TEST METHODS FOR EVALUATING
SOLID WASTE, PHYSICAL/CHEMICAL
 METHODS, SW-846, 3RD EDITION,
      PROPOSED UPDATE II
                \) Printed on Recycled Paper

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      Test Methods for Evaluating Solid Waste, Physical/Chemical Methods

                                 Third  Edition

                          Promulgated Update Package

                                 Instructions


Enclosed is the proposed Update 2 package for "Test Methods for Evaluating Solid
Waste, Physical/Chemical Methods", SW-846,  Third Edition.   Attached is a list
of methods included in the proposed update, indicating whether the method is a
new method, a partially revised method, or a totally revised method.

Do not discard  or replace any of the current  pages  in the  SW-846 manual until
the proposed Update 2  package is  promulgated.  Until promulgation of the update
package, the methods in the update package are not officially part of the SW-846
manual, and thus do not carry the status of EPA approved methods.

Enclosure
        Revised methods are designated by the letter "A" (Revision 1) or the
        letter "B"  (Revision 2)  in  the method  number.   In  order to properly
        document the method revision used, the entire method number, Including
        the letter designation, must be referenced.

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                           TABLE   OF   CONTENTS
                                     VOLUME ONE

                                      SECTION  A
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   Quality Assurance Project Plan
   3.0   Field Operations
   4.0   Laboratory Operations
   5.0   Definitons
   6.0   References

CHAPTER TWO -- CHOOSING THE CORRECT PROCEDURE

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

CHAPTER THREE -- METALLIC ANALYTES

   3.1   Sampling Considerations
   3.2   Sample Preparation Methods

         Method 3005:   Acid Digestion of Waters for Total  Recoverable  or Dissolved
                        Metals for Analysis by  Flame Atomic Absorption  Spectroscopy
                        or Inductively Coupled Plasma  Spectroscopy
         Method 3010:   Acid Digestion of Aqueous Samples and Extracts for Total Metals
                        for Analysis  by  Flame  Atomic Absorption  Spectroscopy  or
                        Inductively Coupled Plasma  Spectroscopy
         Method 3015:   Microwave Assisted  Acid Digestion  of  Aqueous  Samples  and
                        Extracts
         Method 3020:   Acid Digestion of Aqueous Samples and Extracts for Total Metals
                        for Analysis by Graphite Furnace Atomic Absorption Spectroscopy
         Method 3040:   Dissolution Procedure  for Oils, Greases,  or  Waxes
         Method 3050:   Acid Digestion of Sediments, Sludges,  and  Soils

                                    CONTENTS - 1
                                                               Revision  2
                                                               June  1990

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      Method 3051:
      Method 5050:
Microwave Assisted Acid Digestion of Sludges,  Soils,  and Oils
Bomb Combustion Method for Solid Waste
3.3   Methods for Determination of Metals

      Method 6010:   Inductively Coupled Plasma Atomic Emission Spectroscopy
      Method 6020:   Inductively Coupled Plasma Mass Spectrometry
      Method 7000:   Atomic Absorption Methods
      Method 7020:   Aluminum (AA,  Direct Aspiration)
      Method 7040:   Antimony (AA,  Direct Aspiration)
      Method 7041:   Antimony (AA,  Furnace Technique)
      Method 7060:   Arsenic (AA,  Furnace Technique)
      Method 7061:   Arsenic (AA,  Gaseous Hydride)
      Method 7062:   Antimony and  Arsenic (AA, Gaseous Borohydride)
      Method 7080:   Barium (AA, Direct Aspiration)
      Method 7081:   Barium (AA, Furnace Technique)
      Method 7090:   Beryllium (AA,  Direct Aspiration)
      Method 7091:   Beryllium (AA,  Furnace Technique)
      Method 7130:   Cadmium (AA,  Direct Aspiration)
      Method 7131:   Cadmium (AA,  Furnace Technique)
      Method 7140:   Calcium (AA,  Direct Aspiration)
      Method 7190:   Chromium (AA,  Direct Aspiration)
      Method 7191:   Chromium (AA,  Furnace Technique)
      Method 7195:   Chromium,  Hexavalent (Coprecipitation)
      Method 7196:   Chromium,  Hexavalent (Colorimetric)
      Method 7197:   Chromium,  Hexavalent (Chelation/Extraction)
      Method 7198:   Chromium,  Hexavalent (Differential  Pulse Polarography)
      Method 7200:   Cobalt (AA, Direct Aspiration)
      Method 7201:   Cobalt (AA, Furnace Technique)
      Method 7210:   Copper (AA, Direct Aspiration)
      Method 7211:   Copper (AA, Furnace Technique)
      Method 7380:   Iron (AA,  Direct Aspiration)
      Method 7381:   Iron (AA,  Furnace Technique)
      Method 7420:   Lead (AA,  Direct Aspiration)
      Method 7421:   Lead (AA,  Furnace Technique)
      Method 7430:   Lithium (AA,  Direct Aspiration)
      Method 7450:   Magnesium (AA,  Direct Aspiration)
      Method 7460:   Manganese (AA,  Direct Aspiration)
      Method 7461:   Manganese (AA,  Furnace Technique)
      Method 7470:   Mercury in Liquid Waste (Manual Cold-Vapor Technique)
      Method 7471:   Mercury  in Solid  or  Semi sol id  Waste   (Manual  Cold-Vapor
                     Technique)
      Method 7480:   Molybdenum (AA,  Direct Aspiration)
      Method 7481:   Molybdenum (AA,  Furnace Technique)
      Method 7520:   Nickel  (AA, Direct Aspiration)
      Method 7550:   Osmium (AA, Direct Aspiration)
      Method 7610:   Potassium (AA,  Direct Aspiration)
      Method 7740:   Selenium (AA,  Furnace Technique)
      Method 7741:   Selenium (AA,  Gaseous Hydride)
      Method 7742:   Selenium (AA,  Gaseous Borohydride)
      Method 7760:   Silver (AA, Direct Aspiration)
      Method 7761:   Silver (AA, Furnace Technique)
                                 CONTENTS - 2
                                                            Revision 2
                                                            June 1990

