spectrometry (HPLC/TS/MS)  or Ultra-Violet (UV)  Detection.

             8.2.6.6  Method  8325  -  Nonvolatiles  by  High  Performance
     Liquid Chromatography/Particle-Beam/Mass Spectrometry (HPLC/PB/MS)  or
     Ultra-Violet (UV)  Detection.

             8.2.6.7  Method 8330 - Nitroaromatics and Nitramines by High
     Performance Liquid Chromatography (HPLC).

             8.2.6.8  Method  8331  - Tetrazine  by  Reverse  Phase  High
     Performance Liquid Chromatography (HPLC).

             8.2.6.9  Method 8332 - Nitroglycerine  by High  Performance
     Liquid Chromatography (HPLC) or Thin Layer Chromatography (TLC).

             8.2.6.10  Method 8410 - Gas Chromatography/Fourier Transform
     Infrared (GC/FT-IR)  Spectrometry for Semivolatile Organics.

             8.2.6.11  Method 8430 - Bis-(chloroethyl )ether and Hydrolysis
     Products by GC/FT-IR.
                             3500B  -  11                         Revision  2
                                                            January  1995

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             8.2.6.12  Method   8440   -   Total   Recoverable   Petroleum
     Hydrocarbons (TRPH)  by Infrared (IR) Detection.

8.3  Sample Quality Control for Preparation and Analysis

     8.3.1   Documenting  the  effect  of the  matrix  should  include the
analysis of at  least one matrix spike and one duplicate unspiked sample  or
one'tnatrix  spike/matrix spike  duplicate  pair per analytical  batch.  The
decision on whether to prepare and  analyze duplicate  samples or  a  matrix
spike/matrix spike duplicate must be based on a  knowledge of the samples
in the sample batch.  If  samples  are expected to  contain  target analytes,
then laboratories may use one  matrix spike  and a  duplicate analysis of  an
unspiked field  sample.    If samples are not  expected to contain  target
analytes,  the  laboratories should  use  a matrix  spike  and  matrix  spike
duplicate  pair.   See Sec.  5.5  for additional guidance  on  matrix  spike
preparation.

     8.3.2   A Laboratory Control Sample (LCS) should be included with each
analytical   batch.   The  LCS consists of  an  aliquot  of a clean  (control)
matrix similar  to the sample matrix  and of  the  same weight or volume:
e.g., organic-free reagent water for the water matrix or sand or soil (free
of organic  interferences)  for the solid matrix. The  LCS is spiked with the
same analytes at  the  same concentrations as the  matrix spike.   When the
results of  the matrix spike analysis indicate a  potential problem  due  to
the  sample  matrix itself, the LCS  results are  used  to  verify  that the
laboratory  can perform the analysis in a clean matrix.

     8.3.3   The  concentration of the matrix  spike  sample and/or the LCS
should be determined as described in the following sections.

    K        8.3.3.1   If,  as  in  compliance  monitoring, the concentration
     of  a   specific  analyte  in  the sample  is  being  checked  against  a
     regulatory concentration limit, the spike should be at  or below the
     regulatory limit, or 1  - 5  times  the background concentration  (if
     historical data are available), whichever concentration  is higher.

             8.3.3.2   If   historical  data   are   not   available,   it   is
     suggested that an uncontaminated sample  of  the same matrix  from the
     site  be  submitted  for matrix  spiking  purposes to ensure that  high
     concentrations  of target  analytes  and/or   interferences  will not
    "prevent calculation of recoveries.

             8.3.3.3   If  the  concentration  of  a specific analyte in  a
     sample is not being  checked  against  a limit specific to that analyte,
     then the spike should be at the same  concentration  as the reference
     sample (Sec.  8.2.4) or 20 times the estimated quantitation limit (EQL)
     in the matrix  of interest.   It is again  suggested that  a  background
     sample of the same matrix from the  site be  submitted as  a  sample for
     matrix spiking purposes.

     8.3.4   Analyze these QC  samples (the LCS and the  matrix spikes or the
optional matrix  duplicates)  following  the procedure  (Sec.  7.0)  of the
selected determinative  method.    Calculate  and  evaluate the  QC data  as
outlined in Sec.  8.0 of Method 8000.

                            3500B - 12                         Revision 2
                                                             January 1995

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          8.3.5    Blanks  -  Use of method blanks and other blanks are necessary
     to  track  contamination of samples  during  the  sampling  and  analysis
     processes.  Refer to Chapter One for specific quality control  procedures.

          8.3.6    Surrogates -  A surrogate  is  a compound that  is  chemically
     similar to the analyte group but not expected to occur in an environmental
     sample.   Surrogate  should  be added to all samples when  specified  in the
     appropriate  determinative  method  (See  Table  2).   See  Sec. 5.4 for the
     definition of surrogates and additional guidance on surrogates.

     8.4  The  laboratory  must have  procedures in  place  for documenting and
charting the effect of the matrix on method performance.   Refer  to  Chapter One
and Method 8000 for specific guidance on developing method performance data.


9.0  METHOD PERFORMANCE

     9.1  The recovery of surrogates is used to monitor unusual matrix effects,
sample processing  problems, etc.   The recovery  of matrix spiking  compounds
indicates the presence or absence of unusual  matrix effects.

     9.2  The performance  of each 3500 method  will  be  dictated  by  the overall
performance of the sample  preparation in combination with the  cleanup  method
and/or the analytical  determinative  method.


10.0 REFERENCES

     None required.
                                  3500B -  13                         Revision  2
                                                                  January 1995

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                   TABLE 1
SURROGATES FOR SW-846 CHROMATOGRAPHIC METHODS
  FOR SEMIVOLATILE AND NONVOLATILE COMPOUNDS
Method
Number
8041
8061
8070
8081
8082
8091
8100
8111
8121
8131
8141
8151
8270
8275
8280
Method Name
Phenols by GC
Phthalates by GC
Nitrosamines by
GC, Packed Column
Organochlorine
Pesticides by GC
Polychlorinated
Biphenyls by GC
Nitroaromatics by
GC
PAHs by GC,
Packed Column
Haloethers by GC
Chlorinated
Hydrocarbons by
GC
Anilines by GC
Organophosphorus
Pesticides by GC
Acid Herbicides
by GC
Semivolatiles by
GC/MS
Thermal Chromato-
graphy/MS for
Semivolatiles
PCDDs & PCDFs by
LR/MS
Suggested Surrogates
2-Fluorophenol , and
2,4,6-Tribromophenol
Diphenyl phthalate, Diphenyl
isophthalate, and Dibenzyl
phthalate
None Listed""
2,4,5,6-Tetrachloro-m-xylene,
and Decachlorobiphenyl
Decachlorobiphenyl
2-Fluorobiphenyl
2-Fluorobiphenyl , and
1-Fluoronaphthalene
None Listed""
a,2,6-Trichlorotoluene,
2,3,4,5,6-Pentachlorotoluene,
and 1,4-Dichloronaphthalene
None Listed"
None Listed*"
2,4-Dichlorophenylacetic acid
Phenol-d6, 2-Fluorophenol ,
2,4,6-Tribromophenol, Nitro-
benzene-d5, 2-Fluorobiphenyl,
and p-Terphenyl-d14
Not Listed""
Internal standards added at
time of extraction. No
surrogates.
Suggested Water
Concentration
200 M9/L
25 M9/L
100 M9/L
1 M9/L
NA
100 M9/L
100 M9/L
100 M9/L
1 M9/L (for
surrogates 1&2)
10 jitg/L (other
surrogates)
NA
NA
5 M9/L
Base/Neutrals
100 jLig/L &
Acids 200 jug/L
NA
NA
                  3500B  -  14
  Revision 2
January 1995

-------
                                         TABLE 1
                                       (continued)
Method
Number
8290
8310
8318
8321
8325
8330
8331
8332
8410
8430
8440
Method Name
PCDDs & PCDFs by
HR/MS
PAHs by HPLC
Carbamates by
HPLC
Nonvolatiles by
HPLC/TS/MS or
UV/VIS
Nonvolatiles by
HPLC/PB/MS or
UV/Vis
Explosives by
HPLC
Tetrazine by HPLC
Nitroglycerine by
HPLC or TLC
GC/FT-IR for
Semivolatiles
Bis-(chloroethyl )
ether and hydro-
lysis products by
GC/FT-IR
Total Recoverable
Petroleum Hydro-
carbons by IR
Suggested Surrogates
Internal standards added at
time of extraction. No
surrogates.
Decafluorobiphenyl
None Listed""
None Listed"
Benzidine-dg, Caffeine-15N2,
3,3' -dichlorobenzidine-d6,
bis-(perfluorophenyl)-
phenylphosphine oxide
None Listed""
None Listed"
None Listed"
None Listed"
None Listed"
None Listed"
Suggested Water
Concentration
NA
NA
NA
NA
50 /jg/L in
water
NA
NA
NA
NA
NA
NA
      Surrogate  compounds  selected should be  similar in  analytical behavior to
      the  analytes of  interest, but  which  are not  expected to  be present  in  the
      sample matrix  or extract.
GC
HR
LR
NA
TS
PB
MS
Gas chromatography
High Resolution
Low Resolution
Not Available
Thermospray
Particle Beam
Mass Spectrometer
NOTE:   Unless  otherwise
        techniques.
    HPLC     =  High Performance Liquid Chromatography
    PCDD     =  Polychlorinated Dibenzo~2-dioxins
    PCDF     =  Polychlorinated Dibenzofurans
    FT-IR    =  Fourier Transform Infrared Detector
    UV/Vis   =  Ultraviolet/Visible Detector
    TLC      =  Thin Layer Chromatography
    IR       =  Infrared Detector

specified,   all  GC  methods   are  capillary  column
                                       3500B -  15
                                                                       Revision 2
                                                                    January  1995

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                    TABLE 2

MATRIX SPIKES FOR SW-846 CHROMATOGRAPHIC METHODS
   FOR SEMIVOLATILE AND NONVOLATILE COMPOUNDS
Method
Number
8041
8061
8070
8081
8082
8091
8100
8111
8121
8131
8141
8151
8270
8275
8280
8290
Method Name
Phenols by GC
Phthalates by GC
Nitrosamines by
GC, Packed Column
Organochlorine
Pesticides by GC
Polychlorinated
Biphenyls by GC
Nitroaromatics by
GC, Packed Column
PAHs by GC,
Packed Column
Haloethers by GC
Chlorinated
Hydrocarbons by
GC
Anilines by GC
Organophosphorus
Pesticides by GC
Acid Herbicides
by GC
Semivolatiles by
GC/MS
Thermal
Chromatography/MS
for Semivolatiles
PCDDs & PCDFs by
LR/MS
PCDDs & PCDFs by
HR/MS
Suggested Matrix Spike Compounds
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Lindane, Heptachlor, Aldrin,
Dieldrin, Endrin, and 4,4'-DDT
Spike Aroclors 1016 and 1260 or
individual PCB congeners of
interest
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
1,2,4-Trichlorobenzene, Ace-
naphthene, 2,4-Dinitrotoluene,
Pyrene, N-Nitroso-di-n-propylamine,
1,4-Dichlorobenzene, Penta-
chlorophenol , Phenol, 2-Chloro-
phenol , 4-Chloro-3-methylphenol ,
and 4-Nitrophenol
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Suggested
Water Cone.
NA
NA
NA
1 - 10 M9/L
NA
NA
NA
NA
NA
NA
NA
NA
100 M9/L for
base/neutral
compounds
and 200 jug/L
for acid
compounds
NA
NA
1 ng/L (ppt)
                   3500B - 16
  Revision 2
January 1995

-------
                                            TABLE  2
                                          (continued)
Method
Number
8310
8321
8325
8330
8331
8332
8410
8430
8440
Method Name
PAHs by HPLC
Nonvolatiles by
HPLC/TS/MS or
UV/VIS
Nonvolatiles by
HPLC/PB/MS or
UV/Vis
Explosives by
HPLC
Tetrazine by HPLC
Nitroglycerine by
HPLC or TLC
GC/FT-IR for
Semivolatiles
Bis-(chloroethyl )
ether and
hydrolysis
products by
GC/FT-IR
Total Recoverable
Petroleum
Hydrocarbons by
IR
Suggested Matrix Spike Compounds
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Spike analytes of interest
Spike with analyte of interest
Spike with analyte of interest
Primarily a qualitative method
Spike analytes of interest
Spike analytes of interest
Suggested
Water Cone.
NA
NA
NA
NA
NA
NA
NA
100 Mg/L
NA
GC    =  Gas chromatography
HR    =  High Resolution
LR    =  Low Resolution
NA    =  Not Available
TS    =  Thermospray
PB    =  Particle  Beam
MS    =  Mass Spectrometer
HPLC      =  High Performance Liquid Chromatography
PCDD      =  Polychlorinated Dibenzo-g-dioxins
PCDF      =  Polychlorinated Dibenzofurans
FT-IR     =  Fourier Transform Infrared Detector
UV/Vis    =  Ultraviolet/Visible Detector
TLC       =  Thin Layer Chromatography
IR       =  Infrared Detector
NOTE:   Unless   otherwise   specified   all
         techniques.
                GC   methods   are   capillary   column
                                          3500B  -  17
                                                Revision  2
                                             January 1995

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                                 METHOD 3510C

                  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
Section 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.

      1.3  This  method is  restricted  to  use  by  or  under the  supervision of
trained  analysts.    Each  analyst must  demonstrate  the  ability  to  generate
acceptable results with this method.


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  separatory
funnel.

      2.2  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  The decomposition  of  some analytes has  been demonstrated under basic
extraction conditions.   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.   Method 3510 is preferred over Method  3520  for the
analysis of these  classes of  compounds.  However, the  recovery of phenols may be
optimized by using Method 3520, and performing the initial extraction at the acid
pH.


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.
                                  3510C  -  1                         Revision 3
                                                                  January 1995

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     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-569001-0219  or
     equivalent).

          4.3.5    Springs  -   1/2 inch  (Kontes  K-662750 or equivalent).

     NOTE:   The following glassware is recommended for  the  purpose of solvent
             recovery during the concentration procedures requiring the use of
             Kuderna-Danish evaporative concentrators.   Incorporation  of this
             apparatus  may  be  required  by   State  or local   municipality
             regulations that govern air  emissions  of volatile organics.  EPA
             recommends the incorporation  of this type of reclamation system as
             a method  to  implement  an  emissions  reduction  program.   Solvent
             recovery  is   a  means  to  conform with  waste  minimization  and
             pollution prevention initiatives.

     4.4  Solvent  vapor recovery system (Kontes K-545000-1006 or K-547300-0000,
Ace Glass 6614-30, or equivalent).

     4.5  Boiling  chips - Solvent-extracted, approximately 10/40 mesh (silicon
carbide or equivalent).

     4.6  Water   bath   -  Heated,  with  concentric  ring  cover,  capable   of
temperature control (± 5°C).  The bath should be used in a hood.

     4.7  Vials  -  2-mL, glass with Teflon®-!ined screw-caps or crimp tops.

     4.8  pH  indicator  paper  - pH range including  the desired  extraction pH.

     4.9  Erlenmeyer  flask  -  250-mL.

     4.10 Syringe  -  5-mL.

     4.11 Graduated  cylinder  - 1-liter.


                                  3510C -  2                         Revision 3
                                                                  January 1995

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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.   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 to
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride.  If the sodium sulfate  is precleaned  with methylene chloride,
a method blank must be analyzed,  demonstrating that there is no  interference from
the sodium sulfate.

     5.5   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 - All solvents must be  pesticide quality
or equivalent.

           5.6.1   Methylene  chloride,  CH2C12, boiling point 39°C.

           5.6.2   Hexane,  C6H14, boiling point  68.7°C.

           5.6.3   2-Propanol, CH3CH(OH)CH3,  boiling point 82.38C.

           5.6.4   Cyclohexane,  C6H12, boiling point 80.7°C.

           5.6.5   Acetonitrile,  CH3CN,  boiling point 81.6°C.


6.0  SAMPLE  COLLECTION, PRESERVATION,  AND HANDLING

     See   the   introductory   material   to  this   chapter,   Organic  Analytes,
Section 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.
                                   3510C  -  3                         Revision 3
                                                                  January 1995

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     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 using 1:1 (v/v) sulfuric acid or
10 N sodium hydroxide.

     7.3  Add  1.0  ml of  the  surrogate  standards to all  samples,  spikes,  and
blanks (see Method 3500 and the determinative method to be used for details on
the surrogate standard solution and the matrix spike solution).

          7.3.1    For the sample in each analytical  batch  selected for spiking,
     add  1.0 ml of the matrix spiking standard.

          7.3.2    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/^L of
     each  acid  analyte   in   the  extract  to  be  analyzed  (assuming  a  1  juL
     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.

     7.4  Add  60 ml  of methylene  chloride  to  the separatory funnel.

     7.5  Seal and shake the separatory  funnel vigorously for 1-2 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 avoid exposure  of the analyst
            to solvent vapors.

     7.6  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.

     7.7  Repeat the  extraction two more times  using fresh portions of solvent
(Sees. 7.3 through 7.5).   Combine the three solvent extracts.

     7.8   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.

     7.9   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

                                   3510C -  4                         Revision 3
                                                                  January 1995

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acid/neutral or base compounds at low concentrations must be determined, separate
extract analyses may be warranted).

     7.10  Perform  the  concentration  (if necessary)  using the Kuderna-Danish
Technique (Sees. 7.11.1 through 7.11.6).

     7.11  K-D  technique

           7.11.1   Assemble  a Kuderna-Danish (K-D) concentrator  (Sec.  4.3)  by
     attaching a 10-mL concentrator tube to a 500-mL evaporation flask.

           7.11.2   Attach  the solvent vapor recovery glassware  (condenser and
     collection device)  (Sec.  4.4) to the Snyder column of  the  K-D apparatus
     following manufacturer's  instructions.

           7.11.3   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.

           7.11.4   Add  one or two clean boiling chips to the flask and attach a
     three-ball Snyder column.   Prewet  the Snyder  column by  adding about 1  mL
     of methylene  chloride  to  the  top of the  column.   Place  the  K-D apparatus
     on a  hot  water bath (15 - 20°C above the boiling point of the solvent)  so
     that  the  concentrator tube  is partially immersed in the hot  water and the
     entire lower rounded surface of the flask is bathed with  hot vapor.  Adjust
     the  vertical  position  of  the   apparatus  and  the  water temperature  as
     required  to complete the concentration in 10 - 20 minutes.   At the proper
     rate of distillation the balls of the column will actively chatter, but the
     chambers  will not flood.  When the  apparent  volume  of liquid  reaches 1 ml,
     remove the K-D apparatus from  the water bath and allow  it to drain and cool
     for at least  10 minutes.

           7.11.5   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.  7.11.4,  raising the temperature of the water
     bath,  if  necessary, to  maintain  proper distillation.

           7.11.6   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.  7.12 or adjusted to 10.0 mL  with  the  solvent
     last  used.

     7.12  If further concentration is indicated  in  Table 1,  either the micro-
Snyder column technique (7.12.1) or nitrogen blowdown technique (7.12.2) is used
to adjust the extract to  the final  volume required.
                                  3510C  - 5                         Revision 3
                                                                  January 1995

-------
          7.12.1   Micro-Snyder  column  technique

                   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.

          7.12.2   Nitrogen blowdown  technique

                   7.12.2.1  Place  the concentrator  tube in a  warm bath  (35°C)
          and evaporate the  solvent  volume to  0.5  mL using  a  gentle stream of
          clean, dry nitrogen (filtered through a column of activated carbon).

          CAUTION:  New plastic tubing  must not be  used between the carbon trap
                    and the sample, since it  may introduce contaminants.

                   7.12.2.2  The internal wall of the tube must  be rinsed several
          times  with  methylene  chloride  or  appropriate  solvent during  the
          operation.  During evaporation, the  tube  must be positioned to avoid
          water condensation (i.e., the solvent level should be below the level
          of the water  bath).  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 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®-!ined screw-cap or
crimp top, and labeled  appropriately.


8.0  QUALITY CONTROL

     8.1  Any reagent   blanks, matrix  spikes,  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.


                                   3510C  -  6                         Revision 3
                                                                  January 1995

-------
9.0  METHOD  PERFORMANCE
     Refer to the determinative methods  for performance data.

10.0 REFERENCES
     None.
                                  3510C - 7                         Revision 3
                                                                  January 1995

-------
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-------
                                       METHOD 3510C

                       SEPARATORY FUNNEL  LIQUID-LIQUID EXTRACTION
                       7.1 Measure
                        sample into
                     separatory funnel.
                         7.2 Check
                       and adjust pH.
                    7.3 Add appropriate
                   surrogate and matrix
                    spiking standards.
7.8 Adjust
   pH.
   7.3 - 7.7
Extract 3 times
with methylene
   chloride.
               Yes
    7.8  Is
 extraction at
   2nd pH
  required?
                              7.8 Collect and
                             combine extracts.
                                   7.9
                                 GC/MS
                             nalysis (Method
                              8270) being
                               performed?
                    7.9 Combine acid/
                     neutral and base
                     extracts prior to
                     concentration, if
                       appropriate.
                                                     7.10 - 7.11
                                                     Concentrate
                                                       extract.
 7.1 1.5
Is solvent
exchange
required?
   7.11.5 Add
exchange solvent,
  reconcentrate
     extract.
                                                     7.12 Further
                                                  concentrate extract
                                                     if necessary;
                                                  adjust final volume.
                                                     7.12 Perform
                                                     determinative
                                                       method.
                                         3510C  -  9
                                                        Revision 3
                                                      January  1995

-------
                                 METHOD 3520C

                      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
Section 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.

     1.4  This  method is  restricted  to  use  by or  under  the supervision  of
trained  analysts.    Each  analyst  must  demonstrate  the  ability to  generate
acceptable results with this method.


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.

     2.2  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  The decomposition  of  some analytes has been demonstrated under basic
extraction conditions  required  to separate analytes.  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.  Method 3510 is preferred over
Method 3520  for  the  analysis  of  these  classes  of  compounds.   However,  the
recovery of phenols may  be  optimized  by using Method  3520  and performing the
initial  extraction  at  the acid  pH.
                                  3520C - 1                         Revision 3
                                                                  January 1995

-------
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,
584500-0000, 583250-0000, or equivalent).

     4.2   Drying  column  - 20 mm ID Pyrex®  chromatographic  column  with Pyrex®
glass wool at bottom and a Teflon® stopcock.

     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
     equivalent).
     equivalent.
Evaporation
  Attach  to
flask  -     500-mL
 concentrator  tube
 (Kontes  K-570001-500  or
with  springs,   clamps,  or
           4.3.3    Snyder column -
     equivalent).

           4.3.4    Snyder column  -
     equivalent).
                  Three-ball  macro  (Kontes K-503000-0121 or
                   Two-ball  micro  (Kontes  K-569001-0219 or
           4.3.5    Springs  -   1/2  inch  (Kontes  K-662750  or  equivalent).

      NOTE:   The following glassware is recommended for the purpose of solvent
             recovery during the concentration procedures requiring the use of
             Kuderna-Danish evaporative concentrators.   Incorporation of this
             apparatus  may   be   required   by   State   or  local   municipality
             regulations that govern air  emissions  of volatile organics.   EPA
             recommends the incorporation  of this  type of reclamation system as
             a method  to implement an  emissions  reduction program.   Solvent
             recovery  is  a  means  to  conform with  waste  minimization  and
             pollution prevention initiatives.

      4.4   Solvent  vapor recovery system (Kontes K-545000-1006 or K-547300-0000,
Ace Glass 6614-30, or equivalent).

      4.5   Boiling  chips  - Solvent-extracted, approximately 10/40 mesh (silicon
carbide or equivalent).

      4.6   Water  bath  -  Heated,  with  concentric   ring  cover,  capable  of
temperature control (± 5CC).  The bath should be used in a hood.

      4.7   Vials  -  2-mL,  glass with Teflon®-!ined  screw-caps or crimp  tops.
                                   3520C -  2
                                                 Revision 3
                                               January  1995

-------
     4.8   pH  indicator paper -  pH  range  including  the  desired  extraction pH.

     4.9   Heating  mantle  -  Rheostat  controlled.

     4.10  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.

     5.3   Sodium hydroxide solution (ION), NaOH.  Dissolve 40 g  NaOH  in organic-
free reagent water and dilute to 100 ml.

     5.4   Sodium sulfate  (granular,  anhydrous), Na2S04.  Purify by heating at
400°C for 4 hours  in a shallow tray,  or by precleaning the sodium sulfate with
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 -  All solvents must be pesticide quality
or equivalent.

           5.6.1    Methylene  chloride,  CH2C12, boiling point 39°C.

           5.6.2    Hexane,  C6H14, boiling  point  68.7°C.

           5.6.3    2-Propanol, CH3CH(OH)CH3,  boiling point 82.3°C.

           5.6.4    Cyclohexane,  C6H12, boiling point 80.7°C.

           5.6.5    Acetonitrile,  CH3CN, boiling point 81.6°C.


6.0  SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

     See   the   introductory   material  to  this   chapter,   Organic  Analytes,
Section 4.1.
                                  3520C  - 3                         Revision 3
                                                                  January 1995

-------
7.0   PROCEDURE

      7.1   Using  a 1-liter  graduated  cylinder, measure  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.

      7.2   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.

      7.3   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.)

           7.3.1    For the sample in each analytical batch selected for spiking,
      add  1.0  ml of the  matrix  spiking standard.

           7.3.2    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//il_ of  each  base/neutral  analyte  and 200 ng//A of
      each acid  analyte  in the  extract  to   be  analyzed  (assuming  a  1  /xL
      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.

      7.4   Add 300  -  500 ml  of methylene  chloride to the distilling flask.  Add
several boiling chips to the flask.

      7.5   Add sufficient water  to the extractor to ensure proper operation and
extract for 18 - 24 hours.

      7.6   Allow  the  extractor  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 described in Sees. 7.10 - 7.11.

      7.7   If a pH adjustment and  second extraction  is required (see Table 1),
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.

      7.8   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).

      7.9   Perform  concentration   (if  necessary)   using  the  Kuderna-Danish
technique  (Sees. 7.10.1 through 7.10.6).
                                   3520C - 4                        Revision 3
                                                                  January 1995

-------
     7.10 K-D technique

          7.10.1  Assemble  a  Kuderna-Danish (K-D) concentrator  (Sec.  4.3)  by
     attaching a 10-mL concentrator tube to a 500-mL evaporation flask.

          7.10.2  Attach  the  solvent  vapor recovery glassware  (condenser  and
     collection device)  (Sec.  4.4)  to the Snyder column of the  K-D apparatus
     following manufacturer's  instructions.

          7.10.3  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.

          7.10.4  Add one or two clean boiling chips to the flask and attach a
     three-ball Snyder column.   Prewet  the Snyder column by  adding about 1  mL
     of methylene chloride  to  the top of the column.   Place  the  K-D apparatus
     on a hot water bath (15 - 20°C above the boiling point of the  solvent)  so
     that the concentrator tube  is partially immersed in the hot  water and  the
     entire lower rounded surface of the flask is bathed  with hot vapor.  Adjust
     the  vertical  position  of the apparatus  and the  water temperature,  as
     required, to complete the concentration in  10 - 20 minutes.  At the proper
     rate of distillation the  balls of the column will actively chatter, but the
     chambers will  not flood.   When the  apparent volume of liquid reaches 1  mL,
     remove the K-D apparatus  from the water bath and  allow  it to drain and cool
     for at least 10 minutes.

          7.10.5  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. 7.10.4,  raising the temperature of the water
     bath, if necessary, to maintain proper distillation.

          7.10.6  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. 7.11 or adjusted to  10.0  mL with  the solvent
     last used.

     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

                  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 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

                                  3520C -  5                         Revision 3
                                                                  January 1995

-------
          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.

          7.11.2  Nitrogen  blowdown  technique

                  7.11.2.1  Place the concentrator tube  in  a  warm  bath (35°C)
          and  evaporate the solvent  volume  to 0.5 ml using a gentle stream of
          clean,  dry  nitrogen  (filtered through a column of activated carbon).

          CAUTION:  New plastic tubing must  not  be used between the carbon trap
                    and the sample, since it may introduce  contaminants.

                  7.11.2.2  The internal wall of the tube must  be rinsed several
          times  with methylene chloride or  appropriate  solvent  during  the
          operation.  During evaporation, the tube must be  positioned to avoid
          water condensation (i.e., the solvent  level  should be below the level
          of the water  bath).  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.

     7.12 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®-!ined screw-cap or
crimp top, and labeled  appropriately.


8.0  QUALITY CONTROL

     8.1  Any  reagent  blanks,   matrix  spikes,  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

     Refer to  the determinative methods for performance  data.


10.0 REFERENCES

     None.

                                   3520C - 6                         Revision 3
                                                                  January 1995

-------




















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-------
                               METHOD 3520C

                 CONTINUOUS  LIQUID-LIQUID  EXTRACTION
  7.1 Measure sample
     into extractor.
     7.2 Check and
       adjust pH.
  7.3 Add appropriate
  surrogate and matrix
   spiking standards.
  7.4 Add methylene
  chloride to distilling
         flask.
    7.5 Add reagent
   water to extractor;
extract for  18-24 hours;
    collect extract.
        7.6 Is
      extraction
      at 2nd pH
       required?
   7.7 Adjust pH of
 aqueous phase; extract
 for 18-24 hours with
 clean flask and fresh
        solvent.
         7.8
        GC/MS
   analysis (Metho
     8270) being
      performed?
 7.8 Combine extracts
 prior to concentration,
     if appropriate.
  7.9 Concentrate
     extract.
     7.10.5
    Is solvent
    exchange
    required?
                                                               7.10.5 Add exchange
                                                               solvent, concentrate
                                                                     extract.
   7.1 1 Further
concentrate extract
if necessary; adjust
   final volume.
   7.1 2 Perform
   determinative
     method.
                                   3520C  -  8
                                        Revision  3
                                     January 1995

-------
                                  METHOD  3535

                         SOLID-PHASE EXTRACTION (SPE)
1.0   SCOPE AND APPLICATION

      1.1  This  method  describes  a  procedure  for  isolating  target  organic
analytes from aqueous samples  using  solid-phase  extraction  media.   The method
describes conditions  for extracting  organochlorine pesticides  and  phthalate
esters from aqueous matrices including groundwater, wastewater and  TCLP leachates
using disk extraction media.  Performance data for these extractions are provided
in Method 8081 (organochlorine pesticides) and Method 8061 (phthalate esters).
The technique  may also be  applicable  to  semivolatiles  and  other  extractable
compounds.

      1.2  This method  also  provides  procedures  for concentrating extracts and
for solvent exchange.

      1.3  The  method may be  used  for  the extraction  of  additional  target
analytes  or  other  solid-phase  media   if  the  analyst  demonstrates  adequate
performance (e.g., recovery of 70  -  130%) using  spiked sample  matrices and an
appropriate analytical finish from Chapter  Four (Sec. 4.3). Organic-free reagent
water is not considered appropriate for conducting such performance studies.

      1.4  Solid-phase  extraction  is  called  liquid-solid  extraction  in  EPA
Drinking Water Methods.

      1.5  This  method is  restricted to  use  by or  under the supervision of
trained  analysts.    Each analyst  must demonstrate the  ability to  generate
acceptable results with this method.


2.0   SUMMARY OF METHOD

      2.1  A measured volume of sample  is adjusted to a specified pH (see Table
1) and then extracted using a Solid-phase Extraction (SPE) device.

      2.2  Target analytes are eluted  from  the solid-phase media using methylene
chloride or another specified solvent.   The  resulting solvent extract is dried
using sodium sulfate and concentrated.

      2.3  The concentrated  extract may be exchanged into a solvent compatible
with subsequent cleanup  procedures  (Chapter  Four, Section 4.2) or determinative
procedures (Chapter Four, Section 4.3) employed for the measurement of the target
analytes.


3.0   INTERFERENCES

      3.1  Refer to Method 3500.

      3.2  The decomposition of some  analytes has been demonstrated  under basic
extraction conditions.  Organochlorine pesticides may dechlorinate and phthalate

                                   3535 -  1                          Revision 0
                                                                 January 1995

-------
esters may hydrolyze.   The rates  of these reactions increase with increasing pH
and reaction times.

      3.3   Bonded phase silicas (e.g., C18) will hydrolyze on prolonged exposure
to aqueous  samples with pH  less  than 2 or  greater  than 9.   Hydrolysis  will
increase  at the extremes  of  this  pH  range and with  longer  contact  times.
Hydrolysis may reduce  extraction  efficiency  or  cause baseline irregularities.
Styrene  divinylbenzene  (SDB)  extraction  disks  should  be  considered  when
hydrolysis is a problem.

      3.4   Phthalates  are  a ubiquitous  laboratory  contaminant.    All  glass
extraction apparatus should be  used for  this  method because phthalates are used
as release  agents  when  molding rigid plastic (e.g.,  PVC).  A method  blank as
described  in  Chapter  One should  be  analyzed,  demonstrating that there  is no
phthalate contamination of the sodium sulfate  or other reagents  specified in this
method.

      3.5   Sample  particulates  may clog the solid-phase  media and  result in
extremely slow sample  extractions.  Use of an  appropriate  filter  aid will result
in shorter  extractions without  loss  of method  performance  if clogging  is  a
problem.


4.0   APPARATUS AND MATERIALS

      4.1   Solid-phase extraction system -  Empore~ manifold  with 3-90  mm or 6-
47 mm  standard filter apparatus,  or  equivalent.  Automatic or robotic sample
preparation  systems designed for solid-phase media  may  be utilized  for  this
method if adequate  performance  is achieved and all quality control requirements
are satisfied.

           4.1.1    Manifold station -  (Fisher  Scientific 14-378-1B [3-place], 14-
      378-1A [6-place],  or equivalent).

           4.1.2    Standard  Filter Apparatus -  (Fisher   Scientific  14-378-2A
      [47-mm],  14-378-2B  [90-mm],  or  equivalent),   consisting of  a  sample
      reservoir, clamp,  fritted disk  and  filtration head  with  drip tip.

           4.1.3    Tube,  collection -  60-mL  (Kimble 609-58-A16,  or equivalent).
      The  collection tube  should  be of appropriate I.D. and length for the drip
      tip  of the  standard filter  apparatus  to be positioned well into the neck
      of the tube to prevent splattering.

           4.1.4    Filter flask -  2-L with a  ground glass  receiver joint (Kontes
      K-953828-0000,  or  equivalent)   (optional).   May  be  used  to carry out
      individual  disk extractions  with  the  standard   filter  apparatus  and
      collection vial  in  an  ALL GLASS  SYSTEM.

      4.2   Solid-phase Extraction  Disks  - Empore™, 47- or 90-mm, or equivalent.
Guidance  for selecting the  specific disk is  provided in Table 1.

           4.2.1    C18 disks  -  (Fisher Scientific 14-378E  [47-mm], 14-378F  [90-
      mm],  or equivalent).


                                   3535 - 2                         Revision  0
                                                                  January  1995

-------
           4.2.2    Styrene divinylbenzene (SDB-XC) disks - (Fisher Scientific 14-
      378H  [47-mm],  14-378J,  or  equivalent).

      4.3   Filtration  aid  (optional).

           4.3.1    Filter  Aid 400 - (Fisher Scientific  14-378-3, or equivalent).

           4.3.2    In-situ glass micro-fiber prefilter  -  (Whatman GMF  150,  1
      micron  pore  size,  or equivalent).

      4.4   Drying  column - 22-mm ID Pyrex® chromatographic column with a Teflon®
stopcock (Kontes K-420530-0242,  or equivalent).

NOTE:  Fritted glass  discs  used to retain sodium sulfate in  some columns are
       difficult  to  decontaminate after  contact  with highly  contaminated  or
       viscous extracts.  Columns  suitable for this method  use a  small  pad  of
       Pyrex® glass wool to retain the drying agent.

      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 during  short-term storage.

           4.5.2    Evaporation   flask   -   500-mL   (Kontes  K-570001-500,   or
      equivalent).  Attach to concentrator  tube using  springs or clamps.

           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)  (optional).

           4.5.5    Springs -  1/2 inch  (Kontes K-662750,  or equivalent).

Note:  The glassware  in Sec. 4.6  is  recommended for  the  purpose of  solvent
       recovery during  the  concentration  procedures  (Sees.  7.13  and  7.14.1)
       requiring   the  use  of  Kuderna-Danish   evaporative   concentrators.
       Incorporation  of  this  apparatus may  be  required  by  State  or  local
       municipality regulations  that govern air emissions of volatile organics.
       The EPA recommends the incorporation of this  type of  reclamation system
       as  a  method  to  implement  an  emissions  reduction  program.    Solvent
       recovery is  a  means  to  conform  with  waste minimization and  pollution
       prevention initiatives.

      4.6   Solvent  Vapor Recovery System (Kontes  545000-1006 or K-547300-0000,
Ace Glass 6614-30, or equivalent).

      4.7   Boiling chips - Solvent extracted,  approximately 10/40 mesh (silicon
carbide,  or equivalent).

      4.8   Water   bath   -  Heated,  with  concentric   ring  cover,   capable  of
temperature control to ± 5°C.  The bath should be  used in  a  hood.


                                   3535 - 3                         Revision 0
                                                                  January 1995

-------
     4.9   N-Evap - Nitrogen blowdown apparatus, 12- or 24-position (Organomation
Model 112, or equivalent) (optional).

     4.10  Vials, glass  - Sizes  as appropriate,  e.g., 2-mL or 10-mL with PTFE-
fluorocarbon-lined screw caps or crimp tops for storage of extracts.

     4.11  pH  indicator  paper  - Wide pH range  (Fisher Scientific 14-850-13B, or
equivalent).

     4.12  Vacuum system - Capable of maintaining a vacuum of approximately 66 cm
(26 inches) of mercury.

     4.13  Graduated  cylinder  -  Sizes  as  appropriate.

     4.14  Pipets,  disposable  (Fisher  Scientific  13-678-20C,  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 decreasing  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  sulfate (granular,  anhydrous),  Na2S04 -  Purify by heating at
400eC for  4 hours  in a  shallow tray, or by precleaning  the sodium sulfate with
methylene  chloride.

     5.4   Solutions  for adjusting the pH of samples  before extraction.

           5.4.1    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.

           5.4.2    Sodium hydroxide solution  (ION), NaOH - Dissolve 40 g  NaOH in
     organic-free  reagent  water and dilute  to 100 ml.

     5.5   Extraction,  washing, and exchange solvents   -  All  solvent  smust be
pesticide  quality  or equivalent.

           5.5.1    Methylene chloride, CH2C12.

           5.5.2    Hexane,  C6H14.

           5.5.3    Ethyl acetate, CH3C(OH)OCH2CH3.

           5.5.4   Acetonitrile, CH3CN.
                                   3535  - 4                          Revision  0
                                                                  January  1995

-------
           5.5.5    Methanol,  CH3OH.

           5.5.6    Acetone,  (CH3)2CO.


6.0   SAMPLE  COLLECTION,  PRESERVATION, AND HANDLING

      See the introductory material to this chapter, Organic Analytes, Sec. 4.1.


7.0   PROCEDURE

      7.1   Using  a  graduated  cylinder, measure  a 1-liter sample.   Take care to
minimize any loss of sample particulates during this step.

           7.1.1    Add  5.0 mL  of methanol and any surrogate standards specified
      in the  determinative method  to  all  samples and blanks.

           7.1.2    Prepare  matrix spikes  by  adding   specified  matrix  spike
      standards to  representative  sample replicates.   The frequency with which
      matrix  spikes  are prepared and  analyzed is described in Chapter One or as
      part  of the determinative method.

           7.1.3    If cleanup  procedures are to be  employed  that  result in the
      loss  of extract,  adjust the amount of surrogate  and spiking cocktail(s)
      accordingly.   In  the case  of Method 3640, Gel  Permeation Cleanup, double
      the  amount  of  standards to  compensate for the  loss of one  half of the
      extract concentrate when loading the GPC  column.

           7.1.4    If high concentrations of target analytes are anticipated to
      be present  in  samples, a smaller volume may be extracted.

      7.2   Check the pH of the  sample with wide-range pH paper and, if necessary,
adjust the pH to the range  listed in Table 1.   If pH  adjustment  is required,
ensure that analytes are not lost in precipitates  or flocculated  material.

      7.3   Assemble  a manifold for multiple  extractions (Figure 1)  using 47-mm
or 90-mm Empore™ disks.  Use a filter flask with the standard filter apparatus
for  single  extractions.    If  samples  contain   significant  quantities  of
particulates, the use of  a filter aid or  prefilter is advisable.  Empore™ Filter
Aid 400 or Whatman  GMF  150 prefilters are recommended.

           7.3.1    Pour about 40 g of Filter  Aid 400 onto the surface of  the disk
      after assembling  the standard filter apparatus.

           7.3.2    Place  the Whatman GMF 150 on  top  of  the  Empore™ disk prior to
      clamping the glass  reservoir into  the  standard filter apparatus.

      7.4   Wash  the  extraction  apparatus and  disk with  20  mL  of  methylene
chloride introduced by rinsing down  the  sides  of the  glass reservoir.   Pull  a
small amount  of  solvent through  the disk with a vacuum; turn off the vacuum and
allow the  disk to soak  for about one minute.   Pull the remaining solvent through
the disk and  allow  the  disk to dry.


                                   3535  - 5                          Revision  0
                                                                  January 1995

-------
           7.4.1    When  using a filtration aid, adjust the  volume  of all  wash
     solvents  so the entire  filtration bed is  submerged.

           7.4.2    In subsequent conditioning steps, volumes should be adjusted
     so  that  a level  of solvent is always maintained  above the  entire filter
     bed.

     7.5   Continue to wash the extraction apparatus and disk by adding 10 mL of
acetone down the sides of the glass reservoir.   Pull a small amount of solvent
through the disk with a vacuum; turn off the vacuum and allow the disk to soak
for about one  minute.  Pull the remaining solvent through  the disk and allow the
disk to dry.  When  using a  filtration aid, adjust the volume of acetone so that
the entire filtration bed is submerged.

     7.6   Pre-wet  (condition) the  disk by  adding 20 ml  of methanol  to  the
reservoir, pulling a small  amount through the disk  and  then  letting it soak for
about one minute.   Pull most of the  remaining  methanol through the disk, leaving
3 - 5 mm of methanol above the surface of the disk.  From this point until  the
sample extraction  has  been completed,  the surface of the  disk  should  not be
allowed to go  dry.  THIS IS A CRITICAL STEP FOR A UNIFORM FLOW AND GOOD RECOVERY.

           7.6.1    The disk is composed of hydrophobic materials which will  not
     pass  water unless  they  are  pre-wetted  with a  water-miscible solvent.
     Should  a  disk  accidentally  go  dry  during  the  conditioning  step,  the
     methanol  pre-wetting  and water washing  steps must  be repeated prior to
     adding the sample.

           7.6.2    When  using a filtration aid,  adjust the  volume of conditioning
     solvents  so  that the  entire  filtration bed  remains  submerged  until  the
     extraction is completed.

     7.7   Rinse the disk by adding 20  mL of  organic-free reagent water to the
disk and drawing most through, leaving 3 - 5 mm  of water above the  surface of the
disk.

     7.8   Add  a water sample, blank or matrix spike (Sec. 7.1) to the reservoir
and, under full vacuum,  filter as quickly as  the vacuum will allow (at least 10
minutes).  Transfer as  much of the  measured volume  of water  as possible.  After
the sample has passed through  the solid-phase media, dry the  disk by maintaining
vacuum for about 3 minutes.

NOTE:  With heavily particle-laden  samples,  allow the sediment in the sample to
       settle; decant as much liquid as is practical into the reservoir.  After
       most of the aqueous  portion  of  the  sample has  passed through the disk,
       swirl the portion  of the sample  containing  sediment and  add  it to the
       reservoir.    Use  additional   portions  of organic-free reagent water to
       transfer any remaining particulates to the reservoir.  Particulates must
       be  transferred to the reservoir  before all of the  aqueous  sample  has
       passed through the disk.

     7.9   Remove the entire  standard filter assembly (do not disassemble) from
the  manifold  and  insert a  collection  tube.   The  collection tube  should have
sufficient capacity to  hold  all of the elution solvents.   The  drip tip of the
filtration  apparatus  should  be seated  sufficiently  below the  neck  of  the

                                   3535  - 6                          Revision 0
                                                                  January 1995

-------
collection  tube  to prevent  analyte loss  due  to  splattering  when  vacuum  is
applied.  When using a filter flask for single extractions, empty the water from
the flask before inserting the collection tube.

     7.10 Add 5.0  mL  of acetone  to  the disk.   Allow the acetone to spread out
evenly across the disk (or  inert filter) then quickly turn the vacuum on and off
to pull  the  first drops  of  acetone through the disk.   Allow the disk to soak for
15 to 20 seconds before proceeding to Sec. 7.11.

          7.10.1   The  initial elution with a water-miscible  solvent,  i.e.,
     acetone,  improves  the recovery of analytes  trapped in  water-filled pores
     of the  sorbent.  Use  of a water-miscible  solvent is particularly critical
     when methylene chloride  is used as  the  second  elution solvent.

          7.10.2   When  using a filtration  aid,  adjust the volume  of eluting
     solvent so  that  the entire filtration bed is initially submerged.

     7.11 Add 15 ml of  methylene  chloride (or  other suitable  elution solvent,
see Table 1)  to the sample bottle.   Rinse the  bottle thoroughly and,  with the
initial  portion of acetone still  on the disk, transfer the  solvent to the disk
with a disposable pipette,  rinsing down the sides  of  the  filtration reservoir in
the process.  Draw about half of the solvent through the disk  and then release
the vacuum.   Allow the remaining elution solvent to soak the disk and particulate
for about  one minute before drawing the remaining  solvent through the disk under
vacuum.   When using a filtration  aid,  adjust the  volume of  elution solvent  so
that the entire filtration bed is initially submerged.

     7.12 Repeat Sec. 7.11 with a second  15-mL aliquot of elution solvent (see
Table 1).

     7.13 K-D concentration  technique.

          7.13.1   Assemble a Kuderna-Danish  (K-D)  concentrator  by attaching a
     10-mL  concentrator tube  to a 500-mL  evaporation  flask.

          7.13.2   Dry the  combined extracts in  the collection tube (Sees. 7.10-
     7.12)  by passing them through  a  drying column containing  about 10  g  of
     anhydrous   sodium  sulfate.    Collect  the  dried  extract  in  the  K-D
     concentrator.    Use   acidified  sodium  sulfate  (Method 8151)  if  acidic
     analytes  are  to  be measured.

          7.13.3   Rinse the collection tube and drying column into  the K-D flask
     with  an  additional   20-mL  portion  of  solvent  in order  to  achieve  a
     quantitative  transfer.

          7.13.4   Add one  or two clean boiling chips to the flask and attach a
     three-ball  Snyder  column.  Attach  the  solvent  vapor  recovery  glassware
     (condenser and collection device,  see Sec.  4.6) to the Snyder  column of the
     K-D apparatus, following  manufacturer's instructions.  Prewet the  Snyder
     column  by adding  about 1 mL of methylene chloride to the top of the column.
     Place  the K-D apparatus  on  a hot  water  bath  (15 -  20°C above the boiling
     point of the  solvent) so that the concentrator tube is  partially immersed
     in the hot water  and the entire lower rounded  surface  of  the  flask  is
     bathed  with hot vapor.  Adjust the vertical  position of the apparatus and

                                   3535 - 7                         Revision 0
                                                                  January 1995

-------
     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.

                  7.13.4.1  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.

                  7.13.4.2  Reattach   the   Snyder column.     Concentrate  the
          extract, raising the temperature of the water bath,  if necessary, to
          maintain a proper distillation  rate.

          7.13.5  Remove  the  Snyder column.  Rinse the K-D flask and the  lower
     joints of the  Snyder column into the concentrator tube with  1  -  2  ml of
     solvent.   The  extract may  be  further concentrated by using  a technique
     outlined in Sec. 7.14 or adjusted to  a final volume of 5.0 - 10.0 ml  using
     an appropriate solvent (Table 1).

     7.14 If  further  concentration is required,  use either  the  micro-Snyder
column technique (7.14.1)  or nitrogen  blowdown technique (7.14.2).

          7.14.1  Micro-Snyder column technique.

                  7.14.1.1  Add  a fresh clean boiling chip  to  the  concentrator
          tube  and  attach  a  two-ball micro-Snyder  column  directly  to  the
          concentrator  tube.    Attach the solvent  vapor  recovery  glassware
          (condenser and  collection device)  to  the  micro-Snyder  column of the
          K-D  apparatus,  following manufacturer's  instructions.    Prewet  the
          Snyder column by adding 0.5 ml of methylene chloride or the exchange
          solvent  to  the top  of the  column.   Place the  micro-concentration
          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.

                  7.14.1.2  When  the  apparent volume of liquid reaches  0.5 ml,
          remove the  apparatus  from  the  water bath and allow  it  to drain and
          cool for at least 10 minutes. Remove the  Snyder  column and rinse its
          lower  joints into  the concentrator  tube with  0.2  ml  of  solvent.
          Adjust the final extract volume  to  1.0 -  2.0 ml.

          7.14.2  Nitrogen  blowdown technique.

                  7.14.2.1  Place the  concentrator  tube in a  warm bath (30°C)
          and  evaporate the  solvent volume to  0.5 ml using a  gentle stream of
          clean, dry nitrogen (filtered through a column of activated carbon).

CAUTION:  New  plastic  tubing  must  not be  used between  the  carbon  trap  and the
          sample, since it may introduce  phthalate  interferences.


                                   3535 - 8                         Revision 0
                                                                  January  1995

-------
                   7.14.2.2  Rinse down the  internal  wall of  the  concentrator
           tube several times with solvent during  the nitrogen blowdown.  During
           evaporation, position the concentrator  tube  to  avoid condensing water
           into the  extract.   Under  normal  procedures,  the extract must not be
           allowed  to  become dry.

CAUTION:   When the  volume of  solvent  is  reduced  below 1  ml,  some semivolatile
           analytes  such  as cresols  may be lost.

     7.15  The extract may now  be  subjected to cleanup procedures or analyzed for
the target  analytes using the appropriate determinative technique(s).  If further
handling  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,  and  labeled appropriately.  In no case  should the recommended holding
times for analytical procedures provided in Chapter Four,  Table 4-1 be exceeded.


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 general quality control  procedures and Method
3500 for specific QC procedures for extraction  and sample preparation.


9.0  METHOD  PERFORMANCE

     Refer to the determinative methods listed  in Table 1 for performance data.


10.0 REFERENCES

1.   Lopez-Avila,  V., Beckert,  W.,  et. al., "Single  Laboratory  Evaluation of
     Method  8060 -  Phthalate  Esters", EPA/600/4-89/039.

2.   Tomkins,  B.A.,  Merriweather,  R.,  et.  al.,   "Determination  of  Eight
     Organochlorine   Pesticides   at  Low   Nanogram/Liter  Concentrations   in
     Groundwater Using  Filter Disk Extraction and Gas Chromatography",  JAOAC
     International, 75(6), pps.  1091-1099 (1992).
                                   3535 - 9                         Revision 0
                                                                  January 1995

-------
         FIGURE  1
DISK EXTRACTION APPARATUS
                          Reservoir
                          Clamp


                          Empore™
                          Extraction Disk

                         Base
                          (Fritted or with Screen)
                         Drip Tube
                         Filter Flask or Manifold
        3535  -  10
  Revision 0
January 1995

-------
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                                            METHOD  3535
                               SOLID-PHASE  EXTRACTION  (SPE)
     7.1 Measure 1 L of sample.
    Add MeOH and surrogates as
      specified in determinative
   method. Prepare matrix spikes.
   7 2 Adjust pH to range listed
            in Table 1 .
    7 3 Assemble manifold for
       multiple extractions.
              7 3.1
           Do samples
        contain significant
          particulates?
 7 4 Wash extraction apparatus
and disk with methylene chloride.
 7.5 Wash extraction apparatus
     and disk with acetone.
7.6 PreWet disk with MeOH.  Do not
 allow disk to dry before extraction
       has been completed.
    7.7 Rinse disk with water.
                                                                     7.8 Filter sample, blank, or
                                                                    matrix spike as quickly as the
                                                                   vacuum will allow. Dry the disk
                                                                    under vacuum for 3  minutes
                                                                7.9 Remove standard filter assembly
                                                                     and insert collection tube
                                                                    7.10 Add acetone to disk.
                                                                7.11 - 7.12 Add 15 mL of methylene
                                                                chloride to the sample bottle  Rinse
                                                                              Repeat.
                                                                 7.13.1 Assemble K-D concentrator.
                                                                   7.13.2 Dry combined extracts in
                                                                   collection tube by passing them
                                                                 through drying column of anhydrous
                                                                    sodium sulfate  Collect dried
                                                                       extract in concentrator
                                                                   7.13.3 Rinse collection tube and
                                                                     drying column into K-D flask
                                                                   7.13.4 Add boiling chips to flask.
                                                                     Attach 3-ball Snyder column.
                                                                    Complete  the concentration in
                                                                  10-20 mins. Remove K-D apparatus
                                                                 from water bath and allow it to dram
                                                                     and cool for at least 10 mins.
                                             3535  -  12
                                                                                              Revision  0
                                                                                           January  1995

-------
                                          METHOD  3535
                       SOLID-PHASE  EXTRACTION  (SPE)   (Continued)
                                7.13.4.1 Remove Snyder
                                  column. AddSO mL of
                                  exchange solvent and
                                new boiling chip. Reattach
                                 column and concentrate
                                      the extract.
7135 Remove Snyder Column.
                          Yes
                                      7.14.1.1 Add fresh boiling
                                       chip to concentrator tube
                                       and attach 2-ball micro-
                                       Snyder Column. Prewet.
                                       Complete concentration
                                           in 5-10 minutes
7 13 5 Adjust extract to final
    volume of 5-10 ml
7 1 4.2 1 Place concentrator tube in
 warm bath and evaporate solvent
   volume to 0 5 mL using N? .
   7 15 Cleanup or analyze
          extract.
  7.14.1 2 Remove
 apparatus from water
bath and allow to drain
 and cool for 10 mms
  Adjust final extract
  volume to 1-2 mL.
                                           3535  -  13
                                                    Revision 0
                                                 January  1995

-------
                                 METHOD 3540C

                              SOXHLET EXTRACTION
1.0   SCOPE  AND APPLICATION

      1.1  Method  3540  is  a  procedure  for  extracting nonvolatile  and
semivolatile 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.

      1.3  This method  is  restricted to use  by  or  under the  supervision  of
trained analysts.  Each analyst must demonstrate the ability to generate
acceptable results with this method.


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.

      2.2  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

      Refer  to Method 3500.
4.0  APPARATUS AND MATERIALS

     4.1   Soxhlet extractor  -  40 mm  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 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.
                                   3540C  -  1                         Revision 3
                                                                  January 1995

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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    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-569001-0219 or
     equivalent).

          4.3.5    Springs -  1/2  inch  (Kontes K-662750 or equivalent).

NOTE:   The  following glassware  is recommended for  the  purpose of solvent
        recovery during the  concentration procedures requiring the  use of
        Kuderna-Danish evaporative concentrators.   Incorporation of this
        apparatus may be  required by State or local municipality regulations
        that govern  air emissions of volatile organics.  EPA recommends the
        incorporation of  this type of  reclamation system as a method to
        implement an emissions reduction program.   Solvent  recovery is a
        means to conform  with waste  minimization  and pollution prevention
        initiatives.

     4.4  Solvent vapor recovery system (Kontes K-545000-1006 or K-547300-
0000, Ace  Glass 6614-30,  or equivalent).

     4.5  Boiling chips - Solvent-extracted, approximately  10/40 mesh
(silicon carbide or equivalent).

     4.6  Water  bath - Heated, with concentric ring cover,  capable  of
temperature control (± 5°C).   The bath should be  used in a  hood.

     4.7  Vials  - Glass,  2-mL capacity, with Teflon®-!ined  screw or crimp
top.

     4.8  Glass  or paper  thimble or glass wool - Contaminant-free.

     4.9  Heating mantle  - Rheostat controlled.

     4.10 Disposable glass pasteur pipet and bulb.

     4.11 Apparatus  for determining  percent dry weight.

          4.11.1  Drying  oven  -  capable of maintaining  105°C.

          4.11.2  Desiccator.

          4.11.3  Crucibles  -  Porcelain or disposable aluminum.


                                  3540C - 2                         Revision 3
                                                                  January 1995

-------
     4.12 Apparatus  for  grinding

     4.13 Analytical  balance  -  capable  of weighing  to  0.0001  g.


5.0  REAGENTS

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

     5.2  Organic-free reagent  water.   All references  to water  in  this method
refer to organic-free reagent water, as defined in Chapter One.

     5.3  Sodium sulfate  (granular,  anhydrous),  Na2S04.  Purify by heating at
400°C for 4 hours in a shallow  tray, or by precleaning the sodium sulfate with
methylene chloride.  If the sodium sulfate is precleaned with methylene
chloride, a method blank must be analyzed, demonstrating that there  is no
interference from the sodium sulfate.

     5.4  Extraction  solvents  - All  solvents  must be  pesticide  quality or
equivalent.

          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/C6H14.

          NOTE:    This solvent  system  has lower disposal  cost and  lower
                   toxicity.

                   5.4.1.2  Methylene chloride/Acetone (1:1 v/v),
                            CH2C12/CH3COCH3.

          5.4.2    Other  samples shall  be  extracted  using  the  following:

                   5.4.2.1  Methylene chloride,  CH2C12.

                   5.4.2.2  Toluene/Methanol  (10:1)  (v/v),  C6H5CH3/CH3OH.

     5.5  Exchange solvents - All  solvents must  be  pesticide  quality or
equivalent.

          5.5.1    Hexane,  C6H14.

          5.5.2    2-Propanol,  (CH3)2CHOH.

          5.5.3    Cyclohexane,  C6H12.
                                   3540C  -  3                         Revision 3
                                                                  January 1995

-------
           5.5.4    Acetonitrile,  CH3CN.
6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

     See the  introductory material to this chapter, Organic Analytes,
Section 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 multiple phases must
      be prepared by the phase  separation method in Chapter Two before
      extraction.  This  extraction 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
      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 reduced in  size to allow  mixing
      and maximum exposure of the sample  surfaces  for the extraction.  The
      addition of anhydrous  sodium sulfate  to the  sample (1:1) may make  the
      mixture amenable to grinding.

      7.2   Determination of  percent dry weight - When sample results  are to  be
calculated on a dry weight  basis, a second portion of sample should be weighed
at the same time as the  portion  used for analytical  determination.

WARNING:   The drying  oven should be  contained in  a hood or be vented.
           Significant laboratory contamination may result from drying a
           heavily  contaminated sample.

      Immediately after  weighing  the  sample for extraction, weigh 5 -  10 g of
the sample into a tared  crucible.  Dry this  aliquot overnight at 105°C.   Allow
to cool in a desiccator  before weighing.   Calculate the % dry weight as
follows:

                      „.  ,      . , .    g of dry sample  ,nn
                      % dry weight  =	— xlOO
                                       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
                                   3540C -  4                        Revision 3
                                                                  January 1995

-------
below the sample in the Soxhlet extractor is an acceptable alternative for the
thimble.

          7.3.1    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).

          7,3.2    For  the  sample in  each  analytical batch  selected  for
     spiking, add  1.0  mL of the matrix spiking standard.

          7.3.3    For  base/neutral-acid  analysis, the amount  added  of the
     surrogates  and matrix spiking compounds should result in a final
     concentration of  100  ng/VL  of each  base/neutral analyte  and  200  ng/^L  of
     each acid analyte in  the  extract to  be analyzed (assuming  a  1  juL
     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/hour.

     7.5  Allow  the extract to cool  after the extraction  is complete.

     7.6  Assemble a Kuderna-Danish  (K-D)  concentrator  (Sec.  4.3),  if
necessary, by attaching a 10-mL concentrator tube to a  500-mL  evaporation
flask.

     7.7  Attach the solvent  vapor recovery glassware (condenser  and
collection device)  (Sec. 4.4)  to the  Snyder column of the K-D  apparatus
following manufacturer's instructions.

     7.8  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.

     7.9  Add one  or two clean boiling chips to the flask  and attach  a three-
ball Snyder column.  Prewet the Snyder  column by adding  about  1  ml of
methylene chloride to the top of the  column.  Place  the  K-D apparatus on a hot
water bath (15 -  20°C above the boiling point of the solvent)  so that the
concentrator tube is partially immersed in the  hot water and  the entire  lower
rounded surface of the flask is bathed  with hot vapor.   Adjust the vertical
position of the apparatus and the water temperature,  as  required,  to complete
the concentration in 10 - 20 minutes.  At the proper rate of  distillation the
balls of the column will actively chatter, but  the chambers will not flood.
When the apparent volume of liquid  reaches 1-2 ml,  remove the K-D apparatus
from the water bath and allow it to drain and cool  for  at least 10 minutes.

     7.10 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

                                   3540C -  5                         Revision 3
                                                                  January 1995

-------
the extract as described in Sec. 7.9,  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.

     7.11   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. 7.12 or adjusted to  10.0 ml with the solvent last used.

     7.12  If  further concentration  is  indicated  in Table  1,  either micro
Snyder column technique (Sec.  7.12.1)  or nitrogen blowdown technique (Sec.
7.12.2) is used to adjust the  extract  to the final volume required.

           7.12.1   Micro Snyder column  technique

                   7.12.1.1  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.

                   7.12.1.2  When the apparent volume of liquid reaches 0.5 mL,
           remove the K-D  apparatus  from the  water bath and allow  it  to drain
           and cool  for at  least  10 minutes.   Remove  the  Snyder  column and
           rinse the flask  and its  lower joints with  about 0.2 ml  of  solvent
           and add  to the  concentrator  tube.   Adjust  the  final volume to  1.0  -
           2.0 ml,  as  indicated in  Table 1, with  solvent.

           7.12.2   Nitrogen  blowdown technique

                   7.12.2.1  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,  since it may introduce  contaminants.

                   7.12.2.2  The internal  wall of the tube must be rinsed
           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.
                                   3540C  -  6                         Revision 3
                                                                  January 1995

-------
CAUTION:  When  the  volume  of  solvent  is  reduced below 1 mL, semivolatile
          analytes  may  be  lost.

     7.13 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 refrigerate.  If the extract will  be stored longer than
2 days, it should be transferred to a vial with a Teflon®-!ined screw cap or
crimp top, and labeled appropriately.


8.0  QUALITY CONTROL

     8.1  Any reagent blanks, matrix  spikes, 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

     Refer to the determinative methods  for  performance data.


10.0 REFERENCES

     None.
                                  3540C  - 7                         Revision 3
                                                                  January 1995

-------





















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-------
                                          METHOD 3540C

                                      SOXHLET  EXTRACTION
7.1  Select 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 Collect
       extract.
7.8 Dry extract
  with sodium
    sulfate.
7.9 Concentrate
  extract using
 K-D apparatus.
  7.11
Are sulfur
 crystals
 present?
7.12 Perform
determinative
  method.
     7.10
   Is solvent
   exchange
   required?
                               7.10 Add exchange
                              solvent reconcentrate
                                    extract.
                                                               Proceed to
                                                              Method 3660
                                                               for cleanup.
                                           3540C -  9
                                                 Revision 3
                                               January 1995

-------
                                  METHOD 3542

              EXTRACTION  OF SEMIVOLATILE ANALYTES  COLLECTED  USING
                MODIFIED METHOD 5 (METHOD 0010) SAMPLING TRAIN
1.0   SCOPE  AND  APPLICATION

      1.1  This method describes the extraction of semivolatile organic compounds
from  samples  collected by the  EPA  SW-846 Method 0010.  This  method replaces
Section 8.1 of  Method 0010  (Modified Method  5  Sampling Train,  also  known as
SemiVOST) and  Sections 7.1  and 7.2  of Method 8270  (Gas Chromatography/ Mass
Spectrometry for Semivolatile Organics:  Capillary Column Technique), which deal
with sample preparation.  These sections discuss sample preparation procedures.
Section 8.1 of Method  0010 addresses preparation of Method 0010 train components
for  analysis  with very  little detail.    Sections 7.1  and  7.2  of Method 8270
address preparation of water,  soil/sediment,  and  water matrices.   Analytical
procedures  described   in  Section  7.3 of  Method 8270  are  relevant,  with  the
exception  that  the  final volume  of the  extracts  of the Method 0010  train
components must be 5 ml, with surrogate compound concentrations as indicated in
this method.

      1.2  Although  this sample  preparation technique is intended primarily for
gas chromatography/mass spectrometric (GC/MS) analysis following Method 8270, the
extracts prepared according to this  method may be used with  other analytical
methods. The Method 0010  sampling train collects semivolatile organic compounds
with boiling points above lOO'C.  Some of these semivolatile organic compounds
may not be  amenable to gas Chromatography  and will require the application of
high performance liquid Chromatography (HPLC) for quantitative analysis.  The use
of HPLC coupled  with mass  spectrometry (HPLC/MS)  is an analytical technique that
may also be  applied.  A solvent exchange from methylene  chloride to a more polar
solvent such as acetonitrile or extraction with a solvent other than methylene
chloride will probably  be required  for successful application of HPLC techniques.
Some  semivolatile  analytes may require derivatization  for successful  GC/MS
analysis.

      1.3  This  method  is  restricted to  use  by  or  under  the  supervision  of
analysts experienced in the extraction and  concentration of semivolatile organic
compounds  from   the  components of  Method 0010  trains.    Each  analyst  must
demonstrate the ability to generate acceptable results  with this method.


2.0   SUMMARY OF METHOD

      2.1  Samples  generated  by the Method 0010  Sampling  Train  (Method 0010
Sampling Train,  Figure 1) are  separated into  six parts:

          a)  a  particulate matter filter  (labeled in Method 0010 as Container
              No. 1);

          b)  a  front  half rinse (labeled  in Method 0010 as Container No.  2);
                                   3542 - 1                         Revision 0
                                                                  January 1995

-------
          c)  condenser rinse and rinse of all  sampling train components located
              between the filter and  the  sorbent module (labeled in Method 0010
              as Container No. 5);

          d)  sorbent trap section of the organic module (labeled in Method 0010
              as Container No. 3);

          e)  any condensate  and condensate rinse (labeled  in  Method 0010 as
              Container No. 4); and

          f)  silica gel (labeled in  Method 0010 as Container No.  6).

     2.2  The overall  sample  preparation scheme (flowchart) is shown in Figure
3.  The six parts recovered from the Method 0010 sampling train yield three 5-mL
extracts to be analyzed according to  the analytical procedures of Method 8270.

          2.2.1    The  particulate   matter  filter  is  extracted  by  Soxhlet
     (Method 3540),  with  exceptions  as noted).

          2.2.2    The front  half rinse is filtered,  and  any filtrate is added
     to the particulate matter filter for Soxhlet extraction.   The front half
     rinse is a  50:50 mixture of methanol  and methylene  chloride generated by
     rinsing  the  probe  and  the  front  half  of the  filter  holder  in  the
     Method 0010  train.   The  front  half rinse  is  extracted  with  methylene
     chloride by separatory funnel  (Method 3510, with exceptions  as noted) after
     sufficient organic-free  reagent water has been added to make the methylene
     chloride separate as  a  distinct  phase  from the methanol/water.

          2.2.3    The  extracts  from  the  filter and  front half   rinse  are
     combined, moisture is removed by filtering through anhydrous sodium sulfate
     (Na2S04),   and  the combined  extract  is  concentrated  using  a  Kuderna-
     Danish (K-D)  sample  concentrator  (Method  3540) to a final volume of 5 ml.
     The final sample  concentration to 5  ml can be performed more accurately by
     reducing the  volume  of  the sample using a gentle stream of nitrogen or by
     using a micro-K-D.

          2.2.4    The condensate and condensate rinse fractions consist of the
     aqueous contents of the first impinger of the Method 0010  sampling train
     and the 50:50 methanol/methylene chloride rinse  of  the first impinger of
     the  Method 0010  sampling train.   The  condensate  and  condensate rinse
     fractions  are  combined and  extracted with  methylene  chloride  using  a
     separatory  funnel after  sufficient organic-free  reagent water has been
     added  to  make  the methylene chloride separate  from  the  methanol/water
     following  the procedures of Method  3510  (with exceptions as noted).

          2.2.5    After an  initial  methylene chloride extraction  without pH
     adjustment, the pH of the combined condensate/condensate  rinse fraction is
     determined.   If the condensate/condensate rinse  fraction is  acid (pH < 7),
     the  pH is  adjusted to  a  level  less  than  2 and the  methylene chloride
     extraction  is repeated.  The pH of the condensate/condensate rinse fraction
     is  then  made basic  (pH > 12),  and the  methylene chloride extraction is
     repeated.   The methylene chloride extracts are  combined, and moisture is
     removed  by   filtration  through  a   bed   of  anhydrous  Na2S04.     If  the


                                   3542  - 2                         Revision 0
                                                                  January 1995

-------
     condensate/condensate rinse fraction is  found to be basic after the initial
     methylene  chloride  extraction, the pH adjustment sequence is reversed:  a
     basic  extraction  is performed prior  to  an acid extraction,  the methylene
     chloride extracts  are  combined,  the  moisture  is removed, and the extract
     is concentrated to  a volume of 5 ml.

          2.2.6   The XAD-2® sampling module is combined with the filter holder
     back half  rinse and the 50:50 methylene chloride/methanol condenser rinse
     and extracted by Soxhlet  (Method 3540, with exceptions as noted).  Organic-
     free reagent  water is added  to  the  extract to ensure  the  separation of
     methanol/water from the methylene chloride, and a water extraction of the
     methylene  chloride extract is performed.   Moisture  is  removed  from the
     methylene  chloride  extract, which  is then concentrated to a final volume
     of 5 mL for analysis.

          2.2.7   The contents of the remaining impingers are  usually archived,
     but may be extracted by separatory funnel.  The silica gel is reused after
     regeneration  by heating to remove moisture.


3.0  INTERFERENCES

     3.1  Method   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  from  interferences under the
conditions  of the  analysis by  preparing  and analyzing  laboratory  method (or
reagent)  blanks.

          3.1.1    Glassware  must  be  cleaned  thoroughly  before  using.    The
     glassware  should be washed with laboratory detergent in  hot water followed
     by  rinsing with  tap  water and  distilled water.   The glassware may be
     cleaned by baking  in a  glassware  oven at  400°C  for at  least  one  hour.
     After  the glassware has cooled,  the glassware  should be rinsed three times
     with   methanol  and  three  times  with  methylene  chloride.    Volumetric
     glassware  should  not  be  heated  to 400°C.    Rather,  after washing  and
     rinsing,  volumetric glassware may  be  rinsed  with methanol followed by
     methylene  chloride  and allowed to dry in  air.

          3.1.2   The use of high purity reagents and solvents helps to minimize
     interference  problems in sample analysis.

     3.2  Matrix interferences  in  the  analysis may be caused by  components of
the sampling matrix that are extracted  from the samples.  If matrix interferences
interfere  with  the analysis,  sample cleanup procedures  (e.g., Method 3620 or
Method 3610) may be employed to remove or mitigate the interferences.


4.0  APPARATUS  AND MATERIALS

     4.1  Soxhlet  extractor  - 40 mm  I.D.,  with 50-mL round  bottom  flask and
condenser.

     4.2  Boiling  chips -  Teflon®,  solvent  rinsed with  methylene  chloride,
approximately 10/40 mesh.

                                   3542 -  3                         Revision 0
                                                                  January 1995

-------
     4.3   Forceps  - Rinsed with methylene chloride before use.

     4.4   Separatory funnel  - 250-mL or larger, with Teflon® stopcock.

     4.5   Amber glass jar -  500-mL with Teflon®-lined screw cap.

     4.6   Glass funnel  - Long stem.

     4.7   Kuderna-Danish (K-D) apparatus.

           4.7.1    Concentrator tube - 10-mL graduated (Kontes K-570050-1025 or
     equivalent).   Ground-glass  stopper is  used to  prevent  evaporation  of
     extracts.

           4.7.2    Evaporation   flask   -   500-mL   (Kontes   K-570001-500   or
     equivalent).  Attach to concentrator tube with springs.

           4.7.3    Snyder  column  - Three-ball  macro  (Kontes  K-503000-0121  or
     equivalent).

           4.7.4    Snyder  column  -  Two-ball  micro  (Kontes  K-569001-0219  or
     equivalent).

NOTE:   The glassware in  Sec.  4.8 is recommended for  the purpose  of solvent
        recovery during  the  concentration procedures  (Sec.  7.2.3  and  7.3.4)
        requiring   the   use   of  Kuderna-Danish   evaporative   concentrators.
        Incorporation of  this apparatus  may be  required by  State  or  local
        municipality regulations that govern air emissions  of volatile organics.
        EPA recommends the incorporation of this type of reclamation system as
        a method to implement an emissions reduction program.  Solvent recovery
        is a means to conform with waste minimization and pollution prevention
        initiatives.

     4.8   Solvent  vapor recovery system  -  (Kontes  545000-1006 or K-547300-0000,
Ace Glass 6614-30, or equivalent).

     4.9   Glass wool  -  Non-silanized,  pre-cleaned by Soxhlet  extraction with
methylene chloride.  Air dry, store in  pre-cleaned 500-mL jar.

     4.10  Vials -  7- to 10-mL capacity,  calibrated (calibrated centrifuge tubes
may also be used).

     4.11  Heating  mantle - Rheostat-controlled.

     4.12  Water   bath   -  Heated,  with  concentric  ring  cover,  capable  of
temperature control 80eC ± 5°C.   The water bath should  be used in a hood.

     4.13  Gas-tight syringe  - 5-mL to 10-mL capacity.  Gas-tight syringes have
a glass barrel, with a Teflon® plunger to form an effective seal.  The lack of
contact with metal  and the sealing  properties make these  syringes very useful for
transferring liquid solutions.
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      4.14  Nitrogen  blowdown apparatus - Analytical  evaporator such  as The Meyer
N-EVAP Model  111 (Organomation  Associates Inc.,  South Berlin, MA 01549)  or
equivalent.

      4.15  Filter -  Glass- or quartz-fiber filters,  without  organic  binder.  The
filters should be the same as those used in the Method 0010 sampling train.


5.0   REAGENTS

      5.1   Reagent grade chemicals shall be used in  all tests.  Unless otherwise
indicated, 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 sufficient purity to permit its use without compromising the
integrity of the sample.

      5.2   Methanol, CH3OH  - Pesticide quality or equivalent.

      5.3   Methylene chloride,  CH2C12 - Pesticide quality or equivalent.

      5.4   Organic-free  reagent water -  All  references  to  water in  this method
refer to organic-free reagent water, as defined in Chapter One.

      5.5   Sodium hydroxide  solution  (10  Molar)  -  Dissolve  40 g  of sodium
hydroxide (NaOH, ACS reagent grade)  in  organic-free reagent water and dilute to
100 ml.

      5.6   Sulfuric  acid (9 Molar),  H2S04 - Slowly add  50  ml  of concentrated 18 M
H2S04  (ACS reagent grade, specific gravity 1.84) to 50  ml  of organic-free reagent
water.

      5.7   Sodium sulfate, Na2S04 -  ACS,  reagent grade, granular, anhydrous.
Purify by heating at 400°C for four hours in a shallow tray.

      5.8   Surrogate stock solution  - Either surrogates  (e.g.,  the surrogates
used in Method 8270) or isotopically-labeled analogs of the compounds of interest
should be spiked  into the Method 0010 train components prior to extraction.  Both
surrogate and  isotopically-labeled analogs may be used,  if desired.  A surrogate
(i.e., a  compound not expected to  occur in an environmental sample but chemically
similar to analytes) should be added  to each sample, blank, and method spike just
prior to  extraction.   The  recovery of the surrogate  is  used to  monitor  for
unusual matrix  effects  or sample processing  errors.   Normally  three  or more
surrogate are added  for  each analyte group. The surrogate stock solution may be
prepared from pure  standard materials  or  purchased  as a  certified solution.
Prepare the  stock  solution  in  methylene chloride,  using  assayed  liquids  or
solids, as appropriate.
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          5.8.1   The  following compounds are  the surrogates recommended  in
     SW-846 Method 8270:

                  Acid                           Base/Neutral

                  2-Fluorophenol                 2-Fluorobiphenyl
                  2,4,6-Tribromophenol           Nitrobenzene-d5
                  Phenol-de                      Terphenyl-d14

          5.8.2   Prepare a surrogate stock solution in methylene chloride that
     contains the surrogate compounds at a concentration of 5000   g/mL for the
     acidic compounds, and 2500  g/mL for base/neutral  compounds.   Prepare the
     stock  surrogate solution  by  accurately weighing  0.50  ± 0.05 g each  of
     2-fluorobiphenyl, p-terphenyl-du,  and nitrobenzene-d5,  and  1.00 ±  0.05 g
     each of 2,4,6-tribromophenol,  phenol-de, and 2-fluorophenol.   Dissolve the
     materials in methylene chloride  and dilute to volume in a 200-mL volumetric
     flask.  When compound  purity  is assayed to be 96% or greater,  the  weight
     may be used without correction to calculate the concentration of the stock
     solution.

          5.8.3   Transfer  the  stock  solution  into  Teflon®-sealed  screw-cap
     bottles sized to minimize headspace.  Store at 4°C and protect from light.
     Stock  solutions should be checked regularly  for  signs  of degradation  or
     evaporation, especially just prior to preparing  spiking  solutions.   Allow
     solutions to come to room temperature before  use.

          5.8.4   Stock  solutions  should be replaced after one year, or sooner
     if analysis  indicates  a problem.

     5.9  Surrogate  spiking solution - Prepare  a surrogate spiking solution by
transferring a 10-mL aliquot  of the  surrogate  stock  solution (using a 10-mL
volumetric pipet) into a 50-mL volumetric flask containing approximately 20 ml
of methylene  chloride.    Dilute to  a final  volume  of  50 ml with  methylene
chloride.

          5.9.1   Transfer  the surrogate spiking  solution into Teflon®-sealed
     screw-cap bottles appropriately sized to minimize  headspace.  Store at 4°C
     and protect from light.  Spiking solutions  should  be checked regularly for
     signs  of degradation or evaporation,  especially just prior to use.

          5.9.2   Surrogate spiking  solutions  should  be  replaced  after  six
     months, or  sooner if analysis indicates a  problem.

     5.10 Isotopically-labeled analog stock solution -  Either surrogates (e.g.,
the surrogate standards  used in Method 8270) or  isotopically-labeled analogs of
the compounds of interest must be spiked into the Method 0010 train components
prior to extraction.  Both  surrogates and  isotopically-labeled analogs  may be
used, if desired.  The use of isotopically-labeled analogs is optional but highly
recommended.   Common isotopic labels which  are  used  include deuterium  and
carbon-13; homologs  and fluorinated analogs of the compounds of interest may also
be used.  To assess extraction efficiency, use of an isotopically-labeled analog
of the compound  of  interest is  essential.  The  isotopically-labeled analog is
spiked into  the matrix immediately prior to extraction,  and losses of the spiked


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compound can be attributed to the sample extraction/concentration process.  An
isotopically-labeled  analog  stock  solution  can  be made  from  pure  standard
materials  or purchased  as  a  certified solution.    Even  though  the use  of
isotopically-labeled analogs is optional, each compound to be quantitated needs
to be  represented  by a  specific  recovery  standard, whether in  the  surrogate
mixture (Sec. 5.8)  or in a separate spike.

           5.10.1   Prepare an  isotopically-labeled  analog  stock  solution  by
     accurately weighing approximately  0.250 g  of each  of  the  materials  to be
     used.   Dissolve  in  methylene chloride and dilute to volume with methylene
     chloride in a 200-mL volumetric flask.  When  compound purity is assayed to
     be 96% or greater,  the  weight may be used without correction to calculate
     the concentration of the  stock  solution.

           5.10.2   Transfer the  stock  solution  into  Teflon®-sealed  screw-cap
     bottles sized to minimize headspace.   Store at  4°C and protect from light.
     Stock solutions should  be checked regularly  for  signs  of degradation,
     evaporation,  or  isotope  exchange, especially just  prior to  preparing
     spiking solutions from  them.   Allow solution to  come  to room temperature
     before use.

           5.10.3   Stock  solutions  should be replaced after one year,  or sooner
     if analysis indicates a problem.

     5.11  Isotopically-labeled  analog spiking solution

           5.11.1   Prepare   the   isotopically-labeled   analog  standard   by
     transferring a 10-mL aliquot of the stock isotopically-labeled  analog stock
     solution  (using  a 10-mL volumetric pipet)  into  a  50-mL volumetric  flask
     containing approximately  20 ml of methylene chloride.  Dilute  to volume
     with  methylene chloride.  The concentration of  the spiking solution should
     allow the isotopically-labeled analogs to be observed in the final sample
     in  approximately  the  middle  of  the  calibration  range  for  the  gas
     chromatograph/mass  spectrometer, assuming  100% recovery.

           5.11.2   Transfer the solution into Teflon®-sealed  screw-cap bottles
     sized to minimize headspace.  Store at 4°C  and protect from light.  Spiking
     solutions  should  be  checked  regularly   for  signs  of  degradation  or
     evaporation, especially just prior  to use.   Allow solutions to  come to room
     temperature prior to  use.

           5.11.3   Spiking solutions should be  replaced  after six months,  or
     sooner if analysis  indicates a problem.

     5.12  Stock method spike solution - A  method  spike  consists  of a spike of
a clean matrix (i.e.,  clean,  dry XAD-2®,  clean, dry filter, or  water) with a
solution containing the compounds of interest (the method spike solution).  The
compound recoveries obtained  from a method spike demonstrate that the compounds
of interest can be recovered  from the matrix, and aid in elucidating the effects
of the  field matrix.  The method spike solution  can  be made  from pure standard
materials or purchased as certified solutions.  The compounds of  interest for the
field test  should be used as  components  of the method spike solution.   A method
spike is generated  by spiking clean XAD-2® or clean organic-free reagent  water.


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          5.12.1   Prepare a stock method spike solution by accurately weighing
     0.05 g  of  each  of the  compounds of interest.  Dissolve the materials  in
     methylene chloride and  dilute to volume  in a 50-mL volumetric flask.  When
     compound purity  is  assayed  to be 96% or greater, the weight may  be  used
     without correction to calculate the concentration of the stock solution.

          5.12.2   Transfer the stock method spike solution into Teflon®-sealed
     screw-cap bottles sized to minimize headspace.   Store at  4°C  and  protect
     from light.   Stock  solutions  should  be checked  regularly for signs  of
     degradation  or  evaporation,  especially  just  prior to preparing  spiking
     solutions from them.

          5.12.3   Stock solutions should be replaced after one  year,  or sooner
     if analysis  indicates a problem.

     5.13 Method  spike standard solution

          5.13.1   Prepare the method spike standard solution  by transferring a
     25-mL aliquot of the stock method  spike solution (using a 25-mL volumetric
     pipet)  into  a 100-mL volumetric flask containing  approximately  20 mL  of
     methylene chloride.  Dilute to volume with methylene chloride.

          5.13.2   Transfer the method spike standard solution into Teflon®-! ined
     screw-cap bottles appropriately sized  to minimize headspace.  Store at 4"C
     and protect from light.   Spiking solutions should be checked regularly for
     signs of degradation or evaporation, especially just prior to use.

          5.13.3   Spiking solutions should be replaced after  six months,  or
     sooner  if analysis indicates a problem.


6.0  SAMPLE  COLLECTION, PRESERVATION, AND HANDLING

     6.1  The six components  from each Method 0010 sampling train  (Figure 1)
should be stored at 4°C between  the time of sampling and extraction.

     6.2  Each  sample should be  extracted within  14  days  of  collection  and
analyzed within  40 days of extraction.  The  extracted sample should be stored at
4°C.
7.0  PROCEDURE

     7.1  The sample preparation procedure for the  six parts of the Method 0010
train will result in three sample extracts for analysis:

          a)  Particulate matter filter and front half rinse;
          b)  Condensate and condensate rinse; and
          c)  XAD-2® and condenser/back half rinse.

     7.2  Particulate  matter  filter  and  front  half rinse

          7.2.1    Filter - The filter is  identified as Container No.  1 in Method
     0010.
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        7.2.1.1   Using clean forceps, place about 10 Teflon® boiling
chips  into  the  bottom  of  the  round  bottom  flask  of  the  Soxhlet
extractor and connect the Soxhlet extractor to the round bottom flask.

        7.2.1.2   Using a clean syringe or volumetric pipet,  add a 1-
mL aliquot of the  surrogate spiking solution (Sec. 5.9) to the filter.
If  isotopically-labeled  analogs  are  being  used,  the  isotopically-
labeled analog solution (Sec.  5.11) may be added at  this time.   If a
method spike is being prepared, the method spike solution (Sec.  5.13)
may be added at this time.

                  7.2.1.2.1    To  ensure proper  filter spiking,  use a
        volume of approximately 1 ml of spiking solution.   Leave the
        filter  in the  petri  dish,  particulate  material on  top,  for
        spiking.  Add the 1  ml of spiking solution uniformly onto the
        particulate-coated surface of the  filter in the petri dish by
        spotting  small  volumes at multiple filter locations, using a
        syringe.

                  7.2.1.2.2    Repeat   the   spiking   process   with
        isotopically-labeled standards or method  spike  solution,  if
        these solutions are being used.

        7.2.1.3   Using clean  forceps, place the particulate  matter
filter into  a glass thimble and position  the  glass thimble  in  the
Soxhlet extractor,  making  sure that  the  filter will be  completely
submerged in  the  methylene  chloride with  each  cycle of the Soxhlet
extractor.  Place  a piece of pre-cleaned unsilanized glass wool on top
of the filter in  the Soxhlet extractor to  keep  the  filter in  place.
Rinse  the petri  dish three  times  with methylene  chloride and  add
rinses to the Soxhlet.

        7.2.1.4   The front  half  rinse (Container  No.  2) may contain
particulate  material which  has  been  removed from  the probe.   This
particulate  material should be extracted with the filter.

                  7.2.1.4.1    To  separate particulate matter from the
        front  half rinse,  filter  the front half rinse.    To  avoid
        introducing any contamination,  use the same type of  filter
        which has  been used in the  Method  0010  train, from  the same
        lot as the filter in the Method 0010 train.  Filter the Front
        Half  Rinse,  rinse   Container  No.  2 three  times with  10-mL
        aliquots  of methylene chloride,  and  filter the methylene
        chloride  rinses.

                  7.2.1.4.2    Transfer the filter with any particulate
        matter to the Soxhlet extractor with the original filter from
        the Method 0010 train.  Extract the two filters together.

                  7.2.1.4.3    Return the liquid  portion  of Container
        No.  2 to its original container for subsequent extraction or,
        alternatively,  the  front half rinse can  be filtered  directly
        into a separatory funnel  for extraction of the liquid portion
        of the front half rinse.

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             7.2.1.5  Slowly  add  methylene  chloride  to  the  Soxhlet
     extractor  containing the  two  filters  through  the  Soxhlet   (with
     condenser removed),  allowing  the  Soxhlet  to cycle.  Add  sufficient
     solvent to fill  the  round  bottom flask  approximately half full  and
     submerge the thimble containing the filters.

             7.2.1.6  Place a heating mantle  under the round bottom flask
     and connect the upper joint of the Soxhlet to a condenser,  making sure
     that the coolant is flowing through the  condenser.

             7.2.1.7  Allow the  sample to extract for  18 hours, cycling
     approximately once every thirty minutes.

             7.2.1.8  After  cooling,  disconnect  the  extractor from  the
     condenser. Tilt  the  Soxhlet slightly until  the remaining  solvent has
     drained into the round bottom flask.

             7.2.1.9  Transfer  the extract from  the  round bottom  flask
     into a 500-mL amber  glass bottle with Teflon®-!ined screw cap.   The
     bottle should have  been  rinsed three times  each with methanol  and
     methylene chloride.   Rinse  the  round bottom flask three times  with
     approximately 10-mL  aliquots  of methylene chloride and transfer the
     rinses to the amber  bottle.   Store the  filter extract at 4°C  until
     extraction of the filtered front half rinse has been completed.

     7.2.2   Front half  rinse - The  front half  rinse  is identified  as
Container No.  2 in Method 0010.

             7.2.2.1  Transfer the liquid  contents  of the filtered  front
     half rinse sample to a separatory funnel of appropriate size for the
     volume of  the sample (a typical front half  rinse sample is 200  to
     300 ml).   Rinse  the sample  container three  times  with  10-mL aliquots
     of  methylene  chloride,  transferring  the  rinses  to  the  separatory
     funnel after each rinse.

             7.2.2.2  Because the  front half  rinse sample consists  of a
     mixture of methanol  and methylene  chloride,  sufficient organic-free
     reagent water must  be added  to  the  separatory funnel  to cause  the
     organic and  aqueous/methanol  phases  to separate into two distinct
     layers.  The methylene chloride  layer will  be at the bottom  of the
     separatory funnel.   Continue to  add water  until  the bottom  layer
     (methylene chloride)  does  not increase  in  volume.   An  increase  in
     volume can  be monitored  by  marking  the  separatory  funnel  at  the
     position of the phase separation.

NOTE:   The  front  half rinse is  not  spiked with any  surrogate, isotopic
        analog,  or method  spike  solutions because  the  extract from  the
        front half rinse is combined with the extract from the  particulate
        matter  filter  sample.

             7.2.2.3  Add additional methylene chloride, if necessary, so
     that   the   ratio  of  water/methanol  to   methylene  chloride   is
     approximately 3:1.   Add sodium hydroxide (Sec. 5.5) until pH  of the
     water layer is >  11  (but <  14).  Use wide-range pH paper to determine

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     pH.   Shake vigorously  for 2 minutes  with  rapid  arm  motion,  with
     periodic venting to release excess pressure.  Allow the  organic layer
     to separate for at least 10 minutes.   Collect  the  methylene  chloride
     extract in a 500-mL amber glass  bottle with  Teflon®-!ined  screw cap,
     which has  been  rinsed  three  times  each with methanol  and methylene
     chloride.

             7.2.2.4   Add   a   second   volume   of   methylene   chloride
     (approximately  the same  volume as  the  first extraction)  to  the
     separatory funnel and repeat the extraction  procedure,  combining the
     methylene chloride extracts in the amber bottle.

             7.2.2.5   Perform  a third extraction in  the  same manner.

             7.2.2.6   Acidify  the water to a pH <2 (but > 0)  with  sulfuric
     acid (Sec. 5.6)  and repeat Sec.  7.2.2.4 three times.  Measure pH with
     wide-range pH paper.

     7.2.3   Concentration of  filter and  front half  rinse extracts  -  The
combined extracts and rinses of extract  storage  bottles will  have a total
volume of 1 liter or more.

             7.2.3.1   Assemble a Kuderna-Danish concentrator by attaching
     a 10-mL concentrator tube  to a 500-mL evaporative flask  with  clips or
     springs.   Using a clean  pair of  forceps,  place about  five  Teflon®
     boiling chips into the concentrator  tube.   If  the  volume  of extract
     to be concentrated is greater than 500 ml,  repeat  the  concentration
     as many times  as required  using  the same 500-rnL evaporative flask and
     systematically adding remaining  extract.   If repeated concentrations
     are performed, use new boiling chips each time.

             7.2.3.2   Using a clean pair of forceps, place a  small portion
     of precleaned unsilanized glass wool in the  bottom of a long  stem
     funnel, and pour a 2.54-cm (1-in) layer  of cleaned sodium  sulfate
     (Sec. 5.7) on top of the  glass wool  (use  more sodium sulfate,  if
     possible;  fill   the funnel to within  approximately  1.27 cm  (0.5  in)
     of the top).

             7.2.3.3   Rinse  the sodium sulfate  contained  in the  funnel
     three times with methylene  chloride;  discard the rinses.  Support the
     funnel in a ring or clamp above  the flask to prevent tipping.

             7.2.3.4   Place the funnel  into  the  upper  opening  of the  K-D
     flask and slowly pour extracts  from  the Filter  and  Front  Half Rinse
     through the  sodium sulfate.  Rinse  the amber  jars containing  the
     extracts three times, using approximately 10 ml of methylene  chloride
     each time.  Add  the rinses to the funnel.   Rinse  the sodium sulfate
     with methylene chloride to complete the transfer.

NOTE:   During  this  process, monitor the  condition  of  the sodium sulfate
        to determine that the bed of  sodium sulfate is not solidifying and
        exceeding  its drying capacity.  If the sodium  sulfate  bed can be
        stirred and is still  free-flowing, effective moisture removal  from
        the extracts  is occurring.  If the sodium sulfate bed has  begun to

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         solidify,  do  not add more  extract.   Replace the sodium  sulfate
         bed, re-dry the contents of the K-D flask, and continue drying the
         extracts.

             7.2.3.5  Attach  a  three-ball  macro  Snyder column  to the
     evaporative flask.   Prewet the Snyder column by  adding  about  2  ml of
     methylene chloride  to  the top.  Attach  the solvent vapor recovery
     glassware (condenser and collection device) to  the  Snyder column of
     the K-D apparatus,  following manufacturer's instructions.  Place the
     K-D apparatus on  a hot water bath (80  - 85°C) so that the concentrator
     tube is partially immersed in hot water.  Adjust the vertical position
     of the apparatus  and the water temperature as required to complete the
     concentration  in 20  to  30 minutes.    Rinse sides of  K-D  during
     concentration with  a small  volume  of methylene  chloride.  When the
     apparent volume of the liquid reaches  6-8 mL, remove the K-D apparatus
     from the water bath and allow the apparatus to cool  and drain for at
     least 10 minutes.

NOTE:    Never let  the extract in the concentrator tube go to dryness even
         though additional solvent  is  present in the  upper portion of the
         K-D  apparatus.

NOTE:    If  the   sample  concentration   is  not   completed  within the
         anticipated period  of time,  check  the  temperature  of the  water
         bath and check the composition of  the sample.  If the methanol has
         not been completely removed from the methylene chloride extract by
         the  procedures  described in Sees. 7.2.2.2 and  7.2.2.3, residual
         methanol  will concentrate  far slower  than a methylene chloride
         extract  and analytes will  be lost in the  concentration step.   A
         sample  containing methanol  which has  been  concentrating  for  a
         prolonged  period of  time cannot be  recovered,  but extracts  which
         contain  residual  methanol  and have  not  yet been concentrated can
         be recovered  by  performing  the  procedures  in  Sees. 7.2.2.2 and
         7.2.2.3  again.

             7.2.3.6  Remove  the  Snyder  column  and evaporative flask.
     With a clean pair of forceps, add two  new Teflon® boiling chips to the
     concentrator  tube.   Attach  a two-ball  micro Snyder  column  to the
     concentrator  tube.    Attach  the  solvent  vapor recovery glassware
     (condenser  and collection device)  to the  Snyder column of  the K-D
     apparatus, following manufacturer's  instructions.  Prewet  the Snyder
     column  with  about  0.5 ml  of methylene  chloride.   Place  the K-D
     apparatus on  the hot water bath so that  the concentrator  tube  is
     partially immersed  in  hot water, supporting the tube  with a clamp.
     When  the apparent volume of the  liquid reaches  4  -  5 mL,  remove the
     K-D apparatus from the  water bath and allow the apparatus to cool and
     drain for at  least  10 minutes.   If the volume is  greater  than  5 mL,
     add a new boiling  chip  to the concentrator tube,  prewet  the Snyder
     column, and  concentrate  again on the hot water bath.   Transfer the
     extract to  a  calibrated  vial  or  centrifuge tube,  rinse concentrator
     tube with a  minimum  volume of methylene chloride  and add rinses to the
     vial,  and  add methylene chloride, if  necessary,  to attain  a  final
     volume of 5 mL.
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                   Alternatively,  the final concentration may  be  performed by
           blowing  the  surface  of  the solvent  with  a gentle  stream of nitrogen
           using a glass disposable pipet to direct the stream of nitrogen.  When
           the  nitrogen  blowdown  technique  is  used,  care  must  be taken  to
           carefully  rinse  the  sides  of the vessel  using  a minimum quantity of
           methylene  chloride  to  ensure  that  analytes  are  in the  methylene
           chloride solution, not deposited on  the sides of the glass container.
           Perform  the blowdown procedure in a calibrated vial  or centrifuge tube
           which does not contain boiling chips.  The final extract volume must
           be 5 ml.

                   7.2.3.7   Transfer  the  extract to a 10-mL  glass  storage vial
           with a Teflon®-!ined screw  cap.  Label the extract  as  Front Half Rinse
           and Particulate Filter, and store at 4°C  until  analysis  (Sec. 7.3 and
           following  Sections,  Method 8270).  Mark the liquid level on the vial
           to monitor solvent evaporation during storage.

     7.3   Condensate and condensate  rinse  -  The  condensate is identified as
Container No.  4 in Method 0010; the condensate rinse is Container  No. 5.

           7.3.1    Transfer  the   contents  of  both  the  condensate  and  the
     condensate rinse  samples  to a clean separatory funnel (expected volume of
     both  containers  is  approximately 500 ml).    Rinse each  of  the  sample
     containers with three aliquots of methylene chloride (approximately 10 ml
     each), transferring the rinses  to the separatory funnel.

           7.3.2    Using  a clean syringe or volumetric pipet,  add a 1-mL aliquot
     of  the surrogate  solution  (Sec. 5.9)  to the  liquid  in the  separatory
     funnel.  If isotopically-labeled analogs  are being used, the isotopically-
     labeled  analog  solution  (Sec.  5.11)  should   be  added  to the  separatory
     funnel.

           7.3.3    Perform  an  initial  methylene  chloride  extraction  of  the
     combined condensate/condensate rinse which has been spiked with appropriate
     spiking solution(s).  Add organic-free reagent water as needed to ensure
     separation of phases.   After the initial  methylene chloride extraction,
     check the pH  of the condensate/condensate  rinse solution  with  wide-range
     pH paper.

                   7.3.3.1   If the solution is acidic (pH <  7), add  acid until
           the  pH  is  <  2  but > 0  and   perform   another  methylene  chloride
           extraction.  Then make  the  condensate/condensate rinse solution basic
           (pH > 11 but < 14)  and  perform another methylene chloride extraction.
           Combine methylene chloride  extracts, remove moisture, and concentrate
           for analysis.

                   7.3.3.2   If, after the initial methylene chloride extraction,
           the condensate/condensate rinse solution is basic, increase pH until
           the  pH   is  > 11  but <  14,  and  perform  another methylene  chloride
           extraction.  Then make the condensate/condensate rinse solution acidic
           (pH < 2  but  >  0) and perform another  methylene chloride extraction.
           Combine  the  methylene  chloride  extracts,  remove  moisture,  and
           concentrate  the extract for analysis.


                                  3542 - 13                         Revision 0
                                                                  January 1995

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           7.3.4    Refer  to Sec.  7.2.2.2  and following sections for extraction
     and concentration of  the condensate/condensate rinse extract.

     7.4   XAD-2®  - The sorbent trap section of the organic module is identified
as Container  No.  3 in Method 0010.   The sorbent trap section  of  the organic
module shall be used as a sample transport container.

           7.4.1    Using  clean forceps, place about 10 Teflon® boiling chips in
     the bottom of the round bottom flask of the Soxhlet extractor and connect
     the Soxhlet  extractor to the  round  bottom flask.

           7.4.2    Transfer the  XAD-2® to the extraction thimble.   Remove the
     glass wool plug from the XAD-2® trap and add to the thimble of the Soxhlet
     extractor.   If ground glass  stoppers  are  used to seal  the  sorbent trap
     during  shipment,  these ground  glass  stoppers  should  be  rinsed  with
     methylene chloride  and the rinsate  added to the round bottom flask of the
     Soxhlet  extractor.

                   7.4.2.1   If the  XAD-2® is dry  (i.e., free-flowing), pour the
           XAD-2®  directly  into the  thimble (or  directly  into  the Soxhlet
           extractor)  and  rinse the  trap with  methylene chloride,  adding the
           rinses  to the  round bottom  flask.

                   7.4.2.2   If the  XAD-2® is wet, removal  from the trap may be
           difficult.  To accomplish the transfer, flush the resin from the trap
           using   a  Teflon®  wash  bottle  containing  methylene   chloride.
           Alternatively, acidic water (pH < 2)  can be  used to wash the walls of
           the XAD-2®  trap.  Collect  the resin  and solvent  in  a  clean 500-mL
           beaker.  Transfer the  XAD-2®/methylene  chloride from the beaker to the
           extraction   thimble,   taking   care    that   no   solvent   is   lost.
           Alternatively, the XAD-2® can  be  transferred directly to the Soxhlet
           extractor  and the  methylene  chloride rinse  and  transfer solvent
           allowed to drain through the XAD-2® to  the round bottom flask.  Rinse
           the beaker  several times with  methylene chloride,   pouring the rinses
           through the XAD-2® bed once the extraction thimble  is in the Soxhlet
           extractor.  Be sure that a glass wool plug is in place above the XAD-
           2®  to ensure that the  XAD-2® does not  float  out of the thimble.