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         Method 7770:   Sodium (AA, Direct Aspiration)
         Method 7780:   Strontium (AA, Direct Aspiration)
         Method 7840:   Thallium (AA, Direct Aspiration)
         Method 7841:   Thallium (AA, Furnace Technique)
         Method 7870:   Tin (AA, Direct Aspiration)
         Method 7910:   Vanadium (AA, Direct Aspiration)
         Method 7911:   Vanadium (AA, Furnace Technique)
         Method 7950:   Zinc (AA, Direct Aspiration)
         Method 7951:   Zinc (AA, Furnace Technique)

APPENDIX -- COMPANY REFERENCES
                                    CONTENTS - 3
                                                               Revision 2
                                                               June 1990

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                                     VOLUME ONE

                                      SECTION  B
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
ACKNOWLEDGEMENTS

CHAPTER ONE. REPRINTED -- QUALITY CONTROL

   1.0   Introduction
   2.0   Quality Assurance Project Plan
   3.0   Field Operations
   4.0   Laboratory Operations
   5.0   Definitons
   6.0   References

CHAPTER FOUR -- ORGANIC ANALYTES

   4.1   Sampling Considerations
   4.2   Sample Preparation Methods

         4.2.1  Extractions  and Preparations
               Method
               Method
               Method
               Method
               Method
               Method
               Method
               Method
               Method
3500:
3510:
3520:
3540:
3541:
3550:
3580:
5030:
5040:
               Method 5041:


               Method 5100:

               Method 5110:


         4.2.2  Cleanup
Organic Extraction and Sample Preparation
Separatory Funnel Liquid-Liquid Extraction
Continuous Liquid-Liquid Extraction
Soxhlet Extraction
Automated Soxhlet Extraction
Ultrasonic Extraction
Waste Dilution
Purge-and-Trap
Analysis  of  Sorbent  Cartridges from  Volatile  Organic
Sampling   Train    (VOST):      Gas    Chromatography/Mass
Spectrometry Technique
Analysis  of  Sorbent  Cartridges from  Volatile  Organic
Sampling  Train   (VOST):      Wide-bore  Capillary  Gas
Chromatography/Mass Spectrometry Technique
Determination of  the  Volatile Organic Content of Waste
Samples
Determination of  Organic  Phase  Vapor Pressure in Waste
Samples
               Method 3600: Cleanup
               Method 3610: Alumina Column Cleanup
               Method 3611: Alumina Column Cleanup and Separation of Petroleum Wastes
                                    CONTENTS - 4
                                                               Revision 2
                                                               June 1990

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            Method 3620:  Florisil  Column  Cleanup
            Method 3630:  Silica  Gel  Cleanup
            Method 3640:  Gel-Permeation Chromatography  (GPC)  Cleanup
            Method 3650:  Acid-Base Partition  Cleanup
            Method 3660:  Sulfur  Cleanup
            Method 3665:  Sulfuric  Acid/Permanganate Cleanup

4.3   Determination of Organic Analytes

      4.3.1  Gas Chromatographic  Methods
            Method 8000:
            Method 8010:
            Method 8011:

            Method 8015:
            Method 8020:
            Method 8021:
            Method 8030:

            Method 8031:
            Method 8032:
            Method 8040:
            Method 8060:
            Method 8061:

            Method 8070:
            Method 8080:

            Method 8081:

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

            Method 8140:
            Method 8141:

            Method 8150:
            Method 8151:
Gas Chromatography
Halogenated Volatile Organics
1,2-Dibromoethane and l,2-Dibromo-3-chloropropane by Gas
Chromatography
Nonhalogenated Volatile Organics by Gas Chromatography
Aromatic Volatile Organics by Gas Chromatography
Halogenated and Aromatic Volatiles by Gas  Chromatography
using  Electrolytic  Conductivity   and  Photoionization
Detectors in Series: Capillary Column Technique
                                               by
Gas
Acrolein,    Acrylonitrile,     Acetonitrile
Chromatography
Acrylonitrile by Gas Chromatography
Acrylamide by Gas Chromatography
Phenols by Gas Chromatography
Phthalate Esters by Gas Chromatography
Phthalate  Esters  by  Gas  Chromatography:    Capillary
Technique
Nitrosamines by Gas Chromatography
Organochlorine Pesticides and  Polychlorinated  Biphenyls
by Gas Chromatography
Organochlorine Pesticides and  Polychlorinated  Biphenyls
by Gas Chromatography:  Capillary Column Technique
Nitroaromatics and Cyclic Ketones by Gas Chromatography
Polynuclear Aromatic Hydrocarbons by Gas Chromatography
Haloethers by Gas Chromatography
Chlorinated Hydrocarbons by Gas Chromatography
Chlorinated Hydrocarbons by Gas Chromatography:  Capillary
Column Technique
Organophosphorus Pesticides by Gas Chromatography
Organophosphorus   Compounds   by   Gas   Chromatography:
Capillary Column Technique
Chlorinated Herbicides by Gas Chromatography
Chlorinated Herbicides by Gas Chromatography:   Capillary
Column Technique
      4.3.2  Gas Chromatographic/Mass Spectroscopic Methods
            Method 8240:

            Method 8250:
Volatile  Organic  Compounds  by  Gas  Chromatography/Mass
Spectrometry (GC/MS):  Packed Column Technique
Semivolatile Organic Compounds by Gas Chromatography/Mass
Spectrometry (GC/MS):  Packed Column Technique
                                 CONTENTS - 5
                                                            Revision 2
                                                            June 1990

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               Method 8260:

               Method 8270:
               Method 8280:
                Method 8290:
     Volatile  Organic Compounds  by Gas  Chromatography/Mass
     Spectrometry (GC/MS): Capillary Technique
     Semivolatile Organic Compounds  by Gas Chromatography/Mass
     Spectrometry (GC/MS): Capillary Technique
     The  Analysis  of  Polychlorinated  Dibenzo-p-dioxins  and
     Polychlorinated Dibenzofurans
     Appendix A:  Signal-to-Noise Determination Methods
     Appendix B:  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)
         4.3.3  High Performance Liquid Chromatographic Methods
               Method 8310:
               Method 8315:
               Method 8316:

               Method 8318:

               Method 8321:

               Method 8330:

               Method 8331:
     Polynuclear Aromatic Hydrocarbons
     Formaldehyde by High Performance Liquid Chromatography
     Acrylamide, Acrylonitrile and Acrolein by High Performance
     Liquid Chromatography (HPLC)
     N-Methyl   Carbamates   by   High   Performance   Liquid
     Chromatography (HPLC)
     Reverse Phase High Performance Liquid Chromatography with
     Thermospray/Mass Spectrometry (HPLC/TSP/MS) Detection
     Nitroaromatics and Nitramines by High Performance Liquid
     Chromatography (HPLC)
     Tetrazene by High Performance Liquid Chromatography (HPLC)
         4.3.4  Fourier Transform Infrared Methods

               Method 8410:  Semivolatile   Organics  by  Gas  Chromatography/Fourier
                             Transform Infrared  Spectroscopy (GC/FTIR):   Capillary
                             Column  Technique

   4.4   Miscellaneous Screening Methods
         Method 3810:
         Method 3820:
         Method 8275:
Headspace
Hexadecane Extraction and Screening of Purgeable Organics
Semivolatile Organic Compounds by Thermal  Chromatography/Mass
Spectrometry (TC/MS):  Screening Technique
APPENDIX -- COMPANY REFERENCES
                                    CONTENTS - 6
                                                               Revision 2
                                                               June  1990

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                                     VOLUME ONE

                                      SECTION  C
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE

CHAPTER ONE. REPRINTED -- QUALITY CONTROL

   1.0   Introduction
   2.0   Quality Assurance Project Plan
   3.0   Field Operations
   4.0   Laboratory Operations
   5.0   Definitons
   6.0   References