NOTE:      Under no circumstances should methanol  or acetone be used to transfer
           the resin.

                   7.4.2.3   Alternative  approaches to  transfer of  XAD-2® from
           the trap to the  extraction  thimble are discussed below.

                            7.4.2.3.1    The XAD-2® can be transferred directly
                   to  the Soxhlet extractor and the methylene  chloride  rinse and
                   transfer solvent allowed to  drain through the XAD-2® to the
                   round  bottom flask.   If ground glass stoppers  are used to
                   seal  the sorbent  trap during  shipment, these  ground  glass
                   stoppers should be  rinsed  with methylene  chloride and the
                   rinsate   added  to  the round  bottom flask of the Soxhlet
                   extractor.   To  remove  the XAD-2® from  the sampling module,
                   remove  the glass wool  from  the end of the XAD-2® sampling
                   module.   Place  this glass wool  in  the  Soxhlet extractor to

                                   3542  - 14                        Revision 0
                                                                  January 1995

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                   ensure  thorough extraction of the glass wool.  If the XAD-2®
                   is being transferred directly to the Soxhlet extractor, place
                   a  small piece of pre-cleaned glass wool  in  the  side-arm of
                   the  Soxhlet extractor to ensure  that no XAD-2®  enters  the
                   side-arm  of  the  Soxhlet  extractor.     Invert  the  XAD-2®
                   sampling  module  (glass frit up) over  an  extraction thimble
                   contained in a beaker, or directly over the Soxhlet extractor
                   with pre-cleaned glass wool  in the bottom, as shown in Figure
                   2.  Add approximately 5 to 10 ml of methylene chloride above
                   the  glass frit of  the sampling module.   Connect  a  rubber
                   pipet filler  bulb with check valve that has been fitted with
                   a  ball  joint to  the XAD-2®  sampling module.   Using  air
                   pressure  created  by  squeezing  the  bulb,  gently  but  firmly
                   push  the  methylene chloride  through  the frit,  forcing  the
                   XAD-2®  out of the sampling module.  Avoid allowing methylene
                   chloride to be pulled up  into the bulb, since the sample will
                   be compromised  if methylene chloride is  pulled  up  into  the
                   bulb and allowed to become part of the extract.  This process
                   will  need  to  be  repeated 3  to 5 times.   Use a Teflon® wash
                   bottle  containing methylene chloride to  rinse the  walls of
                   the  sampling  module  to transfer  XAD-2®  which  has  been
                   retained  on the walls of the sampling module after transfer
                   of XAD-2® to  the Soxhlet.  A methylene chloride rinse of the
                   walls  will  not  remove all   of  the  XAD-2®,  but  after 3  to
                   5 rinses of the walls of the sampling module, no more than a
                   monolayer  of  XAD-2® particles should be  retained.   If more
                   than  a  monolayer of  XAD-2® remains,  additional  rinses  are
                   required.   The glass  wool  in the  side  arm of  the  Soxhlet
                   extractor must be removed and  added to the Soxhlet.

NOTE:     Under no conditions should methanol or acetone be used in the transfer
          of the XAD-2®.

                            7.4.2.3.2    Alternatively, the  wet XAD-2®  may  be
                   transferred from  the  sampling module to  a piece  of cleaned
                   aluminum  foil by  inverting the  trap (glass  frit up)  and
                   tapping the trap on a solid  surface covered with the cleaned
                   aluminum  foil.    This process  is  slow   and  may result  in
                   breakage  of the  sampling module.    If  ground  glass  stoppers
                   are  used  to  seal  the sorbent  trap during  shipment,  these
                   ground  glass  stoppers  should  be  rinsed  with  methylene
                   chloride  and  the  rinsate  added  to the  round  bottom flask of
                   the Soxhlet extractor.  After the majority of the XAD-2® has
                   been  removed  from  the trap by tapping,  the XAD-2®  on  the
                   aluminum  foil may  be  transferred  to the  extraction thimble.
                   The sampling module should be rinsed with methylene chloride
                   to flush the remaining XAD-2® particles adhering to the glass
                   wall into the extraction thimble.   After all  XAD-2® has been
                   transferred into  the  Soxhlet thimble,  add  a plug  of glass
                   wool to the top of  the XAD-2® to hold the resin  in place.

          7.4.3    With the XAD-2® in the Soxhlet extractor and glass wool on top
     of  the  XAD-2®,  use  a  clean  syringe  or  volumetric pipet  to  add  a  1-mL
     aliquot of the surrogate spiking  solution  to the XAD-2®.  Be sure that  the

                                  3542  - 15                         Revision 0
                                                                  January 1995

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     needle of the syringe penetrates the XAD-2® bed to a depth of at least 1.27
     cm  (0.5  in).   If isotopically-labeled standard  solution or method  spike
     solution is being used, these solutions should be spiked at this time.

          7.4.4    Container No. 5 contains the methylene chloride/methanol rinse
     of the condenser and all  train components from the back half of the filter
     holder  to  the  XAD-2® sampling  module.   These  rinses  consist of  50:50
     methanol:methylene chloride.  Transfer the contents  of Container No. 5 to
     a separatory  funnel  and  rinse the  container with three  10-mL  aliquots of
     methylene chloride.  Add the rinses to the separatory funnel.   Sufficient
     organic-free reagent water must  be  added to the separatory funnel to cause
     the organic and aqueous phases to separate into two distinct layers.  Refer
     to  Sec.  7.2.2.2 and  following  sections  for  preparation  of  a  methylene
     chloride extract from Container No. 5.  Add the  methylene  chloride layer
     from the separatory funnel directly to the Soxhlet extractor containing the
     XAD-2®  or  collect  the  methylene  chloride extract  in  a  container  and
     transfer from  this container to the Soxhlet containing  the  XAD-2®.   Pour
     the  methylene chloride  extract  of the  condenser and  back  half  rinses
     through  the   XAD-2®  in  the  Soxhlet  extractor;  rinse  the  container  or
     separatory funnel 3  times with  approximately  10-mL  aliquots  of methylene
     chloride and  add the  rinses  to the Soxhlet.

          7.4.5    Add additional  methylene chloride to the  Soxhlet extractor,
     if necessary,  pouring approximately 300-400 ml through  the  XAD-2® bed so
     that the round bottom flask  is approximately half-full  and  the XAD-2® bed
     is covered.

          7.4.6    Place  a heating  mantle   under  the   round  bottom  flask  and
     connect the upper joint of the Soxhlet extractor  to a condenser.

NOTE:     Start the extraction process  immediately  after  spiking  is completed
          to ensure that no volatilization of organic  compounds  from the resin
          or  any  spiking  solutions  occurs before  the extraction  process  is
          started.

          7.4.7    Allow the sample to extract for at least 18  hours  but not more
     than 24 hours, cycling once  every  25  - 30 minutes.

NOTE:     Be sure that cooling water for the condensers is cold and circulating.
          Watch the extractor through  two  or three cycles to ensure that the
          extractor is working properly.

          7.4.8    After  the Soxhlet  extractor  has  been cooled,  disconnect the
     extractor  from the condenser and  tilt the extractor slightly  until  the
     remaining solvent in  the Soxhlet has drained into the round bottom flask.

          7.4.9    Inspect the contents  of  the  round bottom  flask to determine
     whether there  is a  visible water layer on  top of the methylene chloride.
     If  no  water  layer  is observed,  transfer the extract into  a  500-mL amber
     glass  bottle  with Teflon®-lined screw cap  for storage  (Sec.  7.2.1.8), or
     proceed directly with removal of moisture and concentration of the extract
     (Sec.  7.2.3.1).  If  a water  layer  is observed in  the Soxhlet round bottom
     flask,  transfer the contents to a separatory funnel,  rinsing  the round
     bottom  flask  three  times with methylene  chloride and adding  the rinsings

                                  3542  - 16                        Revision 0
                                                                  January 1995

-------
     to the separatory funnel.  Drain the methylene chloride from the separatory
     funnel  and  store in  an  amber glass bottle.   Then perform  an  acid/base
     extraction  of the water  layer  remaining  in the  separatory  funnel  (Sec.
     7.3.3).  Add  the methylene chloride extract from the acid/base extraction
     to the methylene chloride extract from  the  round bottom flask in the amber
     glass  jar.    Store the  extract  in  the amber  glass  bottle  at  4°C  for
     subsequent  removal  of moisture  and  concentration following   the  steps
     outlined in Sec. 7.2.3.1.
8.0  QUALITY CONTROL

     8.1   Refer to Chapter One  for specific Quality Control procedures.

     8.2   A  method blank  consists  of  a  clean filter,  clean dry  XAD-2®,  or
organic-free reagent water, which is spiked with surrogates prior to extraction.
The method blank is extracted and concentrated  using the same procedures as the
corresponding sample matrix.   One  method blank is extracted  and  analyzed for
every ten samples.

     8.3   A  method spike consists  of a clean  filter,  XAD-2®,  or  organic-free
reagent water,  which -is  spiked with surrogates, isotopically-labeled standards,
if used, and method spike solution,  if  used,  prior to  extraction.   The method
spike  is  extracted  and  concentrated  using  the  same  procedures  as  the
corresponding sample matrix.  At least one method spike is extracted and analyzed
for every matrix,  with a  frequency of one method spike for every twenty samples.


9.0  METHOD  PERFORMANCE

     9.1   Method  Performance Evaluation  -  Evaluation  of  analytical  procedures
for a selected series of compounds must include the  sample preparation procedures
and each associated analytical determination.   The analytical procedures should
be challenged by  the  test  compounds  spiked at  appropriate  levels  and carried
through all the procedures.

     9.2   Method  Detection Limits - The overall method detection limits (lower
and  upper) need  to  be  determined  on  a  compound-by-compound basis  because
different compounds may  exhibit  different collection,  retention, and extraction
efficiencies as  well   as instrument  minimum  detection  limits.    The  method
detection limit needs to  be quoted relative to a given sample volume.  The upper
limits  for the  method need  to  be determined  relative to  compound retention
volumes (breakthrough).

     9.3   Method  Precision  and Bias  -  The overall  method precision  and bias
needs to be determined on a compound-by-compound basis at a given concentration
level.   The method precision value  would include a combined variability due to
sampling, sample preparation, and instrumental  analysis.  The method bias would
be dependent upon the collection, retention,  and  extraction  efficiency of the
train  components.     The  surrogate  recoveries  shown below  represent  mean
recoveries for  surrogates in  all Method 0010 matrices  in a field dynamic spiking
study.
                                  3542  -  17                         Revision 0
                                                                  January 1995

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10.0 REFERENCES

1.   Bursey, J., Homolya, J., McAllister,  R.,  and McGaughey, J., Laboratory and
     Field Evaluation of the SemiVOST Method, Vols. 1 and 2, U. S. Environmental
     Protection Agency,  EPA/600/4-851/075A, 075B.   1985.

2.   Test Methods for Evaluating Solid Waste.  Physical/Chemical Methods, SW-846
     Manual,  3rd  ed.,   Document  No.  955-001-00000-1.   Available  from  the
     Superintendent of Documents,  U.  S.  Government Printing Office, Washington,
     DC.  November,  1986.

3.   Handbook.    Quality  Assurance/Quality  Control   (QA/QC)  Procedures  for
     Hazardous Waste  Incineration, EPA-625/6-89-023, Cincinnati,  OH.   1990.

4.   Bursey,  J.,  Merrill,  R., McAllister,  R.,  and McGaughey,  J.,  Laboratory
     Validation of VOST and SemiVOST for Halogenated Hydrocarbons from the Clean
     Air  Act Amendments List, Vols.  1  and 2, U. S.  Environmental  Protection
     Agency,  EPA  600/R-93/123a   and  b,  (NTIS  PB93-227163  and  PB93-227171)
     Research Triangle  Park,  NC.  July.  1993.

5.   McGaughey, J., Bursey, J., and Merrill, R.,  Field  Test of a Generic Method
     for  Halogenated  Hydrocarbons,  U.  S.  Environmental  Protection  Agency,
     EPA  600/R-93/101,  (NTIS PB 93-212181),  Research  Triangle  Park,  NC. July,
     1993.
                                   3542 - 18                        Revision 0
                                                                  January  1995

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                                    TABLE  1

                  PRECISION AND BIAS VALUES FOR METHOD 35421
Compound
2-Fluorophenol
Phenol -d5
Nitrobenzene-d5
2-Fluorobiphenyl
2,4,6-Tribromophenol
Terphenyl-du
Mean
Recovery
74.6
77.8
65.6
75.9
67.0
78.6
Standard
Deviation
28.6
27.7
32.5
30.3
34.0
32.4
Relative Standard
Deviation (%)
38.3
35.6
49.6
39.9
50.7
41.3
1   The surrogate recovery values  shown  in Table 1 represent mean recoveries for
   surrogates in all  Method 0010 matrices in a field dynamic spiking study.
                                  3542 - 19
  Revision 0
January 1995

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                    FIGURE  1

           METHOD 0010 SAMPLING  TRAIN
Stac*
                                                                       i
                    3542 - 20
  Revision 0
January 1995

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             FIGURE  2

     TRANSFER OF WET  XAD-2®
                                Rubber
                                 Bulb
M*O,a add«d to XAD-23 Trap
T«flon
-------
                                            FIGURE 3

SAMPLE PREPARATION SCHEME (FLOWCHART)  USING MODIFIED METHOD 5 (METHOD 0010) TRAIN
             XAO-2«
          (Container 3)
    Spike with Surrogates (and
   Isotopically-Labeled Analogs)
                                        Impinger Contents
                                 i       (Impingers 2 and 3)
                                            Archive
       Soxhlet Extraction
         XAD-2® Extract
      Add Sufficient Water
      to Separate into Two
        Phases; Separata
    Extract Water Layer with
   CH2CI2 Adjust pH and Do
Acid/Base or Base/Acid Extraction
   Combine Ct-fe Cl 2 Extracts
Rinse ail of Glassware Between
 Back Half of Filter Holder and
XAD-2® (Filter Holder Back Half
  Connector, and Condenser)
     with CH jCI ^CH pH
         (Container 5)
 Silica Gel
(Impinger 4)
(Container 5)
                                        Weigh in the Field
                                                                                Regenerate
                                                                                  Re-use
       Remove Moisture
         with Na SO
      Concentrate to 5mL
      Analyze by GC/MS
                                           3542  - 22
                                              Revision  0
                                           January 1995

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                          FIGURE 3 (continued)

SAMPLE PREPARATION FLOWCHART USING MODIFIED METHOD 5 (METHOD 0010) TRAIN
^r^n-M?" i Rinse of impinger 1 i Rarticulate Matter
flmpingerl) . CK CL/CH.OH rittar L—
Container4) ' 223 finer -^
(Cnntainar 11

i

1
_| |^ .
j
I Spike with Surrogates,
Tlsotopically -Labeled
' Analogs

Spike with Surrogates and •
Isotopicaily-Labeled Analogs wm
TSoxhlet Extraction
cw n
2 2
Separatory Funnel Extraction !

separate phases)
y ?
y
Extract water Layer with j _
CH, Cl 2, Adjust pH and do CH a
Acid/Base or Base/Acid 1. 2
Extraction E*™*


' Comhina rwnrin |^^
Combine CHjCI 2 Extracrs ^^ 	 Extracts ~~"
1
1
T T
F
Remove Moisture with NajSO^ Remove Moisture with N^ SO4
T T

|
Concentrate to 5mL Concentrate to 5mL
f T

Analyze by GC/MS Analyze by GC/MS
front naff Rinse,
Front Half of Ffter Holder,
-i Probe and Nozzle
f^LJ /•*] //"*IJ /^LJ
Wfij Olj/^" T»"'
(Container 2)
T
Filter Add Filter to
Paniculate Matter Filter
T
Separatory Funnel
Extraction
(Add H20 if necessary to
separate phases)
T
Extract Water Layer with
CH2 Cl j. Adjust pH and do
Acid/Base or Base/Acid
Extraction
f
Save CHj CI2 Layer
(Bottom)

                                3542  -  23
  Revision 0
January 1995

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                                  METHOD  3545

                        ACCELERATED SOLVENT EXTRACTION
1.0   SCOPE AND APPLICATION

      1.1  Method 3545 is a procedure for  extracting water insoluble or slightly
water  soluble  semivolatile  organic compounds  from  soils, clays,  sediments,
sludges, and waste  solids.   The method  uses  elevated  temperature  (100°C)  and
pressure (1500  - 2000 psi) to achieve analyte recoveries equivalent to those from
Soxhlet extraction, using less solvent and taking significantly less time than
the  Soxhlet  procedure.    This  procedure  was  developed  and  validated on  a
commercially-available, automated extraction system.

      1.2  This method  is applicable to the extraction of semivolatile organic
compounds, organophosphorus pesticides, organochlorine pesticides,  chlorinated
herbicides,  and PCBs, which  may then be analyzed by a variety of chromatographic
procedures.

      1.3  This method  has been  validated for solid matrices containing 250 to
12,500  M9/kg  of  semivolatile  organic  compounds,   250  to  2500  M9/kg  of
organophosphorus pesticides, 5 to  250 /^g/kg of organochlorine pesticides, 50 to
5000 M9/kg °f chlorinated herbicides,  and  1 to  1400 /zg/kg  of PCBs.

      1.4  This method is applicable  to  solid samples only, and is most effective
on dry  materials  with  small  particle sizes.   Therefore,  waste samples  must
undergo phase separation, as described  in Chapter Two,  and only the solid phase
material  is  to be  extracted  by this  procedure.   If  possible,  soil/sediment
samples may  be air-dried  and ground  to a  fine  powder prior  to  extraction.
Alternatively,  if the loss of analytes during drying is  a concern, soil/sediment
samples may  be  mixed with anhydrous  sodium sulfate.  The total mass of material
to be prepared  depends on  the specifications of the determinative method and the
sensitivity  required for  the  analysis, but 10  - 30 g  of material  are usually
necessary and can be accommodated by this extraction  procedure.

      1.5   This method  is  restricted  to use  by or  under  the  supervision  of
trained  analysts.    Each analyst  must  demonstrate  the ability  to  generate
acceptable results with this method.


2.0   SUMMARY OF METHOD

      2.1  Samples are mixed with anhydrous sodium sulfate or are air dried, then
ground to 100 - 200 mesh (150 urn to 75 /im), and loaded into the extraction cell.

      2.2  The  powdered  sample is  equilibrated for 5  minutes and extracted for
5 minutes  using elevated temperature (100°C), elevated pressure  (1500-2000 psi),
and the  appropriate solvent  system.   The  solvent systems utilized  for  this
procedure include:

          2.2.1    1:1  acetone/hexane for organochlorine pesticides and  PCBs

          2.2.2    1:1  methylene chloride/acetone for semivolatile  organics

                                   3545 - 1                         Revision 0
                                                                  January 1995

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           2.2.3    1:1 methylene chloride/acetone for organophosphorus pesticides

           2.2.4    2:1 acetone/methylene chloride acidified with phosphoric acid
     for chlorinated herbicides

     2.3   The  extraction  cell  is allowed to cool to room temperature  and the
solvent is collected in a glass vial.

     2.4   The  extract  may be  concentrated,   if  necessary,  and,  as  needed,
exchanged into a  solvent compatible with the cleanup or determinative step being
employed.


3.0  INTERFERENCES

     3.1   Refer  to  Method  3500.

     3.2    If  necessary,  Florisil  and/or  sulfur  cleanup  procedures  may  be
employed.  In such cases, proceed with Method 3620  and/or Method 3660.


4.0  APPARATUS AND  MATERIALS

     4.1   Automated accelerated  solvent extractor - Dionex Accelerated  Solvent
Extractor (or equivalent) with appropriately-sized extraction cells.  Currently,
cells are  available that will accommodate  10 g,  20 g and 30 g samples.  Cells
should be made of stainless steel  or other material  capable of withstanding the
pressure requirements (2000+ psi) necessary for this  procedure.

     4.2   Apparatus for determining percent dry weight

           4.2.1   Oven  - drying

           4.2.2   Desiccator

           4.2.3   Crucibles - porcelain  or  disposable aluminum

     4.3   Apparatus for grinding - capable  of reducing particle  size to <  1 mm.

     4.4   Analytical balance - capable  to  weighing to 0.01  g.

     4.5   Vials  for collection of extracts - 40-mL or 60-mL, pre-cleaned, open
top screw-cap with  PTFE-lined silicone  septum  (Dionex  049459, 049460,  049461,
049462 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.

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      5.2   Organic-free  reagent water.   All  references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Sodium sulfate (granular, anhydrous), Na2S04.   Purify  by heating  at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate  with
methylene chloride.   If the sodium sulfate is precleaned with methylene chloride,
then a method blank must be analyzed demonstrating that there  is  no interference
from the sodium sulfate.

      5.4   Phosphoric acid  solution (see  Sec. 5.5.5).   Prepare a  1:1  (v/v)
solution of 85% phosphoric acid  (H3P04)  in  organic-free reagent water.

      5.5   Extraction solvents

      The  extraction  solvent  to  be employed  depends on the  analytes  to be
extracted, as  described  below.   All  solvents should  be  pesticide  quality or
equivalent.

           5.5.1   Organochlorine  pesticides  are  extracted with acetone/hexane
      (1:1, v/v), CH3COCH3/C6H14.

           5.5.2      Semi volatile  organics   are   extracted   with   methylene
      chloride/acetone (1:1, v/v),  CH2C12/CH3COCH3.

           5.5.3      PCBs  are   extracted  with   hexane/acetone  (1:1,  v/v),
      C6H14/CH3COCH3.

           5.5.4    Organophosphorus pesticides are  extracted  with  methylene
      chloride/acetone (1:1, v/v),  CH2C12/CH3COCH3.

           5.5.5   Chlorinated herbicides are extracted with  acetone/methylene
      chloride/phosphoric acid solution (250:125:15, v/v/v) CH3COCH3/CH2C12/H3P04.
      Make  fresh before each use.

      5.6   Nitrogen gas, high purity.  For  purging the extraction  cell.


6.0   SAMPLE  COLLECTION, PRESERVATION, AND HANDLING

      See  the  introductory material  to this chapter,  Organic  Analysis,
Sec. 4.1.
7.0   PROCEDURE

      7.1   Sample  preparation

           7.1.1    Sediment/soil  samples  - Decant and discard any water  layer on
      a  sediment  sample.    Mix  the  sample  thoroughly,  especially  composited
      samples.   Discard  any foreign objects  such as sticks, leaves,  and rocks.
      Air dry the  sample at  room  temperature for 48 hours in a glass tray or on
      hexane-rinsed  aluminum foil.  Alternatively, mix the  sample with  an equal
      volume of anhydrous sodium sulfate until a free-flowing powder is obtained.


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NOTE:     Dry, finely-ground soil/sediment allows the best extraction efficiency
          for nonvolatile, nonpolar organics, e.g., 4,4'-DDT, PCBs, etc.  Air-
          drying may  not  be  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.   Waste samples - Multiphase waste samples must be prepared by
     the  phase separation  method  in  Chapter Two  before  extraction.    This
     extraction procedure is for solids  only.

          7.1.3    Dry sediment/soil and dry waste samples amenable to  grinding -
     Grind or otherwise reduce the particle size  of the waste so that it either
     passes  through  a  1  mm sieve  or can be  extruded through  a 1 mm hole.
     Disassemble   grinder  between   samples,   according   to   manufacturer's
     instructions,  and  decontaminate with soap and  water,  followed by  acetone
     and hexane rinses.

NOTE:     The note  in Sec. 7.1.1 also  applies to the grinding process.

          7.1.4    Gummy,  fibrous,  or oily materials not  amenable to grinding
     should  be cut, shredded, or otherwise reduced in size to allow mixing and
     maximum exposure of the sample surfaces for the extraction.  The addition
     of  anhydrous   sodium  sulfate  to  the sample (1:1) may make  the  mixture
     amenable to grinding.

     7.2  Determination of percent  dry weight  -  When sample results  are to be
calculated on a dry weight basis,  a second portion of sample should be  weighed
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 sample.

          7.2.1    Immediately  after weighing the sample for extraction, weigh
     5 - 10  g of the  sample into a tared crucible.  Dry this aliquot overnight
     at  105eC.  Allow to  cool  in  a  desiccator before weighing.   Calculate the
     % dry weight  as  follows:

                      ...     ...    g of dry sample   .nn
                      % dry weight =	— x 100
                                      g of sample


     7.3  Grind a  sufficient weight of the dried sample from Sec. 7.1 to yield
the sample weight needed for the determinative method  (usually 10 - 30  g).  Grind
the sample until it passes through a 10 mesh sieve.

     7.4  Transfer the  ground  sample  to  an  extraction  cell of  the appropriate
size for  the  analysis.  Generally, an 11-mL cell will  hold  10 g of  sample, a 22-
ml_ cell  will  hold 20  g of sample,  and a 33-mL cell will hold 30 g of sample.

     7.5  Add the  surrogates listed in the determinative method  to each sample.
Add the matrix spike/matrix spike duplicate compounds listed in the determinative
method to the two additional  aliquots of the sample selected for spiking.


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     7.6   Place  the  extraction  cells  into the autosampler tray.

     7.7   Load the collection tray with the  appropriate number (one per sample)
of 40-mL or 60-mL, precleaned, capped vials  with septa.

     7.8   Recommended  extraction  conditions

           Oven temperature:    100°C
           Pressure:            1500 -  2000 psi
           Static time:         5 min  (after  5 min pre-heat equilibration)
           Flush  volume:        0.6 times  the cell volume
           Nitrogen purge:      45  sec  at  150 psi

           7.8.1   Optimize  the  conditions,   as   needed,   according  to  the
     manufacturer's  instructions.  In general,  the pressure is  not a critical
     parameter,  as the purpose of  pressurizing the extraction cell  is to prevent
     the solvent from  boiling at  the  extraction temperature and to ensure that
     the solvent remains  in  intimate  contact with the sample.  Any pressure in
     the range of 1500 -  2000  psi should suffice.

           7.8.2   Once established,  the same pressure should be  used for all
     samples  extracted for the  same analysis type.

     7.9   Begin  the  extraction  according to the manufacturer's instructions.

     7.10  Collect each extract in  a  clean  40-mL  or 60-mL vial.   Allow the
extracts to cool  after  the  extractions are complete.  Collected extracts will be
approximately 1.2 to 1.4 times the cell volume.

     7.11  The extract  is  now ready for cleanup or  analysis,  depending  on the
extent  of   interferants.   Refer  to  Method 3600  for guidance   on  selecting
appropriate cleanup methods.   Certain cleanup and/or determinative methods may
require a solvent exchange prior to cleanup  and/or sample analysis.

     7.12  The extraction  of  chlorinated herbicides uses phosphoric acid in the
extraction solvent.   Therefore, after extractions are completed,  the extractor
should be rinsed by pumping acetone through  all  lines.


8.0  QUALITY CONTROL

     8.1   Refer  to Chapter One  and Method 8000 for guidance on quality control
procedures.  Refer to Method 3500 for  specific guidance on extraction and sample
preparation procedures.

     8.2   Before processing any samples, the analyst should demonstrate that all
parts of the equipment  in contact with the sample and  reagents are interference-
free.  This is accomplished through the analysis of a  solid matrix method blank
(e.g.,  clean sand).   Each time samples are extracted,  and when there is a change
in reagents, a method blank needs to be extracted and  analyzed for the compounds
of interest.  The method blank should be carried through all stages  of the sample
preparation and  measurement.
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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
procedures. A matrix spike/matrix spike duplicate, or matrix spike and duplicate
sample analysis, and  a laboratory control  sample should be prepared and analyzed
with each batch of samples prepared  by  this procedure, unless the determinative
method provides other guidance.

     8.4   Surrogate  standards  should be added to all  samples when listed in the
appropriate determinative method.


9.0  METHOD PERFORMANCE

     9.1   Chlorinated pesticides  and semivolatile organics

     Single-laboratory  accuracy data were obtained  for chlorinated pesticides
and semivolatile  organics at three different  spiking  concentrations  in three
different soil  types. Spiking  concentrations ranged from 5  to 250 Aig/kg f°r the
chlorinated pesticides  and  from  250  to  12500 M9/kg for  the  semivolatiles.
Spiked samples  were extracted both by the  Dionex Accelerated Solvent Extraction
system and by  a Perstorp  Environmental Soxtec™ (automated  Soxhlet).  Extracts
were analyzed either by Method 8270 or Method 8081.   Method blanks, spikes and
spike duplicates were included for the low concentration spikes; matrix spikes
were included for all other concentrations.   The data  are reported in detail in
Reference  1, and  represent seven replicate  extractions  and  analyses  for each
sample.  Data summary tables are included in Methods 8270 and 8081.

     9.2   Organophosphorus pesticides  and chlorinated herbicides

     Single-laboratory   accuracy   data  were  obtained  for  Organophosphorus
pesticides  (OPPs)   and   chlorinated   herbicides   at  two   different  spiking
concentrations in three different soil types.  Spiking concentrations  ranged from
250 to 2500 jug/kg for the OPPs and from  50  to  5000  /xg/kg  for the chlorinated
herbicides.  Chlorinated herbicides were  spiked with  a mixture of the free acid
and  the  ester (1:1).    Spiked samples  were  extracted both  by  the  Dionex
Accelerated Solvent  Extractor  and  by Soxhlet  for  the  OPPs.    Extracts  were
analyzed by Method 8141.   Spiked  chlorinated herbicides  were extracted by the
Dionex Accelerated  Solvent Extractor  and  by the shaking  method  described in
Method 8151.  Extracts were analyzed by Method 8151.   Method blanks, spikes and
spike duplicates were included for the low concentration spikes; matrix spikes
were included for all other concentrations.   The data  are reported in detail in
Reference  2, and  represent seven replicate  extractions  and  analyses  for each
sample.  Data summary tables are included in Methods 8141 and 8151.

     9.3   PCBs

     Single-laboratory  accuracy data were obtained for PCBs from a soil sample
with PCB content certified by NIST (Standard Reference Material,  SRM  1939, River
Sediment).   A   PCB-contaminated soil was  purchased from a commercial  source.
Spiking or certified concentrations ranged from 1 to 1400 jug/kg.  Samples were
extracted by the Dionex Accelerated Solvent  Extractor and by Soxtec™ (Perstorp
Environmental).  Extracts were  analyzed using Method 8082. Method blanks, spikes
and spike duplicates were  included.  The data are reported in Reference 2, and


                                   3545 - 6                         Revision  0
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represent seven replicate extractions and analyses for each sample.  Data summary
tables are included in Method 8082.
10.0 REFERENCES

1.   B. Richter, Ezzell, J.,  and Felix, D., "Single Laboratory Method Validation
     Report.   Extraction of TCL/PPL  (Target  Compound  List/Priority Pollutant
     List) BNAs and Pesticides using Accelerated Solvent Extraction (ASE) with
     Analytical  Validation  by GC/MS  and  GC/ECD";  Document  116064.A,  Dionex
     Corporation, June  16, 1994.

2.   B. Richter, Ezzell, J.,  and Felix, D., "Single Laboratory Method Validation
     Report.   Extraction of   TCL/PPL (Target  Compound  List/Priority Pollutant
     List)  OPPs,  Chlorinated  Herbicides  and  PCBs using  Accelerated  Solvent
     Extraction (ASE)".  Document  101124, Dionex Corporation, December 2, 1994).
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         METHOD 3545

ACCELERATED SOLVENT EXTRACTION
>
'
7.1 Prepare
sample.
i
r
7.2 Determine
sample % dry
weight.
>
r
7.3 Grind sufficient
weight of the dried
sample.
^
r
7.4 Transfer ground
sample to an
extraction cell.
>
r
7.5 Add surrogates
and matrix spiking
standards.



>,


7.6 Place extraction
cells into auto
sampling train.
>
f
7.7 Load
collection tray.
1
r
7.8 Optimize
conditions of
extractor.
^
r
7.9 Begin
extraction.
i
r
7.10 Collect
extracts and
allow to cool.
>
r
7.1 1 Perform
cleanup or
determinative
method.
           3545 - 8
  Revision 0
January 1995

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                                 METHOD 3550B

                             ULTRASONIC  EXTRACTION


 See Disclaimer.  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 less than or equal to  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 greater  than  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.

     1.4  Ultrasonic  extraction is not as rigorous  a method as other extraction
methods for soil/solids.  Therefore it is critical  that the method be followed
explicitly to maximize its limited extraction efficiency.   This requires that:

          The necessary  equipment must be used (a 3/4" horn and  a minimum of 300
          watts of power);
          The  horn is  properly maintained   (tuned prior  to use  according to
          manufacturer's instructions and that the  tip of the horn is not worn);
          The samples are properly prepared (the sample  is thoroughly mixed with
          anhydrous sodium  sulfate so that  it  exists  as a free flowing powder
          prior to  the  addition of solvent);
          The correct extraction  procedure  is  followed (three  extractions are
          performed with the proper solvent,  the  ultrasonic extraction  is
          performed in  the specified  pulse mode and the tip is positioned just
          below the solvent  surface but  above the  sample); and,
          There is visible  observation  of a very  active mixing of the sample
          throughout  the solvent when the energy pulse  is activated.

     1.5  Very  non-polar organic compounds (e.g. PCBs,  etc.) that are strongly
adsorbed to the soil  matrix  are known to be extracted  less  efficiently using
ultrasonic extraction.   Preliminary results  indicate that use of the 1/4" horn
tip for extracting  high concentrations (greater than 20 mg/kg) of very non-polar
compounds is  inappropriate.   Instead,   use  the 3/4"   horn  to maintain  good
extraction efficiency.

     1.6  Ultrasonic extraction is  not appropriate for use with organophosphorus
compounds because it may  cause the destruction  of  some  of  the  target analytes
during  the extraction  procedure.


                                   3550B  - 1                         Revision 2
                                                                  January 1995

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      1.7   This  method is  restricted  to  use  by or  under  the  supervision  of
trained  analysts.    Each  analyst  must  demonstrate  the  ability  to  generate
acceptable results with this method.

      1.8   This method is not appropriate for applications where high extraction
efficiencies  of  analytes   at  very  low  concentrations  is  necessary  (e.g.,
demonstration of effectiveness of corrective action).


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

      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.

           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.

           4.2.2    Use a  3/4"  horn for  the low concentration  method and a 1/8"
     tapered microtip 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    Drying oven  - capable  of maintaining 105°C.

           4.4.2    Desiccator.
                                   3550B -  2                        Revision 2
                                                                  January 1995

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          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-569001-0219  or
     equivalent).

          4.8.5    Springs  -  1/2 inch  (Kontes  K-662750  or equivalent).

NOTE:   The following  glassware  is  recommended for  the  purpose  of  solvent
        recovery   during the  concentration  procedures requiring  the use of
        Kuderna-Danish   evaporative   concentrators.    Incorporation  of  this
        apparatus  may be required by State  or  local  municipality regulations
        that govern air emissions of volatile  organics.   EPA  recommends  the
        incorporation  of  this  type  of  reclamation  system  as  a method  to
        implement  an emissions reduction  program.  Solvent recovery is a means
        to  conform with waste minimization and pollution prevention initiatives.


     4.9  Solvent  vapor recovery system (Kontes K-545000-1006 or K-547300-0000,
Ace Glass  6614-30,  or equivalent).

     4.10 Boiling  chips  - Solvent-extracted, approximately 10/40 mesh (silicon
carbide or equivalent).

     4.11 Water  bath   -  Heated,  with  concentric  ring  cover,  capable   of
temperature control (± 5°C).   The batch should be used in  a hood.

     4.12 Balance  - Top-loading,  capable of accurately weighing to the nearest
0.01 g.

     4.13 Vials  -  2-mL, for GC autosampler,  with Teflon-lined  screw  caps or
crimp tops.

                                   3550B  - 3                         Revision 2
                                                                  January 1995

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      4.14  Glass  scintillation  vials  -  20-mL, with  Teflon-lined  screw  caps.

      4.15  Spatula  -  Stainless  steel  or Teflon.

      4.16  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
       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.

      4.17  Syringe  -  5-mL.


5.0   REAGENTS

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

      5.2   Organic-free reagent water.   All  references to  water in this method
refer to organic-free reagent water,  as defined in Chapter One.

      5.3   Sodium sulfate  (granular,  anhydrous), Na2S04.   Purify by heating at
400°C for 4 hours  in a shallow tray,  or by precleaning the sodium sulfate with
methylene chloride.  If the sodium sulfate  is precleaned with methylene chloride,
a method blank  must be analyzed, demonstrating that there is no interference from
the sodium sulfate.

      5.4   Extraction solvents  -  All  solvents must  be  pesticide quality or
equivalent.

           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.

           5.4.2    Methylene chloride:Acetone,  CH2C12:CH3COCH3 (1:1,  v:v).

           5.4.3    Methylene chloride,  CH2C12.

           5.4.4    Hexane,  C6H14.

      5.5   Exchange  solvents  -  All  solvents  must  be pesticide quality  or
equivalent.

           5.5.1    Hexane,  C6H14.
                                   3550B - 4                        Revision 2
                                                                  January  1995

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           5.5.2    2-Propanol,  (CH3)2CHOH.

           5.5.3    Cyclohexane,  C6H12.

           5.5.4    Acetonitrile,  CH3CN.

           5.5.5    Methanol,  CH3OH.


6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

     See the introductory material to  this Chapter, Organic Analytes, 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 multiple phases must be
     prepared by  the phase separation method in Chapter Two before extraction.
     This  extraction 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
     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 reduced in size to allow mixing and
     maximum exposure  of the sample surfaces for the extraction.   The addition
     of  anhydrous sodium  sulfate to  the  sample  (1:1)  may  make  the  mixture
     amenable to  grinding.

     7.2   Determination  of percent dry  weight  - When sample  results are to be
calculated on a dry weight basis, a second portion of sample 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
           sample.

     Immediately  after weighing the sample for extraction, weigh 5-10 g of the
sample into a tared crucible.   Dry this  aliquot overnight at 105°C.   Allow to
cool in a desiccator before weighing.   Calculate the  % dry weight as follows:

                     ...     ...    g of dry sample   ....
                     % dry weight =	— x 100
                                      g of sample
                                   3550B  -  5                         Revision 2
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     7.3   Extraction method for samples expected to contain low concentrations
of organics and pesticides (less than or equal  to 20 mg/kg):

           7,3.1    The following steps should be performed rapidly to avoid loss
     of the more volatile extractables.

                   7.3.1.1   Weigh  approximately 30  g  of sample into  a 400-mL
           beaker.   Record the weight to the nearest 0.1 g.

                   7.3.1.2   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.

                   7.3.1.3   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).

                   7.3.1.4   For  the sample in each analytical batch selected for
           spiking,  add 1.0 ml of  the matrix spiking standard.

                   7.3.1.5   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//xL
           of  each  acid analyte  in the  extract  to  be analyzed  (assuming a 1 nl
           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.

                   7.3.1.6  Immediately   add    100    ml  of   1:1   methylene
           chlorideracetone.

           7.3.2    Place   the  bottom  surface  of  the  tip of  the  #207  (or
     equivalent) 3/4 inch disrupter horn about  1/2 inch below the surface  of the
     solvent,  but  above  the sediment layer.

NOTE:   Be sure the  horn is properly  tuned  according to  the  manufacturer's
        instructions.

           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  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-mL 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

                                  3550B - 6                        Revision 2
                                                                  January 1995

-------
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.
Attach  the solvent  vapor  recovery glassware  (condenser  and  collection
device) to the  Snyder column  of  the  Kuderna-Danish apparatus  following
manufacturer's  instructions.    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.

     7.3.10   If further concentration is indicated in Table 1, either micro
Snyder  column  technique (Sec.  7.3.10.1)  or nitrogen blowdown  technique
(Sec. 7.3.10.2)  may  be 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

                             3550B  - 7                         Revision  2
                                                            January 1995

-------
                   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  blowdown 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,
          since it  may  introduce contaminants.

                            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   Extraction method for samples expected to contain high concentrations
of organics  (greater than 20 mg/kg):

           7.4.1    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.

           7.4.2    Add  2 g  of anhydrous sodium sulfate  to  sample  in  the 20-mL
     vial  and mix  well.

           7.4.3    Surrogates are added  to all samples,  spikes, and blanks (see
     Method  3500 for details on the surrogate spiking solution and  on  the matrix
     spike solution).

                   7.4.3.1   Add  1.0 ml  of surrogate spiking solution to sample
           mixture.

                   7.4.3.2   For the sample in each analytical  batch  selected for
           spiking,  add 1.0  ml of the matrix spiking standard.

                                   3550B -  8                        Revision 2
                                                                  January 1995

-------
                   7.4.3.3   For base/neutral-acid  analysis, the amount added of
          the  surrogates and matrix spiking compounds should result in a final
          concentration of 100 ng//LiL of each base/neutral analyte and 200 ng//A
          of each  acid  analyte in  the  extract  to  be  analyzed (assuming  a 1 /xL
          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.

          7.4.4   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:

                   7.4.4.1   For  nonpolar   compounds  (i.e.,   organochlorine
                            pesticides  and  PCBs),  use  hexane  or  appropriate
                            solvent.

                   7.4.4.2   For  other   semivolatile  organics,   use  methylene
                            chloride.

          7.4.5   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  mL or less.

          7.4.6   The extract  is ready for cleanup or analysis, depending on the
     extent of interfering  co-extractives.

     7.5  If analysis of the extract will not be performed immediately, stopper
the concentrator tube and refrigerate.  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.


8.0  QUALITY CONTROL

     8.1  Any  reagent  blanks,  matrix  spike,  and  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

     Refer to  the determinative method  for performance data.
                                  3550B  - 9                         Revision 2
                                                                  January 1995

-------
10.0 REFERENCES

1.   U.S. EPA, Inter!aboratory Comparison Study:  Methods for Volatile and Semi-
     Volatile Compounds, Environmental Monitoring Systems Laboratory, Office of
     Research and Development, Las Vegas, NV, EPA 600/4-84-027, 1984.

2.   Christopher S. Hein, Paul J. Marsden, Arthur S. Shurtleff, "Evaluation of
     Methods 3540 (Soxhlet) and 3550  (Sonication) for Evaluation of Appendix IX
     Analytes from Solid Samples", S-CUBED, Report for EPA Contract 68-03-33-75,
     Work Assignment No. 03, Document No. SSS-R-88-9436, October 1988.
                                  3550B - 10                        Revision 2
                                                                  January 1995

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-------
                                     METHOD 35506

                               ULTRASONIC  EXTRACTION
>
r
7.1 Prepare samples
using appropriate
technique for the
waste matrix.
>
f
7.2 Determine the
percent dry weight
of the sample.
    7.4.1 - 7.4.2 Mix
 sample with anhydrous
     sodium sulfate.
   7.4.3 Add surrogate
     standards to all
    samples, spikes,
       and blanks.
  Is organic
 concentration
expected to be
 < 20 mg/kg?
7.3.1  Mix sample with
  anhydrous sodium
       sulfate.
                          7.3.1  Add surrogate
                            standards to all
                            samples,  spikes,
                              and blanks.
  7.4.4 Adjust volume;
   disrupt sample with
    tapered microtip
    ultrasonic probe.
                             7.3.2 - 7.3.5
                             Ultrasomcally
                         extract sample at least
                          3 times with 3/4 inch
                             disruptor horn.
   7.4.5 Filter extract
  through glass wool.
         7.4.5
       Is further
     concentration
       required?
                                                            7.3.6 Dry and collect
                                                                  extract in
                                                                concentrator.
                           7.3.7 Concentrate
                                extract.
 x^Perform cleanups.
(  or determinative   j
\^    method.     J
                                       3550B  -  13
                                                 Revision  2
                                               January 1995

-------
                    METHOD  355CB
                     (continued)

7.3.8
solvent



Add exchange
; re-concentrate
extract.


/ 7 3

^ Yes / 80|V
"^ V sxcn
	 	 fcJ
7.3.9 Use Method
3660 for cleanup.
7.3.9 Do
 sulfur
crystals
 form?
                            7.3.10 Further
                           concentrate and/or
                            adjust volume.
                             erform cleanup
                            or determinative
                               method.
                      3550B -  14
                                Revision 2
                              January  1995

-------
                                 METHOD 3560

  SUPERCRITICAL FLUID EXTRACTION OF TOTAL RECOVERABLE PETROLEUM HYDROCARBONS


1.0  SCOPE AND APPLICATION

     1.1  Method  3560 describes the  extraction  with supercritical  fluids  of
total recoverable  petroleum hydrocarbons (TRPHs) from soils, sediments, fly ash,
and other solid materials, which are  amenable  to  extraction  with conventional
solvents. The method is suitable for use with any supercritical fluid extraction
(SFE) system that  allows extraction conditions (e.g.,  pressure,  temperature,
flowrate) to be adjusted  to achieve separation of the TRPHs from the matrices of
concern.

     1.2  Method  3560  is not  suitable  for the  extraction of  low-boiling TRPHs
such as gasoline.

     1.3  This method is  restricted  to  use  by or  under  the supervision  of
trained  analysts.    Each analyst  must demonstrate  the  ability to  generate
acceptable results with this method.


2.0  SUMMARY OF METHOD

     2.1  A known amount of sample  is transferred to the  extraction vessel.  The
sample is then  extracted  in the dynamic mode for up  to 30 min with supercritical
carbon dioxide at  340 atm, 80°C and a gas flow rate of 500 -  1000 mL/min.

     2.2  After depressurization of the carbon  dioxide,  the extracted TRPHs are
collected in 3 ml of  tetrachloroethene or other appropriate  solvent (see Sec.
5.3), or on  a sorbent material, depending on the SFE system used.  In the latter
case,  the  analytes  are collected  by   rinsing  the  sorbent  material  with
tetrachloroethene  or other suitable solvent.

     2,3  After   collection,   the   TRPHs   are   analyzed  by   the  appropriate
determinative method.


3.0  INTERFERENCES

     3.1  The  analyst must  demonstrate through the analysis  of reagent blanks
(collection  solvent treated  as  per Sec.  7.4) that the supercritical  fluid
extraction system is free from  interferants.   To do  this,  perform a simulated
extraction using an  empty extraction vessel and a known amount of carbon dioxide
under the same  conditions as those used for sample extraction, and determine the
background  contamination   by  analyzing   the  extract  by   the  appropriate
determinative method (e.g. Methods 8015 or  8440).   If glass  wool  and a drying
agent  are used with the sample,   these  materials  should  be   included  when
performing a reagent blank check.


                                   3560 -  1                         Revision 0
                                                                  January 1995

-------
     3.2   The  extraction  vessel(s),  the  frits,  the  restrictor(s),   and  the
multi-port  valve  may retain  solutes  whenever high-concentration  samples  are
extracted.  It  is,  therefore, good practice to clean  the extraction system after
each extraction.   Replacement  of  the  restrictor may be  necessary when reagent
blanks indicate carryover.  At least  one  reagent  blank  should be prepared and
analyzed daily  when the instrument is in use.  Furthermore,  reagent blanks should
be prepared and analyzed  after each extraction  of a high-concentration sample
(concentration in the high ppm range).  If reagent blanks continue to indicate
contamination,   even  after  replacement   of   the  extraction  vessel  and  the
restrictor, the multi-port valve must be cleaned.


4.0  APPARATUS AND MATERIALS

     4.1   Supercritical  fluid  extractor and  associated hardware.

WARNING:     A safety feature  to prevent overpressurization is required on the
             extractor.    This feature  should  be  designed  to  protect  the
             laboratory personnel and the instrument from possible injuries or
             damage  resulting  from  equipment  failure under high pressure.

           4.1.2    Extraction  vessel - Stainless-steel vessel with end fittings
     and  0.5-or  2-/zm  frits.    Use  the  extraction  vessel  supplied by  the
     manufacturer  of the  SFE  system being  used.   The PEEK  (polyether  ether
     ketone) extraction  vessels supplied  by  Isco, Inc.  are acceptable for use
     with the  Isco SFE system.

           Fittings  used  for  the   extraction   vessel   must   be  capable  of
     withstanding  the required extraction  pressures.   The maximum operating
     pressure  for  most extractors is 500 atm.  However, extractors with higher
     pressure  ratings  are available.   Check  with the  manufacturer of  the
     particular  extraction  system  on  the   maximum operating  pressure  and
     temperature  for that system.  Make sure that  the  extraction vessels are
     rated  for such  pressures  and temperatures.

           4.1.3    Restrictor  - 50 /um  ID x 150 or 375 jum OD x 25 to 60 cm length
     piece  of uncoated  fused-silica tubing  (J&W Scientific or equivalent).
     Other  restrictors may be  used including tapered restrictors,  static pinhole
     restrictors,  frit restrictors and variable  orifice restrictors  (manual and
     computer-controlled), or crimped metal tubing.  Check with the manufacturer
     of  the SFE  system on the advantages  and  disadvantages of  the various
     restrictor designs.

           4.1.4    Collection   device  -  The  extracted  TRPHs can  be collected
     either in vials containing solvent,  or  they can be  trapped on a sorbent
     material  (e.g., octadecyl-bonded  silica, stainless steel beads).

                   4.1.4.1  When the analytes are  collected  in solvent, install
           the  restrictor through  a  hole made  through the cap and septum of the
           vial,  and  position  the  restrictor  end about 0.5 inch from the bottom
           of  the  vial.   A syringe  needle  should  also  be  inserted through the

                                    3560 - 2                         Revision 0
                                                                  January 1995

-------
           septum of the vial (with the tip positioned just below the septum) to
           prevent  buildup of  pressure  in the  vial.   Use  the type  of vials
           appropriate  for the  SFE  system  used.

                   4.1.4.2  When the analytes are trapped  on  a sorbent material,
           it  is important to ensure that breakthrough of the analytes from the
           trap  does  not  occur.   Desorption from  the  trapping medium  can be
           accomplished by increasing  the temperature of the trap  and using a
           solvent  to remove the  analytes.  Use the conditions suggested by the
           manufacturer of the  particular  system to recover  the analytes.