CHAPTER FIVE -- MISCELLANEOUS TEST METHODS

   Method 9010: Total  and Amenable Cyanide (Colorimetric,  Manual)
   Method 9011: Cyanide Extraction Procedure for Solids and Oils
   Method 9012: Total  and Amenable Cyanide (Colorimetric,  Automated UV)
   Method 9020: Total  Organic Hal ides (TOX)
   Method 9021: Purgeable Organic  Hal ides (POX)
   Method 9022: Total  Organic Hal ides (TOX)  by Neutron Activation  Analysis
   Method 9030: Acid-Soluble and Acid-Insoluble  Sulfides
   Method 9031: Extractable Sulfides
   Method 9035: Sulfate (Colorimetric,  Automated,  Chloranilate)
   Method 9036: Sulfate (Colorimetric,  Automated,  Methylthymol  Blue,  AA  II)
   Method 9038: Sulfate (Turbidimetric)
   Method 9056: Ion Chromatography Method
   Method 9060: Total  Organic Carbon
   Method 9065: Phenolics (Spectrophotometric,  Manual  4-AAP with Distillation)
   Method 9066: Phenolics (Colorimetric,  Automated 4-AAP with  Distillation)
   Method 9067: Phenolics (Spectrophotometric,  MBTH with Distllation)
   Method 9070: Total   Recoverable Oil   &  Grease   (Gravimetric,  Separatory  Funnel
                Extraction)
   Method 9071: Oil &  Grease Extraction Method for Sludge  Samples
   Method 9073: Total  Recoverable  Hydrocarbons by Infrared Spectroscopy
   Method 9075: Test Method  for Total  Chlorine  in Used  Oil  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)
   Method 9131: Total  Coliform:  Multiple Tube Fermentation Technique
   Method 9132: Total  Coliform:  Membrane Filter Technique
   Method 9200: Nitrate
   Method 9250: Chloride  (Colorimetric, Automated  Ferricyanide  AAI)
Method 9076:

Method 9077:
                                    CONTENTS - 7
                                                               Revision 2
                                                               June 1990

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   Method 9251: Chloride (Colorimetric,  Automated Ferricyanide AAII)
   Method 9252: Chloride (Titrimetric,  Mercuric Nitrate)
   Method 9253: Chloride (Titrimetric,  Silver Nitrate)
   Method 9320: Radium-228

CHAPTER SIX -- PROPERTIES

   Method 1320: Multiple Extraction Procedure
   Method 1330: Extraction Procedure for Oily Wastes
   Method 9040: pH Electrometric Measurement
   Method 9041: pH Paper Method
   Method 9045: Solid and Waste pH
   Method 9050: Specific Conductance
   Method 9080: Cation-Exchange Capacity of Soils
   Method 9081: Cation-Exchange Capacity of Soils
   Method 9090: Compatibility Test for  Wastes and
   Method 9095: Paint Filter Liquids Test
   Method 9096: Liquid Release Test (LRT) Procedure
   Method 9100: Saturated Hydraulic  Conductivity,  Saturated  Leachate  Conductivity,
                and Intrinsic Permeability
   Method 9310: Gross Alpha & Gross Beta
   Method 9311: Determination  of   Gross   Alpha   Activity  in
                Coprecipitation
   Method 9312: Method for Gross Alpha  in Solid Samples
   Method 9315: Alpha-Emitting Radium Isotopes
                                                  (Ammonium Acetate)
                                                  (Sodium Acetate)
                                                  Membrane Liners
                                                                Drinking   Water  by
                              PART  II    CHARACTERISTICS

CHAPTER SEVEN -- INTRODUCTION AND REGULATORY DEFINITIONS
   7.1
   7.2
   7.3
         Ignitability
         Corrositivity
         Reactivity

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

   7.4   Extraction Procedure Toxicity

CHAPTER EIGHT -- METHODS FOR DETERMINING CHARACTERISTICS

   8.1   Ignitability

         Method 1010:  Pensky-Martens Closed-Cup Method for Determining Ignitability
         Method 1020:  Setaflash Closed-Cup Method for Determining Ignitability

   8.2   Corrosivity

         Method 1110:  Corrosivity Toward Steel

   8.3   Reactivity

                                    CONTENTS - 8
                                                               Revision 2
                                                               June 1990

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   8.4   Toxicity

         Method 1310:   Extraction  Procedure  (EP) Toxicity Test Method and Structural
                        Integrity Test
         Method 1311:   Toxicity Characteristic  Leaching  Procedure
         Method 1312:   Synthetic Precipitation  Leaching  Procedure

APPENDIX -- COMPANY REFERENCES
                                    CONTENTS - 9
                                                               Revision 2
                                                               June 1990

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

   1.0   Introduction
   2.0   Quality Assurance Project Plan
   3.0   Field Operations
   4.0   Laboratory Operations
   5.0   Definitons
   6.0   References
                                 PART III    SAMPLING

CHAPTER NINE -- SAMPLING PLAN

   9.1   Design and Development
   9.2   Implementation

CHAPTER TEN -- SAMPLING METHODS

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

CHAPTER ELEVEN -- GROUND 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

                                    CONTENTS  -  10
                                                               Revision 2
                                                               June 1990

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   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
                                    CONTENTS  -  11
                                                               Revision 2
                                                               June 1990

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                                  CHAPTER  TWO

                        CHOOSING THE CORRECT PROCEDURE
2.1  PURPOSE

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

      2.1.1  Trace Analysis vs. Macroanalvsis

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

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

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

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

      2.1.2   Choice of Apparatus and  Preparation  of Reagents

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


2.2  REQUIRED  INFORMATION

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

      2.2.1   Physical  State(s)  of Sample

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


                                   TWO -  1                        Revision 2
                                                                  November 1990

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

      2.2.2  Analvtes

      Analytes are divided into classes based on  the determinative methods which
are used to identify and quantify  them.  The organic compounds are divided into
different groups as indicated by Tables  2-1 through 2-28.  Some of the analytes
appear on more than one table, as  they  may be determined using any of several
methods.

      2.2.3  Detection Limits Required

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

      2.2.4  Analytical Objective

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

      2.2.5  Detection and Monitoring

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

      Monitoring samples, on the  other  hand, are  analyzed to  confirm existing
and on-going conditions, tracking  the presence or absence of constituents  in an
environmental or process matrix.  A less  compound(s)-specific detection mode may
be used because  the matrix  and the analytical conditions  are well  defined and
stable.

      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 2-29, at the end of this
chapter.   Similar information for solid  matrices may  be found in  Table 3-1

                                   TWO  -  2                       Revision 2
                                                                  November 1990

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(inorganic  analytes)   and  Table  4-1  (organic  analytes).    Samples  must  be
extracted/analyzed within   the  specified holding times for the  results  to be
considered reflective of total concentrations.  Analytical data generated outside
of the specified holding times must be considered to be minimum values only.


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  Determinative Procedures

      The  determinative  methods for organic  analytes have been  divided into
three  categories,  shown  in  Figure  2-2:    gas  chromatography  (GC);  gas
chromatography/mass spectrometry (GC/MS); and high pressure  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  method   of  gas
chromatography.  This  method should  be  consulted prior  to application of any of
the gas chromatographic methods.

      Method 8140 and  8141,  for organophosphorus  pesticides,  and Methods 8150
and 8151,  for  chlorinated herbicides,  are preferred  to GC/MS because  of the
combination of selectivity and sensitivity of the flame photometric, nitrogen-
phosphorus, and electron capture detectors.

      Methods 8240 and  8260 are both GC/MS methods for volatile  analytes.  Method
8240 uses a packed column whereas Method 8260 employs a capillary column.  Better
chromatographic separation of the volatile compounds  may  be obtained  by using
Method 8260 rather than 8240.  Performance criteria will be  based on Method 8260.
Method 5030 has been combined with both Method 8240 and 8260, with which it was
used  exclusively.   A  GC with  a selective  detector  is  also useful   for the
determination of volatile organic compounds in a monitoring scenario, described
in Section 2.2.5.

      Methods 8250 and 8270  are both GC/MS methods  for semi volatile analytes.
Method 8250 uses a packed column whereas Method 8270 employs  a capillary column.
Better chromatographic separation of the semivolatile compounds may be obtained
by using Method 8270 rather  than 8250.   Performance  criteria  will be  based on
Method 8270.
                                    TWO -  3                        Revision 2
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      2.3.2  Cleanup Procedures

      Each  category  in  Figure  2-3,  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.

      2.3.3  Extraction and Sample Preparation Procedures

      Methods for preparing organic  analytes  are  shown  in  Figure  2-4.   Method
3500 and associated  methods should be consulted for further details  on preparing
the sample for analysis.

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

                  2.3.3.1.1  Basic or Neutral  Extraction of Semivolatiles

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

                  2.3.3.1.2  Acidic Extraction of  Phenols and Acids

                  The extract obtained by  performing either Method  3510 or 3520
            at pH 2  will contain the phenols and  acid extractables.
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      2.3.3.2  Solid Samples

      Soxhlet  (Method  3540)  and  ultrasonic  extraction  (Method  3550)
extraction are used with  solid  samples.   Consolidated samples should be
ground  finely enough  to  pass  through  a  9.5 mm  sieve.    In  limited
applications, waste dilution (Method 3580) may be used if the entire sample
is soluble in the specified solvent.

      Method  3540 and  3550  are  neutral-pH  extraction  techniques  and
therefore, depending  on the analysis  requirements,  acid-base partition
cleanup (Method 3650) may be necessary.  Method 3650 will  only be needed
if chromatographic interferences are  severe enough  to prevent detection
of the analytes of interest.  This  separation  will  be most  important if
a GC method is chosen for analysis of the sample.   If GC/MS is used, the
ion  selectivity   of  the  technique  may  compensate  for  chromatographic
interferences.

      2.3.3.3  Oils and Organic Liquids

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

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

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

      2.3.3.4  Sludge Samples

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

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

            2.3.3.4.1  Liquids

            Use of Method  3510 or Method 3520 may be applicable to sludges
      that behave like and  have  the consistency  of aqueous  liquids.
      Ultrasonic  extraction   (Method  3550)  and   Soxhlet  (Method  3540)

                             TWO -  5                        Revision 2
                                                            November 1990

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      procedures  will,  most  likely,   be   ineffective  because  of  the
      overwhelming presence of the liquid aqueous phase.