     4.2   Carbon  dioxide  cylinder  balance (optional) -  Balances  from White
Associates, Catalog No. 30, Scott Specialty Gases Model 5588D, or equivalent, can
be used to monitor the fluid  usage.   Such a device is  useful  because carbon
dioxide tanks used for SFE are  not equipped  with regulators.   This  makes it
difficult to determine when the tank needs to be replaced.

     4.3   Tools required  include:  screwdriver  (flat-blade), adjustable wrench,
pliers, tubing cutter,  and various small open-end wrenches  for small fittings.

     4.4   Magnesium sulfate monohydrate  -  may  be  used as received.

     4.5   Silanized glass wool - requires high-temperature  treatment (bake in
a muffle furnace at 400°C  for 2 to 4 hours) prior to use to remove any petroleum
hydrocarbons.


5.0  REAGENTS

     5.1   Carbon dioxide, C02 - Either supercritical fluid chromatography (SFC)
or SFE-grade C02 is acceptable  for use  in SFE.   Aluminum cylinders are preferred
over steel cylinders.   The cylinders  are  fitted with  eductor tubes, and their
contents are under 1500 psi of helium  head pressure.

     5.2   Carbon dioxide  (C02) for cryogenic cooling - Certain parts of some
models of  extractors (i.e., the  high-pressure  pump head  and the  analyte trap)
must be cooled during use.  The carbon  dioxide used for this  purpose must be dry
(< 50 ppm  water content),  and  it must be  supplied in  tanks  with  a full-length
eductor tube.

     5.3   Tetrachloroethene,  C2C14  (spectrophotometric grade)  - Used  for  the
collection of TRPHs for determination  by IR.  Analyze a reagent blank to ensure
no interferences are present at the TRPH wavelengths.   Chlorofluorocarbons are
not suitable for use with this method  because of risk to  the ozone layer.

     5.4   Other  appropriate pesticide-quality  solvents  may be  used  for  the
collection  of  TRPHs   for  determination  by GC   (i.e.,  methylene  chloride).
Chlorofluorocarbons are not suitable for use with this method because of risk to
the ozone layer.
                                   3560 - 3                         Revision 0
                                                                  January 1995

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     5.5   Copper filings - Copper filings added  to remove elemental sulfur must
have a shiny bright appearance to  be  effective.  To  remove oxides,  treat with
dilute nitric acid,  rinse with reagent water to remove all traces of acid, rinse
with acetone  (copper  will  darken  if  acid  is  still  present), and dry  under a
stream of nitrogen.

     5.6   Drying agents  - Anhydrous magnesium sulfate or diatomaceous  earth.


6.0  SAMPLE  COLLECTION,  PRESERVATION, AND  HANDLING

     6.1   Solid  samples should  be collected  and  stored  as any other solid
samples containing semivolatile organics.

     6.2   See  Chapter  Four  for  guidance relating  to  semivolatile  organics
(including holding times).


7.0  PROCEDURE

     7.1   Determination  of  sample % dry  weight -  In  certain cases,  sample
results are desired  based on  a  dry-weight basis.  When such data are desired, a
separate 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 should be vented.
            Significant  laboratory contamination  may result  from  a  heavily
            contaminated hazardous waste sample.

      Immediately after weighing  the sample for extraction, weigh an additional
5  -  10 g  of the  remaining  sample into a tared  crucible.  Dry  this  aliquot
overnight at 105°C.   Allow to cool in a desiccator before weighing.   Calculate
the % dry weight as follows:

                     ,,  ,     ...   g of dry sample   .nn
                     % dry weight  =	— x 100
                                      g of sample


     7.2   Safety considerations  -  Read  Section  11.0  "Safety" before attempting
to perform this procedure.

     7.3   Sample handling

           7.3.1    Decant and discard  any water layer on  a  sediment sample.  Mix
     the  sample thoroughly,  especially  composited samples. Discard any foreign
     objects such as  sticks, leaves  and rocks.

           7.3.2    Weigh 3 g of sample into a precleaned aluminum dish.  A drying
     agent (e.g.,  anhydrous magnesium  sulfate  or diatomaceous earth)  may be
     added to  samples that contain water in excess of 20%  to increase porosity
     or  to  bind water.   Alternatively,  magnesium sulfate  monohydrate  is an

                                   3560  -  4                         Revision 0
                                                                  January  1995

-------
excellent  drying  agent,  and  the amount  of heat  released (compared  to
anhydrous  magnesium sulfate)  is  small,  thereby minimizing  the loss  of
volatile  petroleum  hydrocarbons.    The  amount  of  the  drying agent  will
depend on the water  content of the sample.  Typically, a ratio of 1:1 works
well for wet  soils  and  sediment materials.  However, a certain  amount  of
water (up to 20 percent) in the sample has been shown to improve recoveries
from  certain matrices;  therefore,  if  the sample  is  dry,  water may
optionally  be added to bring  the moisture content  to approximately  20
percent.

              7.3.2.1   If  drying agent has been added to the sample, store
     the mixture of sample and drying agent  for  several  hours  (preferably
     overnight) at  4°C, with a  minimum of headspace.   This  additional
     storage  time  is necessary to  achieve  acceptable analyte  recovery.
     This  step is not necessary if  the  alternate conditions  described  in
     Sec.  7.4.2.1 are used.

     7.3.3    Transfer the weighed  sample to a clean  extraction vessel. The
volume of  the extraction  vessel should match the sample volume.  Use two
plugs of silanized glass wool to hold the sample  in  place and fill the void
volume (alternatively, drying agent or clean sand  can be  used  to fill the
void volume).  Attach the  end  fittings,  and  install the extraction  vessel
in the oven.  Always use clean frits for each  extraction vessel.

7.4  Sample extraction

     7.4.1    Fill the collection vessel  with 3 ml  of tetrachloroethene  or
other appropriate collection solvent.  Chlorofluorocarbons are not suitable
for use with this method because of risk to the  ozone layer.

     7.4.2    Set the pressure at 340  atm and  the temperature at  80°C.
Follow  the manufacturer's  instructions in  setting up  the  instrument.
Extract for 30 minutes  in the dynamic mode.  Note  the  safety  precautions
in Section 11.0 on venting the instrument into  a chemical  fume hood.

              7.4.2.1  Alternatively, extract with a pressure  greater than
     or equal to 340 atm  at 150°C for 25 minutes,  and a gas flow rate  of
     3500  to  4000  mL/min.  These parameters  dry  the  sample during the
     extraction,  thus  extended  drying is not necessary  for wet samples
     (Sec. 7.3.2.1).

              7.4.2.2  A sorbent trap maintained  above 0°C may be  necessary
     for effective analyte trapping.  The restrictor should resist plugging
     by water, since water released from the sample may pass  through the
     restrictor.

     7.4.3   After  the  extraction  time  has elapsed,  the  system  should
automatically switch to the equilibrate mode.   At  this point, remove the
collection vessel (s) containing the extract.  Since  the depressurization
of the carbon dioxide at the end of the restrictor outlet  results in a gas
flowrate of about  500 to 1000  mL/min,  part of the collection solvent  will

                              3560 -  5                         Revision  0
                                                            January  1995

-------
evaporate during  the  extraction.   However, cooling  caused by the  rapid
expansion of  the  carbon  dioxide  limits  the  loss  of  solvent,  so  that
approximately 2 ml remains  (when tetrachloroethene is used) after a 30 min
extraction.   To  prevent  the  collection solvent from freezing, place  the
collection vial  in a  beaker with  warm water  (approximately 25"C).   The
extract is then  brought  to the desired volume, or concentrated  further.
See Method 3510  for concentration techniques  by micro  Kuderna-Danish  or
nitrogen blowdown.  Concentration must be performed in a chemical fume hood
to prevent contamination of the laboratory environment.

     7.4.4   The   extract   is  ready   for  analysis   by  Method   8015,
Non-halogenated Volatile Organics  by Gas Chromatography,  or Method  8440,
Total Recoverable  Petroleum Hydrocarbons by Infrared Spectrophotometry.

7.5  SFE System Maintenance

     7.5.1   Depressurize   the  system   following   the   manufacturer's
instructions.

     7.5.2   After extraction of an especially tarry sample, the frits may
require replacement to ensure  adequate  extraction fluid  flow  through  the
restrictor.   In addition, very fine particles contained  in samples can clog
the frits necessitating replacement.

     7.5.3   Clean the extraction vessel after each  sample. The  cleaning
procedure depends  on the type  of sample.  After removing  the  bulk of the
extracted sample  from the  extraction vessel, the cell  should  be  scrubbed
with an ionic detergent, water, and a  bottle brush.  After extraction of
tarry materials,  use  solvent rinses  or an  ultrasonic  bath to clean  the
extraction vessel.

     7.5.4   For  samples  known to contain  elemental  sulfur,   use  copper
filings to remove the  dissolved sulfur  from  the fluid.  The copper filings
(1  to  2 g  per  sample)  can  be packed in  a  separate  extraction  vessel
connected to the  outlet end  of the sample extraction vessel,  or  they can
be mixed with the sample, and a plug of  copper filings can be loaded in the
extraction vessel  with the sample such that any sulfur extracted  by  the
carbon  dioxide  can  be  removed  before  the   stream  of  carbon  dioxide
containing the analytes reaches the restrictor.

     7.5.5   The  procedure to be  followed  in  emptying the syringe  pump
depends upon the type  of  fluid being used.   In the case of carbon  dioxide,
which is a gas at ambient  temperature  and pressure,  it is only necessary
to vent the gas  to a  fume  hood by  allowing  it  to expand across the purge
valve.   Follow the manufacturer's instructions  in  emptying  the  syringe
pump.

     7.5.6   To  change fluid supply cylinders  on a  system with a syringe
pump, it is  necessary  to empty the syringe pump  as described in Sec. 7.5.5.
Upon  completion  of the  emptying   procedure, the  piston  will  be  at  its


                              3560 -  6                          Revision 0
                                                            January 1995

-------
     maximum extension,  and the syringe pump outlet valve and purge valve will
     be open.  Then  proceed as follows:

                   7.5.6.1   Connect the new fluid supply cylinder to the syringe
           pump inlet line, and open the supply cylinder valve.

                   7.5.6.2   Open  the pump  inlet valve.  The new fluid will flow
           through  the  inlet line to the syringe pump and out through the vent.

                   7.5.6.3   Close  the  syringe   pump  outlet  valve  and  the
           vent/purge valve.

           7.5.7    Restrictor  removal  and  installation  - Follow manufacturer's
     instructions.   When using fused-silica restrictors,  it may be necessary to
     replace  the  restrictor  after  each  sample,  especially when  extracting
     samples contaminated with heavy  oils.


8.0  QUALITY CONTROL

     8.1   Refer  to Chapter One  and  Method  8000 for specific  quality control
procedures and to Method 3500 for sample preparation quality control procedures.

     8.2   Each  time  samples  are  extracted,  and when  there  is a  change  in
reagents,  a reagent blank should be prepared and analyzed for the compounds of
interest as a safeguard against chronic laboratory contamination.  Any reagent
blanks, matrix spike  samples, or replicate  samples should be subjected to exactly
the same analytical procedures (Sec. 7.4)  as those used on actual samples.

     8.3   All instrument operating conditions and parameters must be recorded.


9.0  METHOD PERFORMANCE

     9.1   Refer  to Methods 8440  and 8015  for performance  data.

     9.2   Use standard reference materials to establish the performance of the
method with contaminated samples.


10.0 REFERENCES

1.   Lopez-Avila,  V., N.S. Dodhiwala, J.   Benedicto, and R. Young, (W. Beckert,
     Project Officer), "SFE/IR for the Determination of Petroleum Hydrocarbons
     in Soils and Sediments", EPA 600/X-92-046, US EPA, Environmental Monitoring
     Systems Laboratory, Las Vegas, NV, April, 1992.

2.   Pyle, S.M.,  and M.M. Setty,  "Supercritical Fluid Extraction  of High-Sulfur
     Soils with  Use  of a Copper Scavenger", Talanta,  1991, 38 (10), 1125-1128.
                                   3560 - 7                         Revision 0
                                                                  January 1995

-------
3.   Bruce,  M.L.,  "Supercritical  Fluid Extraction  (SFE)  of Total  Petroleum
     Hydrocarbons  (TPHs)  with  Analysis  by  Infrared Spectroscopy",  Proceedings
     of the  Eighth Annual Waste Testing and Quality Assurance Symposium, July,
     1992.
11.0 SAFETY

     11.1  When  liquid  carbon  dioxide  comes  in  contact with skin,  it can cause
"burns" because of its low temperature  (-78'C).  Burns are especially severe when
C02 is  modified with organic liquids.

     11.2  The  extraction  fluid, which may contain a modifier, usually exhausts
through an exhaust  gas  and  liquid waste port on the  rear  of the  panel  of the
extractor.   This  port must  be  connected to a  chemical  fume hood  to prevent
contamination of the laboratory atmosphere.

     11.3  Combining  modifiers   with   supercritical   fluids   requires   an
understanding and evaluation of the potential chemical interaction between the
modifier and the  supercritical  fluid,  and between  the  supercritical  fluid or
modifier and the analyte(s) or matrix.

     11.4  When  carbon dioxide is used  for  cryogenic  cooling, typical coolant
consumption is 5 L/min, which results in a carbon dioxide level  of 900 ppm for
a room of 4.5 m x  3.0 m x  2.5  m, assuming  10  air exchanges per hour.  The NIOSH
time-weighted average  (TWA) concentration is 9000  ppm (American Conference of
Governmental Industrial Hygienists, 1991-1992).
                                   3560 - 8                         Revision 0
                                                                  January 1995

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                                METHOD  3560



SUPERCRITICAL FLUID EXTRACTION OF TOTAL RECOVERABLE PETROLEUM HYDROCARBONS
>
r
7.1 Determine sample
% dry weight.
>
r
7.3 Clean and weigh
sample. Add drying
agent if necessary.
Transfer weighed
portion to
extraction vessel.
>
r
7.4.1 Fill collection
vessel with solvent.
^
f
7.4.2 Follow
manufacturer's
instructions for 7.4.3
sample extraction.
^
r
7.4.4 Analyze sample
by Method 8015 or
Method 8440.
^
r
7.5 Follow
manufacturer's
instructions for
system maintenance.
^
'
                                   3560  -  9

-------
                                  METHOD  3561

      SUPERCRITICAL  FLUID EXTRACTION  OF POLYNUCLEAR AROMATIC  HYDROCARBONS


1.0   SCOPE AND APPLICATION

      1.1  Method  3561 describes  the  extraction with supercritical  fluids of
polynuclear aromatic  hydrocarbons (PAHs) from soils, sediments,  fly ash,  and
other  solid  materials,  which are  amenable  to  extraction  with  conventional
solvents. The method is suitable for use with any supercritical fluid extraction
(SFE)  system that  allows extraction conditions  (e.g.,  pressure,  temperature,
flowrate) to be adjusted to  achieve  separation of the PAHs from the matrices of
concern.  The following compounds may be determined by this method:


	Compound	CAS Noa	

                  Acenaphthene                           83-32-9
                  Acenaphthylene                        208-96-8
                  Anthracene                            120-12-7
                  Benz(a)anthracene                      56-55-3
                  Benzo(b)fluoranthene                  205-99-2
                  Benzo(k)fluoranthene                  207-08-9
                  Benzo(g,h,i)perylene                  191-24-2
                  Benzo(a)pyrene                         50-32-8
                  Chrysene                              218-01-9
                  Dibenz(a,h)anthracene                  53-70-3
                  Fluoranthene                          206-44-0
                  Fluorene                               86-73-7
                  Indeno(l,2,3-cd)pyrene                193-39-5
                  Naphthalene                            91-20-3
                  Phenanthrene                           85-01-8
                  Pyrene                                129-00-0


                  a Chemical Abstracts Registry Number


      1.2  Method  3561  is not suitable for the  extraction  of PAHs from liquid
samples without some treatment to the  liquid prior to introduction into the SFE
to "stabilize" the  liquid to avoid  the  sample  being extruded  through the  end
pieces of the extraction vessel without the benefit of SFE.

      1.3  The  extraction conditions listed in  this  procedure  (Sec.  7.5)  were
used to develop the data  using  a variable  restrictor and  solid trapping media
referenced in Sec. 9.2.  Other extraction conditions and equipment are acceptable
as  long  as  appropriate  method  performance  is demonstrated.    The  method
performance demonstration  should be  based  on  the  extraction  of  a  certified
sample, not  on  spiked  soil/solids.   Alternatively, a  comparison of  SFE  and
Soxhlet extraction data using an  environmentally contaminated PAH sample may be
performed.   Follow  the guidance  for  the initial demonstration  of laboratory
                                   3561 - 1                         Revision 0
                                                                  January 1995

-------
proficiency found in Section 8.0 of  Method 3500, but utilize a weathered sample
instead of a spiked sample.

      1.4   This  method  is  restricted  to use  by or  under the  supervision  of
trained  analysts.    Each  analyst  must  demonstrate  the  ability  to  generate
acceptable results with this method.


2.0   SUMMARY OF  METHOD

      2.1   The  method is  divided  into three  discrete  steps.    The extraction
conditions for the first two steps are designed  to ensure the best recovery for
the range  of volatilities  found among  the  PAHs.  The third step  is  used  as a
final   sweep  of  modifier within  the  system.   It  should be  noted  that  the
separation of the PAHs into the two arbitrary classes of the "more volatile PAHs"
(step 1) and the "lesser  volatile PAHs"  (step 2)  is  not  a clean separation  of
compounds, but a rough group separation depending upon the actual compounds and
their relative abundance in the  sample matrix.  The net sum of the two groups is
recombined in  the  end  and  thus empirically  does  not  depend  upon  a discrete
definition or naming of the compounds in each group.

           2.1.1    Step  1 - The more volatile PAHs are extracted and recovered
      in this step  using  pure  C02 at moderately low density and temperature and
      with  cold  trapping  on an ODS trap.  These PAHs  are  reconstituted into  an
      autosampler vial with  0.8  ml collected  fraction volume.

           2.1.2    Step  2 - The lesser volatile PAHs  are  removed  in  this  step
      using a  mixture of C02 with water  and  methanol  as  the  extraction fluid,
      higher  operating  temperature and  density in  the extraction region,  and a
      higher temperature  in  the  trapping  region with the ODS.   The PAHs are not
      reconstituted  directly after the second  step.

           2.1.3    Step  3 -  A  short third step with pure C02 (but with all  other
      conditions  as  in the  second step) is used to purge the system of modifier
      before  depressurization.   The  analytes  recovered  in  the  second step  (and
      possibly,   any  moved  during  the  beginning  of  the  third  step)   are
      reconstituted  in the  same  autosampler vial containing the first fraction,
      using another  0.8-mL  collected fraction  volume.  Therefore, all  recovered
      analytes are merged automatically into  a single  fraction to be analyzed by
      HPLC.

      2.2   There  are  also  optional  extraction  solvents   and  SFE  extraction
conditions provided that are more amenable  to GC and GC/MS analysis.


3.0   INTERFERENCES

      3.1   The  analyst  must demonstrate  through the analysis  of reagent blanks
(collection  solvent treated  as per  Sec.  7.4) that  the  supercritical  fluid
extraction system  is  free  from  interferants.   To  do  this,  perform a simulated
extraction using an empty extraction vessel  and a known  amount of carbon dioxide
under the same  conditions as those used for  sample  extraction, and determine the
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background  contamination   by   analyzing  the  extract  by   the  appropriate
determinative method.

     3.2   The extraction vessel(s), the end-frits, the nozzle [restrictor(s)],
and  the  multi-port  valve(s)  may  retain  solutes whenever  high-concentration
samples are extracted.  It  is,  therefore, good practice to clean the extraction
system after such  extractions.   Replacement of suspected parts  of the system
should be  done when  reagent blanks indicate carryover.  At  least  one reagent
blank  should  be  prepared  and  analyzed daily when  the instrument is  in  use.
Furthermore, reagent  blanks should be prepared and analyzed after each extraction
of a  high-concentration sample  (high  part  per million  or  mg/Kg  range).   If
reagent blanks continue to  indicate contamination,  even after  replacement of the
extraction vessel  (and the restrictor,  if a fixed restrictor system is used), the
multi-port valve must  be cleaned.   The operator must  be  ever vigilant against
impurities arising from liquid  solvents  and  carbon  dioxide  itself.  Avoid any
apparatus, valves, solenoids,  and  other  hardware  that contain lubricants, and
chlorofluorohydrocarbon materials  that  can serve  as background  contaminant
sources.

     3.3   When using modifiers,  it  is  important to consider that the modifiers
at collection regions that  are  colder than the boiling point of the modifier(s)
may cause some modifier condensation in  that region.  Depending upon  the specific
design of the instrumentation and the quantities of modifiers used  within a step,
there is a potential problem of flooding the collection region  and thereby losing
the analytes of  interest.   With SFE instrumentation  employing  solid (packed)
traps  for the collection  and  concentration  of  the  extracted  components,  a
convenient guideline  is to think of the  trap  as  a packed GC  column during the
extraction step (the  C02 and  any modifiers are the gaseous mobile phase) and as
a packed LC column during the reconstitution step.  Therefore, migration during
the "GC-column-like"  operation should be minimized by the selection of various
parameters: trap temperature,  chemical  activity of  the packing,  expended flow
rates, and extraction times (how long the migration has to proceed).  Migration
during  the  "LC-column-like"  operation should   be   controlled  to  trade-off
band-broadening with  elution time through the use of reconstitution  solvent flow
rate and composition  and the trap temperature during reconstitution.

     3.4   Refer to Method 3500, Section 3.0  for general extraction  interference
guidance.


4.0  APPARATUS AND MATERIALS

     4.1   Supercritical  fluid  extractor   and   associated   hardware   -   Any
supercritical fluid extraction  system that can achieve  the extraction conditions
and performance specifications detailed in  this procedure may be used.

     Figure 1 depicts a typical supercritical  fluid extractor system,  including
a carbon dioxide source, a pumping system (liquid carbon dioxide), an extraction
thimble, a restriction device, and analyte collection device, temperature control
systems for several zones, and an overall system controller.  The lower left-hand
side of  Figure  1 depicts  a cylinder  of liquid  carbon dioxide,  which  is the
extractant  fluid.   The carbon dioxide is  provided  as a  liquid-gas  mixture.
Because the liquid is  the  more dense  of the two  phases, it  is drawn from the


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bottom of the  tank  with  an eductor tube.  It  is  essential  that  a full-length
eductor tube is  installed  in the cylinder, regardless of the  grade  of carbon
dioxide used.  The  carbon  dioxide remains a liquid throughout the  pumping or
compression  zones,   and  passes  through  small-diameter metal  tubing  as  it
approaches the extraction thimble.  Some systems may include a preheating zone
in front of the extraction zone, so that supercritical temperature, pressure, and
density conditions are applied immediately to the analyte matrix in the thimble.
Analytes are collected just beyond the  exit end  of the restrictor, either 1) on
an impinged surface, such as a small, packed trap, or 2)  in  an empty vial  or a
vial containing an appropriate liquid.

WARNING:   A  safety  feature to prevent over-pressurization  is  required on the
          extractor.  This feature should be designed to protect the laboratory
          personnel   and  the  instrument  from  possible  injuries  or  damage
          resulting  from equipment  failure under  high pressure.

          4.1.1    Extraction vessel  -  Stainless-steel vessel with end fittings
     with 2  jum frits.  Use the  extraction vessel  supplied  by the manufacturer
     of the SFE system being used.  Fittings used for the extraction vessel must
     be capable of withstanding the required extraction pressures.  The maximum
     operating  pressure for most  extractors   is  450 atm.    Check with  the
     manufacturer of the particular extraction  system on the maximum operating
     pressure  and temperature for that system.   Make  sure  that the extraction
     vessels are  rated for  such  pressures  and  temperatures.

          4.1.2    Restrictor -  This  method was  developed   with  continuously
     variable nozzle  restrictors which do not have a need to  avoid water in the
     sample.  If a fixed restrictor is  used, additional validation must be done
     to verify that water from the sample moisture does not adversely affect GC
     or  GC/MS chromatography.   Indeed,  this  method  depends  upon  continuous
     addition  of enough  water  to  exceed  the  solubility limit  in  water
     supercritical  (and sub-critical)  carbon dioxide fluid.

          4.1.3    Collection device  - This method is based on a solid trap used
     at both sub-ambient and above ambient temperatures for different sub-sets
     of the  method.   However, data are  also presented on the use  of a liquid
     trap  (see Sec.  9.0).

                   4.1.3.1   When the analytes  are collected  in  solvent,  care
          must be taken in validation of the method, particularly for the first
          eight PAH compounds (Method 8310 elution order) which are often poorly
          recovered  in liquid traps.  The use of a glass wool plug in the inner
          tube of the collection vial improves  recoveries.   Flow must not be so
          high  as  to reduce  the  collection  solvent to  dryness.    A  15-mL
          collection solvent volume  is  recommended.

                   4.1.3.2   When the analytes are trapped on  a sorbent material,
          use ODS (Hypersil ODS was used to develop the method performance data
          for  the  solid  sorbent  trap), 30-40  micrometer   particle  diameter
          commonly  used in  solid phase  extraction  (SPE)  cartridges.   Other
          trapping materials have also  been found to provide acceptable results,
          e.g. diol,  however,  if other material is  used it  should demonstrate
          equivalent trapping efficiency to the ODS.


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      4.2   Carbon  dioxide  cylinder  balance  (optional)  -  Balances  from White
Associates, Catalog No.  30,  or Scott Specialty Gases Model  5588D, or equivalent,
can be used to monitor the fluid usage.   Such  a device  is  useful because carbon
dioxide tanks  used  for SFE  are  not  equipped with regulators.  This makes it
difficult to determine when  the tank needs to be replaced.

      4.3   Filter  paper disks to be placed at  both ends of the sample.   Disks may
be  cored   from  Whatman  Qualitative  filter  paper,  Catalog  No.   1003-055,  or
equivalent;  or from  Baxter glass  fiber filter  paper,   0.5  /urn,   Catalog  No.
F232.2-21, or equivalent.


5.0   REAGENTS

      5.1   Carbon  dioxide, C02 -  Either supercritical fluid  chromatography (SFC)-
grade or  SFE-grade  C02  is acceptable for use in SFE.   Aluminum  cylinders are
preferred over steel cylinders.   The  cylinders are  fitted  with eductor tubes or
siphon tubes depending upon  the definition of the supplier.

      5.2   Carbon  dioxide (C02)  for cryogenic cooling  - Certain parts of some
models of  extractors  (i.e.,  the high-pressure pump head  and the  analyte trap)
must be cooled  during  use.  The carbon dioxide  used for this purpose must be dry,
and should be supplied in tanks with full-length eductor  tubes.

      5.3   Modifiers  (also  called co-solvents)  were  added to  the  bulk C02
extraction fluid through the use of a separate (stand-alone) HPLC pump with the
output joined  in  a TEE-piece to  the flowing carbon dioxide  stream  after the
carbon dioxide pump  but  before the extraction vessel.  The  modifier solvents are
methanol,  water, and methylene chloride  (HPLC grade),  forming extraction fluid
mixtures  of  95/1/4  (v/v/v)  C02/methanol/water  for HPLC  analysis  and  95/1/4
(v/v/v) C02/methanol/methylene chloride in the case where  GC or GC/MS was used
for the analytical measurement.   There  are concerns about  the 4% water modifier
leaving residual  water  in the  collection trap  that could  have a detrimental
effect  on  the gas  chromatographic separation.    Hence,   the  extraction  fluid
composition  of  95/1/4 (v/v/v)  C02/water/methanol  should  be  altered  to  95/1/4
(v/v/v) C02/methylene chloride/methanol  - with some of the other  parameters in
the SFE method modified slightly as described in Section  7.0.

      5.4   Reconstitution  solvents - The reconstitution solvents dispensed by the
SFE instruments using  solid phase trapping  may  be the  same  material used for
liquid trapping.  This method was developed only with sub-ambient solid trapping.
These same  solvents were used  to  prepare the internal and  external standard
solutions.  A 50/50  (v/v) mixture of acetonitrile/tetrahydrofuran (THF) was used
when HPLC analysis was chosen: both were HPLC grade.   A 75/25 (v/v)  mixture of
methylene chloride/isooctane was used when GC/MS was chosen for the  analytical
measurement.  In addition, data  from  a different laboratory using a liquid trap
are referenced in Sec. 9.3.

      5.5   Internal  standards  - The  recommended   internal  standard  for  HPLC
analysis is biphenyl.   Prepare a stock  solution at  a concentration of 20 g/L in
a 50/50 (v/v)  acetonitrile/THF  mixture.   The internal  standards  specified in
Method 8270 may be used for GC/MS analysis.
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     5.6   Surrogates  -  Recommended  surrogates  are bromobenzene (early eluter)
and p-quaterphenyl (late eluter available from ChemService, West Chester, PA).
Prepare  a stock  solution  at  a  concentration of  10  g/L in  a 50/50  (v/v)
acetonitrile/THF mixture.  Apply 150-/iL aliquots to the  soil samples within the
extraction vessels at the exit end  of the flow-through vessels.   It  has been
observed that very small  volumes (10 pi) of a concentrated  surrogate mixture
(100-1000 g/L) often gave  poor recoveries while adding  larger volumes of more
dilute surrogate solution to the sample matrix achieved the expected recoveries.

     5.7   Copper  powder (electrolytic  grade)  - Added to samples which contain
elemental sulfur.  It is pretreated  by  sequentially rinsing 20 g with 150 mL of
organic-free reagent  water, 150 ml of acetone, 150  ml  of  hexane, and then drying
in a rotary evaporator.   The powder is then kept under argon until used.  Copper
powder must have a shiny bright appearance to be effective.  If it has oxidized
and turned dark it should not be used.

     5.8   Sodium  sulfate, anhydrous (12-60 mesh),  Baker  Analyzed or equivalent.


6.0  SAMPLE  COLLECTION,  PRESERVATION,  AND HANDLING

     6.1   See the introductory material to this Chapter, Organic Analytes, Sec.
4.1.

     6.2   Solid samples for this procedure should be collected and stored  as any
other solid samples containing semivolatile organics.


7.0  PROCEDURE

     7.1   Sample  handling - Decant and discard any  water  layer on  a sediment
sample.  Mix the sample  thoroughly,  especially  composited samples.  Discard any
foreign objects such as pieces of wood, glass,  sticks, leaves and rocks.

     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
separate portion  of sample  for this determination  should be weighed out at the
same time as the  portion  used  for analytical  determination.   Also,  a moisture
content in the sample  between 10  - 50% for the GC/MS extraction method, provided
the  best extraction  efficiency  for   the procedure   as  written.   Therefore,
determination of % moisture is necessary in this case.

WARNING:   The drying oven  should be contained in a hood  or  vented.  Significant
           laboratory  contamination  may  result  from  a heavily  contaminated
           hazardous waste sample.

           7.2.1    Immediately  after weighing the  sample for extraction, weigh
     an additional 5 -  10 g of the sample into  a tared crucible.  Determine the
     % dry weight of the sample by drying overnight at 105'C.  Allow to cool in
     a desiccator before weighing.
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          7.2.2    Calculate  the  % dry  weight  as  follows:

                     -.  ,     ...   g of dry sample   ,nn
                     % dry weight =	— x 100
                                      g of sample


     7.3  Safety considerations  -  Read Sec. 11.0 "Safety" before attempting to
perform this procedure.

     7.4  Sample grinding  and  homogenization.

NOTE:  Sample grinding  is  a  critical step in  the SFE process.   The soil/solid
       must  be a fine  particle to  ensure  efficient extraction.

          7.4.1    Mix  at  least  100  grams of sample  with an equal  volume of
     carbon  dioxide solid  "snow"  prepared from  the extraction  grade  carbon
     dioxide.  Place this in a small  food-type chopper,  and grind for about one
     minute.  Place the chopped  sample on a clean surface and allow the carbon
     dioxide to sublime  away.  As soon as the sample appears free-flowing and
     without  the   solid  carbon  dioxide,  weigh   the  sample  and  place  in  the
     extraction vessel.    This procedure will ensure  the homogeneity  of  the
     sample without loss of the volatile analytes and also retains the original
     moisture content  of the sample.

          7.4.2    Weigh  2.0   to 3.0  g  of  the  homogenized  sample   into  a
     pre-cleaned aluminum  dish.   (Up to  10  g  of  sample can be  extracted using
     the  conditions  outlined in  this procedure.)   If  sample moisture content
     exceeds 50%,  add  a  plug  (1  -  2  g)  of anhydrous sodium sulfate (Sec. 5.8)
     next to the frit in the extraction vessel.   Do not  add any drying agent of
     any  kind directly to  the  sample.  This method depends upon the controlled
     addition  of  water  throughout  the   procedure.   Any  drying  agents  will
     interfere with the process.

          7.4.3    For  samples known to  contain  elemental sulfur,  use  copper
     powder  (electrolytic grade) to remove the dissolved sulfur from the sample
     and carbon dioxide eluant.  The copper powder (1 to 2 grams per sample) can
     be packed in  a separate vessel between the extraction vessel  and the nozzle
     (restrictor)  or  better, mixed with  the  sample in  the  extraction  vessel
     itself.   Alternatively,  a  plug of  copper  powder  may  be  placed  in  the
     extraction vessel beyond  the  sample  before  the exit-frits.

          7.4.4    Transfer half  of the weighed sample to the extraction vessel.
     Add  150 (j,L of surrogate solution  to  the  sample in  the vessel and then add
     the remainder of the  sample material.  To ensure efficient extraction, it
     is very important that  the  extraction  vessel  be completely  full  to avoid
     any dead volume.  If any dead volume exists,  fill the space with an inert,
     porous material,  e.g., pre-cleaned  Pyrex® glass wool, Celite®, etc.

     7.5  Sample  extraction -  This section  contains  recommended  extraction
parameters for both HPLC and GC  (including GC/MS) analyses.

NOTE:  The C02/modifiers used for GC  or GC/MS  analysis extract more efficiently
       when  the  soil  moisture content  is between 10  to 50%.    If  the  sample


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  content is less than 10%,  add 0.5 ml of water per gram of sample  to  the
  sample before placing it in the extraction vessel.

     7.5.1   The following conditions for Step  1  (collection  of  the more
volatile PAHs)  are grouped according to function.

             7.5.1.1   Extraction

             Pressure:                         1750  psi  (120 bar)
             Density:                          0.30  g/mL
             Extraction chamber temperature:   80°C
             Extraction fluid composition:     C02
             Static equilibration time:        10  minutes
             Dynamic extraction time:          10  minutes
             Extraction fluid flow rate:       2.0  mL/min

     Resultant  thimble-volumes-swept = 9.1 (this is  equivalent to 20 ml of
     liquid carbon dioxide at  a reference temperature of  4.0°C, density
     0.96 g/mL  or 19.2 g of carbon dioxide).

             7.5.1.2   Collection  (during extraction)

             Trap packing:                 ODS
             Trap temperature:             -5°C
             Nozzle temperature:           80°C (variable restrictor)

             7.5.1.3   Reconstitution  (of collected  extracts)

             Rinse solvent for HPLC:       50/50 (v/v) THF/acetonitrile
             Rinse solvent for GC:         75/25 (v/v) CH2Cl2/isooctane
             Collected fraction volume:    0.8 ml
             Trap temperature:             60°C
             Nozzle temperature:           45°C (variable restrictor)
             Rinse solvent flow rate:      1.0 mL/min

     The extract should be properly labeled  with fraction designation  and
     vial number.

     7.5.2   The following conditions for Step  2 (collection of the  lesser
volatile PAHs)  are grouped according to function.

             7.5.2.1   Extraction  •

             Pessure:                          4900  psi  (338 bar)
             Density:                          0.63  g/mL
             Extraction chamber temperature:   120°C
             Extraction fluid for HPLC:        95/1/4  (v/v/v)
                                               C02/methanol/water
             Extraction fluid for GC:          95/1/4  (v/v/v)
                                               C02/methanol/CH2Cl2
             Static equilibration time:        10  minutes
             Dynamic extraction time:          30  minutes
             Extraction fluid flow rate:       4.0  mL/min


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           Resultant  thimble-volumes-swept = 25  (equivalent to 120 ml of liquid
           carbon  dioxide  at reference temperature of 4.0°C,  density 1.06 g/mL
           or  127  g of carbon  dioxide).

                   7.5.2.2  Collection (during Extraction)

                   Trap packing:                     ODS
                   Trap temperature:                 80°C
                   Nozzle  temperature:               80°C (variable restrictor)

                   7.5.2.3  Reconstitution (of collected extracts) - none.

           7.5.3    The following conditions for Step 3 (final  sweep of modifiers)
      are grouped  according  to function.

                   7.5.3.1  Extraction

                   Pressure:                        4900 psi  (338 bar)
                   Density:                          0.63 g/mL
                   Extraction  chamber temperature:   120°C
                   Extraction  fluid composition:     C02
                   Static  equilibration time:        5 minutes
                   Dynamic extraction time:          10 minutes
                   C02 flow  rate:                    4.0 mL/min

           Resultant  thimble-volumes-swept  = 8 (equivalent to 40 mi of liquid
           carbon  dioxide  at reference temperature of 4.0°C,  density 1.06 g/mL
           or  42.4 g  carbon  dioxide).

                   7.5.3.2  Collection (during Extraction)

                   Trap packing:                     ODS
                   Trap temperature:                 80°C
                   Nozzle  temperature:               80°C (variable restrictor)

NOTE:   All three steps consume a total of 188.6 g of carbon dioxide.

                   7.5.3.3  Reconstitution (of collected extracts)

                   Rinse solvent  for  HPLC:           50/50 (v/v) THF/acetonitrile
                   Rinse solvent  for  GC:             75/25 (v/v) CH2Cl2/isooctane
                   Collected fraction volume:        0.8 mL
                  Trap temperature for HPLC:        80°C
                  Trap temperature for GC:          60°C
                   Nozzle  temperature:               45°C (variable restrictor)
                   Rinse solvent  flow rate:          1.0 mL/min

           The extract should  be properly labeled with fraction destination and
           vial number.

           7.5.4   The combined extract volumes consist of 1.6 mL.  The extract
      is ready for the analysis by Methods 8310  (HPLC),  8270 (GC/MS),  or 8100
      (GC/FID).    Note that there  are no  performance data  available  on the


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     analysis of  SFE  PAH  extracts  by  Method  8100.   Furthermore,  the procedure
     is more susceptible  to  interferences in complex samples.

NOTE:   If  a fixed  restrictor  and liquid  trapping  are  used,  a  restrictor
       temperature in the range of 100 to 150°C is recommended.

           7.5.5   When GC or GC/MS analysis procedures are to be used and sulfur
     interference becomes apparent at  time of analysis, Method 3660 may be used
     to remove the sulfur from the extract.

     7.6   SFE System  Maintenance

           7.6.1   Depressurize   the   system  following   the   manufacturer's
     instructions.

           7.6.2   After   extraction   of  an  especially  "tarry"  sample,  the
     end-frits of the extraction vessel may require replacement if not extensive
     cleanup to ensure adequate extraction fluid flow without excessive pressure
     drop due to the  system plumbing.  In addition,  very fine particles may clog
     the  exit  frit requiring  its  replacement.  By  placing a layer  of  inert
     material such as Celite® or sea  sand above the sample  prior  to  the exit
     frit  (and placing disks  of filter paper on  top of the inert material), this
     maintenance  may  be delayed for some period of operation.

           7.6.3   Clean the extraction vessel after each extraction  sample.  The
     cleaning procedure  depends  upon  the type  of sample.   After  removing the
     bulk  of the  extracted sample  matrix from  the  extraction vessel,  the cell
     and  end-frits should be scrubbed with  an aqueous detergent,  water  and a
     stiff brush.  Placing the parts in an ultrasonic bath with a warm detergent
     solution is  very helpful.  The parts should be rinsed with reagent water.
     The  ultrasonic  bath  treatment should  then be  repeated with  either methyl
     alcohol or acetone or both followed by  air drying.


8.0  QUALITY CONTROL

     8.1   Refer  to  Chapter One and Method  8000 for specific  Quality Control
procedures and to  Method 3500 for sample preparation quality control procedures.

     8.2   Each  time   samples  are  extracted,  and when  there is  a change  in
reagents, a reagent blank should be prepared and analyzed for the compounds of
interest as a safeguard against chronic laboratory contamination.   Any reagent
blanks, matrix spike samples,  or replicate samples should be  subjected to exactly
the same analytical  procedures (Sec. 7.4) as those used on actual  samples.

     8.3   All instrument operation conditions and parameters should  be recorded.


9.0  METHOD PERFORMANCE

     9.1   Using Method 8310,  an HPLC  method  with either UV/Vis or fluorescence
detection,  expected  minimum  detection limits  are  between  0.010 -  1.00  mg/Kg
depending  upon  the  actual analyte  and  detector.   The  estimated  quantitation
limits (EQLs) would range  from 0.10 - 10 mg/Kg depending on analyte and detector.

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Using  Method 8270,  a  GC/MS  method,  expected minimum  detection  limits  are
approximately 0.70 mg/kg.   The  estimated quantitation limits (EQLs) for GC/MS
would be approximately 7 mg/Kg.  The MDLs and  EQLs listed above are based on a
3-g sample.

      9.2   Single  laboratory precision and accuracy data  based  on this method
(using a variable restrictor and solid  trapping material)  were obtained for the
method analytes by the extraction of two reference materials (one a  lake sediment
from Environment Canada  and the other a  marine sediment from the National Science
and Engineering  Research  Council of Canada, both  naturally  contaminated with
PAHs).  The SEE instrument used for  these  extractions was a  Hewlett-Packard Model
7680.   Analysis was  by  GC/MS.   The data  were  taken from Reference 2.  Average
recoveries from six replicate extractions ranged from 85 to 148%  (overall average
of 100%) based on the certified  value  (or a Soxhlet value if a certified value
was  unavailable  for a  specific  analyte)  for the   lake  sediment.   Average
recoveries  from  three replicate extractions ranged  from 73 to  133% (overall
average of 92%) based on the certified  value for the marine sediment.  The data
are found  in a table in Method 8270.

      9.3   Single  laboratory precision  and accuracy data based  on  the use of a
fixed restrictor  and liquid trapping  were  obtained  for  twelve of  the method
analytes by the extraction of a certified  reference material obtained  from Fisher
Scientific  (a soil naturally contaminated with  PAHs).   The SFE instrument used
for these extractions was a Dionex Model 703-M.   Analysis was by  GC/MS.  The data
were taken from Reference 4.  Average recoveries from four  replicate extractions
ranged from 60 to 122%  (overall  average  of  89%) based on  the certified value.
Following  are the instrument  conditions  that were  utilized  to  extract a 3.4 g
sample:   Pressure -  300 atm; Time - 60  min.; Extraction  fluid - C02; Modifier -
10% 1:1 (v/v) methanol/methylene chloride; Oven temperature - 80°C; Restrictor
temperature - 120°C;  and, Trapping  fluid -  chloroform (methylene  chloride has
also been  used).  The data are found in  a table in Method 8270.

      9.4   Single  laboratory precision  and accuracy data  based  on this method
(using a variable restrictor and solid  trapping material)  were obtained for the
method analytes  by  the  extraction  of  a  well-characterized  reference material
naturally contaminated with  PAHs.  The SFE instrument used  for these extractions
was a Hewlett-Packard Model 7680.   Analysis was by HPLC.   The  data were taken
from Reference 3.  Average  recoveries  from  three  replicate  extractions ranged
from 85.7 to 153%  (overall average of 107%) based on the Soxhlet  value.  The data
may be presented in  a future revision of Method 8310.


10.0  REFERENCES

1.    D.R.  Gere,  C.R.  Knipe,  P.  Castelli, J. Hedrick,  L.G. Randall,  J. Orolin,
      H. Schulenberg-Schell, R. Schuster,  H.B. Lee,  and L.  Doherty  "Bridging the
      Automation Gap between Sample  Preparation  and Analysis:  SFE, GC, GC/MSD and
      HPLC  Applied to Environmental  Samples", J. Chromatographic  Science 31(7)
      245-258 (July 1993).

2.    H.B.  Lee, T.E.  Peart, R.L.  Hong-You, and D.R.  Gere,  "Supercritical  Carbon
      Dioxide Extraction of Polycyclic Aromatic  Hydrocarbons from Sediments", J.
      Chromatography, A 653  83-91 (1993).


                                   3561 -  11                         Revision 0
                                                                  January 1995

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3.    Personal   communication  from  H.   Schulenberg-Schel1,   Hewlett-Packard
      Waldbronn  Site,  #8  Hewlett-Packard  Strasse, D7517 Waldbronn  2,  Germany.

4.    Personal  communication from Sue  Warner,  EPA  Region  3,  Central Regional
      Laboratory,  839  Bestgate  Road, Annapolis, MD  21401.

5.    W. Beckert,  "An Overview of the EPA's Supercritical Fluid Extraction (SFE)
      Methods  Development Program," ACS   Symposium:   Supercritical  Fluids  in
      Analytical Chemistry sponsored by the Division of Analytical Chemistry at
      the  201st  National  Meeting of the American Chemical  Society, Atlanta, GA,
      April  14-19,  1991.

6.    V.  Lopez-Avila,  N.S.  Dodhiwala,  and  J.  Benedicto,  Evaluation of Various
      Supercritical  Fluid  Extraction   Systems for Extracting  Organics  from
      Environmental  Samples,  Final Report  for Work Assignment 1-1, EPA Contract
      68-C1-0029,  Environmental Monitoring Systems Laboratory, Office of Research
      and  Development,  U.S.  Environmental  Protection Agency,  Las  Vegas,  NV
      89119,  February,  1992.

7.    S.  Bowadt  and  B.  Johansson,  "Analysis  of  PCB's  in  Sulfur-Containing
      Sediments  by Off-line  SFE", Analytical Chemistry, 66,  No. 5, 667, (1994).


11.0  SAFETY

      11.1  When  liquid carbon dioxide  comes in contact with skin, it can cause
"burns" because of its low temperature  (-78°C).  Burns are  especially severe when
C02 is modified with organic liquids.

      11.2  The extraction fluid, which may  contain a modifier, usually exhausts
through an exhaust  gas  and  liquid  waste  port on the  rear  of  the panel  of the
extractor.   This  port must  be connected  to  a  chemical  fume hood  to prevent
contamination of  the laboratory atmosphere.

      11.3  Combining  modifiers   with   supercritical   fluids    requires   an
understanding and evaluation of the potential chemical interaction between the
modifier and the  supercritical fluid,  and between the supercritical fluid or
modifier and the  analyte(s) or matrix.

      11.4  When  carbon dioxide is used for cryogenic  cooling,  typical coolant
consumption is 5  L/min,  which  results  in  a carbon dioxide level  of 900 ppm for
a room of 4.5 m x 3.0 m  x 2.5  m, assuming  10 air exchanges  per hour.
                                   3561  -  12                         Revision 0
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                                         Pit I HOD  3561

SUPERCRITICAL FLUID EXTRACTION  OF POLYNUCLEAR  AROMATIC  HYDROCARBONS
                                      7 1 Use appropriate
                                       •ample handling.
                                      7.2 Determine aample
                                         % dry weight.
                                        7.4.1 Grind 4
                                         homogenize
                                      •ample with dry ice.
                                       7.4.2 We.gh 2-3 g
                                          of urn pie.
                                                             7 4.3 Add copper
                                                             powder to •ample.
                                        7 4.4Tranefer
                                      weighed temple to
                                      extraction veeaei and
                                        add aurrogatea.
                                         7.6  Sample
                                          extraction.
                                      7.6.1 Collection of
                                      more volatile PAHa.
                                       7.6.2 Collection of
                                       non-volatile PAHa.
                                      7.6.3 Final modifier
                                           •weep.
                                      7 6.4 Combine extract*
                                      and perform determin-
                                      ative method
                                       HPLC (Method 8310)
                                      GC/M8 (Method 8270)
                                      or GC (Method 6100.)
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                                 METHOD 3585

                     WASTE DILUTION FOR VOLATILE ORGANICS
1.0  SCOPE AND APPLICATION

     1.1  This method describes a solvent dilution of a non-aqueous waste sample
prior to direct injection analysis.   It  is designed for use in conjunction with
GC  or  GC/MS  analysis  of wastes  that may  contain  organic  chemicals  at  a
concentration greater than 1 mg/kg and that are  soluble in the dilution solvent.
Method 3585 has adequate sensitivity  to determine the regulatory concentrations
of the Toxicity Characteristic (TC)  Rule.

     1.2  This  method may be  used with n-hexadecane for direct  injection  of
target volatiles in oily matrices.

     1.3  Use  of a 1  -  2 /iL injection of a 1:1 dilution can be used to provide
detection limits of 0.5  ppm for volatile target  analytes with a sensitive GC/MS.

     1.4  This  method  is  restricted to  use  by or  under  the  supervision  of
trained  analysts.    Each  analyst  must demonstrate  the  ability  to  generate
acceptable results with this method.


2.0  SUMMARY OF METHOD

     2.1  Highly contaminated or highly complex samples may be diluted prior to
analysis for volatiles using direct  injection.

     2.2  One gram of sample is weighed into a  capped tube or volumetric flask.
The sample is diluted to  2.0  -  10.0  mL  with n-hexadecane  or  other appropriate
solvent.

     2.3  Diluted  samples  are  injected  into the GC or GC/MS for analysis.


3.0  INTERFERENCES

     3.1  Use  of  a  direct injection  procedure will  result  in  considerable
contamination  of  injection  ports,   injection  port  liners,   GC  columns,  and
detectors. A Pyrex® wool plug  should  be placed into the injection port liner and
the liner should be changed after every 12 hours of sample analysis.

     3.2  The solvent used for waste  dilution may contain volatile contaminants
that could interfere with analyses.

          3.2.1    n-Hexadecane elutes after target volatiles.  However, volatile
     impurities  in n-hexadecane  may  interfere with analyses.

          3.2.2    Each  lot of n-hexadecane (or  any other  solvent  used  for
     dilution) must  be  analyzed  for  impurities prior to use.
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     3.3  The presence of methanol  and other oxygenated solvents in samples may
lead to baseline humps that interfere with qualitative and quantitative analysis
of early eluting target analytes when direct  injection is employed.


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 -  2- or 10-mL  (optional).

     4.9  Direct  injection  liner (HP catalogue #18740-80200 or  equivalent)  -
Modify with a 1-cm plug of Pyrex® wool  placed  approximately  50-60 mm down the
length of the  injection port (towards the oven).   A  0.53 mm ID column is mounted
1 cm  into the liner from  the  oven  side  of  the injection port,  according to
manufacturer's specifications.   Following is an  example of the placement of the
glass wool in the liner.
                        ptu.ro.
                          Figure  1   Modified  Injector



5.0  REAGENTS

     n-Hexadecane,  C16H34  -  Pesticide quality or equivalent.


6.0  SAMPLE  COLLECTION, PRESERVATION, AND  HANDLING

     See the introductory material  to this  chapter, Organic Analytes, Sec. 4.1.


7.0  PROCEDURE

     7.1   Samples  consisting of  multiple phases must  be prepared by the phase
separation method (Chapter Two) before extraction.   The oil  phase  is prepared as


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outlined below.  An aqueous phase is prepared and analyzed following the guidance
in Method 5030.

     7.2  The  sample dilution  may  be performed in  a 2- or  10-mL  volumetric
flask.   If disposable glassware  is preferred, the 10-dram vial may be calibrated
for use.  Pipet  2.0 ml of methanol  into  the vial  and mark the  bottom of the
meniscus.  Discard this solvent.  Dry the vial.

     7.3  Transfer  approximately 1  g of  the oil  phase of the  sample to a vial
or volumetric flask  (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  Immediately  dilute  to volume with n-hexadecane or other appropriate
solvent.  The choice  of  solvents  is dependent on  the nature  of  the target
analytes.  n-Hexadecane is late  eluting  and,  therefore, presents  no solvent
interference for the majority of volatile organics.  An early eluting solvent,
e.g., pentane or hexane, may  be chosen if  the  target analytes  are mid to late
eluting.

     7.5  Add surrogate spiking solution, if required, for the analytical method
to be employed.

     7.6  Cap and shake the sample  for 2 minutes.

     7.7  The extract  is  ready for  analysis by GC  Methods 8015  or 8021,  or by
GC/MS Method 8260.


8.0  QUALITY CONTROL

     8.1  Refer  to  Chapter One, Method 8000,  and  the  analytical  method  to be
employed, for specific quality control procedures.

     8.2  Each  time samples  are prepared  and  analyzed,  and  when there  is  a
change  in reagents,  a reagent  blank  should  be prepared  and analyzed  for the
compounds of interest as a safeguard against chronic  laboratory contamination.
Any  reagent  blanks,  matrix  spike  samples, or replicate  samples   should  be
subjected to  exactly the  same  analytical  procedures as  those used  on actual
samples.

     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  fewer samples must contain:  a reagent
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.

     8.4  Surrogates should  be  added to  all  samples  when  specified in  the
appropriate  determinative  method.
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9.0  METHOD PERFORMANCE

     Refer to the determinative methods for performance data.


10.0 REFERENCES

     1.   Marsden,  P.J.,  Colby,   B.N.,  and  Helms,   C.L.,  "Determining  TCLP
          Volatiles  at Regulatory  Levels  in Waste  Oil",  Proceedings  of the
          Eighth  Annual  Waste Testing and Quality Assurance  Symposium, July,
          1992.
                                   3585 - 4
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         METHOD 3585

WASTE DILUTION FOR VOLATILES
         Is
       sample
     multiphase?
     Oil phase
     or aqueous
     phase to be
     analyzed?
     See Phase
 Separation Method,
    Chapter Two.
Prepare and analyze
 by Method 5030.
  7.2 - 7.4 Perform
sample dilution with
 appropriate  solvent.
 7.5 Add surrogate
 spiking solution if
    required by
   determinative
      method.
7.6 Cap and shake
sample and solvent
  for 2 minutes.
      Perform
   determinative
      method.
           3585 - 5
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                                  METHOD  5000

               SAMPLE  PREPARATION  FOR  VOLATILE ORGANIC  COMPOUNDS
1.0  SCOPE AND APPLICATION

      1.1   Method  5000 provides general  guidance  on the  selection  of sample
preparation methods (purge-and-trap, extraction, azeotropic distillation, vacuum
distillation,  dilution,   headspace,  etc.)  for  introducing  volatile  organic
compounds into a detection device (outlined in the determinative methods).  The
matrices include aqueous,  soil/sediment, solid waste,  organic  solvents, air, and
oily waste.  Other waste  matrices may  be adaptable to one  or more of the listed
preparation methods.

      1.2  Method 5000 also  provides specific  information  pertaining to analyte
interferences, preparation  of  calibration  and spiking  standards,  and specific
quality control that should be applied to each preparative method.

      1.3   The following table  is  presented  as a  reference  guide  to  sample
preparation techniques for volatile organic compounds:
               SAMPLE PREPARATION METHODS FOR VOLATILE ORGANICS
Method #
3585
5021
5030
5031
5032
5035
5041
Matrix
Oily waste
Solids
Aqueous
Aqueous
Aqueous & solids
Solids, organic
solvents, oily waste
Air sampled by VOST
Preparation Type
Solvent dilution
Automated
headspace
Purge-and-trap
Azeotropic
distillation
Vacuum
distillation
Closed system
Purge-and-trap
Purge-and-trap
from VOST
Analytes
VOCs
VOCs
VOCs
Polar VOCs
Non polar and
polar VOCs
VOCs
Volatile POHCs
       VOCs = Volatile Organic Compounds
       VOST = Volatile Organic Sampling Train
      POHCs = Principal Organic Hazardous Constituents

      1.4  Method 3585 provides guidance  for  dilution  and  direct injection of
oily waste samples  (e.g. waste oil or oily waste  that filters during TCLP sample
preparation) for volatile organic analysis.
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      1.5  The following  table is presented as a reference guide to air sampling
methods found in Chapter Ten that interface with the volatile organic methods:
              AIR SAMPLING  METHODS  FOR  VOLATILE ORGANIC COMPOUNDS
                          FROM CHAPTER TEN OF SW-846
Method #
0011
0030
0031
0040
0100
Sampling Method
Aqueous solution
of DNPH
Resin/charcoal
Resin/Anasorb
747
Tedlar® bag
DNPH coated
silica gel
Sample Preparation
Solvent extraction
Purge-and-trap by
5041
Purge-and-trap by
5041
Direct analysis
with sample loop
Solvent extraction
Analytes
Formaldehyde plus
aldehydes & ketones
Volatile organics
Volatile organics
Volatile organics
Formaldehyde plus
aldehydes & ketones
      DNPH = Dinitrophenylhydrazine
2.0  SUMMARY OF METHOD

      2.1  Method  5000 provides general  information that is common to each of the
methods listed in Sec. 1.0.  Specifically this includes:  interference problems
that are common to any volatile organic sample preparation method; preparation
of  calibration standards,  internal  standards,  surrogate  spikes,  laboratory
control  samples  (LCSs),  and  matrix  spikes;  a  brief summary  of each  of the
methods; and the specific quality control  that should  be applied to each of the
preparative methods.
      2.2
interface
matrices.
  Table  1  provides  guidance on  which  sample  preparation  methods
with each  volatile  organic determinative method,  for a variety  of
3.0  INTERFERENCES

      3.1   Samples requiring  analysis  for volatile organic  compounds  can be
contaminated by diffusion of volatile organics (particularly chlorofluorocarbons
and methylene chloride) through the sample container septum during shipment and
storage.   A field blank prepared  from  organic-free reagent  water and carried
through sampling and subsequent storage and handling can serve as a check on such
contamination.

      3.2   Solvents, reagents, glassware,  and other sample processing hardware
may yield artifacts and/or interferences to sample analysis. All these materials
must be demonstrated to  be free from interferences  under the conditions of the
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analysis  by analyzing  method  blanks.    Specific  selection  of reagents  and
purification of solvents by distillation  in all-glass systems may be necessary.
Refer to each method for specific  guidance on quality control procedures and to
Chapter Four for guidance on the cleaning of glassware.

      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.  Therefore, frequent
bake-out and purging of the entire system may be required.  This is especially
true for purge-and-trap systems which are often subject to such contamination.

      3.4   The  laboratory where  volatile analysis   is  performed  should  be
completely free of solvents.

            3.4.1   Special  precautions must  be taken to  determine  methylene
      chloride.  The analytical  and sample storage area should be isolated from
      all atmospheric sources of methylene chloride, otherwise random background
      levels will result.

            3.4.2  Since methylene chloride will permeate through PTFE tubing,
      all GC carrier gas lines and purge gas plumbing should be constructed of
      stainless steel or copper tubing.

            3.4.3  Laboratory  worker's  clothing  previously exposed to methylene
      chloride  fumes  during  common  liquid/liquid  extraction  procedures  can
      contribute to sample contamination.

            3.4.4   The  presence of other  organic  solvents in  the laboratory
      where volatile organics are analyzed will also lead to random background
      levels and the same precautions must be  taken.

      3.5  Interference  problems specific to the sample preparation methods are
discussed in the individual methods.
4.0  APPARATUS AND MATERIALS

      Refer to the specific method of interest for a description of the apparatus
and materials needed.
5.0  REAGENTS

      5.1  Refer  to  the  specific method of interest for  a  description  of the
solvents and other reagents needed.

      5.2  Organic-free reagent water.   All  references  to water in this  method
refer to organic-free reagent water as defined in Chapter One.

      5.3   Stock standards  for spiking  solutions  -  Stock solutions may  be
prepared from pure standard materials or purchased as certified solutions.  The
stock solutions used for the calibration standards are acceptable (dilutions must
be made in  a water miscible solvent) except for the quality control check sample

                                   5000 -  3                          Revision 0
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stock concentrate which must be prepared independently to serve as a check on the
accuracy of the calibration solution.

            5.3.1   Purgeable  stock  standards  -  Prepare  stock standards  in
      methanol using assayed liquids  or gases, as  appropriate.   Because of the
      toxicity  of  some  of  the  organohalides,   primary  dilutions  of  these
      materials should be prepared in a hood.

                  5.3.1.1  Place  about  9.8  ml of  methanol in a  10  ml,  tared,
            ground-glass-stoppered volumetric  flask.  Allow the flask to stand,
            unstoppered,  for about 10 min or until all  alcohol-wetted surfaces
            have dried.   Weigh the flask to the nearest 0.0001  g.

                  5.3.1.2  Using a 100 jtiL syringe, immediately add two or more
            drops of assayed reference material to  the flask, then reweigh.  The
            liquid must fall directly  into  the  alcohol  without  contacting the
            neck of the flask.

                  5.3.1.3   Reweigh,  dilute to volume, stopper,  then mix  by
            inverting the flask several times.  Calculate  the concentration in
            milligrams per  liter  (mg/L) from the net  gain  in  weight.   When
            compound purity is assayed to be 96% or greater,  the weight may be
            used without  correction to  calculate the concentration of the stock
            standard.  Commercially prepared stock standards may be used at any
            concentration if they are  certified  by the manufacturer  or  by an
            independent source.

                  5.3.1.4    Transfer  the  stock   standard  solution  into  a
            Teflon®-sealed screw-cap  bottle.   Store, with minimal headspace, at
            -10°C to -20eC and protect from light.

                  5.3.1.5  Refer to the determinative  method for holding times
            of the stock solutions.

            5.3.2  Non-purgeable stock standards -  Non-purgeable stock solutions
      may be  prepared  from  pure standard materials or  purchased as certified
      solutions.   Refer to the individual  determinative method  for additional
      guidance.

      5.4  Surrogate standards - A surrogate standard (i.e., a compound that is
chemically  similar to  the  analyte  group  but  not expected  to  occur  in  an
environmental sample) should be added to each  sample, blank, laboratory control
sample and  matrix spike  sample just prior  to extraction  or processing.   The
recovery of the surrogate standard is  used to monitor for unusual matrix effects,
gross  sample  processing  errors,  etc.    Surrogate  recovery  is  evaluated  for
acceptance by  determining whether the  measured  concentration  falls within the
acceptance limits.

            5.4.1  Recommended surrogates for  certain analyte groups are listed
      in Table 2.  For methods where  no recommended surrogates are listed, the
      laboratory  is  free  to  select  compounds  that  fall within  the definition
      provided above.  Even compounds that are on the method analyte  list may be
      used  as  surrogates  as long as  historical data  are available to ensure


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      their absence at a given site.  Normally one or more surrogates are added
      for each analyte group.

            5.4.2   Prepare  a  surrogate spiking  concentrate  by mixing  stock
      standards  prepared  above  and  diluting with  a water-miscible  solvent.
      Commercially-prepared spiking solutions are acceptable.  The concentration
      for volatile organic analysis by purge-and-trap should be such that a 10
      H\.  aliquot  when  added  directly  to  5  ml  of  sample  provides  the
      concentrations listed in Table 2.  The spiking  volumes are normally listed
      in each  preparation  method.   Where concentrations are not  specified,  a
      concentration in the sample of 10 times the estimated quantitation limit
      is recommended.   If  the surrogate quantitation  limit  is unknown,  the
      average  estimated  quantitation  limit of  method  target  analytes  may be
      utilized to estimate a surrogate quantitation limit.

      5.5  Matrix spike standards - Prepare a matrix  spike concentrate by mixing
stock standards  as prepared  above  and  diluting  with a  water miscible solvent.
Commercially prepared spiking solutions  are acceptable.   The stock standards are
to be independent of the calibration standard.

            5.5.1   A few methods  provide  guidance  on  concentrations  and  the
      selection of compounds for matrix spikes  (see  Table 3).  For example,  the
      recommended purgeable matrix  spiking solution for Methods 8021  and 8260 is
      as follows:   Prepare a  spiking  solution  in methanol that  contains  the
      following compounds at a concentration of 25 mg/L.

                        Purqeable orqanics

                        1,1-Dichloroethene
                        Trichloroethene
                        Chlorobenzene
                        Toluene
                        Benzene

            5.5.2  For methods with no  guidance,  select five or more analytes
      (select  all  analytes  for methods with five  or less) from  each  analyte
      group for use in a spiking solution.  Where matrix  spike concentrations in
      the  sample are  not  listed  it  should  be  at or  below  the  regulatory
      concentration or,  1 to 5 times higher than the background concentration,
      whichever, concentration would be larger.

      5.6  Laboratory control  spike standard -   Use the matrix  spike standard
prepared in Sec.  5.5  as  the spike standard for the laboratory  control  sample
(LCS).  The LCS should be  spiked  at the  same concentration as the matrix spike.


6.0  SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

      See Chapters Two and Four for guidance on sample collection, preservation,
and handling.
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7.0  PROCEDURE

      Water, soil/sediment,  sludge,  and waste samples requiring  analysis  for
volatile organics are extracted and/or introduced into the GC and/or GC/MS system
by various methods (see Table 1).  This  manual contains method choices that are
dependent  on  the  matrix,   the   physical  properties  of  the  analytes,  the
sophistication and cost of equipment  available to  a  given  laboratory,  and the
turn-around time  required  for sample preparation.   The  following  is  a  brief
summary of each of the sample preparation/introduction techniques:

      7.1  Method 3585:  This method describes a solvent  dilution (hexadecane)
technique followed  by  direct injection  into a sensitive GC/MS  system  for the
analysis of volatiles  in oily waste.  Method  3585  has  adequate  sensitivity to
determine the regulatory concentrations for TCLP oily waste that filters.  Direct
injection is  very simple,  provides  quick  turnaround and  requires  no  special
hardware.  However,  the GC/MS system must be quite sensitive, has the potential
for instrument contamination  and is more subject  to matrix difficulties.  Method
3585 lends itself best when performing analysis  for small  groups of samples.

      7.2  Method 5021:  This method describes an automated headspace analysis
for soils  and  other solid matrices.   The solid sample  is placed  in  a  tared
septum-sealed vial at time of sampling.   A matrix modifier is added containing
internal and/or surrogate standards.  The sample vial is placed into an automated
equilibrium headspace sampler which automatically equilibrates the sample at 85"C
and mixes  it  by mechanical   vibration.    A  measured  volume  of headspace  is
automatically introduced into a GC or GC/MS system for  volatile organic analysis.
The method is automated and causes no equipment contamination, however, it does
require a relatively expensive automated headspace device.

      7.3  Method 5030:  This method describes the technique of purge-and-trap
for the  introduction  of purgeable  organics into  a  gas  chromatograph.   This
procedure  is applicable for use with  aqueous   samples  and  aqueous  miscible
extracts prepared by Method 5035.  An inert gas  is bubbled through the-sample,
which will  efficiently  transfer the purgeable organics from  the aqueous phase to
the vapor phase.   The vapor phase  is swept through  a sorbent  trap where the
purgeables  are  trapped.   After purging  is  completed,  the trap  is  heated and
backflushed  with  the  inert  gas   to   desorb   the   purgeables  onto   a  gas
chromatographic  column.    Purge-and-trap  is  easily  automated,   provides  good
precision and accuracy, but,  is  limited  to  analytes that purge efficiently from
water  and  requires expensive purge-and-trap  devices.   The system  is easily
contaminated  by  samples containing  compounds at  mg/L concentrations.   This
procedure may be used  for the analysis of gasoline in various aqueous matrices.

      7.4   Method  5031:   This  method  describes  an  azeotropic  distillation
technique for the analysis  of nonpurgeable, water soluble,  volatile organics in
aqueous samples.   The sample is distilled in an azeotropic distillation apparatus
(guidance for an optional micro-distillation apparatus is also included) followed
by direct aqueous injection  from  the analyte  enriched  distillate into  a  GC or
GC/MS system.  The method is not readily  automated except for the  GC/MS analysis,
requires a  1 hour distillation and covers a limited group of analytes.

      7.5    Method  5032:    This  method  describes   a closed  system  vacuum
distillation  technique  for  the  analysis  of  volatile  organics  including
nonpurgeable, water soluble,  volatile organics in aqueous samples.  The sample

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is  introduced   into  a  sample flask  which  is  then  attached  to  the  vacuum
distillation apparatus.  The sample chamber pressure is reduced and remains at
approximately 10 torr  (vapor  pressure  of water) as water  is  removed  from the
sample.  The vapor is passed over a condenser coil  chilled to a temperature of
-10eC or less, which results in the condensation of water vapor.  The uncondensed
distillate is cryogenically trapped  on a section of 1/8  inch  stainless steel
tubing  chilled  to  the temperature  of liquid  nitrogen  (-196°C).   After  an
appropriate distillation period,  which  may  vary  due to matrix or analyte group,
the condensate contained in the cryotrap is thermally desorbed and transferred
to the gas chromatograph using helium carrier gas.  This method very efficiently
extracts  organics  from a  variety of matrices.   The method requires  a vacuum
system, cryogenic cooling, and is not  readily automated,  except for  the GC/MS
analysis.

      7.6  Method 5035:  This method describes a closed-system purge-and-trap for
the analysis of  volatile organics that are purgeable  from a water/soil matrix at
40°C.    It  is  amenable  to  soil/sediment  and  any   solid  waste  sample  of  a
consistency similar to soil.   It differs from the original  soil method in Method
5030 in that a sample  (normally 5 g)  is placed  into  the sample vial at time of
sampling.  The sample remains hermetically sealed from sampling through analysis
as the closed-system purge-and-trap device  automatically adds a measured amount
of organic-free  reagent water  and standards and then performs the purge-and-trap
process.  The method provides more accurate data than  the original method because
the sample container is not opened.   However, it does require a purge-and-trap
device specially modified to  add the water and  standards  without breaking the
hermetic  seal.  It also includes a technique for  the  extraction of oily waste
using methanol.   This procedure may be  used for the analysis  of  gasoline in
various solid matrices.

      7.7  Method 5041:  This method is  applicable  to  the analysis of sorbent
cartridges from  a volatile organic sampling  train (VOST). The sorbent cartridges
are placed in a  thermal desorber  which  in turn is attached to a standard purge-
and-trap device.  Analysis may be by GC or GC/MS

      7.8  Sample analysis -  For samples  requiring  volatile  organic  analysis,
sample handling devices in some  of the methods  described  above are interfaced
directly to a gas chromatograph or gas chromatographic/mass spectrometer system.
A  few  of the sample  preparation methods  require injection  of  an extract  or
distillate into  the GC or  GC/MS.  See Table 1 for more guidance on which sample
preparation methods interface to each determinative  method.


8.0  QUALITY CONTROL

      8.1  Refer to  Chapter  One  and Method  8000 for  specific  quality control
procedures.   Each  laboratory  using  SW-846  methods  should maintain  a  formal
quality assurance program.

      8.2    Initial   Demonstration   of Proficiency  -  Each  laboratory  must
demonstrate initial proficiency with each sample preparation and determinative
method combination it  utilizes,  by generating data  of  acceptable accuracy and
precision for target analytes  in  a clean reference matrix.  This will  include a
combination of the sample preparation method (usually a 5000 series method for
volatile  organics) and the determinative method  (an  8000  series method).   The

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laboratory must  also  repeat the  following  operations  whenever new  staff  are
trained or significant changes in instrumentation are made.

            8.2.1  The reference  samples  are  prepared  from  a  spiking solution
      containing each  analyte  of interest.   The reference  sample  concentrate
      (spiking  solution)  may  be prepared  from pure  standard materials,  or
      purchased  as  certified  solutions.   If  prepared  by the  laboratory,  the
      reference sample concentrate must be made using stock standards prepared
      independently from those used for calibration.

            8.2.2   The  procedure  for preparation  of  the  reference  sample
      concentrate is dependent upon the method  being evaluated.   Guidance  for
      reference sample concentrations  for  certain methods are listed below.   In
      other cases,  the determinative methods contain  guidance  on preparing  the
      reference sample concentrate and the reference sample.  If no guidance is
      provided, prepare a reference sample  concentrate  in methanol.   Spike at
      the concentration the method performance data is  based  on.   The  spike
      volume added to water should not exceed 1 mi/I  so that the spike solvent
      will not decrease extraction efficiency.   If the method lacks performance
      data,  prepare a  reference  standard  concentrate at such  a concentration
      that the spike will provide  a concentration in the  clean matrix that is 10
      - 50 times the MDL for each analyte  in that matrix.

            The concentration  of  the target analytes in the reference sample may
      need to  be adjusted  to  more accurately reflect the  concentrations  that
      will be analyzed in the laboratory.  If the concentration  of an analyte is
      being  evaluated relative  to a  regulatory limit,  see  Sec.  8.3.3  for
      information on selecting an appropriate spiking level.

            8.2.3  To  evaluate the performance of the total  analytical process,
      the reference samples  must  be handled in exactly the same manner as actual
      samples.  Use a  clean  matrix for spiking purposes (one that does not have
      any target or  interference compounds) e.g., organic-free reagent water for
      the water matrix or sand or soil (free of organic interferences) for the
      solid matrix.   Because  of  the volatility of these compounds,  the  spike
      must be  introduced  directly into the matrix  while the  matrix is  in  a
      sealed container (e.g.,  a gas tight  syringe or  purge  device).

            8.2.4  Preparation of reference samples

                  8.2.4.1    When   analyzing  aqueous  samples by purge-and-trap
            Method 5030, prepare  reference sample concentrates  containing each
            target analyte  at  a concentration of 10 mg/L  in methanol.  For water
            samples,  spike  100 ml of  organic-free reagent  water with 200  /uL
            which provides  a  20   p,g/L  concentration  in  the reference sample.
            Quickly transfer the  spiked water  to four, 5-mL gas-tight syringes.
            The  samples  are  ready for  analysis using  Method  5030 and  the
            appropriate determinative method.

                  8.2.4.2  When analyzing  soil or other solid samples by purge-
            and-trap by Method 5035,  add 10  /iL of reference sample concentrate
            directly to the purge device  as specified  in Sec.  7.0.   For oily
            waste analysis  by  Method 3585 or the high concentration technique in
            Method 5035, add  10  pi of reference sample  concentrate  (dissolved

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      in methanol) directly to the oily waste just prior to the addition
      of the  extraction solvent.  The  concentration in the  oily waste
      should be 10 -  50 times  greater  than  the  determinative  method MDL
      for each analyte.  Prepare four replicates.

            8.2.4.3  When analyzing matrices using equilibrium headspace
      Method  5021,  azeotropic  distillation  Method  5031,  or  vacuum
      distillation  by   Method  5032,   prepare   the   reference  sample
      concentrate as  per Sec.  8.2.4.1.  Add sufficient reference sample
      concentrate to the volume of organic-free reagent water specified in
      these methods to provide a concentration in  the water that is 10 -
      50 times greater than the determinative method MDL for each analyte.
      Prepare four replicates.

            8.2.4.4  For methods 8031,  8032, 8315  and 8316,  analyze four
      portions of the  water sample volume specified in each method, spiked
      at  a  concentration  that  is  10  -  50  times  greater  than  the
      determinative method MDL for each analyte.

      8.2.5  Analyze  replicate aliquots  (at  least  four) of the well-mixed
reference samples by  the same  procedures  used to  analyze actual samples
(Sec. 7.0 of each  of the methods).  This will  include a combination of the
sample  preparation  method (usually  a  5000  series method  for  volatile
organics) and the determinative  method  (an  8000 series method).  Follow
the guidance on data  calculation and  interpretation presented in Method
8000, Sec. 8.0.

8.3  Sample Quality Control  for Preparation and  Analysis

      8.3.1   Documenting the  effect  of  the  matrix should  include the
analysis of at  least one matrix spike and one duplicate unspiked sample or
one matrix spike/matrix  spike  duplicate pair  per  analytical  batch.   The
decision on whether to prepare and analyze duplicate samples or a matrix
spike/matrix spike duplicate must be based on a  knowledge of the samples
in the sample batch.   If samples  are expected  to contain target analytes,
then laboratories may  use one  matrix spike and a duplicate analysis of an
unspiked field  sample.   If samples are  not  expected  to  contain target
analytes, the  laboratories  should use a  matrix spike and  matrix spike
duplicate pair.   See  Sec. 5.5  for additional guidance on  matrix spike
preparation.

      8.3.2  A  Laboratory  Control  Sample  (LCS)  should  be  included  with
each  analytical  batch.   The  LCS consists  of an aliquot  of  a  clean
(control) matrix similar to the  sample matrix and of the same weight or
volume.     The  LCS is  spiked  with  the  same  analytes  at  the  same
concentrations as the  matrix  spike.  When  the  results of the matrix spike
analysis indicates a  potential problem due  to the sample matrix itself,
the LCS  results  are used to  verify that  the  laboratory  can  perform the
analysis in a clean matrix.

      For the laboratory control sample,  use  a  clean matrix for spiking
purposes (one that does not  have any target  or interference  compounds)
e.g., organic-free reagent  water for the water matrix or sand  or  soil
(free of  organic  interferences)  for the  solid  matrix.   Because  of the

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      volatility of these  compounds, the spike must be introduced directly into
      the matrix while the matrix is in a sealed container  (e.g.,  a  gas  tight
      syringe or purge device).

            8.3.3  The concentration of the  matrix  spike sample and/or the LCS
      should be determined as described in the following Sections.

                  8.3.3.1   If, as in compliance monitoring, the concentration of
            a  specific analyte  in the   sample  is  being  checked  against  a
            regulatory concentration limit,  the spike should be at or below the
            regulatory limit, or 1  - 5 times  the background  concentration (if
            historical data are available),  whichever concentration is higher.

                  If historical  data are not available,  it is suggested that an
            uncontaminated sample of the same  matrix from the site be submitted
            for matrix spiking purposes to  ensure  that  high  concentrations of
            target analytes and/or interferences will  not prevent calculation of
            recoveries.

                  8.3.3.2    If the  concentration of  a  specific  analyte  in  a
            sample  is not  being checked  against  a  limit  specific  to  that
            analyte, then  the spike should be  at  the  same concentration as the
            reference sample  (Sec. 8.2.4) or 20 times the estimated quantitation
            limit (EQL) in the matrix  of interest.   It  is again suggested that
            a background sample of the same matrix from the site be submitted as
            a sample for matrix spiking purposes.

            8.3.4  Analyze these QC samples (the LCS and the  matrix  spikes or
      the optional matrix  duplicates) following the procedure (Sec. 7.0) of the
      selected determinative  method.   Calculate  and evaluate  the QC  data as
      outlined in Sec. 8.0 of Method 8000.

            8.3.5  Blanks  - Use  of method  blanks and other blanks are necessary
      to  track contamination  of  samples during  the   sampling  and  analysis
      processes.  Refer to Chapter One for specific quality control  procedures.

            8.3.6   Surrogates - A  surrogate  standard  is  a compound  that is
      chemically similar to the  analyte group but  not expected to  occur  in an
      environmental sample.  Surrogate  standards should  be added to all samples
      when specified in the appropriate determinative  method  (See Table 2).  See
      Sec.  5.4  for the definition  of surrogates  and  additional   guidance on
      surrogates.

      8.4   The laboratory must  have procedures  in place for  documenting and
charting the effect of the matrix on method performance.  Refer to Chapter One
and Method 8000 for specific guidance  on developing method  performance data.


9.0  METHOD PERFORMANCE

      9.1  The recovery of  surrogate standards  is  used to monitor unusual matrix
effects, sample processing problems, etc,  in  each sample.   The recovery of matrix
spiking compounds, when compared to  laboratory control sample (LCS) recoveries,
indicates the presence or  absence of unusual matrix effects.

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      9.2  The performance of  each  5000  series  method  will  be dictated by the
overall performance of the sample preparation in  combination with the analytical
determinative method.

      9.3  Multi-lab and/or single-lab performance data are found at the end of
most 8000 series analytical methods.


10.0  REFERENCES

      None required.
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                             TABLE 1
       COMBINATIONS OF VOLATILE ORGANIC SAMPLE PREPARATION
               AND DETERMINATIVE METHODS  FOR SW-846
Method
#
8011
8015
8021
8031
8032
8033
8260
8315
8316
Method Name
EDB & DBCP by GC/ECD
Nonhalogenated VOCs by
GC/FID
Halogenated and
Aromatic VOCs by
GC/ELCD & PID
Acrylonitrile by
GC/NPD
Acryl amide by GC/ECD
Acetonitrile by GC/NPD
Volatile Organic
Compounds by GC/MS
Carbonyl Compounds by
HPLC
Acryl amide and
Acrylonitrile by HPLC
Aqueous
Samples
8011
5030,
5031, 5032
5030, 5032
8031,
5030, 5032
8032
5031
5030,
5031, 5032
8315
8316
Soil/Solid
Samples
NL
5021, 5031
5032, 5035
5021,
5032, 5035
5032, 5035
NL
NL
5021, 5031
5032, 5035
8315
NL
Waste
Samples
NL
5032,
5035
5032,
5035
5032,
5035
NL
NL
5032,
5035
8315
NL
Air
Samples
NL
NL
NL
NL
NL
NL
0030, 0031/
5041, 0040
0011, 0100/
8315
NL
   NL = None listed
   GC = Gas Chromatography
  EDB = Ethylene Dibromide (1,2-dibromoethane)
  ECD = Electron Capture Detector
  FID = Flame lonization Detector
  NPD = Nitrogen-Phosphorus Detector
  PID = Photoionization Detector
 DBCP = l,2-Dibromo-3-chloropropane
 VOCs = Volatile Organic Compounds
 ELCD = Electrolytic Conductivity Detector
GC/MS = Gas Chromatography/Mass Spectrometry
 HPLC = High Performance Liquid Chromatography
                             5000  -  12
  Revision 0
January 1995

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                              TABLE  2

           SURROGATES FOR SW-846  CHROMATOGRAPHIC  METHODS
                  FOR VOLATILE ORGANIC COMPOUNDS
Method
#
8011
8015
8021
8031
8032
8033
8260
8315
8316
Method Name
EDB & DBCP by GC/ECD
Nonhalogenated VOCs by
GC/FID
Halogenated and
Aromatic VOCs by
GC/ELCD & PID
Acrylonitrile by
GC/NPD
Acryl amide by GC/ECD
Acetonitrile by GC/NPD
Volatile Organic
Compounds by GC/MS
Carbonyl Compounds by
HPLC
Acryl amide and
Acrylonitrile by HPLC
Suggested Surrogates
NL
NL
Bromochl oromethane ,
2-bromo-l-chloropropane,
1,4-dichlorobutane
NL
NL
NL
Toluene-d8,
l,2-dichloroethane-d4,
4-bromofluorobenzene (BFB),
dibromofluoromethane
NL
NL
Suggested Water
Concentration
NL
NL
150 ng/5 mL
sample
NL
NL
NL
250 ng/5 mL
water
NL
NL
   NL = None listed
   GC = Gas Chromatography
  EDB = Ethylene Dibromide (1,2-dibromoethane)
  ECD = Electron Capture Detector
  FID = Flame lonization Detector
  NPD = Nitrogen-Phosphorus Detector
  PID = Photoionization Detector
 DBCP = l,2-Dibromo-3-chloropropane
 VOCs = Volatile Organic Compounds
 HECD = Electrolytic Conductivity Detector
GC/MS = Gas Chromatography/Mass Spectrometry
 HPLC = High Performance Liquid Chromatography
                             5000  -  13
  Revision 0
January 1995

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                             TABLE 3

         MATRIX SPIKES FOR SW-846 CHROMATOGRAPHIC  METHODS
                  FOR VOLATILE  ORGANIC COMPOUNDS
Method
#
8011
8015
8021
8031
8032
8033
8260
8315
8316
Method Name
EDB & DBCP by GC/ECD
Nonhalogenated VOCs by
GC/FID
Halogenated and
Aromatic VOCs by
GC/ELCD & PID
Acrylonitrile by GC/NPD
Acryl amide by GC/ECD
Acetonitrile by GC/NPD
Volatile Organic
Compounds by GC/MS
Carbonyl Compounds by
HPLC
Acryl amide and
Acrylonitrile by HPLC
Specified Matrix Spiking
Compounds
Spike with analytes of
interest.
Spike with analytes of
interest.
1,1-Dichloroethene,
trichloroethene, benzene,
toluene, chlorobenzene
Spike with analyte of
interest.
Spike with analyte of
interest.
Spike with analyte of
interest.
1,1-Dichloroethene,
trichloroethene, benzene,
toluene, chlorobenzene
Spike with analytes of
interest.
Spike with analytes of
interest.
Concentration in
a Water Sample
NL
NL
250 ng/5 mL
sample or 50
M9/L
NL
NL
NL
250 ng/5 mL
sample or 50
M9/L
NL
NL
   NL = None listed
   GC = Gas Chromatography
  EDB = Ethylene Dibromide (1,2-dibromoethane)
  ECD = Electron Capture Detector
  FID = Flame lonization Detector
  NPD = Nitrogen-Phosphorus Detector
  PID = Photoionization Detector
 DBCP = l,2-Dibromo-3-chloropropane
 VOCs = Volatile Organic Compounds
 HECD = Electrolytic Conductivity Detector
GC/MS = Gas Chromatography/Mass Spectrometry
 HPLC = High Performance Liquid Chromatography
                             5000  -  14
  Revision 0
January 1995

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                                  METHOD  5021

         VOLATILE ORGANIC COMPOUNDS IN SOILS AND OTHER SOLID MATRICES
                     USING EQUILIBRIUM HEADSPACE ANALYSIS
1.0  SCOPE AND APPLICATION

      1.1   Method 5021  is a  general  purpose method  for the  preparation  of
volatile  organic  compounds  (VOCs)  in  soils/sediments and  solid wastes  for
determination by gas chromatography (GC) or gas chromatography/mass spectrometry
(GC/MS).  The method is applicable to a wide range of organic compounds that have
sufficiently high volatility to be effectively removed from soil samples using
an equilibrium headspace procedure. The following compounds have  been determined
in soils using Method 5021:
                  Compound                             CAS No.'
                  Benzene                              71-43-2
                  Bromochloromethane                   74-97-5
                  Bromodichloromethane                 75-27-4
                  Bromoform                            75-25-2
                  Bromomethane                         74-83-9
                  Carbon tetrachloride                 56-23-5
                  Chlorobenzene                       108-90-7
                  Chloroethane                         75-00-3
                  Chloroform                           67-66-3
                  Chloromethane                        74-87-3
                  Dibromochloromethane                124-48-1
                  l,2-Dibromo-3-chloropropane          96-12-8
                  1,2-Dibromoethane                   106-93-4
                  Dibromomethane                       74-95-3
                  1,2-Dichlorobenzene                  95-50-1
                  1,3-Dichlorobenzene                 541-73-1
                  1,4-Dichlorobenzene                 106-46-7
                  Dichlorodifluoromethane              75-71-8
                  1,1-Dichloroethane                   75-34-3
                  1,2-Dichloroethane                  107-06-2
                  1,1-Dichloroethene                   75-35-4
                  trans-1,2-Dichloroethene            156-60-5
                  1,2-Dichloropropane                  78-87-5
                  Ethylbenzene                        100-41-4
                  Hexachlorobutadiene                  87-68-3
                  Methylene chloride                   75-09-2
                  Naphthalene                          91-20-3
                  Styrene                             100-42-5
                  1,1,1,2-Tetrachloroethane           630-20-6
                  1,1,2,2-Tetrachloroethane            79-34-5
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                  Compound                             CAS No."


                  Tetrachloroethene                   127-18-4
                  Toluene                             108-88-3
                  1,2,4-Trichlorobenzene              120-82-1
                  1,1,1-Trichloroethane                71-55-6
                  1,1,2-Trichloroethane                79-00-5
                  Trichloroethene                      79-01-6
                  Trichlorofluoromethane               75-69-4
                  1,2,3-Trichloropropane               96-18-4
                  Vinyl chloride                       75-01-4
                  o-Xylene                             95-47-6
                  m-Xylene                            108-38-3
                  p-Xylene                            106-42-3
                  Gasoline Range Petroleum Hydrocarbons


            a  Chemical  Abstract Services Registry Number.


      1.2   Method detection  limits (MDL),  using Method 8260,  are compound,
matrix, and instrument dependent and vary from approximately 0.1 to 3.4 M9/kg.
The applicable  concentration  range of  this  method is approximately  10 or 20
jug/kg to  200  M9/kg.   Analytes  that are inefficiently extracted from the soil
will not be detected when present at low  concentrations, but they can be measured
with acceptable accuracy and precision when present in sufficient concentrations.

      1.3  The following compounds  may also be analyzed by this  procedure or may
be used as surrogates:

                  Compound Name                        CAS No."

                  Bromobenzene                        108-86-1
                  n-Butylbenzene                      104-51-8
                  sec-Butyl benzene                    135-98-8
                  tert-Butylbenzene                    98-06-6
                  2-Chlorotoluene                      95-49-8
                  4-Chlorotoluene                     106-43-4
                  cis-l,2-Dichloroethene              156-59-4
                  1,3-Dichloropropane                 142-28-9
                  2,2-Dichloropropane                 590-20-7
                  1,1-Dichloropropene                 563-58-6
                  Isopropylbenzene                     98-82-8
                  4-Isopropyltoluene                   99-87-6
                  n-Propylbenzene                     103-65-1
                  1,2,3-Trichlorobenzene               87-61-6
                  1,2,4-Trimethylbenzene               95-63-6
                  1,3,5-Trimethylbenzene              108-67-8


            "  Chemical  Abstract Services Registry Number.
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      1.4   Alternatively,  the method may  be  utilized as  an  automated sample
introduction device as a means for screening samples for volatile organics.  A
suggested configuration is to interface it to Method 8021 but use very minimal
calibration and quality control,  i.e.,  a reagent blank and a single calibration
standard, to obtain semiquantitative data.

      1.5  Method 5021 may be applicable to other compounds that have sufficient
volatility to be removed from the soil matrix using the conditions described in
this method.   It may  also be applicable to both  listed  and non-listed target
analytes in other matrices.

      1.6   This  method  is  restricted to use by,   or  under  the supervision of,
analysts experienced in volatile organic analysis in general  and specifically the
use of  equilibrium headspace devices  interfaced  to the determinative method
selected by the analyst.


2.0  SUMMARY OF METHOD

      2.1  Volatile organic compounds (VOCs) are determined  from at least a 2 g
soil sample by placing the sample into a crimp-seal or screw  top glass headspace
vial at time of sampling.  Each soil sample is fortified with a matrix modifying
solution and internal standards and surrogate compounds.  This may be done either
in the field or in  the laboratory upon receipt of samples.  Additional sample is
collected in a VOA vial  for  dry weight determination  and for high concentration
determination if the sample concentration requires it.   In  the laboratory, the
vials are rotated to allow for diffusion of the internal standards and surrogates
throughout  the  matrix.   The vials are placed in  the autosampler  carousel  and
maintained  at  room temperature.   Approximately  1  hour prior  to  analysis,  the
individual  vials are moved  to a heated zone and  allowed to equilibrate.   The
sample is then mixed by mechanical vibration while the elevated temperature is
maintained.   The autosampler then pressurizes  the vial  with  helium,  allows a
portion to enter a  sample loop which is then swept through  a  heated transfer line
onto the GC column.  Determinative analysis is  performed using the appropriate
GC or GC/MS method.


3.0  INTERFERENCES

      3.1  Volatile organic  analyses  are subject to major interference problems
because of the prevalence of volatile organics in a  laboratory.  See Method 5000,
Sec. 3.0 for common problems and precautions to  be followed.

      3.2   The  sample  matrix itself can cause severe interferences  by one of
several processes or a combination of these processes.   These include, but are
not necessarily limited  to, the absorption potential  of the soil, the biological
activity of the soil, and the actual composition of the soil.  Soils high in oily
material  and  organic  sludge wastes  inhibit  the  partitioning of  the volatile
target analytes into the headspace, therefore, recoveries will  be low.  This so-
called "matrix effect"  can be difficult, if not impossible,   to overcome.  It is
recommended  that  surrogates  or  additional  deuterated   compounds  (for  GC/MS
methods) be added to a  matrix and analyzed to determine the  percent recovery of
these compounds. The calculated percent recovery can give some  indication of the
degree of the matrix effect,  but not necessarily correct for  it.  Alternatively,

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the use of the high concentration procedure in this method should minimize the
problem with oily waste and other organic sludge wastes.


4.0  EQUIPMENT AND SUPPLIES

      4.1  Sample Containers - Clear glass, 22 ml soil  vials, compatible with the
analytical system.   The vial must be capable of being  hermetically sealed in the
field (either crimp  cap or screw cap)  and be equipped with a Teflon®-!ined septum
which demonstrates  minimum bleed at  elevated temperatures while maintaining the
seal.  Ideally,  the  vials  and septa should have a uniform tare weight.  Prior to
use, wash  the vials and  septa with detergent  solution,  then rinse with tap
followed by distilled water.   Place  vials and  septa  in  an  oven  at  105'C for 1
hour, then remove and allow to  cool.  Store in  an area free of organic solvents.

      4.2  Headspace System  -  The system described  in  this method utilizes a
totally automated equilibrium  headspace  analyzer.  Such systems  are available
from several  commercial   sources.    The  system used must  meet  the  following
specifications.

            4.2.1  It must be capable of establishing  a reproducible equilibrium
      at elevated temperatures  between a wide  variety of  sample  types  and the
      headspace.  Once this is done, the  system must be capable of accurately
      injecting  a  representative   portion  of  the headspace   into   a  gas
      chromatograph fitted with a capillary column.  This must be accomplished
      without adversely  affecting  the  chromatography   or  the detector.   The
      conditions selected for the equipment used in developing this method are
      listed  in Sec. 7.0.   Other equipment and conditions may be  used  if the
      analyst generates and records accuracy,  precision, and MDL data that are
      comparable to the data in Sec.  9.0  of Method  8260.  The equipment used to
      develop this  method  and generate the accuracy and precision data listed in
      Method 8260 was  a Tekmar  Model  7000 Equilibrium Headspace Autosampler and
      a Tekmar 7050 Carousel  (Tekmar Co., 7143  East Kemper Road, Cincinnati, OH
      45249).

      4.3  Field Sampling Equipment

            4.3.1   A  soil  sampler  which  delivers  at  least  2  g  of soil  is
      necessary, e.g.,  Purge-and-Trap Soil Sampler  Model  3780PT  (Associated
      Design and Manufacturing Company, 814 North Henry Street,  Alexandria, VA
      22314), or equivalent.

            4.3.2   An automatic syringe  or  bottle-top  dispenser calibrated to
      deliver 10.0  ml of  matrix modifier solution, e.g.,  Automatic Vaccinator
      Model C1377SN (NASCO, 901 Jamesville Ave., P.O.  Box 901,  Fort Atkinson, WI
      53538), or equivalent.

            4.3.3  An automatic syringe calibrated to  deliver internal standards
      and surrogate analytes.

            4.3.4   Crimping tool  for sample vials.  If  using  screw top  vials,
      this is not needed.
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      4.4  Miscellaneous Equipment

            4.4.1  VGA vials  -  40  or  60 ml VGA vials with Teflon®-faced septa
      and crimp  seal  caps or  screw  top caps.   These vials will  be  used for
      sample screening, high concentration analysis (if needed) and dry weight
      determination.
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.   Purchase  in  small  quantities (\  Liter  or 1  Liter  size)  to
minimize contamination.

      5.3   See  the determinative method  and  Method 5000 for  guidance  on the
preparation of stock standards and a secondary  standard for internal standards,
calibration standards, and surrogates.

            5.3.1    Calibration  spiking   solutions  -  Prepare  five  spiking
      solutions  in methanol  that  contain  all  the target  analytes and the
      surrogate  standards.   The  concentrations  of the  calibration  solutions
      should be such that the  addition of 1.0 juL of each to the  22 mL vials will
      bracket the analytical  range  of the  detector, e.g.,  for Method 8260 the
      suggested concentration  range  for target analytes and surrogates  is 5, 10,
      20, 40 and 50 mg/L.  The suggested concentration of internal standards is
      20 mg/L (internal  standards  may be omitted for the GC methods if desired).
      The internal standard may be  added  separately using 1.0  juL  or premixed
      with the calibration standards maintaining a 20 mg/L concentration in each
      calibration  standard.   These concentrations  may vary depending  on the
      relative sensitivity of  the  GC/MS system or any other determinative method
      that is utilized.

            5.3.2  Internal  and  surrogate standards - Follow the recommendations
      of the determinative methods for the selection of internal and surrogate
      standards.  A concentration of 20 mg/L in methanol  for both internal and
      surrogate  standards  will  be  needed   for  spiking  each  sample.    If
      determination is by GC,  external standard calibration may  be preferred and
      the internal standard is omitted.  The concentration may vary depending on
      the relative sensitivity  of the GC/MS  system  or any other determinative
      method that is utilized.

      5.4  Blank Preparation - Transfer 10.0 mL (Sec.  5.6) of matrix modifying
solution to a sample vial.  Add the prescribed amounts  of the  internal standards
and surrogate compounds,  and  seal the vial.   Place it in  the  autosampler and
analyze in the same manner as an unknown sample.  Analyzing the blank in this way
will indicate possible problems with the  autosampler  as  well as the headspace
device.
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      5.5  Preparation of Calibration  Standards  - Prepare calibration standards
in the same manner as  the  blanks (Sec.  5.4) using the  standards prepared in Sec.
5.3.1.

      5.6   Matrix  Modifying  Solution  -  Using  a  pH meter, add  concentrated
phosphoric acid (H3P04)  dropwise to 500 ml of organic-free reagent water until
the pH is 2.  Add 180 g of NaCl.  Mix well until all  components are dissolved.
Analyze  a  10.0 ml  portion  from each  batch  per Sec.  5.4  to verify  that  the
solution is free of contaminants.  Store in a sealed bottle in  an area free of
organic chemicals at 4'C.

WARNING:    The matrix  modifying  solution may  not  be  appropriate  for  soil
            samples having organic carbon content.   See Sec. 6.1.2.


6.0  SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1  Two alternative procedures are presented  for  low concentration sample
collection in  special headspace sample  vials.   In  either  case,  collect 3 or 4
vials of sample from each sampling point  to allow sample  reanalysis  if necessary.
In addition, a separate portion of sample  is taken  for dry weight determination
and high concentration  analysis (if necessary).   Prepare a  trip  blank in  the
laboratory prior  to shipping the sample  vials  to  the  field.  Add  10.0  mL of
matrix modifying solution to a clean 22 mL sample vial (Sec.  4.1).  The internal
and surrogate standards are added just prior to analysis.

            6.1.1  Without matrix modifying solution and standards  - Standard 22
      mL  crimp  cap  or  screw top  glass  headspace  vials (Sec.  4.1)  with
      Teflon®-faced septa are used. Add 2-3 cm  (approximately 2 g) of the soil
      sample  (using the purge-and-trap soil sampler,  Sec.  4.3.1) to a tared 22
      mL headspace vial  and  seal immediately with the Teflon® side  of the septum
      facing toward the sample. The samples should  be introduced into the vials
      gently to reduce  agitation which might drive off volatile compounds.

NOTE: If high concentrations of volatile organics are expected (greater than 200
      M9Ag),  collection  of the sample  in the 22 mL  vial  without the addition
      of matrix modifying solution  allows direct addition of methanol as per the
      high concentration  method in Sec. 7.5.

            6.1.2   With matrix modifying solution and  standards  -  Add 2-3 cm
      (approximately  2  g) of soil sample  to  a  tared 22 mL  soil  vial  using a
      purge-and-trap soil sampler (Sec.  4.3.1).  Add 10.0 mL  of matrix modifying
      solution and  the  appropriate  amount of  internal  and surrogate standards
      called  for  in the determinative method.   Seal  the vial immediately with
      the Teflon® side of the septum facing toward  the  sample.  The sample must
      remain hermetically sealed until the septum is  punctured by the headspace
      analyzer.

WARNING:    Preliminary indications are that soil samples having organic carbon
            content may yield low recoveries when the matrix modifying solution
            (Sec.  5.6)  is  used.   The  matrix  modifying  solution may  not be
            appropriate for these samples.
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            6.1.3 Prepare a field blank  by  adding  10.0  mL of matrix modifying
      solution plus internal and surrogate standards to a clean 22 mL vial.

NOTE: The  addition  of  the matrix  modifying  solution  and  the  internal  and
      surrogate standards at the time of  sampling (Sec. 6.1.2) is the preferred
      option unless high concentrations of volatile organics  are expected.  The
      matrix modifying solution minimizes dehydrohalogenation reactions through
      pH adjustment,  eliminates biodegradation of the  analytes  and minimizes
      losses of  analytes by volatility  since the vial  is not opened  in  the
      laboratory.  The  downside is  increased  opportunity  for contamination of
      the matrix modifier and  standards  in  a  field  sampling  situation.   Also,
      skilled personnel  are required to precisely and accurately add the matrix
      modifying solution, and especially the internal  and surrogate standards.
      These problems  are minimized  when  added  in the  laboratory (Sec.  6.1.1),
      however,  there  is  the  likelihood of  significant  losses  of  volatile
      analytes when the vial is reopened in the laboratory.