            2.3.3.4.2  Solids

            Soxhlet (Method 3540)  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.

            2.3.3.4.3  Emulsions

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

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

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

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

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

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

      2.3.3.5  Multiphase Samples

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

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

                             TWO  - 6                        Revision 2
                                                            November 1990

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      with Figures 2-1 through 2-4  for  further  guidance.   Figure 2-5 outlines
      the testing sequence for determining  if a waste  exhibits  one  or more of
      the characteristics of a hazardous waste.

2.4  CHARACTERISTICS

      2.4.1  EP and TCLP extracts

      The leachate obtained from using either the EP (Figure 2-6A) or the TCLP
(Figure 2-6B)  is  an aqueous  sample and,  therefore, requires  further solvent
extraction prior  to  the analysis of  semivolatile  compounds.    Figure  3  gives
further information on aqueous sample extraction.

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

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

      Due  to  the high  concentration  of  acetate  in the  TCLP extract,  it is
recommended that purge-and-trap/GC/MS, Methods 8240 or 8260, 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 2-7A,  2-7B,  and 2-7C.  Quantitation  limits for
the metallic analytes should correspond to the drinking water  limits which are
available.

      2.5.1 Special Techniques for Metal Analvtes

      All  atomic  absorption  analyses  must  be  performed  using  background
correction (i.e..  Zeeman, Smith-Hieftje or deuterium arc). Background correction
by  the  deuterium  arc   technique  may  not adequately  compensate  for  high
concentrations of certain interferants in arsenic and selenium analyses (i.e.,
Al, Fe).  Zeeman or Smith-Hieftje background correction, or appropriate matrix
modification,  may allow analysis  for low  concentrations  of  selenium in the
presence of high  concentrations  of  iron,  and  low concentrations of arsenic in
the presence of high concentrations of  aluminum.   If significant interference
is suspected, the analyst must switch  to an  alternate wavelength, or take other
appropriate actions to compensate for the interference effects.

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


                                    TWO  -  7                        Revision 2
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      Cadmium and antimony should be determined by  GFAA. These two elements are
analyzed by GFAA to achieve lower detection limits. Typical  GFAA detection limits
for antimony and cadmium are 3 jzg/L and 0.1  ng/l, compared  to  60 M9/L and 3 M9/L
by ICP.

      All  furnace  atomic absorption analysis should be carried  out  using the
exact matrix modifiers listed below. (See also the appropriate methods.)

            Element(s)                 Modifier

            As and Se               Nickel  Nitrate
            Pb                      Phosphoric Acid
            Cd                      Ammonium Phosphate
            Sb                      Ammonium Nitrate
            Tl                      Platinum/Palladium

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

      2.5.2  Special Techniques for Indicated Analvtes and Anions

      If  an  Auto-Analyzer  is   used  to  read  the  cyanide  distillates,  the
spectrophotometer must  be  used  with a 50 mm path  length  cell.  If  a  sample is
found to  contain  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
     Chromatoqraphv; (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.

4.   Jarrell   Ash  Corporation,   590  Lincoln  Street,   Box  9036,  Waltham,  MA
     02254-9036.
                                    TWO -  8                        Revision 2
                                                                  November 1990

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           TABLE 2-1.
ORGANIC COMPOUND CLASSIFICATIONS
CompoundTable(s)
Acenaphthene
Acenaphthylene
Acetaldehyde
Acetone
Acetonitrile
Acetophenone
2-Acetylaminofluorene
l-Acetyl-2-thiourea
Acifluorfen
Acrolein (Propenal)
Aery! amide
Acrylonitrile
Aldicarb (Temik)
Aldicarb Sulfone
Aldrin
Ally! alcohol
Allyl chloride
4-Aminobiphenyl
2-Aminoanthraquinone
Aminoazobenzene
3-Amino-9-ethylcarbazole
Aniline
Anilazine
o-Anisidine
Anthracene
Aramite
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Asulam
Azinphos ethyl
Azinphos methyl
Barban
Bentazon
Benzal chloride
Benz(a)anthracene
Benzene
Benzidine
Benzoic acid
Benzo(b)fluoranthene
Benzo ( j ) f 1 uoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
2-14, 2-19
2-14, 2-19
2-23
2-13
2-13, 2-16
2-14
2-14
2-14
2-10
2-13, 2-16, 2-24
2-21, 2-24
2-13, 2-16, 2-24
2-25
2-25
2-9, 2-14, 2-22
2-13
2-13, 2-11
2-14
2-14
2-14
2-14
2-14
2-14
2-14
2-14, 2-19
2-14
2-9, 2-14
2-9, 2-14
2-9, 2-14
2-9, 2-14
2-9, 2-14
2-9, 2-14
2-9, 2-14
2-26
2-8
2-8, 2-14
2-14
2-10
2-18
2-7, 2-14, 2-19
2-12, 2-13, 2-17
2-14
2-2, 2-14
2-7, 2-14, 2-19
2-19
2-14, 2-19, 2-22
2-14, 2-19
             TWO  -  9
Revision 2
November  1990