            6.1.4  Fill  a 40 or 60 ml VGA vial from each sampling point to use
      for dry weight determination,  sample screening and for high concentration
      analysis (if necessary).   Sample screening is optional  since there is no
      danger of contaminating the headspace device because of carryover from a
      high concentration sample.

      6.2  Sample Storage

            6.2.1  Store samples at  4°C until analysis.   The sample storage area
      must be free of organic solvent vapors.

            6.2.2  All samples  should be  analyzed within 14 days of collection.
      Samples  not  analyzed  within   this  period must  be   noted  and data  are
      considered minimum values.
7.0  PROCEDURE

      7.1  Sample screening - This method (using the low concentration approach),
used in conjunction with either Methods 8015 (GC/FID)  or 8021 (GC/PID/ELCD), may
be used as a sample screening method prior to any of the sample introduction -
GC/MS  configurations  to  assist  the  analyst in  determining   the  approximate
concentration of volatile organics present  in  a  sample.   This  is especially
critical prior  to  the use of  volatile  organic analysis by purge-and-trap  to
prevent the contamination of the system by high concentration  samples.  It can
also be helpful  prior  to  the  use  of this headspace method, to determine whether
to proceed with the low concentration method or the high concentration method.
High concentrations of volatiles  will  not contaminate the headspace device.
However,  it  may create   contamination  problems in  the GC or GC/MS system.
Whenever this method is utilized  for sample screening, very minimal  calibration
and  QC  are suggested.    In  most cases,  a  reagent  blank  and  a single  point
calibration are sufficient.

      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 from  the 40 or 60
mL VOA vial (Sec.  6.1.3).

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WARNING:    The  drying  oven  should  be  contained  in  a  hood  or  vented.
            Significant  laboratory contamination  may result  from  a  heavily
            contaminated hazardous waste sample.

            7.2.1  Immediately after weighing the sample for extraction, weigh
      5-10 g of the sample  into a tared crucible.  Determine the % dry weight of
      the sample by drying  overnight  at  105°C.   Allow to cool  in a desiccator
      before weighing.  Calculate the % dry weight as follows:

                        % dry weight = q of dry sample x 100
                                         g of sample

      7.3   The  Low  Concentration Method  utilizing  an  equilibrium headspace
technique is found in  Sec. 7.4 and sample preparation for  the High Concentration
Method is found  in Sec. 7.5.  The high concentration method is recommended for
samples that obviously contain oily material or organic sludge waste (see Sec.
3.3).  See Method 5000, Sec. 7.0  for  guidance  on the  selection of a GC or GC/MS
determinative method.   For  the analysis of gasoline, use Method 8021 with GC/PID
for BTEX in series with Method 8015 with the GC/FID detector for hydrocarbons.
If GC/MS analysis  is preferred for BTEX in gasoline, follow Method 8260.

      7.4  Low concentration method for soil/sediment and solid waste amenable
to the equilibrium headspace method.  (Approximate concentration  range of 0.5 to
200 jug/kg - the  concentration range is dependent upon the determinative method
and the sensitivity of each analyte.)

            7.4.1  Calibration:   Prior to  using  this  introduction technique for
      any  GC  or  GC/MS  method,  the  system  must  be  calibrated.    General
      calibration  procedures  are  discussed  in   Method  8000,   while  the
      determinative methods and  Method  5000  provide  specific  information on
      calibration  and  preparation  of standards.   Normally,  external standard
      calibration  is  preferred  for  the  GC  methods  because  of  possible
      interference problems with internal standards.   If interferences are not
      a  problem, based on  historical  data, internal  standard  calibration is
      acceptable.    The  GC/MS   methods   normally   utilize  internal  standard
      calibration.    The  GC/MS  methods  require   instrument  tuning prior to
      proceeding with calibration.

                   7.4.1.1   Initial calibration:   Prepare five  22 mL vials, as
            described, in Sec. 5.5, and a  reagent  blank (Sec. 5.4), and proceed
            according to Sec. 7.4.2 and the  determinative method selected.  The
            mixing step is  eliminated since no  soil  is present in the vial.

                   7.4.1.2   Calibration  verification:  Prepare  a  single 22 mL
            vial as described in Sec. 5.5 by spiking with the midconcentration
            calibration standard.  Proceed according to Sec. 7.4.2.4  (beginning
            by  placing the vial   into  the  autosampler)  and  the determinative
            method.

            7.4.2   Headspace operating conditions  -  The conditions described
      throughout Sec.  7.4  were  experimentally optimized  using  the equipment
      described  in Sec. 4.2.1.  If other systems are utilized,  it is recommended
      that the manufacturer's conditions be  followed.  However, the criteria for
      this configuration in Method 8260 must be met  or exceeded.

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                  7.4.2.1  This method is designed for a 2 g sample size.  The
            sample is prepared in the  field  by adding 2 g of the soil sample to
            the 22 ml crimp-seal  or screw top glass headspace vial as described
            in Sec. 6.1.

                  7.4.2.2   Prior to analysis, weigh  the sealed vial  and its
            contents to 0.01 g.  If the matrix modifying solution was added at
            the time of sampling (Sec. 6.1.2),  the tare weight includes the 10
            ml of matrix modifying solution.

                  7.4.2.3  If the matrix modifying solution was  not added at the
            time of sampling (Sec.  6.1.1), unseal  the vial, rapidly add 10.0 ml
            of matrix modifying  solution and 1 nl of  the 20 mg/L internal (if
            necessary) and surrogate standards (individually or as a mixture).
            Immediately reseal the vial.

NOTE: Only open  and  prepare one vial  at  a  time  to minimize loss  of volatile
      organics.

                  7.4.2.4  Mix the  samples (on a rotator or shaker) for at least
            2  min.    Place the  vials  in the  autosampler  carrousel at  room
            temperature.  The individual  vials are moved  to a heating zone, and
            allowed to  equilibrate for 50 min at 85°C.   Each  sample  is then
            mixed by  mechanical  vibration for 10  min  at a mix  power  of 7.67
            Watts  while maintaining  the temperature  at 85°C.   The vial  is
            allowed to  pressure  equilibrate for  5 sec.   The  autosampler then
            raises the vial causing a  stationary needle to puncture the septum,
            and pressurize the vial with helium at 10 psi.

                  7.4.2.5  The pressurized headspace is then vented through a 1
            mL  sample  loop  to  the  atmosphere  for  15  sec.    The  sample  is
            equilibrated within the loop  for 5 sec.  Finally the carrier gas, at
            a flow rate of 1.0 mL/min,  backflushes the sample loop sweeping the
            sample through the heated transfer line onto the GC column.

                  7.4.2.6   Proceed with  the  analysis  as  per the determinative
            method of choice.

      7.5  High concentration method

            7.5.1   If the sample was  collected  by Sec.  6.1.1  with  no  matrix
      modifying solution added at time of sampling, add 10.0 ml of methanol to
      the high level  soil  sample  within the tared  22 ml  vial.  (Weigh the sample
      to the nearest 0.01 g prior to the addition of methanol.)

            7.5.2  Otherwise, transfer approximately 2 g of sample from the 40
      or 60 ml VOA vial  into a tared 22 ml sample  vial  (Sec. 5.1).  Add 10.0 mL
      of methanol.

            7.5.3  Mix by shaking for 10 min at  room temperature.  Decant 2 mL
      of the methanol to  a screw top vial with Teflon®  faced  septa  and  seal.
      Withdraw 10 juL, or appropriate volume  of extract  from Table 2, and inject
      into a  22  mL vial containing 10.0 mL of matrix modifying  solution and
      internal standards (if required)  and surrogates.   Analyze  by the headspace

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      procedure by  placing  the  vial  into the autosampler  and  proceeding with
      Sec. 7.4.2.4.
8.0  QUALITY CONTROL

      8.1   Refer to Chapter One  for specific quality control  procedures and
Method 5000 for sample preparation QC procedures.

      8.2  Before processing any samples, the analyst should demonstrate through
the analysis of an organic-free reagent water method 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 blank samples should be carried
through all stages of the sample preparation and measurement.

      8.3    Initial   Demonstration  of  Proficiency   -  Each  laboratory  must
demonstrate initial proficiency with each sample preparation and determinative
method combination it utilizes, by generating data of acceptable accuracy and
precision for target analytes in a  clean matrix.  The laboratory must also repeat
the following operations whenever new staff are trained or significant changes
in  instrumentation are  made.   See Sec.  8.0 of Methods 5000 and  8000 for
information on how to accomplish this demonstration.

      8.4  Sample Quality Control  for Preparation and  Analysis -  See Sec. 8.0 in
Method 5000 and Method 8000 for procedures to follow to demonstrate acceptable
continuing performance on each set of samples to be analyzed.   This includes the
method blank, either a matrix spike/matrix spike duplicate or  a matrix spike and
duplicate sample analysis,  a laboratory control sample (LCS) and  the addition of
surrogates to each sample and QC sample.

      8.5   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.  Whenever possible, the  laboratory should  analyze standard reference
materials and participate in relevant performance evaluation studies.


9.0  METHOD PERFORMANCE

      9.1  Single laboratory accuracy and precision  data were obtained for the
method analytes in two soil matrices: sand and a surface garden soil.  These data
are found in tables in Method 8260.
10.0  REFERENCES

1.    Flores, P., Bellar,  T.,  "Determination  of Volatile Organic Compounds in
      Soils  using Equilibrium  Headspace  Analysis  and  Capillary Column  Gas
      Chromatography/Mass Spectrometry", U.S. Environmental Protection Agency,
      Office  of  Research  and Development,  Environmental Monitoring  Systems
      Laboratory, Cincinnati, OH, December, 1992.
                                   5021  -  10                        Revision 0
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2.    Code of Federal Regulations, 40, Ch. 1, Part 136, Appendix B.

3.    loffe, B.V., Vitenberg, A.G., "Headspace Analysis and Related Methods in
      Gas Chromatography", John Wiley and Sons, 1984.
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                             TABLE  1
          DETERMINATIVE METHODS  INTERFACED TO METHOD 5021
Method      Method Name
Number
i
8015        Nonhalogenated Volatile Organics Using GC/FID
8021        Halogenated and Aromatic  Volatiles  by GC with  Detectors  in
            Series: Capillary Column
8260        Volatile Organics by GC/MS:  Capillary Column
                             TABLE  2
       QUANTITY  OF  METHANOL  EXTRACT  REQUIRED  FOR ANALYSIS OF
                HIGH-CONCENTRATION SOILS/SEDIMENTS
          Approximate                         Volume of
      Concentration Range                  Methanol  Extract8
        500-10,000  Mg/kg                         100 ML
      1,000-20,000  jug/kg                          50 ML
      5,000-100,000 M9/kg                          10 ML
     25,000-500,000 M9/kg               100 ML of 1/50 dilution b
Calculate appropriate dilution  factor  for  concentrations  exceeding this
table.

    * The volume of methanol added to 5 mL of water being purged should be
      kept constant.  Therefore, add to the 5 mL syringe whatever volume
      of methanol is necessary to maintain a volume of 100 ML added to the
      syringe.

    b Dilute an aliquot of the methanol extract and  then take  100 ML for
      analysis.
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                                            METHOD  5021
           VOLATILE ORGANIC  COMPOUNDS  IN  SOILS  AND  OTHER SOLID MATRICES
                           USING EQUILIBRIUM  HEADSPACE  ANALYSIS
  7.2 Determine sample
       dry weight.
          7.3
     Choose low or
   high concentration
    method bated on
        sample
        make-up.
7.4.1 Perform calibration
       and verify.
                      Low Cone. Method
            High Cone
              Method
                                                           7.4.2
                                                        Was 10 0 mL
                                                     of matrix modifyin
                                                      solution added to
                                                       samples at the
                                                       time of sample
                                                         collection?
                             7.4.2 Rapidly add 10.0 mL
                             of matrix modifying solution
                               and 1>iL of internal and
                                surrogate standard.
      7.5.1
      Were
 sample* collecte
without addition of
 matrix modifying
     solution?
                                                    7.4.2 Weigh the sealed
                                                       vials to 0.01 g.
  7.5.2 Tranafer approx.
   2g of sample into a
   tared 22 mL sample
  vial and add 10.0 mL
      of methanol.
                                                    7.4.2.4 Mix samples on
                                                    rotator or shaker for at
                                                       least 2 minutet.
  7.5.3 Mix by shaking
for 10 mm. at room temp.
Decant 2 mL of methanol.
                                                    7.4.2.4 - 7.4.2.5 Place
                                                    samples in auto-sampler
                                                   to be heated, equilibrated,
                                                   vibrated, pressurized with
                                                     helium, and injected.
7.5.3 Withdraw appropriate
  volume of extract and
  inject into 22 mL vial
  containing 10.0 mL of
     matrix modifying
   solution and internal
 standards and surrogates.
   7.4.2.6 Proceed with
    analyst* as par the
   determinative method
       of choice.
                                              5021  -  13
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                                 METHOD 5030B

                      PURGE-AND-TRAP FOR AQUEOUS SAMPLES
1.0   SCOPE AND APPLICATION

      1.1   This method describes a purge-and-trap procedure for the analysis of
volatile organic compounds (VOCs)  in aqueous samples and water miscible liquid
samples.  It also describes the analysis  of high  concentration  soil  and waste
sample extracts prepared in Method 5035.  The gas chromatographic determinative
steps are found in Methods 8015 and 8021.  The method is  also  applicable to GC/MS
Method 8260.

      1.2   Method 5030 can be used for most volatile organic compounds that have
boiling  points  below 200°C and  are insoluble  or  slightly soluble  in  water.
Volatile water-soluble compounds can be included in this analytical  technique;
however, quantitation limits (by GC or GC/MS) are approximately ten times higher
because of poor purging efficiency.   The method is also limited to compounds that
elute as  sharp  peaks  from a GC column packed with  graphitized  carbon  lightly
coated with a carbowax or  a coated capillary column.   Such compounds include low
molecular  weight  halogenated  hydrocarbons,  aromatics,   ketones,   nitriles,
acetates, acrylates, ethers, and sulfides.

      1.3   Method 5030,  in conjunction with Method 8015 (GC/FID),  may  be used
for the analysis of the aliphatic hydrocarbon fraction in the light ends of total
petroleum hydrocarbons, e.g.,  gasoline.   For the aromatic fraction  (BTEX), use
Method 5030 and Method 8021 (GC/PID).  A total determinative  analysis of gasoline
fractions may be obtained  using Methods 8021 GC/PID)  in  series with Method 8015.

      1.4   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 or  by dilution  of the sample prior to the purge-and-
trap process.

      1.5   This method  is  restricted  to  use by  or under  the  supervision of
trained  analysts.    Each   analyst  must demonstrate the  ability  to  generate
acceptable results with this method.


2.0   SUMMARY OF METHOD

      2.1   Aqueous Samples:  An inert  gas is bubbled through  a  portion of the
aqueous  sample  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   High Concentration Extracts from Method 5035:   An aliquot  of the
extract prepared in Method 5035 is  combined with organic free  reagent water in
the   purging  chamber.    It is then analyzed  by  purge-and-trap  GC or  GC/MS
following the normal aqueous method.

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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
contamination under the conditions  of the analysis by running laboratory reagent
blanks.    The use  of  non-polytetrafluoroethylene  (non-PTFE)  plastic  coating,
non-PTFE thread  sealants,  or flow  controllers  with rubber components  in  the
purging  device must be avoided, since such materials out-gas organic compounds
which will  be  concentrated  in the  trap during the  purge  operation.   These
compounds will result in interferences or false positives in the determinative
step.

      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  volatiles  analysis  is  performed  should  be
completely  free  of solvents.  Special  precautions  must  be  taken  to determine
methylene chloride.  The analytical and  sample  storage  areas should be isolated
from all  atmospheric sources  of methylene chloride.   Otherwise random background
levels will  result. Since methylene chloride will permeate through PTFE tubing,
all  GC  carrier  gas lines  and purge gas  plumbing should  be constructed  of
stainless steel  or copper tubing.   Laboratory workers' clothing  previously
exposed   to  methylene  chloride fumes during  common  liquid/liquid  extraction
procedures can contribute to sample contamination.  The presence of other organic
solvents in the laboratory where volatile organics  are analyzed will also lead
to random background levels  and the same precautions must be taken.


4.0   APPARATUS AND MATERIALS

      4.1   Microsyringes - 10 /nL,  25 jxL, 100 /iL, 250 juL, 500 /uL, and 1,000 /iL.
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   Two 5-mL glass  hypodermic syringes with Luer-Lok tip (other sizes are
acceptable  depending on  sample volume used).
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      4.4   Volumetric flasks, Class A  -  10 mL and 100 mL,  with  ground-glass
stoppers.

      4.5   Vials - 2 ml, for GC autosampler.

      4.6   Purge-and-trap device:  The  purge-and-trap device consists of three
separate pieces of  equipment:  the  sample  purger,  the trap,  and the desorber.
Several  complete devices are commercially  available.

            4.6.1 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
      or improved performance is demonstrated.

            4.6.2 The trap used to develop  this method was  25  cm  long  with  an
      inside diameter of 0.105 in.   Starting from  the  inlet,  the trap contains
      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
      fluorocarbons of similar volatility,  the charcoal can  be eliminated and
      the polymer increased  to fill 2/3  of the trap.  If only compounds  boiling
      above 35°C  are  to  be  analyzed,  both  the silica gel  and  charcoal  can  be
      eliminated  and  the polymer increased to fill  the  entire trap.   Before
      initial  use,   the  trap  should  be  conditioned  overnight   at 180°C  by
      backflushing with  an inert gas flow of at least 20 mL/min.  Vent the trap
      effluent to the hood,  not to  the  analytical  column.   Prior to daily use,
      the trap should be  conditioned for 10 min at 180°C with backflushing.  The
      trap may  be  vented to the analytical column during daily conditioning;
      however, the column must be run  through the  temperature program prior  to
      analysis of samples.

            4.6.3 The desorber must be  capable of rapidly heating the  trap  to
      180°C  for  desorption.   The polymer  section  of the  trap should  not  be
      heated higher  than 180°C,  and  the remaining sections  should not exceed
      220°C during bake-out  mode.  The desorber design illustrated   in Figures 2
      and 3 meet these criteria.

            4.6.4 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.

            4.6.5 Trap Packing Materials

                  4.6.5.1     2,6-Diphenylene  oxide   polymer  -   60/80  mesh,
            chromatographic grade (Tenax GC or equivalent).

                  4.6.5.2     Methyl   silicone   packing   -   OV-1  (3%)   on
            Chromosorb-W, 60/80 mesh  or equivalent.

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                  4.6.5.3     Silica gel  -  35/60 mesh, Davison,  grade 15  or
            equivalent.

                  4.6.5.4     Coconut  charcoal  -  Prepare from  Barnebey  Cheney,
            CA-580-26,  or equivalent,  by crushing through  26 mesh  screen.

                  4.6.5.5     Alternate Trap Materials: A number of hydrophobic
            carbon molecular sieve and graphitized carbon  black materials  have
            been developed.   Various combinations of these materials  have  been
            shown to provide retention  properties similar  to  the  Tenax\Silica
            gel\Carbon  trap.  Alternate trap construction with such materials is
            allowed, provided that the adsorption  and desorption characteristics
            obtained achieve   equivalent  or  better  method   sensitivity   and
            precision  in comparison  to  the  performance  documented  in   the
            Determinative Method.

                        4.6.5.5.1     The following alternatives have been shown
                  to be viable for most analytes  of concern:

                  7.6-cm Carbopack™ B/1.3-cm Carboseive™  S-III
                  VOCARB 3000 - 10.0-cm Carbopack™ B /6.0-cm  Carboxin™ 1000/
                  1.0-cm Carboxin™ 1001
                  VOCARB  4000  -   8.5-cm  Carbopack™  C/lO.O-cm   Carbopack™
                  B/6.0-cm Carboxin™  1000/1.0-cm Carboxin™ 1001

                  These  combinations   require   rapid  heating  to desorption
                  temperatures  of  245°C  to  270°C   (follow  manufacturer's
                  instructions).  At these increased temperatures, catalytic and
                  thermal decomposition  of  analytes has  been reported.   The
                  VOCARB  4000  combination  has   also  been   demonstrated  to
                  catalytically break  down  2-chloroethyl  vinyl ether,   and  to
                  partially  decompose  2,2-dichloropropane.     Bromoform   and
                  bromomethane have shown some  thermal  decomposition.

                        4.6.5.5.2   The amount of thermal decomposition products
                  formed must be routinely tracked by  daily monitoring of the
                  formation of chloromethane and bromomethane. A  daily check
                  standard  containing  surrogates,   internal   standards,   and
                  20 M9/L bromoform must  be analyzed  prior to the analysis of
                  the daily  check  standard.   If  levels  of   chloromethane  or
                  bromomethane exceed  0.5  jug/L,  then the  trap   may  be  too
                  contaminated with salts or  tightly  bound contamination for
                  analysis to  continue.  The  trap must  be  replaced  and the
                  system recalibrated.

NOTE:  Even newly constructed traps may have become contaminated prior to their
      first use from airborne vapors.  These highly adsorptive materials must be
      kept tightly sealed in an area of minimum organic vapor  contamination.

      4.7   Heater  or  heated oil   bath - capable  of maintaining  the  purging
chamber to within 1°C,  over a temperature range from ambient  to 100°C.
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      4.8   Capillary GC  Columns  - Any  GC  column  that meets  the  performance
specifications  of the  determinative method  may  be  used.  See the  specific
determinative method for recommended  columns,  conditions and retention times.

            4.8.1 The wide-bore columns have the capacity to accept the standard
      gas flows from the trap during  thermal desorption, and chromatography can
      begin with  the  onset of  thermal desorption.   Depending  on  the pumping
      capacity of the MS,  an additional interface between the end of the column
      and the MS may be required.  An open  split interface ,  an all-glass jet
      separator, or a cryogenic (Sec. 4.8.2) device are acceptable interfaces.
      The type of interface and  its adjustments can  have  a significant impact on
      the  method detection  limits.    Other  interfaces can  be  used if  the
      performance specifications described in this  method  can be achieved.

            4.8.2 A system  using  a narrow bore column will  require  lower gas
      flows of approximately 2-4 mL/minute.  Because of  these low desorption
      flows, early eluting analytes need  to be refocussed  to elute in a narrow
      band.  This refocussing may be carried out by  using a cryogenic interface.
      This  type of  interface  usually uses  liquid nitrogen  to condense  the
      desorbed sample components in  a narrow  band  on  an uncoated fused silica
      precolumn.  When  all components have  been desorbed  form  the  trap,  the
      interface is rapidly heated  under a stream of carrier gas to transfer the
      analytes  to  the analytical   column.   The end  of the  analytical  column
      should  be  placed  within  a  few mm  of  the MS ion  source.   A  potential
      problem with this  interface  is  blockage  of the interface by ice caused by
      desorbing water from the trap.  This condition will result  in a major loss
      in sensitivity  and  chromatographic resolution.    Low surrogate  compound
      recoveries can be  a sign that this  is occurring.


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   See the determinative method and Method 5000 for  guidance on internal
and surrogate standards.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   Refer to the introductory material  to this chapter, Organic Analytes,
Sec. 4.1.  Samples should be stored in capped bottles, with minimum headspace,
at 4°C or less in an  area  free of solvent  fumes.  The size of any bubble caused
by degassing upon cooling the sample  should  not exceed 5-6 mm.  When a bubble
is present, also observe the cap and septum to ensure that a  proper seal was made
at time  of sampling.    Is  there any  evidence  of leakage?   If  the  sample was
improperly sealed, the sample should be discarded.

      6.2   All samples  should be analyzed within 14 days of  collection.  Samples
not analyzed within this period must  be  noted and  data  are considered minimum
values.
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7.0   PROCEDURE

      7.1   The purge-and-trap technique for aqueous samples is found in Sec. 7.2
and guidance for analysis of solvent extracts from the High Concentration Method
in Method 5035  is found in Sec. 7.3.  The gas chromatographic determinative steps
are found  in Methods  8015 and 8021.   The  method is also applicable  to GC/MS
Method 8260. For the analysis of gasoline,  use Method 8021 with GC/PID for BTEX
in series with  Method 8015 with the GC/FID detector for hydrocarbons.

      7.2   This section provides guidance on the analysis of aqueous samples and
samples that are water miscible,  by purge-and-trap  analysis.

            7.2.1 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  5000 give details  on  preparation  of
      standards.    The  GC/MS  methods  require  instrument  tuning  prior  to
      proceeding with calibration.

                  7.2.1.1     Assemble a purge-and-trap device  that meets the
            specification in Sec. 4.6.   Condition the  Tenax  trap overnight at
            180°C  (condition  other  traps  at the  manufacturers  recommended
            temperature)  in the purge  mode  with  an inert  gas  flow of  at least
            20  mL/min.  Prior  to  use,  condition the trap daily for  10 min while
            backflushing at 180°C with the column at  220°C.

                  7.2.1.2     Connect  the  purge-and-trap  device  to  a  gas
            chromatograph or gas  chromatograph/mass spectrometer system.

                  7.2.1.3     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 (a 10 ml or 25 ml syringe may be used if preferred) 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 pi or 25  ]LtL micro-syringe
            equipped  with a  long  needle  (Sec.  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 10.0  juL of the internal  standard solution.
            Close the 2-way syringe valve at the sample  inlet.  (The calibration
            standard,  internal  standard and  surrogate standard may  be added
            directly to the organic free reagent  water in the syringe prior to
            transferring the water to the purging device, see Sec. 7.2.4.7).
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            7.2.1.4     Follow the  purge-and-trap analysis as outlined in
      Sec. 7.2.4.

            7.2.1.5     Calculate response  factors  (RF)  or  calibration
      factors  (CF)  for  each  analyte  of  interest  using  the  procedure
      described in Method 8000.

            7.2.1.6     The  average  CF  (external  standards)   or   RF
      (internal  standards)  must  be calculated for  each  compound.   For
      GC/MS analysis,  a system performance check must be made before this
      calibration curve is used  (see Method 8260).  If the  purge-and-trap
      procedure is used with  Method 8021, evaluate  the response  for  the
      following  four  compounds:    chloromethane;   1,1-dichloroethane;
      bromoform; and 1,1,2,2-tetrachloroethane.  They are used to check
      for  proper purge  flow  and  to  check  for  degradation  caused  by
      contaminated lines or active  sites in  the system.

                  7.2.1.6.1   Chloromethane:   This compound  is the most
            likely compound to be lost if the purge  flow  is  too fast.

                  7.2.1.6.2   Bromoform:  This compound is  one   of  the
            compounds most likely to be purged very poorly  if  the purge
            flow  is  too slow.   Cold  spots  and/or  active  sites   in  the
            transfer lines may adversely affect response.

                  7.2.1.6.3   1 , 1 , 2 , 2-Tetrachl oroet h ane    and
            1,1-dichloroethane:     These  compounds  are  degraded   by
            contaminated transfer lines in purge-and-trap  systems and/or
            active sites in trapping  materials.

            7.2.1.7     The analytes in Method 8021 normally are not  as
      strongly  affected  by  small  changes  in  purge  flow  or   system
      contamination.  When analyzing for very late eluting compounds with
      Method  8021  (i.e.,  hexachlorobutadiene,  1,2,3-trichlorobenzene,
      etc.),  cross  contamination  and  memory  effects  from   a  high
      concentration sample  or even the standard  are  a common problem.
      Extra rinsing of the purge  chamber after analysis normally corrects
      this. The newer purge-and-trap  systems often  overcome  this  problem
      with  better bakeout  of the  system following the  purge-and-trap
      process.  Also, the charcoal traps retain  less moisture and decrease
      the problem.

      7.2.2 Calibration verification:  Refer to Method 8000 for details on
calibration verification.

            7.2.2.1     To  prepare  a  calibration   standard,  inject  an
      appropriate volume of a  primary dilution  standard to an aliquot  of
      organic  free  reagent water  in  a  volumetric  flask,  a gas  tight
    •  syringe, or to a purge device,  and inject an  appropriate  amount  of
      internal standard to the organic  free reagent water.   Be sure  the
      same  amount  of internal standard  is  added to  each standard  and
      sample.    The  volume  of  organic  free  reagent  water  used  for
      calibration  must  be  the  same  volume  used   for  sample analysis
      (normally 5 ml).  The surrogate  and internal standard solutions must

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be added with a syringe  needle long enough to ensure addition below
the surface  of the  water.   Assemble the  purge-and-trap  device as
outlined  in   4.6.    Follow the  guidance  for  the  purge-and-trap
procedure in Sec. 7.2.4.  Ongoing GC or GC/MS calibration criteria
must be met as specified in Method 8000 before analyzing samples.

7.2.3 Sample screening

      7.2.3.1     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  (Method  5021) 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.

7.2.4 Sample introduction and purging

      7.2.4.1     All samples and standard solutions must  be allowed
to warm to ambient temperature before analysis.

      7.2.4.2     Assemble the purge-and-trap device.  The operating
conditions  for the  GC  and GC/MS  are  given  in  Sec.  7.0  of  the
specific determinative  method to  be  employed.   Whole oven cooling
may be needed for certain GC columns and/or certain GC/MS  systems to
achieve  adequate resolution of  the gases.   Normally a 30 meter
wide-bore column will require cooling the GC oven to 25°C or below
for resolution of the gases.

      7.2.4.3     GC or  GC/MS calibration verification criteria must
be met (Method 8000) before analyzing samples.

      7.2.4.4     Adjust  the  purge  gas  flow  rate  (nitrogen  or
helium) to 25-40 mL/min (also see Table 1 for guidance on specific
analyte groups), 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.

      7.2.4.5     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

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properly.  Filling one 10 or 25 ml  syringe  would  allow the use of
only one syringe.   If a second analysis is  needed from a syringe, it
must be analyzed within 24 hr.  Care  must be taken to prevent air
from leaking into the syringe.

      7.2.4.6     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.

            7.2.4.6.1   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.

            7.2.4.6.2   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.

            7.2.4.6.3   Inject the proper aliquot  of  samples from
      the syringe prepared in Sec.  7.2.4.5 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.

            7.2.4.6.4   Fill  a 5 ml  syringe with the diluted sample
      as in Sec. 7.2.4.5.

      7.2.4.7     Add 10.0 juL of surrogate spiking solution (found
in each determinative method, Sec. 5.0) and, if applicable, 10.0 /zL
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 (10.0 juL)  to the sample at
this time.

      7.2.4.8     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.

      7.2.4.9     Close both valves  and purge the sample  for the
time  and  at  the  temperature  specified  in  Table 1.    For  GC/MS
analysis using  Method  8260,  purge  time  is  11 minutes  at ambient
temperature.

7.2.5 Sample desorption

      7.2.5.1     Non-cryogenic interface  -  After the  11  minute
purge (also see Table 1 for guidance  on specific  analyte groups),
place the purge-and-trap system in the desorb mode and preheat the
trap to 180°C (temperature may  vary depending  on the trap material)
without a flow of  desorption gas.   Certain  purge-and-trap systems
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allow the  use  of a  dry  purge at  this  point to  eliminate  excess
moisture from the gas lines.  Then simultaneously,  start the flow of
desorption gas at  15  mL/minute (10 mL/minute may  be  adequate for
certain traps)  for  about  four minutes  (1.5 min is normally adequate
for analytes in Method 8015); begin the temperature program of the
gas chromatograph;  and,  start  data  acquisition.   The  15  mL/minute
desorption gas flow rate pertains  to  the  standard silica gel  trap
and a GC equipped with a wide bore capillary column.

      7.2.5.2     Cryogenic interface - After the 11  minute purge,
place the purge-and-trap system  in  the  desorb mode, make sure the
cryogenic interface is  -150°C  or lower, and rapidly heat the trap to
180°C (temperature may vary  depending  on  the trap material)  while
backflushing with an inert gas at  4 mL/minute for about  5 minutes
(1.5 min is normally adequate for analytes  in Method 8015).  At the
end of  the  5-minute desorption cycle,  rapidly  heat the  cryogenic
trap to 250°C;  simultaneously begin the temperature program of the
gas chromatograph,  and, start the data acquisition.

7.2.6 Trap Reconditioning

      7.2.6.1     After desorbing the sample, recondition the trap
by returning the purge-and-trap device to the purge mode.  Wait 15
sec; then close the  syringe valve on the purging  device to begin gas
flow through the  trap.  The trap temperature should be maintained at
180°C for Methods 8021 and 8260,  and  210°C for  Method 8015.   Trap
temperatures up  to 220°C  may be  employed.   However, the  higher
temperatures will  shorten the useful  life of   the  trap.   (Trap
temperatures may vary  depending on  the  trap  material).   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.

      7.2.6.2     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
methanol followed by organic  free reagent water)  to avoid carryover
of volatile organics into subsequent analyses.

7.2.7 Interpretation and calculation of data

      7.2.7.1     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 the analysis of
organic free reagent water.   If  the blank analysis is not free of
interferences, the system must be decontaminated.  Sample analysis
may not resume  until  a blank can meet the organic-free reagent water
criteria specified  in Chapter One.

      7.2.7.2     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

                      5030B  -  10                         Revision  2
                                                      January  1995

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            specific determinative method  for details on  calculating analyte
            response.

            7.2.8 Analysis of water-miscible liquids

                  7.2.8.1     Water-miscible  liquids   are  analyzed   as  water
            samples after first diluting them at least  50-fold with organic-free
            reagent water.

                  7.2.8.2     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.

                  7.2.8.3     Alternatively,  prepare  dilutions  directly  in  a
            5 ml syringe  filled  with  organic-free  reagent water by  adding at
            least 20.0 ,LiL,  but  not  more than 100.0 /uL of  liquid  sample.   The
            sample  is  ready  for addition  of  surrogate  and,   if  applicable,
            internal and matrix spiking standards.

      7.3   This section provides guidance on the  analysis of solvent extracts
from High Concentration Samples prepared by Method  5035.

            7.3.1 The GC or GC/MS system should  be set up as in Sec. 7.0 of the
      specific determinative method.   This should be done prior to the addition
      of the solvent extract to organic-free reagent water.

            7.3.2 Table 2 can be used to determine the  volume of solvent extract
      to add  to  the 5 mL of organic-free reagent  water  for analysis.   If  a
      screening  procedure was  followed,  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  100.0 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 Remove  the plunger  from  a  5.0  ml Luer-lok type syringe
      equipped with a syringe valve and fill  until overflowing with organic-free
      reagent water. Replace the plunger and compress  the water to vent trapped
      air.   Adjust  the volume to  4.9  ml.  Pull the plunger  back to  5.0  mL to
      allow volume for  the addition of the sample extract and of standards.  Add
      10.0  /xL  of internal standard  solution.  Also add the  volume  of solvent
      extract determined in  Sec.  7.3.2 and a  volume of the same solvent used in
      Method 5035 to total 100.0 /zL (excluding methanol in standards).

            7.3.4 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.

            7.3.5 Proceed  with  the   analysis  as  outlined  in  the  specific
      determinative method.   Analyze all reagent blanks on the  same instrument
                                  5030B - 11                        Revision 2
                                                                  January 1995

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      as that  used for  the samples.   The standards  and  blanks  should  also
      contain 100.0 juL of methanol to simulate the sample conditions.

      7.4   Sample analysis:

            7.4.1 The samples prepared by this method may be analyzed by Methods
      8015, 8021,  and  8260.   Refer to these methods  for appropriate analysis
      conditions.  For  the analysis of gasoline, use Method 8021 with GC/PID for
      BTEX in series with Method 8015 with the GC/FID detector for hydrocarbons.


8.0   QUALITY CONTROL

      8.1   Refer  to Chapter One  for specific quality  control  procedures and
Method 5000 for sample preparation QC procedures.

      8.2   Before processing any samples,  the analyst should demonstrate through
the analysis of an organic-free reagent water method 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 blank samples 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.   Each  analysis batch of  20 or  less  samples must  contain:  a reagent
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.

      8.4   Surrogate standards should be  added to all  samples when  specified in
the appropriate determinative method


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.

2.    Bellar, T.,  "Measurement of  Volatile  Organic Compounds in  Soils  Using
      Modified    Purge-and-Trap    and    Capillary    Gas   Chromatography/Mass
      Spectrometry",   U.S.   Environmental   Protection  Agency,   Environmental
      Monitoring Systems Laboratory, Cincinnati, OH, November, 1991.
                                  5030B - 12                        Revision 2
                                                                  January 1995

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                                TABLE  1
                  PURGE-AND-TRAP OPERATING  PARAMETERS

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)

8015
N2 or He
20
15.0 ±0.1
85 ±2
180
20-60
1.5
Analysis Method
8021/8260
N2 or He
40
11.0 ±0.1
Ambient
180
20-601
4
1  The desorption flow rate  for Method 8021 with a wide bore capillary column
  will optimize at approximately 10 to 15 mL/minute.
                              5030B - 13                        Revision 2
                                                              January 1995

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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 jxg/kg                             100 /*L
             1,000-20,000 Mg/kg                              50 /*L
             5,000-100,000 M9/kg                             10 ni
            25,000-500,000 Mg/kg                100 /uL of 1/50 dilution6


Calculate appropriate dilution factor for concentrations exceeding this table.

    8 The volume of methanol  added to 5  mL of water being purged should be kept
      constant.  Therefore, add to the 5 mL syringe whatever volume of methanol
      is necessary to maintain a volume of 100 ^l added to the syringe.

    b Dilute  an  aliquot  of  the  methanol  extract and  then  take  100 nl  for
      analysis.
                                  5030B - 14                        Revision 2
                                                                  January 1995

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         FIGURE  1
EXAMPLE  OF PURGING  DEVICE
      CtfT 1M M O.O
             7 CM 20 OMJQC STMMOf NC
                                     OO
                             /^ STAINLESS STEEL
        5030B -  15
  Revision 2
January  1995

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                     FIGURE 2
    EXAMPLE OF TRAP PACKINGS  AND CONSTRUCTION
          TO  INCLUDE  DESORB CAPABILITY
PACKING OCTAM.
CONSTRUCTION OCTAA.
    *• S MM 
-------
                             FIGURE 3
            SCHEMATIC OF TYPICAL PURGE AND  TRAP DEVICE
                            PURGE MODE
CARWERGAS
PLOW CONTROL
PRESSURE
REGULATOR
UOU10 INJECTION PORTS

   i—COLUMN OVEN
   UW-,
   UUUV
                                                 CONFIRMATORY COLUMN
                                               TO DETECTOR
                                                 ANALYTICAL COLUMN
PURGE GAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
                              OPTIONAL **ORT COLUMN
                              SELECTION VALVE
                                       TRAP INLET
                                      TRAP
                                      2TC
                                 PURGING
                                 DEVICE
             NOTE
             ALL UNES BETWEEN TRAP
             AND OC SHOULD BE HEATED
             TO «TC
                             5030B - 17
                            Revision 2
                          January 1995

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                             FIGURE  4
            SCHEMATIC OF TYPICAL  PURGE AND TRAP  DEVICE
                           DESORB MODE
CARRfcTROAB
FLOW CONTROL
PRESSURE
REGULATOR
UOUK) INJfCnON PORTS
    — COLUMN OVEN
                               OPTIONAL *PORT COLUMN
                               SELECTION VALVE
               CONFIRMATORY COLUMN

              TO DETECTOR
                                                 ANALYTICAL COLUMN
PU«G€GAS
R.OW CONTROL
13X MOLECULAR
SIEVE FILTER
                                               NOTE
                                               ALL UNES BETWEEN TRAP
                                               AND OC SHOULD BE HEATED
                                               TO«TC
                             5030B  -  18
                            Revision  2
                          January  1995

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               METHOD  5030B
PURGE-AND-TRAP  FOR AQUEOUS  SAMPLES
                                               Use Method 8015 (GC/FID) for
                                               hydrocarbons and 3021
                                               (GC/PID) for BTEX
                        Solvent Extract from
                        High Concentration
                        Method in 5035
    7 3 1 Set up GC or GC/MS system as described in
    Section 7.0 of determinative method to be used
     732 Use Table 3 to determine volume of extract
     to add to 5 ml water for analysis
                     I
    733 Fill 5 mL Luerlock Syringe until overflowing
    with water Replace plunger and compress water.
    Adjust volume to 4.9 mL  Add 10 uL internal std.,
    volume of extract determined in Section 7.3 2, and
    same solvent used in Method 5035 to total 100 uL
      7 3.4 Attach syringe-syringe valve assembly to
      syringe valve on purging device Inject water/
      MeOH sample into purging chamber
                      I
      735 Analyze as per specific determinative
      method.
                 5030B  -   19
   Revision  2
January 1995

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                    METHOD  5030B
                       continued
                Aqueous or water-misable sample
7 2 1 Perform initial GC calibration using Methods 5000,8000. and the
     determinative method to be used  Perform instrument tuning prior to
     calibration for QC/MS
     .1 Assemble purge-and-trap device per Section 4 6.
       Condition Tenax trap
      2 Connect purge-and-trap device to GC or GC/MS
     .3 Prepare calibrator) stds directly in purging device  Add
       5 ml water to device with a synnge  Uptake appropriate
       volume of standard with a rricro-synnge and add to water in device
       Add 10 uL of internal std. Close synnge valve  Introduce
       sample and  purge as per Section 7 Z4
                           I
  7.2.2 Perform calibration verification as required by Method 8000
       1 Prepare calibration std  by injecting appropriate
       volume of primary std. to water and adding
       appropriate amount of internal std
                 7 2.3 Screen sample if necessary
 7.2.4 Sample introduction and purging
      .1 Warm samples to room temp. (7 2.8' Dilute water-mtscible
      liquids at least 50x with water)
       4 Adjust purge gas flow rate
       5 Pour sample into synnge barrel just short of overflowing
        Replace plunger and compress sample  Open valve
        and vent while adjusting volume to 5 mU
       6 Dilute sample if necessary.
       7 Add 10 uL of surrogate spiking soln and 10 uL of internal
        std.. if required
      .8 Attach synnge-synnge valve assembly to synnge valve on
        purging device Open valves and inject sample into purging
        chamber
       9 Close valves and purge as per Table 2
                       5030B  -  20
    Revision   2
January  1995

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                                              METHOD  5030B
                                                continued
                                          7.2.5 Sample desorption
7.2.5.1 Place system in desorb mode
and preheat trap to 180C without
gas flow Simultaneously start flow
of gas, temp, program of GC, and
data acquisition.
7.2.5.2 Place system in desorb mode
and rapidly heat trap to 180C while
backflushing with inert gas for 5 min.
Rapidly heat trap to 250C.
Simultaneously begin temp, program
of GC and data acquisition.
                                                    7.2.6
                                                 Recondition
                                                    trap
                                            727 Interpret data and
                                            calculate results.
                                                5030B -  21
                      Revision  2
                   January 1995

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                                  METHOD 5031

  VOLATILE. NONPURGEABLE. WATER-SOLUBLE COMPOUNDS BY AZEOTROPIC DISTILLATION


1.0   SCOPE AND APPLICATION

      1.1   This method describes a procedure for separation of nonpurgeable,
water-soluble, and volatile organic compounds in aqueous samples or leachates
from solid matrices using azeotropic distillation.  The appropriate gas
chromatographic/mass spectrometric (GC/MS) determinative steps are found in
Method 8260.  The appropriate gas chromatographic/flame ionization (GC/FID)
determinative steps are found in Method 8015.  This separation method should
be used as an alternative to Method 5030 for compounds that are difficult to
purge and trap.  Method 5031 is useful in the determination of the following
compounds:
                  Compound Name                       CAS No."
                  Acetone                              67-64-1
                  Acetonitrile                         75-05-8
                  Acrolein                            107-02-8
                  Acrylonitrile                       107-13-1
                  Allyl alcohol                       107-18-6
                  1-Butanol                           104-51-8
                  t-Butyl alcohol                      75-65-0
                  Crotonaldehyde                      123-73-9
                  1,4-Dioxane                         123-91-1
                  Ethanol                              64-17-5
                  Ethyl Acetate                       141-78-6
                  Ethylene oxide                       75-21-8
                  Isobutyl alcohol                     78-83-1
                  Methanol                             67-56-1
                  Methyl ethyl ketone                  78-93-3
                  Methyl isobutyl ketone              108-10-1
                  N-Nitroso-di-n-butylamine           924-16-3
                  Paraldehyde                         123-63-7
                  2-Pentanone                         107-87-9
                  2-Picoline                          109-06-8
                  1-Propanol                           71-23-8
                  2-Propanol                           67-63-0
                  Propionitrile                       107-12-0
                  Pyridine                            110-86-1
                  o-Toluidine                          95-53-4
            " Chemical  Abstract  Services  Registry  Number
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      1.2   Additional compounds may be separated successfully using this
method.  However, use of this method to detect and measure additional  analytes
may be done only after the laboratory obtains acceptable accuracy and
precision data for each additional analyte.  In general, compounds that form a
water azeotrope that is greater than 50% analyte, with this azeotrope boiling
at less than 100°C, can be successfully distilled.  The initial study to
determine the ability of this method to separate compounds found that the
following compounds perform poorly in this method:5

      Compound              CAS No.        Compound               CAS No.

      Aniline               62-53-3        Methacrylonitrile      126-98-7
      Dimethylformamide     68-12-2        Phenol                 108-95-2
      2-Ethoxyethanol      110-80-5        Propargyl alcohol      107-19-7

      1.3   The method detection limits (MDLs) and analyte concentration
ranges are listed in the appropriate determinative methods.  The MDL for a
sample may differ from those listed, depending on the nature of interferences
in the sample matrix.

      1.4   This method is restricted to use by or under the supervision of
analysts experienced in procedures involving quantitative separation
techniques.  Each analyst must demonstrate the ability to generate acceptable
results with this method.
2.0   SUMMARY OF METHOD

      2.1   An azeotrope is a liquid mixture of two or more substances which
behaves like a single substance, in that it boils at a constant temperature
and the vapors released have a constant composition.  Azeotropic distillation
is a technique which uses the ability of selected organic compounds to form
binary azeotropes with water to facilitate the separation of the compounds
from a complex matrix.

      2.2   Macrodistillation technique:  One liter of the sample is buffered
to pH 7, spiked with the surrogate spiking solution, and brought to boiling in
a 2 L distillation flask.  The polar, volatile organic compounds (VOCs)
distill into the distillate chamber for 1 hour, and are retained there
(Figure 1).  The condensate overflows back into the pot and contacts the
rising steam.  The VOCs are stripped from the steam and are recycled back into
the distillate chamber.  Analytes are detected and quantitated by either
direct aqueous injection GC/MS or GC/FID.

      2.3   Microdistillation technique:  An aliquot (normally 5 g or 40 ml)
of sample is azeotropically distilled, and the first 100 /xL of distillate are
collected.  The water soluble volatile organic compounds are concentrated into
the distillate using a microdistillation system.  Most semi- and non-volatile
interferences remain in the boiling flask.  Use of an internal standard is
recommended to improve method precision.  Concentration factors are typically
one and two orders of magnitude for soil and water matrices, respectively.
The distillation takes five to six minutes.  Analytes are detected and
quantitated by either direct aqueous injection GC/MS or GC/FID.


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3.0   INTERFERENCES

      3.1   Method interference may be caused by contaminants in solvents,
reagents, glassware and other sample processing hardware that lead to discrete
artifacts and/or elevated baselines in the chromatograms.  All  of these
materials must be routinely demonstrated to be free from interferences under
the conditions of the analysis by running laboratory method blanks.

            3.1.1 Glassware must be scrupulously cleaned.  Clean all glassware
      as soon as possible after use by rinsing with the last solvent used.
      This should be followed by detergent washing with hot water, and rinses
      with tap water and organic-free reagent water.  It should then be
      drained dry, and heated in a laboratory oven at 150°C for several hours
      before use.   After drying and cooling, glassware should  be stored in a
      clean environment to prevent any accumulation of dust or  other
      contaminants.  Phenol and aniline are particularly difficult to clean
      from glassware.

            3.1.2 Interfering contamination may occur when a sample containing
      low concentrations of volatile organic compounds is analyzed immediately
      after a sample containing high concentrations.  One or more blanks
      should be run to check for cross-contamination.

            3.1.3 After analysis of a sample containing high concentrations of
      volatile organic compounds, one or more blanks should be  analyzed to
      check for cross contamination.

      3.2   Matrix interferences may be caused by contaminants  that are in the
sample.   The extent of matrix interferences will vary considerably from source
to source, depending upon the nature and diversity of the matrix being
sampled.  If significant interferences occur in subsequent samples, additional
cleanup may be necessary.


4.0   APPARATUS AND MATERIALS

      4.1    Macrodistillation System:

            4.1.1 Round bottom flask,  2 L, 14/20 ground glass joint.

            4.1.2 Vigreux column, 20 cm long, 14/20 ground glass joint.

            4.1.3 Modified Nielson-Kryger apparatus (Figure 1).   This
      glassware can be made by a glassblower, or a similar apparatus can be
      purchased and then modified by a glassblower according to  the dimensions
      given in Figure 1.

            4.1.4 Recirculating, submersible pumps - One for each distillation
      apparatus.  Alternatively, a water chiller may be used in  place of a
      recirculating submersible pump,  with ice water, if the chiller can
      maintain a temperature of 0°C to 5eC in all  distillation  condensers.

            4.1.5 Five-gallon container - Preferably insulated,  holds ice
      water to maintain condenser temperature.

                                   5031 - 3                         Revision 0
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      4.1.6 Volumetric glassware - 10 ml class A volumetric flasks and
volumetric pipets of various sizes, 1 to 3 ml.

      4.1.7 Sample/standard vials - 4 dram glass Teflon®-! ined screw cap
or crimp top vials.

      4.1.8 pH Paper - narrow range (6.0-8.0).

4.2   Microdistillation System:

      4.2.1 Wadsworth MicroVOC3 System", Shamrock Glass, or equivalent:

            4.2.1.1     Round bottom flask, 100 ml, 14/20 ground glass
      joint.

            4.2.1.2     Fractionation column,  14/20 ground glass joint,
      1.6 cm OD, 1.3 cm ID, 60 cm length (see Figure 2).

            4.2.1.3     Pipe insulation, polyurethane foam, 1.5 inch OD,
      0.5 inch ID, 55 cm in length.

            4.2.1.4     Glass beads, 5 mm OD.

            4.2.1.5     Keck clamps for 14/20 ground glass joint.

            4.2.1.6     Glass reducing union,  14/20 ground glass joint
      to 6 mm OD tube (see Figure 3).

            4.2.1.7     Stainless steel reducing union, 1/16 inch to 1/4
      inch.

            4.2.1.8     Air condenser, Teflon® tubing, 1/16 inch OD to
      1/32 inch ID (40 cm in length, or equivalent).

      4.2.2 Support stand with rod, 1 meter.

      4.2.3 Three finger clamps.

      4.2.4 Heating mantle, Glas-Col, 115 volts, 230 watts, STM 400, or
equivalent.

      4.2.5 Temperature controller, Glas-Col PL-115-Cordtrol, 115 volts,
600 watts, or equivalent.

      4.2.6 Porous carbon boiling chips, VWR Catalog No. 26397-409, or
equivalent.

      4.2.7 Autosampler vials - glass, with Teflon®-!ined screw cap or
top vials.

      4.2.8 Autosampler vial inserts, 100 jitL  - The  vial may be
calibrated by dispensing a known volume of liquid into it, and marking
the side of the vial.
                             5031 - 4                         Revision 0
                                                            January 1995

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      4.3   Balance - Analytical, capable of weighing 0.0001 g.

      4.4   Microsyringes - Various sizes.


5.0   REAGENTS

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

      5.2   Organic-free Reagent Water - All references to water in this
method refer to organic-free reagent water as defined in Chapter One.

      5.3   Potassium phosphate, monobasic, KH2P04  (macrodistillation
technique).

      5.4   Sodium phosphate, dibasic, Na2HP04  (macrodistillation technique).

      5.5   Sodium chloride, NaCl (macrodistillation technique).

      5.6   Stock Standard Solutions - Prepared from pure standard materials
or from purchased certified solutions.

            5.6.1 Prepare, in organic-free reagent water, a set of stock
      standard solutions each containing one of the target analytes.  Place
      about 9.0 ml of organic-free reagent water in a 10 ml tared,  ground-
      glass stoppered volumetric flask.  Weigh the flask to the interest
      0.0001 g.  Add the assayed reference material, as described below:

                  5.6.1.1     Liquids - Using a 100 /zL syringe, immediately
            add two or more drops of assayed reference material to the flask
            using the known density as an approximate guide to place 0.100 g
            in the flask.  The liquid must fall directly into the water
            without contacting the neck of the flask.

                  5.6.1.2     Solids - Add enough material to achieve
            approximately 0.100 g in the flask.

NOTE: The solubility of N-nitroso-di-n-butylamine in water is approximately
      1000 mg/L.  All other stock solutions should be 10,000 mg/L.

            5.6.2 Reweigh, dilute to volume, stopper, and then mix by
      inverting the flask several times.  Calculate the concentration in
      milligrams per liter (mg/L) from the net gain in weight.  When compound
      purity is assayed to be 96% or greater, the weight may be used without
      correction to calculate the concentration of the stock standard.
      Commercially prepared stock standards may be used at any concentration
      if they are certified by the manufacturer or by an independent source.


                                   5031 - 5                         Revision 0
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            5.6.3 Transfer the stock standard solution into a Teflon®-sealed
      screw cap bottle.  Store, with minimal headspace, at 4°C, and protect
      from light.

            5.6.4 Prepare fresh stock standard every month.  Reactive
      compounds, such as acrylonitrile and N-nitroso-di-n-butylamine, may need
      to be prepared more frequently.  Standards must be monitored closely.
      See individual determinative methods for calibration requirements.

      5.7   Secondary dilution standards - Using stock standard solutions,
prepare secondary dilution standards, in organic-free reagent water,
containing the compounds of interest, either singly or mixed together.
Secondary dilution standards should be checked frequently for signs of
degradation or evaporation, especially just prior to preparing calibration
standards from them.  Store in a vial with minimal headspace for 1 week only.

      5.8   Stock Surrogate Solutions and Surrogate Spiking Solution

            5.8.1 GC/MS Surrogates - Recommended surrogates for GC/MS analysis
      (Method 8260) include de-acetone,  d3-acetonitrile,  d3-methanol,  d5-
      pyridine, d8-l,4-dioxane, and d5-phenol.   Although  not  all  the analytes
      will have corresponding surrogates readily available, their use allows
      very accurate quantitation by isotope dilution methods.  The stock
      surrogate solutions should be prepared as in Sec. 5.6, and a surrogate
      spiking solution should be prepared from the stocks at a concentration
      so that addition of 50 /iL of the spiking solution to the sample will
      produce a sample distillate with a concentration in the middle of the
      instrument calibration range, nominally 1000 mg/L.  Each sample
      undergoing GC/MS analysis must be spiked with the spiking solution prior
      to distillation (nominal 50 jug added to the sample).

            5.8.2 GC/FID Surrogates - Fluorinated alcohols and ketones may be
      used as surrogates when GC/FID analysis (Method 8015) is used, provided
      that the surrogates do not coelute with the target analytes.  No single
      surrogate can be recommended, at present, when every compound listed in
      Sec. 1.1 is included in the analyte list.  Nominally 50 jug of each
      fluorinated surrogate should be added to each sample prior to
      distillation.

NOTE: For small volume samples, the use of a spike volume greater than 200 /iL
      may excessively dilute the sample and reduce analyte recovery.

      5.9   Internal standards

            5.9.1 GC/MS Internal Standards - The recommended internal
      standards when using GC/MS analysis (Method 8260) are du-diglyme
      (diethylene glycol dimethyl ether), d6-isopropyl alcohol, d7-dimethyl
      formamide, and d5-benzyl alcohol.   Other compounds may be used as
      internal standards provided they exhibit similar retention times to the
      compounds being detected.  Care should be taken to avoid acquiring
      compounds in which active hydrogens are deuterium labeled, and which
      would exchange with the aqueous matrix.  It is recommended that the
      secondary dilution standard be prepared at a concentration of 1000 mg/L.


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      Each distillate will be spiked at a concentration corresponding to 10
      ppm of the internal standards after distillation and just before GC/MS
      analysis.

            5.9.2 GC/FID Internal Standards - Halogenated alcohols, ketones,
      and nitriles may be used as internal standards when GC/FID analysis
      (Method 8015) is used.  The recommended internal standards are
      hexafluoro-2-propanol, hexafluoro-2-methyl-2-propanol,  and 2-
      chloroacetonitrile.  Nominally 5 to 50 ^g of each internal standard
      should be added to each sample prior to distillation.  The total spike
      volume should be less than 1 ml to avoid excessively diluting the sample
      and lowering analyte recovery.  Ethanol or other alcohols may be used as
      internal standards, provided that they are neither target analytes nor
      present in the sample.

      5.10  Calibration standards

            5.10.1      Prepare calibration standards using the recommended
      analyte, surrogate, and internal standard concentrations as specified in
      the appropriate determinative method (Methods 8015 or 8260).   All
      calibration standards should be prepared by the same procedure as the
      samples to be analyzed.

      5.11  All standards should be stored at 4°C in Teflon®-!ined, screw-
capped vials with minimal headspace.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the introductory material to this Chapter, Organic Analytes,
Sec. 4.1.

NOTE: At this time, the effect of reducing agents or preservatives on method
      performance has not been evaluated.  Preservation of samples is
      difficult because almost all preservatives could potentially interfere
      with the analysis.  Storage at 4°C appears to be the best way to
      preserve most samples until analysis.

      6.2   Samples should be analyzed within 14 days of sample collection.

      6.3   The distillate should be stored at 4°C prior to analysis.  It is
recommended that the distillate be analyzed within 24 hours of distillation.
Distillates must be analyzed within 7 days of distillation.


7.0   PROCEDURE

      7.1   Macrodistillation procedure:

            7.1.1 Set up the azeotropic distillation apparatus as shown in
      Figure 1.  Fill the 5 gallon insulated container with ice and water, or
      connect the condenser to a chiller.  It is very important to maintain a
      temperature of 0°C to 5°C in the condensers.


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      7.1.2 Measure all aliquot of sample with a 1000 mL graduated
cylinder, and transfer it to a 1 L Erlenmeyer flask.  Add 3.40 g KH2P04,
and 3.55 g Na2HP04,  and  slowly  stir with  a  stir  bar  and  stir  plate  until
dissolved.  Check the pH with narrow range pH paper.  The pH of the
sample should be between 6.8 and 7.0.  Add more Na2HP04  if too acidic,
or more KH2P04 if too basic.

      7.1.3 Transfer the buffered sample to a 2 L round-bottomed flask.
Add 250 g of NaCl.  Addition of salt has been shown to increase method
efficiency for some of the compounds.

      7.1.4 Spike the sample with 50 /zL  surrogate spiking solution  (See
Sec. 5.8).

      7.1.5 Attach the Vigreux column to the flask and then the
condenser.

      7.1.6 Turn on the circulating pumps or chiller and heating
mantles.  After boiling has begun, the heating mantle voltage can be
reduced approximately 10% to 15% to maintain an even boiling.

      7.1.7 30 min after boiling begins, use a 5 ml syringe to remove
the distillate from the reservoir and place it into a preweighed
Teflon®-!ined screw cap vial.  Take a second sample after an additional
30 minutes have elapsed and combine it with the first sample.  Determine
the weight of the distillate.

      7.1.8 Add an amount of internal standard spiking solution so that
the distillate will have a concentration of 10 mg/L.  (For example, a 6
ml distillate would need 60 pg of internal standard).  Mix well and
store at 4°C until analysis.

7.2   Microdistillation procedure

      7.2.1 Aqueous samples

            7.2.1.1     Add 40 ml of the well-mixed sample to a 100 ml
      round bottom flask.  A smaller volume may be used if sample volume
      is limited, but the concentration  factor will be reduced
      accordingly.

            7.2.1.2     Add appropriate  volumes of the surrogate
      standards, internal standards and  matrix spiking solutions.

            7.2.1.3     Add 5 to 10 boiling chips to the flask, and
      place the flask in the heating mantle.

      7.2.2 Solid samples

            7.2.2.1     Add 5 g of sample to a 100 ml round bottom
      flask.
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                  7.2.2.2     Add appropriate volumes of the surrogate
            standards, internal standards, and matrix spiking solutions.

                  7.2.2.3     Add 40 ml of organic-free reagent water to the
            flask, and place the flask in the heating mantle.

            7.2.3 Assemble the micro distillation system (see Figure 4).

                  7.2.3.1     Attach the air condenser to the stainless steel
            reducing union (see Figure 3).  The air condenser and reducing
            unions must be completely dry to avoid diluting or contaminating
            the distillate.

                  7.2.3.2     Fill the fractionation column with glass beads.
            The fractionation column and glass beads must be completely dry.

                  7.2.3.3     Insulate the column with polyurethane foam.
            Attach the fractionation column to the 100 ml round bottom flask.
            Adjust a three finger clamp to hold the column upright

                  7.2.3.4     Attach the reducing union assembly to the top of
            the fractionation column, and hold in place with a Keck or three-
            finger clamp.

                  7.2.3.5     Place the free end of the air condenser into the
            collection vial.

            7.2.4 Heat the sample at a rate sufficient to bring it to a boil
      in 2-4 minutes for water samples, and 3-5 minutes for solid samples.
      Using the heating mantle assembly described in Sec. 4.2.4, these rates
      correspond to settings of 75% and 60% on the rheostat, respectively.

            7.2.5 Collect the first 100 /xL of distillate in a calibrated
      microvial.

                  7.2.5.1     Some bubbles may be present in the condenser.
            This may make collecting exactly 100 juL difficult, but acceptable
            results can be obtained with practice.

NOTE: Once steam begins to collect at the top of the fractionation column, it
      normally takes less than 10 seconds for 100 pi of distillate to be
      collected.

                  7.2.5.2     As the distillate collects in the collection
            vial, slowly back the air condenser tube out of the micro-vial as
            it fills.  This allows the bubbles to escape without dislodging
            the distillate from the micro-vial.  Remove the free end of the
            condenser from the vial when the collected volume reaches 100  /LtL.

                  7.2.5.3     A larger volume of distillate may be collected
            by using a larger vial.  In this case, the concentration factor
            will be reduced accordingly.  Collecting a larger volume will
            require longer condensation times, and may require water cooling
            of the condenser.  The steam flow rate continues to increase after

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            the first 100 p.1 of distillate is produced.  This flow can
            overwhelm the cooling capacity of the air condenser.   Lengthening
            the condenser to 100 cm may also be helpful.

NOTE: When 100 /A of distillate is collected from a 40 ml or 5 g sample, the
      theoretical concentration factors are 400 and 50, respectively.   Typical
      absolute recoveries of target analytes are 10% to 40%.   Thus,  the actual
      concentration factor is about 2 orders of magnitude for water samples
      and 1 order of magnitude for solid samples.  Distilling all  calibration
      standards compensates for low absolute recoveries.

            7.2.6 Cap the collection vial and store at 4°C until  the
      distillate is analyzed.

            7.2.7 Turn off the heating mantle and allow the system to cool.
      Do not attempt to disassemble the apparatus while it is hot.
      Significant steam pressure has built up within the system during
      distillation.  Disassembly could lead to a sudden release of steam.  The
      use of a smaller ID condenser or higher heating rates is not
      recommended, since this may cause the steam within the system to reach
      an unsafe pressure.

      7.3   Sample Analysis

            7.3.1 The samples prepared by this method may be analyzed by the
      appropriate GC or GC/MS method, such as Methods 8015 and 8260.  Refer to
      these methods for appropriate analysis conditions.

            7.3.2 All distillates and standards must be allowed to warm to
      ambient temperature before analysis.


8.0   QUALITY CONTROL

      8.1   Refer to Chapter One and Method 8000 for specific quality control
procedures.

      8.2   To establish the ability to generate data of acceptable accuracy
and precision refer to Method 8000 and the determinative method to be used.


9.0   METHOD PERFORMANCE

      9.1   See Methods 8015 and 8260 for performance data.


10.0  REFERENCES

1.    Peters, T.L.  "Steam Distillation Apparatus for Concentration of Trace
      Water Soluble Organics"; Anal Chem., 1980, 52(1), 211-213.

2.    Cramer, P.M., Wilner, J., and Stanley, J.S., "Final Report:   Method for
      Polar, Water Soluble, Nonpurgeable Volatile Organics (VOCs)", For U.S.


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      EPA, Environmental Monitoring Support Laboratory, EPA Contract No. 68-
      C8-0041.

3.    Lee, R.P., Bruce, M.L., and Stephens, M.W., "Test Method Petition to
      Distill Water Soluble Volatile Organic Compounds from Aqueous Samples by
      Azeotropic Microdistillation", submitted by Wadsworth/ALERT Laboratories
      Inc., N. Canton, OH, January, 1991.

4.    Bruce, M.L., Lee, R.P., and Stephens, M.W., "Concentration of Water
      Soluble Volatile Organic Compounds from Aqueous Samples by Azeotropic
      Microdistillation", Environ. Sci.  Techno!., 1992, 26, 160-163.


11.0  SAFETY

      11.1  The following target analytes are known or suspect to be human
carcinogens:  acrylonitrile and 1,4-dioxane.  Pure standard materials and
stock standard solutions of these compounds should be handled in a hood.
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          FIGURE 1.
AZEOTROPIC MACRODISTILLATION SYSTEM
    32mm
                    Cooling water
                      Collection Chamber
                       (Volume » 5 mi.)
                         Overflow tube
                          (4 mm OD)
                           Stopcock
         5031 - 12
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     FIGURE 2.
FRACTIONATION COLUMN
          14/20 Ground Glass
         Glass
         indentations
          14/20 Ground Glass
     5031  - 13
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                          FIGURE 3.
               AIR CONDENSER AND REDUCING UNIONS
                                                                      i
                                       Air Condenser
       Stainless Steal
       Reducing Union
                                     A OD Teflon® Tube
Glass Reducing Union
                                       6 mm 00 Tube
                                         14/20 Ground Glass Joint
                         5031 -  14
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             FIGURE 4.
AZEOTROPIC MICRODISTILLATION SYSTEM
                         Collection Vial
  Fractionation Column
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                                            METHOD 5031
  VOLATILE,  NONPURGEABLE,  WATER-SOLUBLE  COMPOUNDS  BY  AZEOTROPIC DISTILLATION
   7.1.1 Set up azeotrople
   distillation apparatus.
     Maintain a temp, of
   0-5°C in condensers.
  7.1.2 Transfer 1 L sample
  to Erlenmeyer flask. Add
   KH2P04 and  Na2HP04.
    Dissolve. Adjust pH.
          I
  7.1.3 Transfer buffered
   sample to 2  L round-
  bottom and add NaCI.
 7.1 .4 Spike sample with
surrogate spiking solution.
  7.1.5 Attach Vigreux
 column and condenser.
  7.1.6 Turn on pumps or
chiller and heating mantles
    Maintain even boil.
                                                                              7.2.1.1  Transfer 40 ml
                                                                                 sample to 100 ml
                                                                                   round-bottom.
 7.1.7 Boil 30 mm. Remove
distillate and place into pre-
 weighed vial. Boil 30 mm.
more. Remove distillate and
combine with first sample.
         Weigh.
   7.1 .8 Add internal std.
  spiking soln. to distillate
 concentration  of 10 ug/mL.
      Mix and  store at
      4C until analysis.
                                           7.2.2.1 Add 5g of
                                           sample to  1 00 mL
                                             round-bottom.
                                        7.2.2.2 Add appropriate
                                         volumes of surrogate
                                        stds., internal stds. and
                                        matrix spiking solution.
                                          7.2.2.3 Add 40 mL
                                            of organic-free
                                            reagent water.
                                                                              7.2.1.2 Add appropriate
                                                                            volumes of surrogate stds.
                                                                             internal  stds.,  and matrix
                                                                                 spiking solutions.
7.2.1
.3 Add boiling
chips.
                                                                                     1
                                                                                  7.2.4 Assemble
                                                                                  microdistillation
                                                                                system as in Figure 4.
                                                                                7.2.5 Heat to boiling
                                                                                     in 2-4 min.
7.2.6 Collect the 1st
 lOOuL distillate in a
 calibrated microvial.
                                                                              7.2.7 Cap vial and store
                                                                               at 4°C until analysis.
                                                                               7.2.8 Allow system to
                                                                               cool then disassemble.
                                                                                   7.3 Analyze
                                                                                  by appropriate
                                                                                  GC or GC/MS
                                                                                     method.
                                            5031  -  16
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                                  METHOD  5032

               VOLATILE  ORGANIC  COMPOUNDS BY VACUUM DISTILLATION
1.0  SCOPE AND APPLICATION

      1.1  Method 5032  is  used to determine  volatile organic compounds  in  a
variety of liquid,  solid,  oily waste matrices, and animal tissues.  This method
is  applicable  to  nearly  all  types  of  matrices  regardless  of water,  soil,
sediment,  sludge,  oil,  and  biota  content.    Method  5032  is  useful   in  the
determination of the following compounds:
Compound Name
Acetone
Acrolein
Acrylonitrile
Benzene
Bromodichloromethane
Bromoform
Bromomethane
2-Butanone
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chi orodi bromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Di bromomethane
l,4-Dichloro-2-butene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Ethanol
Ethyl benzene
Ethyl methacrylate
2-Hexanone
lodomethane
Methylene chloride
4-Methyl -2-pentanone
Styrene
1,1,2 , 2-Tetrachl oroethane
CAS No.8
67-64-1
107-02-8
107-13-1
71-43-2
75-27-4
75-25-2
74-83-9
78-93-3
75-15-0
56-23-5
108-90-7
124-48-1
75-00-3
110-75-8
67-66-3
74-87-3
74-95-3
764-41-0
75-71-8
75-35-4
107-06-2
75-35-3
156-60-5
78-87-5
10061-01-5
10061-02-6
64-17-5
100-41-4
97-63-2
591-78-6
74-88-4
75-09-2
108-10-1
100-42-5
79-34-5
                                    5032-1
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            Compound Name                       CAS No.a


        Tetrachloroethene                         127-18-4
        Toluene                                   108-88-3
        1,1,1-Trichloroethane                      71-55-6
        1,1,2-Trichloroethane                      79-00-5
        Trichloroethene                            79-01-6
        Trichlorofluoromethane                     75-69-4
        1,2,3-Trichloropropane                     96-18-4
        Vinyl acetate                             108-05-4
        Vinyl chloride                             75-00-3
        m-Xylene                                  108-38-3
        p-Xylene                                  106-42-3
        o-Xylene                                   95-47-6


            8  Chemical  Abstract Services Registry Number.


      1.2  This method can be used to quantify most volatile organic compounds
that have a boiling point below 180°C and are insoluble or slightly soluble in
water.  Reference Method 8260 for a list of compounds, retention times, and their
characteristic ions that have been  evaluated  on  the vacuum distillation GC/MS
system.  Method 8260  also  presents  a list of compounds  that  represent a wide
range of physical  properties.  These compounds have been minimally investigated
to assist in identifying potential analytes of this method.

      1.3  The method  detection  limits (MDL) determined are identified in tables
located in Method 8260.  Samples that require  dilution will have proportionately
higher detection limits.

      1.4  Method 5032 is based  on a vacuum distillation and cryogenic trapping
procedure followed by gas chromatography/mass spectrometry.  Alternate columns
and detectors may be substituted when appropriate.

      1.5  This method  is  restricted to use by,  or  under the  supervision of,
experienced personnel  who are familiar with the techniques of vacuum distillation
and experienced in  the  use of gas  chromatographs  and  mass  spectrometers as a
quantitative  tool.    Each  analyst  must  demonstrate  the  ability  to  generate
acceptable results with this method.


2.0  SUMMARY OF METHOD

      2.1  The sample is introduced  into a sample flask which is then attached
to the  apparatus  (Figure  1).   The  sample chamber pressure  is  reduced  using a
vacuum pump and remains at  approximately 10  torr (vapor pressure of water) as
water  is  removed  from the  sample.   The  vapor is  passed  over  a condenser coil
chilled to a temperature of -10°C  or less, which results in the condensation of
water vapor.  The  uncondensed  distillate  is  cryogenically trapped on a section


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of 1/8 inch  stainless steel tubing chilled to the temperature of liquid nitrogen
(-196°C).  After an appropriate distillation period which may vary due to matrix
or analyte. group,  the condensate contained in the cryotrap is thermally desorbed
and transferred to the gas chromatograph using helium carrier gas.

      2.2 It  is emphasized that the apparatus conditions are optimized to remove
analyte from  the  sample matrix  and  isolate water  from the distillate.   The
conditions may be  varied to optimize  the  method for  a given analyte or group of
analytes.  The length of time required for distillation may vary due to matrix
effects or the analyte group of interest.  Operating parameters may be varied to
achieve optimum analyte recovery.


3.0  INTERFERENCES

      3.1   Method  interference  may  be  caused by  contaminants in  solvents,
reagents, glassware, and other sample processing hardware that lead to discrete
artifacts and/or elevated baseline in the chromatograms.

            3.1.1   Interferences distilled from the sample will vary from source
      to source,  depending on the particular sample or matrix.   The analytical
      system should be checked to insure freedom from interferences by analyzing
      method blanks under identical  conditions of analysis.

            3.1.2    The  apparatus can  be  decontaminated with  a  ten  minute
      evacuation of the  distillation apparatus while the  condenser  coils are
      heated to 45°C.

      3.2  The laboratory where analysis  is to be performed should be completely
free of  solvents.   Many common  solvents,  most notably  acetone  and  methylene
chloride, are  frequently  found  in   laboratories  at low  levels.   The  sample
receiving chamber  should be loaded  in  a clean environment to  eliminate  this
problem.
                                                                   trip blanks
                                                                    e.    It  is
                                                                           are
      3.3  Samples may be contaminated during shipment.  Field and •
should  be  analyzed  to  insure  integrity  of the  transported  sampl_.
recommended  that  wherever  possible,   samples  aliquots  and  surrogates
transferred directly to  sample  flasks  in the field, weighed  and  sealed using
0-ring connections.

      3.4  Impurities in purge gas and from organic compounds out-gassing from
plumbing 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 including laboratory reagent blanks.   All gas lines should be
equipped with hydrocarbon and oxygen removal traps.


4.0  APPARATUS AND MATERIALS

      4.1  Microsyringes:  10 ^U 25 /uL, 100 »L, 250 jttL,  500  juL,  and  1000  ^uL.
These syringes should be equipped with a 20 gauge  (0.006 in.  ID)  needle.

      4.2  Syringe:  5 ml and 10 ml gas tight,  with Luer Lock tip and  needles.


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      4.3  Balance:  Analytical,  capable  of accurately weighing 0.0001 g, and a
top loading balance capable of weighing 0.1  g.

      4.4  Balance weights:  Stainless steel  S-class weights ranging from 5 mg
to 100 g.

      4.5  Sample Flask:  100 ml  Pyrex® bulb joined to a 15 mm ID Pyrex® 0-ring
connector.  The  flask must be capable of being  pumped  down to a  pressure of
10 mtorr without  implosion.  The flask is  sealed for sample storage with a Buna-N
0-ring, a 15 mm ID 0-ring connector cap,  and a pinch clamp.

      4.6  Vacuum distillation apparatus (See Figure  1):  The  basic apparatus
consists of a  sample  chamber connected to  a condenser which is attached to a
heated six port valve (V4).  The sampling valve  is connected to the following;

      1)   condenser (by way of Vacuum Pump  Valve - V3)
      2)   vacuum pump
      3)   cryotrap
      4)   gas chromatograph/mass spectrometer

      The sampling valve  (V4)  is  heated  to  prevent condensation  and potential
carryover.

      The circulating system which supplies the  condenser coils consists of a
cryogenic cooler with reservoir  and  an elevated  temperature bath  (45°C).  The
coolant reservoir may be filled with isopropyl alcohol or other appropriate fluid
such as salt water.   The fluid  is  circulated through the condenser coils with a
peristaltic pump  and  the alternating  of bath  fluids are accomplished  by the
circulating fluid valve (V3).

      The apparatus is heated to a temperature sufficient to prevent condensation
of analytes onto condenser walls, valves, and connections.  The temperature of
the transfer  line  from  the sampling  valve to the  gas chromatograph should be
heated to the upper temperature utilized by  the  GC program.

      Pi rani gauges are recommended at the sample chamber, condenser and vacuum
pump for distillation monitoring. Edwards pirani  gauge model  1001  with pirani
gauge head model  PRH10K or equivalent.

      The dimensions of the various parts of the apparatus are as  follows:

      1)   The loop on which the  sample  is condensed  is  an  8  inch  by 1/8 inch
           stainless steel piece of tubing.

      2)   The condenser is 12 inches long and 2 inches  in diameter.  The ends
           are made of  1/2  inch  ground glass  and  are  secured  to  all stainless
           steel  joints by the  use of  1/2 inch Buna rubber 0-rings.  The cooling
           coils  within  the  condenser  are made  of  3/16   inch  glass  which
           terminate  as 1/4  inch tubing fittings on  the    exterior  of the
           condensers.

      3)   The cooling liquid passing through the condenser  is routed from the
           refrigerant reservoir using 1/4 inch  pure silicone tubing.


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      4)   The tubing between the  GC  inlet  and  the   six port valve is made of
           1/16 inch capillary fused silica lined stainless steel.

      5)   The sampling  chamber  valve (VI)  and the vacuum  pump  valve V3) are
           made of 1/2 inch stainless steel.

      6)   The circulating fluid valve (V2) is made of 1/4 inch brass.

      7)   The six  port  sampling valve  (V4)  is made of  stainless  steel  with
           Teflon® internal parts.

      4.7  Gas chromatograph/ mass spectrometer system:

            4.7.1 Gas chromatograph:     An analytical  system  complete with a
      temperature-programmable gas chromatograph  and  all  required accessories
      including syringes, analytical  columns,  and gases.

            4.7.2 Column:     30  m by 0.7 mm  ID fused silica capillary column
      chemically bonded  with  methylphenyl  cyanopropyl  silicone J&W DB-624, or
      equivalent, 3.0 /xm film thickness.

            4.7.3 Mass spectrometer:      Capable  of scanning  from  35-350 amu
      every 2  sec.  or less,  using 70  volts (nominal) electron  energy in the
      electron impact mode  and producing a mass  spectrum that  meets  all the
      criteria listed in  Method 8260 when 50 ng of  4-bromofluorobenzene  (BFB) is
      injected through the gas chromatograph inlet.

            4.7.4 Gas chromatograph/  mass  spectrometer  heated  jet  separator
      interface:     A heated glass jet separator interface capable of removing
      from  10  to 40  mL/min  of  helium  from  the exit  end  of the wide  bore
      capillary column.   The interface  should  have the ability  to  be heated
      through a range of 100 to 220°C.


5.0  REAGENTS

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

      5.2  Organic-free reagent water - All  references to water in this method
refer to organic-free reagent water,  as defined in Chapter One.

      5.3  Methanol:   CH3OH,  purge and trap grade or equivalent.  Store apart
from other solvents.

      5.4  Standard solutions:     Stock  solutions  may  be prepared from  pure
standard materials or purchased as  certified solutions.  Prepare stock standard
solutions in methanol,  using assayed  liquids or gases, as appropriate.
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            5.4.1 Place about 9.8 ml of methanol in a  10 ml tared, ground-glass-
      stoppered volumetric flask.  Allow  the  flask to  stand,  unstoppered,  for
      about 10 min or until all alcohol-wetted surfaces have dried.  Weigh the
      flask to the nearest 0.1 mg.

            5.4.2 Add the assayed reference material, as described below.

                  5.4.2.1  Liquids:  Using a 100 pi syringe,  immediately add two
            or more  drops of  assayed  reference  material  to the  flask;  then
            reweigh.   The  liquid  must  fall directly into  the  alcohol  without
            contacting the neck of the  flask.

                  5.4.2.2  Gases:  To prepare  standards  for any compounds that
            boil  below 30°C (e.g.,  bromomethane, chloroethane, chloromethane, or
            vinyl chloride),  fill  a 5  ml  valved gas-tight syringe with  the
            reference standard to the 5.0 mL  mark.  Lower  the  needle  to 5 mm
            above  the methanol  meniscus.    Slowly  introduce  the  reference
            standard  above the surface  of the  liquid.    The  heavy gas  will
            rapidly dissolve in the methanol.  Standards may also be prepared by
            using a  lecture bottle equipped  with a  septum.    Attach  Teflon®
            tubing to the  side-arm relief valve  and  direct a gentle stream of
            gas onto the methanol  meniscus.

            5.4.3 Reweigh, dilute to volume, stopper, and mix by inverting the
      flask  several  times.    Calculate  the concentration  in  micrograms  per
      micro!iter (jig//iL) from  the net gain  in weight.  When compound purity is
      assayed to  be 96% or  greater, the weight  may be  used without correction to
      calculate the concentration  of the  stock  standard.  Commercially prepared
      stock standards may be used  at any  concentration if they are certified by
      the manufacturer or by an independent source.

            5.4.4 Transfer the stock  standard solution  into  a Teflon®-sealed
      screw cap  bottle.   Store, with minimal  headspace,  at  -10  to -20°C  and
      protect from light.

            5.4.5 Prepare  fresh  gas  standards  every  two  months.   Reactive
      compounds  such  as  2-chloroethylvinyl ether  and  styrene may  need  to be
      prepared more frequently. All other standards must be replaced after six
      months, or sooner if comparison with check  standards  indicates a problem.

      5.5  Secondary dilution standards:  Using  stock standard solutions, prepare
in methanol secondary dilution standards containing the compounds of interest,
either singly or mixed together.  Secondary dilution standards must be stored
with minimal headspace and  should be checked frequently  for  signs of degradation
or evaporation,  especially just prior to preparing calibration standards from
them.

      5.6  Surrogate standards:  The surrogates  recommended are toluene-d8, 4-
bromofluorobenzene, and l,2-dichloroethane-d4.   Other compounds may be used as
surrogates, depending upon  the analysis requirements.  A stock surrogate solution
in methanol  should  be prepared as described  in   Section 5.1,  and  a surrogate
standard spiking solution should be prepared from the stock at a concentration
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of 25 ng/ml in methanol .  Each sample undergoing GC/MS analysis must be spiked
with 10 juL of the surrogate spiking solution prior to analysis.

      5.7  Internal  Standards:   It is  recommended  that one or  more internal
standards  be  selected  from:   bromochloromethane,  1,4-difluorobenzene,  vinyl
chloride-dg,  chlorobenzene-d5.   The  compound(s)  selected  should  demonstrate
minimal matrix effects.  Other compounds maybe used as internal standards as long
as they have retention times similar to the compounds being detected by GC/MS.
Method 8260 should be reviewed to  select  compounds  appropriate for the matrix
being tested.   Prepare internal standard stock and secondary dilution standards
in methanol using  the  procedures  described  in  Sections  5.1  and 5.2.   It  is
recommended that  the  secondary  dilution  standard  should be  prepared  at  a
concentration of 25 /j.g/ml of  each  internal  standard  compound.   Addition  of 10
fj,L of  this  standard  to  5.0  ml of  sample or calibration  standard would be  the
equivalent of 50 M9/L-

      5.8  4-Bromofluorobenzene (BFB)  standard:  A standard solution containing
25 ng/^L of BFB in methanol  should be prepared.

      5.9  Calibration  standards:   Calibration standards  at minimum  of five
concentration  levels  should be prepared from the secondary  dilution of  stock
standards (see Sections  5.1  and 5.2).   Prepare these solutions in reagent water
or purge and trap  grade  methanol.   One  of the concentration levels should be at
a concentration near,  but above,  the  method  detection limit.    The remaining
concentration  levels should  correspond to the expected range of concentrations
found  in  real  samples  and  should  not exceed the  working range of  the  GC/MS
system.  Each  standard should  contain  each analyte for detection by this method
(e.g.,  some or  all  of the  compounds  listed  in  Method 8260 may  be included).
Store for one  week or less at -10 to -20°C  in  a  vial  with  minimal  headspace.

      5.10 Matrix spiking  standards: matrix spiking standards should be prepared
from volatile organic compounds which  will be representative of the compounds
being   investigated.     The   suggested  compounds   are   1,2-dichloroethene,
trichloroethene, chlorobenzene, toluene, and benzene.   The standard should  be
prepared in methanol,  with each compound present  at  a concentration of 25
      5.11 Great care must be taken  to  maintain  the  integrity of all standard
solutions.  It  is recommended that  all  standards by  stored at -10 to -20°C in
screw-cap amber bottles with Teflon® liners.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See  the  introductory material to  this chapter,  Organic  Analytes,
Section 4.1 .

      6.2  Samples  to  be  analyzed   for  volatile compounds  should  be  stored
separately from standards and other samples.
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7.0  PROCEDURE

      7.1  Recommended GC/MS operating conditions:

      Electron energy:             70 volts (nominal)
      Mass range:                  35-350 amu
      Scan time:                   To give  8 scans/peak but  not  to  exceed  3
                                   sec/scan
      Initial  column temperature:  10°C
      Initial  hold time:           3.0 min
      Column ramp rate:            5.0°C/min
      Final  column temperature:     230°C
      Final  hold time:             1.0 min

      7.2  Initial calibration for vacuum distillation procedure:

            7.2.1   Turn the six port sampling  valve  (V4)  handle to  the  load
      position.

            7.2.2   Place  a  styrofoam cup under the sample loop and  secure in
      place.  Loop the cup with liquid N2.  Recharge the styrofoam cup under the
      sample loop throughout the distillation with  liquid N2  as  necessary.

            7.2.3  Turn the sample chamber  valve (VI)  to the off  position and
      remove the sample container.

            7.2.4    Load  the  standard,   containing   surrogates  and  internal
      standards, into the sample flask and attach to the apparatus.

            7.2.5  Turn the coolant/heat valve (V2) to  circulate coolant through
      the condenser  coils.   Be  sure  all  connections  are complete  and  sealed
      properly.   Open  the  sample chamber  valve to  begin  the  distillation.
      Continue distillation for 10 minutes.

NOTE: IF PIRANI GAUGES ARE USED:   After five minutes of distillation the Pirani
      gauge at the  vacuum pump should indicate  about  0.1 torr,  and  the  Pirani
      gauge at the  condenser and  should  indicate 250  torr  or less.   After ten
      minutes of distillation the Pirani gauge at the sample chamber should read
      approximately 10 torr.  If  these pressures  are not  attained a leak may be
      present  and  the distillation  may  not  be  successful.    Distillation
      performance   surrogates  should   be  evaluated  for   acceptability  of
      distillation.

            7.2.6  Setup the data system  for acquisition  of the data file.  This
      may be done prior to  the beginning  of step 1.   While distillation times
      may be  variable depending  on  sample  matrix,  the data  system  should be
      ready and  the GC oven  at  equilibrium  by  the  time the distillation is
      complete.

            7.2.7   Once  the  distillation  is complete  GC/MS analyses  may be
      performed.  Turn  the  sampling  valve handle to  the  inject  position while
      maintaining the styrofoam cup with liquid N2 in place.  Rapidly remove the
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      styrofoam cup  and  replace with the  beaker  of (90°C)  hot tap  water and
      commence GC/MS data acquisition.

            7.2.8  Once acquisition has begun the  sample  chamber  valve may be
      closed and the sample flask removed.

            7.2.9   The  distillation apparatus can  then  readied for  the  next
      analyses.  This is performed  by switching the  vacuum  pump valve (V3) to
      the  vacuum  pump position  which  disconnects  the vacuum  stream  to  the
      sampling valve (V4).   The  condenser circulating fluid is then switched to
      the heated fluid (45°C) by  switching valve V2.  Evacuate the distillation
      system for 10 minutes.  It is recommended  that a liquid nitrogen cooling
      trap be placed between valve V3 and  the vacuum pump to prevent degradation
      of the vacuum due to overload of  moisture  in the vacuum pump oil.

      7.3  Calibration response factors:   Calculate according to Method 8260.

      7.4  Sample preparation:

            7.4.1 Liquid:   Liquid samples should be  stored with minimal  or no
      headspace to minimize the loss of highly volatile analytes.   Samples may
      be preserved with ascorbic acid to  stop biological  degradation which may
      occur in water samples.

            7.4.2 Solid/Soil:     Solid  and   soil  samples  should  be  rapidly
      withdrawn from their sample container and  weighed while still  cold.   The
      sample is then rapidly transferred to  the sample  chamber  and  secured to
      prevent loss of analytes.

            7.4.3 Tissue:  Tissue samples which are fleshy may have to be minced
      into smaller pieces to get them through the  neck  of the sample chamber.
      This is best  accomplished by freezing the sample in liquid nitrogen before
      any additional processing  takes place.  Biota containing leaves and other
      softer samples may be minced using  clean scissors.


8.0  QUALITY CONTROL

      8.1  Refer to  Chapter One and Method 8000 for  specific quality control
procedures.

      8.2  Before processing any samples,  the analyst should demonstrate through
the analysis of a reagent water method blank that all glassware and reagents are
interference free.   Each  time a set of samples is analyzed, or  there is a change
in reagents,  a method blank should be processed as a  safeguard against laboratory
contamination.  The blank samples should be carried  through all stages of sample
preparation and measurement.

      8.3  To establish the  ability  to generate data of acceptable accuracy and
precision refer to Method 8000  and the  determinative method to be used.

      8.4  Matrix and distillation performance surrogates.
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            8.4.1  Matrix effects  and distillation performance may be monitored
      separately  through  the  use  of   surrogates.     Compounds   that  have
      demonstrated  minimal  matrix  effects  such   as  vinyl  chloride-d3  and
      bromochloromethane may  be  added  directly to  the  matrix and  used  as an
      internal standard.   Tables  located  in Method  8260  present  recovery data
      from water, soil  and  oil matrices that should be considered when selecting
      surrogates.   Compounds  that have  demonstrated  matrix effects  and/or
      distillation losses (i.e.,  pyridine-d5, 2-fluorophenol for matrix effects
      and l,2-dichlorobenzene-d4 for distillation  performance) are recommended
      as surrogates.

            8.4.2      The  use  of  multiple  matrix surrogates  and  multiple
      distillation performance surrogates  are  recommended.   It  is  recommended
      that distillation  effect surrogates  be  relatively insoluble  in  water.
      Matrix monitoring  compounds should  be selected to  bracket  the physical
      properties of the analytes of interest.  If matrix effects have been shown
      or  are  suspected  for  a chosen  distillation  surrogate  compound,  the
      distillation surrogates  should be  added to  the sample  flask  in  an open
      mini-vial suspended above the sample by a wire  stand.  Multiple surrogates
      for monitoring  one  or  more classes of  compounds  are recommended  for
      evaluating matrix effects.

      8.5  Standard  quality assurance practices should be  used with this method.
Field replicates should be collected to validate the precision of the sampling
technique.  Laboratory replicates should be analyzed to validate  the precision
of the  analysis.   Fortified  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 fortified samples  do  not
indicate sufficient  sensitivity to detect <1 /ig/g of  the analytes in the sample,
then the sensitivity of the instrument should be increased,  or a  larger amount
of the sample should be used.


9.0  METHOD PERFORMANCE

      9.1  Performance  data  for  Method 5032 are provided in  tables in  Method
8260.


10.0  REFERENCES

1.   Hiatt,  M.H.  "Analysis  of  Fish  and  Sediment  For  Volatile  Priority
     Pollutants", Analytical Chemistry 1981, 53 (9), 1541.

2.   Hiatt, M.H.  "Determination of Volatile Organic Compounds in Fish Samples by
     Vacuum  Distillation  and  Fused  Silica Capillary Gas  Chromatography/Mass
     Spectrometry";  Analytical Chemistry 1983, 55  (3),  506.

3.   United  States  Patent  4,600,559.     "Vacuum  Extractor  with  Cryogenic
     Concentration and Capillary  Interface", held  by the U.S. EPA.
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       Gas Chromalograph/ Mass Spectrometer



                                  Sampling Valve (V4)
*. Vacuum
  Pump


— Vacuum

 Pump Valve V3
Condenser
      Sample
      Chamber
                                       Cryotrap
                                  Sample
                                  Chamber
                                  Valve

                                   (V1)
                                                       Refrigerent
                                                          Bath
                                                   ; Circulating Fluid

                                                     Valve (V2)
                            Figure 1
              VACUUM DISTILLATION  CONFIGURATION
                             5032-11
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                      METHOD 5032

VOLATILE ORGANIC COMPOUNDS BY VACUUM DISTILLATION
>
r
Sample
preparation.
>
t
7.1 Establish
instrument set-up.
>
r
7.2 Calibrate for
and perform vacuum
distillation.
>
r
7.2.7 Begin GC/MS
data acquisition.
                        5032-12
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                                  METHOD  5035

                CLOSED-SYSTEM PURGE-AND-TRAP AND  EXTRACTION  FOR
                  VOLATILE  ORGANICS  IN  SOIL AND WASTE  SAMPLES
1.0  SCOPE AND APPLICATION

      1.1  This method describes  a closed-system purge-and-trap process for the
analysis  of  low  concentrations of  volatile  organic  compounds  (VOCs)  in
soils/sediments  and  solid waste.    Guidance  is  also  provided  for  sample
preparation  of   soils,   solid  waste  and  non-aqueous   liquids   with   high
concentrations of volatile organics.  The gas chromatographic determinative steps
are found  in  Methods 8015 and 8021.   The method is also  applicable  to  GC/MS
Method 8260.

      1.2  The low soil method differs from  the low soil/sediment method in the
original Method 5030 because the hermetic seal of the sample  vial is never broken
from time of sampling to time  of  analysis.  Since  the  sample is never exposed to
the atmosphere  after  sampling,  the  loss of VOCs is negligible.   Therefore,
concentration data obtained using Method 5035 would be expected to be higher and
more representative  of the soil  contamination at time of  sampling,  than  that
obtained using the original low soil method (i.e. subsampling a portion of sample
from the sample vial in the laboratory).   The applicable concentration range of
the low soil method is dependent  on the  determinative  method, matrix,  and
compound.  However,  it will generally fall in the 0.5 to  200 /xg/kg range.   The
estimated quantitation limit range for high concentration analysis of soil and
waste samples  will  be in  the  1  to  20 mg/kg  range.   However,  this  is  highly
dependent on interferences.

      1.3  Method 5035 can  be used for most volatile organic compounds that have
boiling  points  below  200°C and  are  insoluble or slightly  soluble  in  water.
Volatile, water-soluble compounds can  be  included  in this analytical  technique;
however, quantitation limits (by  GC or GC/MS) are  approximately ten times higher
because of poor purging efficiency. The method is also limited to compounds that
elute as  sharp  peaks from a  GC  column packed with  graphitized carbon lightly
coated with a carbowax or a coated capillary column.   Such compounds include low
molecular  weight  halogenated  hydrocarbons,  aromatics,   ketones,   nitriles,
acetates, acrylates, ethers,  and sulfides.

      1.4  Method 5035, in conjunction  with Method 8015 (GC/FID), may be used for
the analysis of  the  aliphatic  hydrocarbon fraction  in  the  light  ends of total
petroleum hydrocarbons, e.g.,  gasoline.   For the  aromatic fraction (BTEX), use
Method 5035 and Method 8021 (GC/PID).  A total determinative  analysis of gasoline
fractions may be obtained using Method 8021  in series with  Method 8015.

      1.5  Samples should be screened, prior to application of  this  method, to
avoid contamination of the  purge-and-trap system by samples  that fall  beyond the
concentration range of the low concentration method.

      1.6   This method  is restricted to use  by  or under the supervision of
trained  analysts.    Each  analyst  must  demonstrate  the ability to  generate
acceptable results with this  method.


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2.0  SUMMARY OF METHOD

      2.1   Low Concentration Method:   Volatile organic compounds  (VOCs)  are
determined from a 5 g soil  sample  by  placing the sample, at time of collection,
into a specially designed,  fritted, 40-mL vial.  A stirring  bar  is added and, if
desired, preservative may be  added as well.  The vial  is then sealed and shipped
to a laboratory or appropriate analysis site.   The entire vial  is then placed,
unopened, into  the instrument carousel.  Immediately before  analysis,  water,
surrogate standards  and  internal  standards  are  automatically  added  without
breaking the hermetic seal  on  the  sample vial.   The slurry is preheated to 40°C,
then  purged  by  passing  an  inert  gas through  the bottom of  the vial  while
mechanical agitation  is  being provided by the magnetic stirring  bar.   Purged
components then travel  via a  transfer line to a trap.  When purging is complete,
the trap  is  heated and  backflushed  with  helium to desorb the trapped  sample
components  into  a  gas  chromatographic  (GC)  column   interfaced  to  a  mass
spectrometer (MS) or a specific detector, depending on the determinative method
selected.

      2.2  High Concentration Method:  If the sample introduction technique in
Sec. 2.1  is  not applicable,   a portion  of the sample is dispersed  in  a water
miscible solvent to dissolve the volatile organic constituents.  An aliquot of
the solution is combined  with  water in a specially designed  purging chamber.  It
is then analyzed by purge-and-trap GC following the water purge-and-trap method
(Method 5030).


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
contamination under the conditions of the analysis by running laboratory reagent
blanks.   The use  of non-polytetrafluoroethylene  (non-PTFE)  plastic  coating,
non-PTFE  thread sealants,  or flow controllers  with rubber components  in  the
purging device  must be avoided, since such materials out-gas organic compounds
which  will  be  concentrated  in  the  trap  during  the  purge operation.   These
compounds will  result  in interferences or false positives in the determinative
step.

      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.  Special precautions must be  taken to determine

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methylene chloride.  The analytical and sample storage area should be isolated
from all atmospheric sources of methylene chloride, otherwise random background
levels will result. Since methylene chloride will permeate through PTFE tubing,
all  GC  carrier  gas  lines  and purge  gas  plumbing  should  be constructed  of
stainless  steel  or copper  tubing.   Laboratory  workers'  clothing  previously
exposed  to methylene  chloride fumes  during  common  liquid/liquid  extraction
procedures can contribute to sample contamination.  The presence of other organic
solvents in the laboratory where volatile organics are analyzed will  also lead
to random background levels and the same precautions must be taken.


4.0  APPARATUS AND MATERIALS

      4.1  Sample Containers/Purge Device -  40-mL clear soil  vials with a special
frit  (Figure  1) available  from  Dynatech  Precision  Sampling  Corporation  (or
equivalent).  Each  vial should be  equipped with two PTFE-faced silicone septa (or
equivalent) which demonstrate minimal  bleed at elevated temperatures.  Prior to
use, wash vials and septa with detergent and rinse with tap and distilled water.
Allow the vials and septa to air  dry at room temperature, place in a 105°C oven
for  one  hour,  then remove  and allow  to cool  in an  area known to be  free  of
organics.  Be sure the PTFE side of each septum is toward the sample.

      4.2   Purge-and-Trap  System - The  system  used for purging  and  trapping
consists of two pieces of equipment linked together to form a hybrid system.  The
first piece of equipment performs  as the automated sample preparation and purging
device while the other piece of equipment contains the trap  and functions as the
desorber.  Systems  are commercially available from several sources that meet all
of the following specifications.

NOTE: The  equipment  used to  develop  this method  was a  Dynatech PTA-30  W/S
      Autosampler  (Dynatech Precision Sampling Corporation, 8275  West El Cajon
      Drive, Baton Rouge, LA  70815).   See  the Disclaimer at the  front  of this
      manual for guidance on the use of alternative equipment.

            4.2.1  The purging device should be capable  of accepting the 40-mL
      soil vial and maintaining the vial at 40°C while the inert gas is  allowed
      to pass through the sample effectively purging it.  The device should also
      be capable of  introducing  19 mL of  organic-free reagent water  into  the
      purging device without venting the headspace of the vial.  It should also
      be capable of  stirring the  sample during  purging.    The analytes being
      purged must be allowed to escape the  vial  through  an  inert  transfer line
      maintained at an elevated temperature. After passing through the transfer
      line, the analytes are then allowed to concentrate  on a trap.

            4.2.2  The  trap  used to develop  this method was 25 centimeters long,
      had   an   inside    diameter   of   0.105  inches  and   was  packed  with
      Carbopack/Carbosieve  (Supelco,  Inc.).   Traps  that  demonstrate  similar
      hydrophobic  and   retention   properties  may  be used.    The  trap  must
      demonstrate sufficient adsorption and desorption characteristics  to meet
      the method MDLs of all the  target analytes for a given Project and the QC
      requirements  in  Method  8000  and the  Determinative   Method.   The  most
      difficult are the  gases and especially dichlorodifluoromethane.   Also,
      demonstrate that  the trap is  capable  of desorbing the late eluting target
      analytes.