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TABLE 2-1.
(Continued)
Compound
Benzo(a)pyrene
p-Benzoquinone
Benzotrichloride
Benzyl alcohol
Benzyl benzoate
Butyl benzyl phthalate
Benzyl chloride
BHC (Hexachlorocyclohexane)
•y-BHC (Lindane, gamma-Hexachlorocyclohexane)
a-BHC (al pha-Hexachl orocycl ohexane)
/3-BHC (beta-Hexachl orocycl ohexane)
6-BHC (del ta-Hexachl orocycl ohexane)
Bis(2-n-butoxyethyl) phthalate (BBEP)
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Bis(2-ethoxyethyl) phthalate (BEEP)
Bis(2-ethylhexyl) phthalate
Bis(2-methoxyethyl) phthalate (BMEP)
Bis(4-methyl-2-pentyl) phthalate (BMPP)
Bolstar (Sulprofos)
Bromoacetone
Bromobenzene
Bromochl oromethane
Bromodichloromethane
4-Bromof 1 uorobenzene
Bromoform
Bromomethane
4-Bromophenyl phenyl ether
Bromoxynil
2-Butanone (Methyl ethyl ketone)
2-sec-Butyl -4,6-dinitrophenol (DNBP)
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Caffeine
Captafol
Captan
Carbofenthion
Carbaryl
Carbazole
Carbofuran
Carbophenothion
Carbon disulfide
Carbon tetrachloride
Chloramben
Table(s)
2-7, 2-14,
2-14
2-18
2-14
2-3
2-3, 2-14
2-11, 2-13,
2-18
2-9, 2-14,
2-9, 2-14,
2-9, 2-14,
2-9, 2-14,
2-3
2-6, 2-11,
2-6, 2-14
2-6, 2-14
2-3
2-3, 2-14
2-3
2-3
2-8
2-11, 2-13
2-11, 2-12,
2-12, 2-13
2-11, 2-12,
2-13
2-11, 2-12,
2-11, 2-12,
2-6, 2-14
2-14
2-13
2-2, 2-14
2-12, 2-13
2-12, 2-13
2-12, 2-13
2-26
2-14
2-14
2-8
2-14, 2-25
2-22
2-14, 2-25
2-14
2-13
2-11, 2-12,
2-10

2-19, 2-22





2-18

2-18
2-18
2-18
2-18

2-14








2-13

2-13

2-13
2-13
















2-13

TWO - 10
Revision 2
November 1990

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                                TABLE  2-1.
                                (Continued)
Compound
Table(s)
Chlordane
Chlorfenvinphos
Chlorinated dibenzodioxins
4-Chloro-3-methyl phenol
Chloroacetaldehyde
4-Chloroaniline
Chlorobenzene
Chlorobenzilate
Chlorodibromomethane
Chloroethane
2-Chloroethanol
Bi s (2-chl oroethoxy)methane
Bis(2-chloroethyl) sulfide*
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane
Bis(2-chloroisopropyl) ether
Chloromethane
5-Chloro-2-methylaniline
Chloromethyl methyl ether
4-Chloro-3-methyl phenol
1-Chloronaphthalene
2-Chl oronaphthal ene
2-Chlorophenol
4-Chloro-l,2-phenylenediamine
4-Chl oro- 1 , 3-phenyl enedi ami ne
4-Chlorophenyl phenyl ether
Chloroprene
3-Chloropropiom'trile
Chlorotoluene(s)
2-Chlorotoluene
4-Chlorotoluene
5-Chloro-o-toluidine
3- (Chloromethyl Jpyridine hydrochloride
Chlorpyrifos
Chrysene
Coumaphos
Coumarin Dyes
Creosote
p-Cresidine
Cresols (methyl phenols) (Cresylic acids)
o-Cresol (2-methyl phenol)
m-Cresol (3-methyl phenol)
p-Cresol (4-methylphenol)
Crotoxyphos
2-Cyclohexyl-4,6-dinitrophenol
2,4-D
2-7, 2-9, 2-14
2-8, 2-14
2-7
2-2, 2-14
2-11
2-14
2-11, 2-12, 2-13, 2-17
2-14
2-13
2-11, 2-12, 2-13
2-11, 2-13
2-11
2-13
2-11, 2-13
2-11, 2-12, 2-13
2-11
2-11
2-11, 2-12, 2-13
2-14
2-11
2-22
2-14, 2-22
2-14, 2-18
2-2, 2-14, 2-22
2-14
2-14
2-6, 2-14
2-11, 2-13
2-13
2-11
2-12, 2-13
2-11, 2-12, 2-13
2-14
2-14
2-8
2-7, 2-14, 2-19
2-8, 2-14
2-26
2-7
2-14
2-2, 2-7
2-14
2-14
2-14
2-14
2-2, 2-14
2-10
                                TWO - 11
                 Revision 2
                 November 1990