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NOTE: Check  the  response  of  the  brominated  compounds  when  using  these
      alternative charcoal traps (especially Vocarb 4000), as some degradation
      has been noted relating  to the higher desorption temperatures (especially
      temperatures above 240 - 250"C).  2-Chloroethyl  vinyl ether is degraded on
      Vocarb 4000 but performs adequately when Vocarb 3000  is  used.  The primary
      criteria,  as  stated above,  is  that  all  target  analytes  meet  the  MDL
      requirements for a given project.

                  4.2.2.1  The desorber for the above trap must  be capable of
            rapidly heating the trap to 245"C prior to the  beginning of the flow
            of desorption  gas.   Several commercial  desorbers  (purge-and-trap
            units) are available.

            4.2.3  The standard trap used in  previous  EPA purge-and-trap methods
      is also acceptable.   This trap is 25 cm long  and has  an  inside diameter of
      at least  0.105 in.   Starting from the  inlet, the  trap   contains  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.   If  it is not  necessary to  analyze  for
      dichlorodifluoromethane or other fluorocarbons  of similar volatility,  the
      charcoal can be eliminated and the polymer  increased to  fill  2/3 of  the
      trap.   If only compounds boiling above 35'C 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, this  trap  should be conditioned
      overnight at  180'C  by  backflushing with  an  inert gas  flow  of at least
      20 mL/min.   Vent  the trap effluent to  the  hood,  not  to  the analytical
      column.  Prior to  daily  use,  the trap  should be conditioned for 10 min at
      180"C with backflushing.  The trap may be vented to the analytical column
      during daily  conditioning; however,  the  column must be  run  through  the
      temperature program prior to analysis of samples.

                  4.2.3.1  Trap Packing Materials

                        4.2.3.1.1   2,6-Diphenylene oxide polymer - 60/80 mesh,
                  chromatographic  grade (Tenax GC or equivalent).

                        4.2.3.1.2    Methyl  silicone packing -  OV-1  (3%)  on
                  Chromosorb-W, 60/80 mesh or equivalent.

                        4.2.3.1.3   Silica gel - 35/60 mesh, Davison, grade 15 or
                  equivalent.

                        4.2.3.1.4    Coconut  charcoal  -  Prepare  from Barnebey
                  Cheney, CA-580-26,  or  equivalent, by crushing through 26 mesh
                  screen.

                  4.2.3.2  The desorber  for  the trap  must  be  capable of rapidly
            heating the trap to 180"C for desorption.   The polymer section of
            the trap should not be heated higher than 180°C,  and the remaining
            sections should not exceed 2208C during the bake-out mode.

                  4.2.3.3  Prior to initial use, condition  the trap overnight at
            180°C  in the purge mode  with  an  inert  gas  flow  of at  least

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            20 mL/min.  Prior to daily use,  condition the trap for 10 min while
            backflushing at 180'C with the GC column at 220°C.

      4.3  Syringe and Syringe Valves

            4.3.1   Two  25-mL  glass  hypodermic  syringes  with  Luer-Lok  (or
      equivalent) tip  (other  sizes  are acceptable depending on  sample volume
      used).

            4.3.2  Three 2-way syringe valves with Luer ends.

            4.3.3  One 25-^1  micro  syringe  with  a  2  inch  x  0.006 inch ID,  22/j
      bevel needle (Hamilton #702N or equivalent).

            4.3.4  Micro syringes - 10, 100 /iL.

            4.3.5  Syringes -  0.5, 1.0, and 5-mL,  gas tight with shut-off valve.

      4.4  Miscellaneous

            4.4.1  Glass vials  -  60 ml,  septum sealed,  to collect samples for
      screening, dry weight determination, and high concentration analysis (if
      needed).

            4.4.2  Top-loading balance - 0.1 g.

            4.4.3   Glass  scintillation  vials  -  20 ml,  with screw-caps  and
      Teflon® liners or glass  culture tubes  with screw-caps and Teflon® liners.

            4.4.4   Volumetric  flasks,  Class A  -  10 mL  and  100  ml_,  with
      ground-glass stoppers.

            4.4.5  Vials - 2 ml, for GC autosampler.

            4.4.6  Spatula - Stainless steel.

            4.4.7  Disposable pipets - Pasteur.


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   Polyethylene  glycol, H(OCH2CH2)nOH  -  Free of  interferences  at  the
detection limit of the target analytes.

      5.4  See the determinative method and Method 5000  for guidance on internal
and surrogate standards.
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6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   Sample Collection  - Refer  to the  introductory  material to  this
chapter, Organic Analytes, Sec. 4.1.

            6.1.1  Weigh the assembled soil sample vial containing the stirring
      bar to 0.1 g.  Ship the tared  sampling vial to the sampling site with the
      seals intact.  Open  the large chamber containing  the  stirring bar, and add
      about 5 grams (2-3 centimeters) of soil  on  top  of the stirring bar (wear
      gloves whenever  handling the  tared  containers).    Immediately  seal  and
      store  at  4°C.    (Samples may be weighed  in the  field  if  a means  is
      available to weigh to  0.1 g.)   Do not interchange seals and stirring bars
      with other soil vials.   It is advisable  to  collect  duplicate  samples in
      the special tared sample/purge vials in case reanalysis of the sample is
      required.

            6.1.2  Collect additional duplicate aliquots of each  sample in 60 mL
      glass vials (septum sealed)  for screening, dry weight determination, and
      high concentration analysis  (if needed).

      6.2  Sample Storage -  Refer to the introductory material to this chapter,
Organic Analytes, Sec.  4.1.

            6.2.1  Store samples at  4°C until  analysis. The sample storage area
      should be free of organic solvent vapors.

            6.2.2  All  samples  should be analyzed within 14 days of collection.
      Samples not  analyzed  within   this  period must  be  noted  and data  are
      considered minimum values.
7.0  PROCEDURE

      7.1  The Low Concentration Method utilizing a closed-system purge-and-trap
technique is found  in Sec. 7.2 and sample preparation  for the High Concentration
Method is found  in Sec.  7.3.   The  gas chromatographic determinative steps are
found in Methods 8015 and 8021.  The method is also applicable to GC/MS Method
8260.  For  the  analysis  of gasoline,  use Method 8021 with  GC/PID  for BTEX in
series with Method 8015 with the GC/FID detector for hydrocarbons.

      7.2  Low Concentration Method for Soil/Sediment and Solid Waste Amenable
to the Closed-system Purge-and-Trap Method   (Approximate concentration range of
0.5 to 200 jug/kg - the concentration range is dependent upon the determinative
method and the sensitivity of each analyte.)

            7.2.1   Initial  calibration:    Prior  to  using this  introduction
      technique  for  any  GC  or GC/MS  method,  the  system must  be  calibrated.
      General calibration  procedures  are discussed in Method  8000,  while the
      determinative methods  and Method  5000  provide specific  information on
      calibration and  preparation  of  standards.   Normally,  external  standard
      calibration  is  preferred  for  the  GC  methods  because  of  possible
      interference problems with internal standards.   If interferences are not
      a  problem,  based on historical  data,  internal standard  calibration is
      acceptable.    The   GC/MS  methods  normally  utilize  internal  standard

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      calibration.   The  GC/MS  methods  require  instrument  tuning  prior  to
      proceeding with calibration.

                  7.2.1.1   Assemble a  purge-and-trap device  that meets  the
            specification in Sec. 4.2 and is interfaced to a gas chromatograph
            or a  gas  chromatograph/mass  spectrometer system.   Before  initial
            use,  a Carbopack/Carbosieve trap should be conditioned overnight at
            245°C  by  backflushing  with  an inert  gas flow  of  at  least  20
            mL/minute.    (If  other trapping materials are  substituted  for  the
            Carbopack/Carbosieve, follow  the manufacturers recommendations  for
            conditioning.  See  Sec.  4.2.3.3 for guidance  on  conditioning  the
            trap.)  Vent the trap effluent  to the room, not to the analytical
            column.  Prior to daily use,  the trap should be conditioned for 10
            minutes at 245°C with backflushing.   The trap  may be vented to  the
            analytical  column during  daily conditioning;   however, the column
            must be run  through the temperature program prior  to  analysis of
            samples.

                  7.2.1.2    To   prepare  a  calibration  standard,  inject   an
            appropriate  volume   of  a  primary   dilution  standard  (containing
            analytes and  surrogates) to an aliquot of organic-free reagent water
            in a  volumetric  flask,  a gas tight  syringe,  or to 10 ml  of this
            solution in  a  soil  vial,  and inject  an  appropriate amount  of
            internal standards  to the organic-free reagent  water.  Be sure that
            the same amount of internal standards are added  to each standard and
            sample.    The  volume  of  organic-free  reagent  water  used  for
            calibration  must be  the  same  volume  used  for  sample  analysis
            (normally 10 ml).   The surrogate and internal  standard  solutions
            must be added with  a syringe  needle  long enough to ensure addition
            below the surface of the water.   Prior  to purging, heat the sample
            vial  to 40°C for 1.5 minutes.

NOTE: The device on the autosampler  that  introduces the solution containing  the
      internal standards  and surrogates  must  be disabled  during  calibration.
      Aqueous standards are not  stable and  should be  discarded  after one hour
      unless  transferred  to  a  sample  bottle  (or gas  tight syringe)  with  no
      headspace and sealed immediately.

                  7.2.1.3 Carry out the purge-and-trap procedure as outlined in
            Sec.  7.2.4.4.

                  7.2.1.4    Calculate  response   factors   (RF)   or  calibration
            factors  (CF)  for each  analyte of  interest  using the  procedure
            described in Method 8000.

                  7.2.1.5  The  average CF (external  standards) or RF  (internal
            standards must be calculated for each compound.   For GC/MS analysis,
            a system performance check must be made before  this  calibration
            curve is used  (see Method 8260).  If  the purge-and-trap procedure is
            used with Method  8021, evaluate  the  response for the following four
            compounds:     chloromethane;   1,1-dichloroethane;   bromoform;  and
            1,1,2,2-tetrachloroethane.  They are used to check for proper purge
            flow and to check for degradation caused  by contaminated lines or
            active sites in  the system.

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                        7.2.1.5.1   Chloromethane:   This  compound is the  most
                  likely compound  to  be lost if the  purge  flow is too  fast.

                        7.2.1.5.2   Bromoform:    This  compound  is  one of  the
                  compounds most likely to be purged very poorly if the  purge
                  flow is  too  slow.    Cold  spots and/or  active sites in  the
                  transfer lines may  adversely  affect  response.

                        7.2.1.5.3   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.

                  7.2.1.6  When analyzing for very late eluting  compounds  with
            Method  8021   (i.e.,  hexachlorobutadiene,   1,2,3-trichlorobenzene,
            etc.),  cross  contamination  and  memory  effects   from   a   high
            concentration sample  or  even the  standard are  a common  problem.
            Extra rinsing of  the purge chamber after analysis normally  corrects
            this.  The newer  purge-and-trap systems often  overcome this problem
            with  better  bakeout  of  the system  following the  purge-and-trap
            process.  Also, the charcoal traps retain less moisture and  decrease
            the problem.

            7.2.2  Calibration  verification:   Refer  to Method  8000 for details
      on calibration verification.

                  7.2.2.2    To prepare  a  calibration  standard,  inject  an
            appropriate  volume of  a  primary  dilution  standard  (containing
            analytes and  surrogates) to an aliquot of organic-free reagent water
            in a  volumetric  flask, a gas tight  syringe,  or  to  10 ml  of  this
            solution  in  a  soil  vial,  and  inject  an appropriate  amount  of
            internal standards  to  the organic-free reagent water.  Be  sure the
            same  amount  of  internal  standards  are added  to each standard and
            sample.    The volume of  organic-free  reagent  water  used  for
            calibration  must  be  the  same  volume  used   for  sample  analysis
            (normally  10 mL).   The  surrogate and internal standard  solutions
            must be added with  a syringe needle long enough  to ensure  addition
            below the surface of the water.  Assemble the  purge-and-trap device
            as outlined in 7.2.4.2.   Prior to purging,  heat  the sample vial  to
            40°C  for  1.5 minutes.   Follow  the  guidance for  the  purge-and-trap
            procedure  in  Sec.  7.2.4.4.   GC or GC/MS  calibration verification
            criteria must be met  as specified  in  Method 8000  before  analyzing
            samples.

NOTE: The device on the autosampler that  introduces the solution containing the
      internal standards  and surrogates  must be  disabled during calibration.
      Aqueous standards are  not stable and  should be  discarded  after  one  hour
      unless  transferred  to  a  sample  bottle (or gas  tight  syringe)   with  no
      headspace and sealed immediately.
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7.2.3  Sample screening

      7.2.3.1  It is highly recommended that all  samples be screened
prior to the purge-and-trap GC or GC/MS analysis. These samples may
contain  percent   quantities  of   purgeable  organics  that  will
contaminate  the  purge-and-trap  system  thereby requiring extensive
cleanup  and  instrument  downtime.   See Sec.  7.2.3.2  for suggested
screening techniques.  Use the screening data to determine whether
to  use  the  Low  Concentration  closed-system  purge-and-trap  or to
prepare samples by the High Concentration method.

      7.2.3.2  Two suggested screening techniques are:  the use of
an  automated headspace  sampler  (Method 5021)  interfaced  to a gas
chromatograph (GC) equipped with a photo ionization detector (PID)
and  an  electrolytic conductivity  detector (HECD)  in  series;  or,
extraction of the sample with hexadecane  (Method 3820) and analysis
of the extract on a GC equipped with a FID and/or an ECD.  Use the
Low  Concentration closed-system  purge-and-trap if  the  estimated
concentration falls within  the  calibration range  of the selected
determinative method.   If the concentration  exceeds the calibration
range, then  prepare  the samples by the  High  Concentration method
(Sec. 7.3).

7.2.4  Sample purge-and-trap

      7.2.4.1  This method is designed  for a 5-g sample size, but
other  amounts  (1 to  10  g)  may be  used.    The  soil  vial  is
hermetically  sealed  at  the sampling  site,  and MUST  remain  so to
guarantee the  validity  of the  sample.   Gloves must  be  worn when
handling the sample vial  since the vial has been tared.   If any soil
is noted on  the  exterior  of the vial  or  cap,  it must be carefully
removed  prior  to weighing.   Weigh the  vial  and contents  to the
nearest 0.1 g unless  the sample weight was determined in the field.

      7.2.4.2   Assemble  a  purge-and-trap  device  that  meets  the
specification    in   Sec.   4.2.       Before    initial    use,   a
Carbopack/Carbosieve trap should be conditioned overnight at 245°C
by  backflushing  with  an  inert  gas flow of  at least  20 mL/minute.
(If   other   trapping   materials   are   substituted   for   the
Carbopack/Carbosieve, follow the manufacturers recommendations for
conditioning.  See Sec.  4.2.3.3 for guidance on  conditioning the
trap.)  Vent  the  trap effluent  to  the  room, not to the analytical
column.   Prior to daily use,  the trap should be conditioned for 10
minutes at 245°C with backflushing.  The trap may be vented to the
analytical  column  during  daily  conditioning;  however,  the column
must be  run  through  the temperature program  prior  to analysis of
samples.

      7.2.4.3  Without disturbing  the  hermetic  seal  on the sample
vial,  add  10 mL  of  organic-free  reagent  water,  the  internal
standards, and the surrogate compounds.  This is carried out using
the automated sampler.   Other volumes of organic-free reagent water
may be used.  However,  it  is  imperative  that all  samples, blanks,
and calibration  standards have exactly  the same final  volume of

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organic-free reagent  water.   For  the  sample selected  for  matrix
spiking, add 10 /iL  of the  matrix  spike  solution  specified in Sec.
5.0 of Method  5000.   The concentration  for a 5  g  sample  would be
equivalent to  50  M9/kg  of each matrix  spike  analyte.    Prior to
purging, heat the sample vial to 40°C for 1.5 minutes.

      7.2.4.4  Purge the sample  at  a  flow rate of 40 mL/minute (the
flow rate may  vary from 20  to  40  mL/min depending  in  the  target
analyte group)  with  helium  or another inert gas for  11 minutes while
the sample is  being agitated.   The purged  analytes are  allowed to
flow out of the vial through a glass-lined transfer line to a trap
packed with suitable sorbent materials.

7.2.5  Sample Desorption

      7.2.5.1  Non-cryogenic interface - After the  11 minute purge,
place the purge-and-trap system in the desorb mode and preheat the
trap  to  245°C    without  a  flow  of  desorption  gas.     Then,
simultaneously, start the flow of desorption gas at  10 mL/minute for
about four minutes  (1.5 min is normally adequate  for analytes in
Method   8015);   begin   the   temperature   program  of   the   gas
chromatograph;  and start data acquisition.

      7.2.5.2   Cryogenic interface  - After the  11  minute  purge,
place the purge-and-trap system in the  desorb mode,  make  sure the
cryogenic interface is -150°C or lower, and rapidly  heat  the trap to
245eC while backflushing with an inert gas  at 4 mL/minute for about
5 minutes  (1.5 min is  normally adequate for analytes  in Methods
8015).  At the  end  of the  5-minute desorption  cycle, rapidly heat
the cryogenic  trap  to 250"C;  simultaneously begin  the temperature
program of the gas chromatograph and start the data acquisition.

7.2.6  Trap Reconditioning

      7.2.6.1  After desorbing the sample for 4 minutes, recondition
the trap by returning the purge-and-trap system to the purge mode.
Maintain the trap temperature at  245°C  (dependent  on trap packing
materials).   After approximately  10 minutes, turn  off  the  trap
heater and halt the purge flow through the trap.   When the trap is
cool the next sample can be analyzed.

7.2.7  Data Interpretation

      7.2.7.1  Perform qualitative  and quantitative analysis on the
data following  the  guidance  given  in the determinative  method and
Method 8000.   If  concentrations of any  target  analyte exceeds the
calibration range of the analyte,  it  will be necessary to reanalyze
the sample by the High Concentration Method.

7.2.8  Determination of % Dry Weight

      7.2.8.1   Weigh  5-10  g  of  the sample  from the 60 mL  VGA vial
into a tared crucible.
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NOTE: It Is highly recommended that no samples for dry weight determination be
      withdrawn from the 60 ml VGA vial until it is certain that no analytical
      samples  will  be needed  for High  Concentration analysis.   This  is  to
      minimize loss  of volatiles and  to  avoid sample contamination  from the
      laboratory atmosphere.

                  7.2.8.2  Determine the % dry  weight of  the sample by drying
            overnight at 105"C.   Allow  to cool in a desiccator before weighing:

                  % dry weight = q of dry sample x 100
                                    g of sample

WARNING:    The  drying  oven  should  be  contained  in  a  hood  or  vented.
            Significant  laboratory  contamination  may result  from a  heavily
            contaminated hazardous waste sample.

      7.3  High Concentration Method for Soil, Solid Waste  and Nonaqueous Liquid
Waste with Concentrations Generally Greater Than 200
            7.3.1  The method  for  soil  is based on a methanol  extraction.   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  hexadecane  (Sec.   7.3.1.6)  or  possibly
      polyethylene glycol  (PEG).  (Perform a solubility test with about one gram
      of sample and 10 mL of each solvent if the solubility is unknown,  before
      proceeding.  Discard this  test  solution.)  An aliquot of the extract is
      added  to  organic-free  reagent  water  containing  surrogate  and,  if
      applicable,  internal  and  matrix  spiking standards.   This  is  analyzed
      according to Method 5030.

                  7.3.1.1  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.

                  7.3.1.2   For  soil  and  solid waste  that  is insoluble  in
            methanol, weigh 4 g (wet weight)  of sample into  a tared 20 ml vial.
            Use a top-loading balance.  Note and record the  actual weight to 0.1
            gram and determine the  percent dry  weight of the sample using the
            procedure in Sec. 7.1.8.  Quickly add 9.0  mL of methanol;  then add
            1.0 mL of the  surrogate  spiking solution to the  vial.  Cap and shake
            for 2 min.

                  7.3.1.3  For waste  that is  soluble  in  methanol  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.)
            Quickly add  1.0  mL of  surrogate  spiking  solution  to the  vial  or
            flask and dilute  to 10.0 mL with  the appropriate solvent.  Shake the
            vial to mix the contents.   For certain  oily  liquids, the following
            methanol  dilution/extraction  has  proved effective.   Shake  1  g of
            oily liquid with  10 mL of methanol (2 minute shake) which results in
            the target analytes being extracted into the methanol along with the

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            majority of the  oily waste (some of the oil may still be floating on
            the surface).  If oil is floating on the surface, transfer 1 to 2 ml
            to a clean  GC  vial  using  a  Pasteur pipet.  Ensure  that no  oil  is
            transferred to the  vial.  Add  10 - 50 /j.1 of the methanol extract to
            5 ml  of organic-free  reagent  water for  purge-and-trap  analysis.
            Prior to using this technique, test it by spiking  a 1  g aliquot of
            the oily  waste with  a matrix  spike  mixture of  the   analytes  of
            concern  (10 -  50  jiL  of  the  matrix  spike  standard  dissolved  in
            methanol).  Shake the vial  to disperse the matrix  spike throughout
            the oil prior to adding the 10  mL  of  methanol  extraction  solvent.
            Compare the  data with  single-lab data  for  oily  waste  presented in
            Method 8260.  If recovery is not within the limits presented for the
            majority of compounds,  use the hexadecane dilution technique in Sec.
            7.3.1.6.

NOTE: Sections 7.3.1.1  through  7.3.1.3  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.

                  7.3.1.4   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  solvent  used  for
            extraction  or  dissolution  to a  separate GC  vial  for use  as  the
            method blank for each set of samples.

                  7.3.1.5  The  extracts must be stored at  4°C in  the dark, prior
            to analysis.  An appropriate  aliquot  of the  extract (see  Table 2)
            will  be added to 5  mL of organic-free  reagent water  and analyzed as
            per Method 5030.  Proceed to Sec. 7.0  in Method 5030 and follow the
            guidance for the analysis of high concentration samples.

                  7.3.1.6  For waste,  soil  or solids, where methanol or PEG are
            not effective solvents  (e.g.,  those  samples consisting primarily of
            petroleum  or  coking  waste)  dilute  or  extract  with  hexadecane
            following the guidance in Method 3585.


8.0  QUALITY CONTROL

      8.1   Refer  to Chapter One  for  specific  quality control  procedures  and
Method 5000 for sample  preparation QC procedures.

      8.2  Before  processing any samples, the analyst should demonstrate through
the analysis of an organic-free reagent water method 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 blank samples 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.  Each  analysis  batch  of 20 or  less  samples must  contain:  a reagent
blank;  either a  matrix spike/matrix spike  duplicate or  a matrix spike  and


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duplicate  sample  analysis;  and  a   laboratory  control  sample,  unless  the
determinative method provides other guidance.

      8.4  Surrogate standards should be  added to all samples when specified in
the appropriate determinative method.


9.0  METHOD PERFORMANCE

      9.1  Single laboratory accuracy and precision data were obtained for the
method analytes in three  soil matrices, sand, a soil  collected  10  feet below the
surface of a hazardous landfill,  called  C-Horizon,  and  a surface garden soil.
Each sample was  fortified  with the analytes at a concentration  of  20 ng/5 g,
which is equivalent to 4  jug/kg.  These data are listed in  tables found in Method
8260.

      9.2   Single laboratory  accuracy  and  precision  data were  obtained  for
certain  method analytes when  extracting  oily  liquid using  methanol  as  the
extraction solvent.  The data are presented  in  a  table in Method  8260.   The
compounds were spiked into  three  portions  of an oily  liquid (taken from a waste
site) following the procedure for matrix spiking described in Sec.  7.3.1.3.  This
represents a worst case set of data based  on recovery data from many sources of
oily liquid.


10.0  REFERENCES

1.    Bellar,  T.,  "Measurement of Volatile Organic Compounds in  Soils Using
      Modified    Purge-and-Trap    and   Capillary    Gas    Chromatography/Mass
      Spectrometry"  U.S.   Environmental    Protection  Agency,   Environmental
      Monitoring Systems Laboratory,  Cincinnati,  OH, November 1991.

2.    Strattan, L.,  Private communication on methanol extraction of oil, U.S.
      Environmental  Protection  Agency,   National  Enforcement  Investigations
      Center, Denver, CO, October, 1992.
                                   5035  -  13                         Revision 0
                                                                  January 1995

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                                   TABLE  1

             QUANTITY OF  METHANOL  EXTRACT  REQUIRED  FOR ANALYSIS OF
                      HIGH-CONCENTRATION SOILS/SEDIMENTS
                Approximate                         Volume of
            Concentration Range                  Methanol  Extract8


              500-10,000 /ig/kg                         100 juL
            1,000-20,000 MgAg                          so pi
            5,000-100,000 /zg/kg                         10 ^L
           25,000-500,000 jug/kg               100 juL of 1/50 dilution6


Calculate appropriate dilution factor for concentrations  exceeding this table.

    8 The volume of methanol  added to  5 mL of water being purged should be kept
      constant.  Therefore,  add to the 5 mL syringe whatever volume of methanol
      is necessary to maintain a volume of 100 fj,L added to the syringe.

    b Dilute  an aliquot of  the  methanol  extract and  then take  100 /zL  for
      analysis.
                                   5035 -  14                        Revision 0
                                                                  January 1995

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    FIGURE 1
DYNATECH SOIL VIAL
DYNATECH
SOIL  VIAL
    5035 - 15
 Revision 0
January 1995

-------
 72.1 & 72.2 Interface
 purge & trap system to
 GC or GC/MS system
 and calibrate as per
 proper 8000 method.
         I
 723 Screen sample to
 ensure that it is low
 concentration.
 7 2.4 1  Weigh sample
 unless weight was
 determined in the field
  7242 Prepare the
  purge & trap system for
  sample analysis.
 724.3 Add 10 ml of
 reagent water plus
 surrogates and internal
 standards if required.
7244 Purge the sample
at 40 C for 11 minutes
 7.2.5.1 Desorption
 conditions for
 non-cryogenic interface.
                                        METHOD  5035
                            CLOSED-SYSTEM  PURGE-AND-TRAP
73 1.2 Weigh 4 g into a
20 ml vial. Add 9 ml of
methanol and 1 ml of
surrogate spike. Shake
for 2 minutes
                       7.3.1.4 Transfer 1 ml
                       of extract into a GC
                       vial.
73.1.3 Weigh 1  g into
a vial. Add 1 mL of
surrogate spike and
dilute to 10 ml with
methanol.
Hexadecane Soluble
7.3.1.6 Go to Method
3585.
                        7.3 1 5 Proceed to
                        Section 7 of Method
                        5030 for guidance on
                        purge & trap analysis
                        by GC or GC/MS.
 7 2 5.2 Desorption
 conditions for cryogenic
 interface
7.2.6.1 Recondition
trap at appropriate temp.
\
I
7.2.7.1 Data
interpretation based on
appropriate 8000 method.



7.2.8 Determine % dry
weight for soil/sediment.
                                          5035  -  16
                                                        Revision  0
                                                     January 199S
                                 i

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                                 METHOD 5041A

      ANALYSIS  FOR DESORPTION  OF  SORBENT  CARTRIDGES  FROM  VOLATILE  ORGANIC
                SAMPLING TRAIN (VOST):  CAPILLARY  GC/MS  TECHNIQUE
1.0  SCOPE AND APPLICATION

      1.1  This method describes  the  desorption  of volatile principal organic
hazardous  constituents   (POHCs)  collected  from  the  stack  gas  effluents  of
hazardous waste incinerators  using  the VOST methodology  (1)  with  analysis by
GC/MS  (Method  8260).   For  a comprehensive  description  of the  VOST sampling
methodology see Method 0030.   The  following  compounds may be determined by this
method:
            Compound
CAS No.1
Acetone
Acrylonitrile
Benzene
Bromodi chl oromethane
Bromoformb
Bromomethane0
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chlorodibromomethane
Chl oroethane0
Chloroform
Chl oromethane0
Dibromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Ethyl benzene6
lodomethane
Methylene chloride
Styrene6
1,1,2 , 2-Tetrachl oroethaneb
Tetrachl oroethene
Toluene
1,1,1 -Trichl oroethane
1 , 1 , 2-Trichl oroethane
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
71-55-6
79-00-5
                                  (continued)
                                  5041A  - 1
                 Revision 1
               January 1995

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            Compound                               CAS No.a


            Trichloroethene                        79-01-6
            Trichlorofluoromethane                 75-69-4
            l,2,3-Trichloropropaneb                96-18-4
            Vinyl chloride6                        75-01-4
            Xylenesb


         a   Chemical Abstract Services Registry Number.

         b   Boiling point of this compound is above 132°C.  Method 0030 is not
            appropriate for quantitative sampling of this analyte.

         c   Boiling point  of this  compound  is  below 30°C. Special precautions
            must be taken when sampling for this analyte by Method 0030.  Refer
            to Section 1.3 for discussion.

      1.2  This  method  is most successfully applied to the  analysis of non-polar
organic compounds with boiling points  between 30°C  and  100°C.  Data are applied
to the calculation of destruction and removal  efficiency (ORE), with limitations
discussed below.

      1.3  This method may be applied to analysis of many compounds which boil
above 100"C,  but Method 0030 is always inappropriate for collection of compounds
with boiling  points above 132'C.  All target analytes with boiling points greater
than 132eC  are so noted in the target analyte  list presented in Section  1.1.  Use
of Method 0030  for  collection  of compounds  boiling between  100'C  and  132°C is
often  possible,   and  must be  decided  based on  case  by  case inspection  of
information  such as  sampling  method  collection  efficiency,  tube  desorption
efficiency, and analytical method precision  and  bias.  An  organic compound with
a boiling point  below  30°C may break  through the  sorbent under the conditions
used for sample  collection.   Quantitative values  obtained  for compounds with
boiling points below 30"C must be qualified,  since  the value obtained represents
a minimum value  for the compound if breakthrough has occurred.  In certain cases,
additional  QC measures may have been taken during sampling very low boilers with
Method  0030.     This  information  should   be   considered   during  the   data
interpretation stage.

      1.4  When  Method 5041  is used for survey  analyses,  values for compounds
boiling above 132°C may be reported and qualified since the quantity obtained
represents a minimum value for  the  compound.  These minimum values  should not be
used for trial burn ORE calculations or to prove insignificant risk.

      1.5  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
higher than quantitation  limits for water insoluble compounds  (if the compounds


                                   5041A - 2                         Revision  1
                                                                  January 1995

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can be recovered at all) because the purging efficiency from water (and possibly
from Tenax-GC®)  is poor.

      1.6   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 jug/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.   Method 8260
presents method detection limits for a range of volatile compounds  analyzed  by
this method interfaced to a GC/MS with wide bore capillary methodology.

      1.7  This  method  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).

      2.2  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.

      2.3  The volatile organic compounds desorbed from the analytical trap are
determined by Method 8260 (Figure 3).


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®-!ined 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 need to  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.

      3.2    At  least   one   pair   of  blank  cartridges   (one  Tenax-GC®,  one
Tenax-GC®/charcoal) must be included with shipment of cartridges to a hazardous


                                   5041A -  3                         Revision 1
                                                                 January 1995

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waste incinerator site as trip blanks.  These trip  blanks are treated like field
blanks except that the end caps are not removed during storage at the site.  This
pair of traps are analyzed to monitor  potential contamination which  may occur
during storage and shipment.

      3.3  Analytical  system blanks are needed 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  needed 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
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

                                   5041A  - 4                        Revision 1
                                                                  January 1995

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quantitative calculations can be made and the tubes which have been sampled under
the same conditions will  yield no valid data for any of the saturated compounds.
In the presence of  a very high organic loading, even if the compounds of interest
are not saturated,  the  instrumentation is so saturated that the linear range has
been surpassed.  When instrument saturation occurs, it is possible that compounds
of  interest cannot  even  be  identified correctly  because  a  saturated  mass
spectrometer may  mis-assign masses.    Even  if compounds of interest  can  be
identified,  accurate  quantitative  calculations  are  impossible  at  detector
saturation.  No determination can be made  at  detector  saturation,  even if the
target compound  itself  is not saturated.  At detector saturation, a negative bias
will be encountered in analytical measurements and no accurate  calculation can
be made for the Destruction and Removal  Efficiency if analytical  values may be
biased negatively.

      3.8  The recoveries  of the  surrogate  compounds,  which are  spiked on the
VOST tubes  immediately before analysis, should  be  monitored carefully  as  an
overall indicator  of the  performance of the methodology.  Since  the  matrix of
stack emissions  is so variable, only a general  guideline for  recovery of 50-150%
can be used for  surrogates. The  analyst cannot use the surrogate recoveries as
a guide for correction  of compound recoveries.   The surrogates are valuable only
as a general indicator of correct operation of the methodology.   If surrogates
are not observed or if recovery  of one or more of  the surrogates is outside the
50-150% range, the  VOST methodology is not operating correctly. The cause of the
failure  in  the  methodology  is  not  obvious.   The  matrix  of stack  emissions
contains large amounts  of water,  may be highly acidic, and  may  contain large
amounts  of target  and non-target  organic  compounds.    Chemical  and  surface
interactions may be occurring on the  tubes.  If recoveries of surrogate compounds
are  extremely  low  or  surrogate compounds  cannot even be  identified  in  the
analytical  process, then failure  to observe an analyte may or may not imply that
the compound of  interest has been removed from the emissions with a high degree
of efficiency (that is, the Destruction  and Removal Efficiency for that analyte
is high).


4.0  APPARATUS AND MATERIALS

      4.1  Tube desorption  apparatus: Acceptable performance of the methodology
requires:

         1) temperature  regulation   to  ensure  that tube  temperature  during
            desorption is regulated to  180°C ± 10°;

         2) good contact between tubes and the heating apparatus to ensure that
            the  sorbent  bed  is  thoroughly  and uniformly heated  to  facilitate
            desorption of organic compounds; and

         3) gas-tight connections to the ends  of the tubes to ensure  flow of
            desorption  gas through the  tubes  without  leakage  during  the
            heating/desorption process.   A  simple clamshell  heater which will
            hold tubes which are  3/4" in  outer diameter will  perform acceptably
            as a desorption apparatus.

      4.2   Purge-and-trap  device:   The  purge-and-trap device is  described  in
Method 5030, Section 4.0.

                                  5041A - 5                         Revision 1
                                                                  January 1995

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            4.2.1  The cartridge thermal desorption  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.

            4.2.2   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.

      4.3  The gas chromatograph/mass  spectrometer/data system and recommended
GC columns are described in Method  8260,  Section 4.0.

      4.4  Wrenches:   9/16",  1/2",  7/16", and 5/16".

      4.5  Teflon® tubing:  1/8" diameter.

      4.6  Syringes:  25 juL syringes (2),  10 p.1  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
necessary.

      4.9  Volumetric flasks:   5 ml, class  A with ground glass stopper.

      4.10  Injector port or  equivalent,  heated to 180"C for loading standards
onto VOST tubes prior to analysis.

      4.11  Vials:  2 ml, with Teflon®-lined screw caps or crimp tops.

      4.12  Syringe:   5 mL, gas-tight  with  shutoff valve.


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.

NOTE: 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.
                                   5041A  -  6                         Revision 1
                                                                  January 1995

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      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  Surrogate standards:  The recommended surrogates are listed in Method
8260, Section 5.0.   A stock surrogate compound  solution in high purity methanol
should be  prepared  as  described in Section 5.0,  Method  8260, and a surrogate
standard spiking solution should be prepared from the stock at a concentration
of 250 M9/10 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 )LtL of the surrogate spiking  solution prior  to  GC/MS analysis.

      5.5   Internal  standards:   The recommended  internal  standards  for GC/MS
analysis are listed  in Method 8260, Section 5.0.  Prepare internal standard stock
and secondary dilution standards  in high  purity  methanol using  the procedures
described in Section 5.0  of Method 8260.  The secondary dilution standard should
be prepared  at  a concentration  of 25  mg/L of each  of  the  internal  standard
compounds.  Addition of  10 juL  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.

      5.6  Great care must  be  taken to maintain  the  integrity of  all  standard
solutions.  All  standards of volatile compounds in methanol should be stored at
-10°C to  -20"C  in  amber  bottles with  Teflon®-!ined  screw  caps  or crimp tops.
In addition,  careful  attention must be paid to the use  of syringes designated for
a specific purpose or for use  with only a single standard solution since cross
contamination of volatile organic standards can occurs  very readily.


6.0  SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1  See Method 0030 for the VOST Sampling Methodology.

      6.2  VOST samples  are collected  on  paired  cartridges.   The  first of the
pair of  sorbent cartridges is  packed  with approximately  1.6 g  of  Tenax-GC®
resin.  The second  cartridge of the pair is packed with  Tenax-GC® and petroleum
based charcoal  (3:1  by volume;  approximately  1 g of each).   In sampling,  the
emissions gas stream passes through the Tenax-GC® layer first and  then through
the charcoal  layer.   The Tenax-GC® is cleaned and  reused;  charcoal  is not reused
when tubes are prepared.  Sorbent is cleaned  and the tubes  are  packed.  The tubes
are desorbed and subjected to  a blank  check prior to being sent to the field.
When the tubes are used for sampling (see Figure 5 for  a schematic diagram of the
Volatile Organic Sampling Train  (VOST)), cooling water  is  circulated  to  the
condensers and the temperature  of the cooling water is maintained near 0"C.  The
end caps of  the  sorbent  cartridges are placed in a  clean,  screw  capped glass
container during sample collection.

      6.3  After the apparatus  is leak checked,  sample  collection  is accomplished
by opening the valve to the first condenser, turning  on  the pump,  and sampling
at a rate of 1 liter/min for 20 minutes.   The volume  of sample for any pair of
traps should not exceed 20 liters.  An  alternative set of conditions for sample
collection requires  sampling at  a reduced flow rate, where the overall volume of


                                   5041A - 7                         Revision 1
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sample collected  is  5  liters at a rate  of  0.25  L/min for 20 minutes.  The  20
minute period is necessary for collecting an integrated sample.

      6.4  Following collection of 20  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 suitable environment  for storage and transport  until analysis.  The sample
is considered 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.

      6.7  All sample cartridges are kept  in coolers on cold  packs after exposure
and during shipment.   Upon receipt  at the laboratory, the cartridges are stored
in a refrigerator at 4°C until analysis.
                                         i
7.0  PROCEDURE
      7.1    Recommended  operating  conditions  for  cartridge  desorber  and
purge-and-trap unit, are:
      Cartridge Desorption Oven
      Desorb Temperature
      Desorb Time
      Desorption Gas Flow
      Desorption/Carrier Gas

      Purge-and-Trap Concentrator
      Analytical Trap Desorption Flow
      Purge Temperature
      Purge Time
      Analytical Trap Desorb Temp.
      Analytical Trap Desorb Time

      Gas Chromatograph
      Column
      Carrier Gas Flow
      Makeup Gas Flow
      Injector Temperature
      Transfer Oven Temperature
      Initial Temperature
      Initial Hold Time
      Program Rate

      Final Temperature
      Final Hold Time
180'C
11 minutes
40 mL/min
Helium, Grade
   5.0
2.5 mL/min
Ambient
11 minutes
180°C
5 minutes
helium
30 m x 0.53 mm  ID,
(J&W   Scientific),   3
thickness, or equivalent
15 mL/min
15 mL/min
200°C
240°C
5°C
2 minutes
6°C/min
       coated with DB-624
                 m   film
240°C
1 minute or until
       elution ceases
                                   5041A -  8
                          Revision 1
                        January 1995
                              i

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      Mass Spectrometer
      Manifold Temperature                105*C
      Scan Rate                           1 sec/cycle
      Mass Range                          35-260 amu
      Electron Energy                     70 eV (nominal)
      Source Temperature                  According    to    manufacturer's
                                          specifications

      7.2  Each GC/MS system must  be hardware tuned to meet the BFB criteria in
Method 8260.

      7.3  Assemble and operate a purge-and-trap device as per Method 5030.

      7.4  Connect the purge-and-trap device to a gas chromatograph.

      7.5  Assemble a VOST tube desorption apparatus which meets the requirements
of Section 4.1.

      7.6  Connect the VOST tube desorption apparatus to the purge-and-trap unit.

      7.7  Spiking standards onto VOST tubes:   For this procedure,  the system
will be calibrated using the internal  standard procedure.   Internal  standards,
surrogates, and calibration standards in methanolic solution will be spiked onto
cleaned VOST tubes for proper calibration  of  the  system.   These  standards 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  Prepare a syringe  with the appropriate  volume  of methanolic
      standard solution (either surrogates, internal standards,  or calibration
      compounds).

            7.7.2  With the injector port heated to 180°C,  and with an inert gas
      flow of 10 mL/min through the injector port,  connect the paired VOST tubes
      (connected as  in  Figure  1,  with gas  flow in the same direction  as the
      sampling gas flow)  to  the  injector port; tighten with a wrench  so that
      there is  no  leakage of gas.   If  separate tubes  are being  analyzed, an
      individual Tenax® or Tenax®/charcoal  tube is  connected to the  injector.

            7.7.3  After directing the gas flow through the VOST  tubes, slowly
      inject the first standard  solution  over  a  period of 25 seconds.  Wait for
      5 seconds before withdrawing the syringe from the injector  port.

            7.7.4  Inject  a  second standard  (if required)  over a  period of 25
      seconds and wait for 5 seconds before withdrawing the syringe from the
      injector port.

            7.7.5  Repeat the  sequence  above,  as  required,  until all  of the
      necessary compounds are spiked  onto the VOST tubes.

            7.7.6  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

                                  5041A  -  9                         Revision 1
                                                                  January 1995

-------
      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.

      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  Cool  the oven of the gas chromatograph to subambient temperature with
liquid nitrogen.

      7.12  Prepare the GC/MS system for data acquisition  as per Method 8260.

      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.  Perform the remainder of the purge and trap  process as described
in Method 5030, Section 7.0.

      7.14  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
on paired tubes.   If tubes are being analyzed individually, a calibration should
be performed on  individual Tenax® only tubes  and Tenax®/charcoal tubes.

            7.14.1   Prepare  the calibration  standards by spiking  VOST tubes
      using the  procedure described  in Section 7.7.   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.

            7.14.2   Continue  the initial calibration  process  as  described in
      Method 8260, Section 7.0.  The same criteria  for SPCC, CCC and linearity
      must be met.

      7.15  GC/MS Calibration Verification

            7.15.1   Prior to the  analysis of samples, purge  5-50 ng  of the
      4-bromofluorobenzene standard.  The resultant mass spectrum for BFB must
      meet  all  of the criteria given in  Method 8260 before  sample  analysis
      begins.    These  criteria  must  be  demonstrated  every  twelve  hours  of
      operation.

                                  5041A - 10                        Revision 1
                                                                  January 1995

-------
      7.15.2  Perform calibration verification as per Method 8260, Section
7.0.  The same criteria for SPCC,  linearity and internal standard response
check must be met.  See the next section for  special guidance on the CCCs.

      7.15.3  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.   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.

      7.15.4   Internal  standard  responses  and  retention  times  in the
calibration verification standard must be evaluated immediately after or
during data acquisition.  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 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  calibration  verification
standard, 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  verification 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.

7.16  GC/MS Analysis of Samples

      7.16.1  Set  up the cartridge  desorption  unit,  purge-and-trap unit
(Method 5030), and GC/MS (Method 8260)  as described above or as described
in the indicated methods.

      7.16.2   BFB tuning  criteria and  GC/MS  calibration  verification
criteria in Method 8260 must be met before analyzing  samples.  (See Sec.
7.15)

      7.16.3   Adjust  the  helium  purge  gas  flow  rate  (through  the
cartridges and purge vessel)  to  approximately 40 mL/min.  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.
                            5041A - 11                        Revision 1
                                                            January 1995

-------
            7.16.4  The first  analysis performed after the tuning check and the
      calibration or calibration verification  should  be  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 Section 7.7.   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.

            7.16.5  Use organic-free reagent water  as  described in Chapter One
      for the purge vessel.

            7.16.6  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.
      Alternatively,  the  data may  be flagged  in  the  report  as  "extrapolated
      beyond the upper range of the  calibration."

            7.16.7   The use  of  the secondary  ions shown  in  Method 8260  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.

            7.16.8  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 is necessary.   More extensive guidance
      on corrective maintenance of the purge and trap and  GC/MS system are found
      in Section 7.0  of their  respective methods (Method 5030 and Method 8260).

      7.17  Qualitative analysis:  Follow the procedure on qualitative analysis
found in Section 7.0 of Method 8260.

      7.18  Quantitative analysis:   See Method  8260 for overall  information on
alternative approaches to quantitation.

            7.18.1  Calculate the amount in  ng  of  each  identified  analyte from
      the VOST tubes  following the guidance on calculations presented in Section
      7.0 of Method 8260.

            7.18.2  The  choice of methods for  evaluating data collected using
      the VOST methodology for incinerator trial burns is  a regulatory decision.
      Contact the local  regulatory agencies to which VOST  data are submitted for
      information on data reporting  preferences.


                                  5041A -  12                        Revision 1
                                                                  January 1995

-------
            7.18.3  The  total  amount of the POHCs of  interest  collected  on a
      pair of traps should be summed.

            7.18.4  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.

            7.18.5    Where  applicable,  an  estimate  of  concentration  for
      noncalibrated components in the sample may be made.   Follow the guidance
      in Method 8260,  Section 7.0 that covers this issue.

            7.18.6  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.  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  Refer to Chapter  One and  Section 8.0 of Methods 5000  and 8000 for
specific quality control  procedures.  Each laboratory using SW-846 methods should
maintain a formal  quality assurance program.

      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 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    Initial  Demonstration   of   Proficiency  -  Each  laboratory  must
demonstrate initial proficiency with  each sample preparation and determinative
method combination  it  utilizes,  by generating  data of acceptable  accuracy and
precision for  target  analytes  in a clean matrix.  The laboratory  should also
repeat the following  operations  whenever new  staff are trained  or significant
changes in instrumentation are made.   See Section 8.0 of Methods 5000 and 8000
for information on how to accomplish  this demonstration.

            8.3.1    A  reference  sample  concentrate  is needed containing  each
      analyte  at  a concentration  of 10 mg/L  in high  purity  methanol.   The
      reference sample concentrate may be prepared from pure standard materials
      or purchased as  certified solutions.   If  the reference sample concentrate

                                  5041A  - 13                        Revision 1
                                                                  January 1995

-------
      is prepared by the laboratory, it must be prepared using stock standards
      prepared independently from the stock standards used for calibration.

            8.3.2  Spike four pairs of cleaned, prepared VOST tubes  with  10  ^L
      of the QC  check  sample concentrate and  analyze these  spiked  VOST  tubes
      according to the method beginning in Section 7.0.

            8.3.3  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.

            8.3.4  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
      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.   See  also  further information on this subject  found in Method
      8000, Section 8.0.

      8.4  Sample Quality Control for Preparation and Analysis - See Section 8.0
in Method 5000 and Method 8000 for procedures to follow to demonstrate acceptable
continuing performance on each set  of samples to be analyzed.  This includes the
method blank (Section 8.2), a laboratory control sample (LCS) and the addition
of surrogates to each sample and QC sample.

            8.4.1  The LCS is prepared by spiking reference sample concentrate
      (noted in Section 8.3) onto a clean VOST tube.

            8.4.2  If surrogate  recovery  is not within the limits established by
      the laboratory,  the  following  procedures are  necessary:  (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

                                  5041A  - 14                        Revision  1
                                                                  January 1995

-------
      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.


9.0  METHOD PERFORMANCE

      9.1   Method  detection limit (MDL)  is defined in Chapter One.   The MDL
actually  achieved  in  a  given  analysis  will   vary depending  upon  instrument
sensitivity and the effects of the matrix.

      9.2  The MDL  concentrations for  VOST analytes can be found in Section 9.0
of Method 8260.
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 Water
      and Wastewater,  ASTM STP 686, pp 108-129,  1979.
                                  5041A - 15                        Revision 1
                                                                  January 1995

-------
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                                    METHOD  5041A
           ANALYSIS  FOR DESORPTION OF SORBENT CARTRIDGES  FROM
 VOLATILE  ORGANIC  SAMPLING  TRAIN (VOST):  CAPILLARY COLUMN TECHNIQUE
     7.1 Establish
     conditions for
   cartridge desorp-
   tion oven, purge-
and-trap concentrator,
     GC, and MS.
   7.2 Tune GC/MS
    with BFB and
   check calibration
      curve (see
    Section 7.1 5).
      7.3 - 7.6
    Assemble the
       system.
  7.7. Calibrate the
  instrument system
using the internal std.
procedure. Stds. and
calibration compounds
are spiked into cleaned
VOST tubes using the
  flash evaporation
      technique.
    7.8 Prep the
   purge-and-trap
   unit with 5  mL
    organic-free
   reagent water.
     7.9 Connect
     paired VOST
     tubes to the
     gas lines for
     desorption.
                                    7.10 Initiate
                                   tube desorption/
                                     purge and
                                      heating.
 7.1 1 Set the GC
oven to subambient
   temperature
    with liquid
     nitrogen.
   7.12 Prep the
  GC/MS system
     for data
    aquisition.
7.13 After the tube/
  water purge time,
     attach the
  analytical trap to
   the GC/MS for
    desorption.
 7.14 Perform initial
 calibration of VOST
      tubes.
                                7.15 Calibrate GC/MS
                                  and perform SPCC
                                  and CCC calibration
                                     verification.
                                     7.16 GC/MS
                                      analysis of
                                       samples.
                                   7.17 Qualitative
                                   analysis of data;
                                      refer to
                                    Method 8260,
                                    Section 7.0.
 7.18 Quantitative
analysis of data for
  compounds of
     interest.
(      Stop     |
                                     5041A  - 21
                                                Revision  1
                                             January  1995

-------
4.2  SAMPLE PREPARATION METHODS

     4.2.2  CLEANUP
         The following methods are included in this section:
         Method 3600C:
         Method 3610B:
         Method 3611B:
         Method
         Method
         Method
         Method
         Method
         Method
3620B:
3630C:
3640A:
3650B:
3660B:
3665A:
Cleanup
Alumina Cleanup
Alumina   Column   Cleanup   and  Separation   of
Petroleum Wastes
Florisil Cleanup
Silica Gel Cleanup
Gel-Permeation Cleanup
Acid-Base Partition Cleanup
Sulfur Cleanup
Sulfuric Acid/Permanganate Cleanup
                                 FOUR - 9
                                                 Revision 3
                                               January 1995

-------