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TABLE 2-1.
(Continued)
Compound
Dalapon
2,4-DB
DCPA diacid
4,4'-DDD
4,4'-DDE
4,4'-DDT
Demeton-o,s
Diallate (cis, trans)
2,4-Diaminotoluene
Diamyl phthalate (DAP)
Diazinon
Dibenz(a,h)acridine
Dibenz (a, h) anthracene
Dibenz(a,j)acridine
Dibenzo(a,e)pyrene
Dibenzo(a,h)pyrene
Dibenzo(a,i)pyrene
7H-Dibenzo(c,g)carbazole
Dibenzofuran
Dibenzothiophene
Di bromochl oromethane
1 , 2-Di bromo-3-chl oropropane
1,2-Dibromoethane
Dibromomethane
Di-n-butyl phthalate
Dicamba
Di chl one
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Dichlorobenzene(s)
3,3'-Dichlorobenzidine
3,5-Dichlorobenzoic acid
l,4-Dichloro-2-butene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene (Vinylidene chloride)
cis-1, 2-Di chl oroethene
trans -1, 2-Di chl oroethene
Di chl oromethane (Methylene chloride)
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorophenoxyacetic acid
Dichloroprop
1, 2-Di chl oropropane
1,3-Dichloropropane
Table(s)
2-10
2-10
2-10
2-9, 2-14
2-9, 2-14
2-9, 2-14
2-8, 2-14
2-14
2-14
2-3
2-8
2-19
2-14, 2-19
2-14, 2-19
2-19, 2-14
2-19
2-19
2-19
2-14
2-22
2-11, 2-12, 2-13
2-11, 2-13, 2-14
2-12, 2-13
2-11, 2-12, 2-13
2-3, 2-14
2-10
2-14
2-11, 2-12, 2-13,
2-11, 2-12, 2-13,
2-11, 2-12, 2-13,
2-7, 2-18
2-14
2-10
2-11, 2-13
2-11, 2-12, 2-13
2-11, 2-12, 2-13
2-11, 2-12, 2-13
2-11, 2-12, 2-13
2-12, 2-13
2-11, 2-12, 2-13
2-11, 2-12, 2-13
2-2, 2-14, 2-22
2-2, 2-14
2-7
2-10
2-11, 2-12, 2-13
2-12, 2-13




























2-14, 2-17, 2-18
2-14, 2-17, 2-18
2-14, 2-17, 2-18

















TWO - 12
Revision 2
November 1990

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TABLE 2-1.
(Continued)
Compound
2,2-Dichloropropane
l,3-Dichloro-2-propanol
1,1-Dichloropropene
cis-l,3-Dichloropropene
trans - 1 , 3-Di chl oropropene
Dichlorvos
Dicrotophos
Dicyclohexyl phthalate (DCP)
Dieldrin
l,2:3,4-Diepoxybutane
Diethyl ether
Diethylstilbestrol
Diethyl sulfate
Diethyl phthalate
1,4-Difluorobenzene
Dihexyl phthalate (DHP)
Dihydrosaffrole
Diisobutyl phthalate (DIBP)
Dimethoate
3,3'-Dimethoxybenzidine
3, 3' -Dimethyl benzidine
Dimethyl phthalate
p-Dimethylaminoazobenzene
7,12-Dimethylbenz(a)anthracene
a-,a-Dimethylphenethylamine
2,4-Dimethylphenol
4, 6-Dinitro-2-methyl phenol
Dinitrobenzene
1,2-Dinitrobenzene
1,3-Dinitrobenzene (DNB)
1,4-Dinitrobenzene
4,6-Dinitro-o-cresol
2,4-Dinitrophenol
2,4-Dinitrotoluene (24DNT)
2,6-Dinitrotoluene (26DNT)
Dinocap
Dinonyl phthalate
Dinoseb
Di-n-octyl phthalate
Dioxacarb
1,4-Dioxane
Dioxathion
Diphenylamine
1,2-Diphenylhydantoin
1,2-Diphenylhydrazine
Disperse Blue 3
Table(s)
2-12, 2-13
2-11, 2-13
2-12, 2-13
2-11, 2-13
2-11, 2-13
2-8, 2-14, 2-26
2-14
2-3
2-9, 2-14
2-13
2-15
2-14
2-14
2-3, 2-14
2-13
2-3
2-14
2-3
2-8, 2-14, 2-26
2-14
2-14
2-3, 2-14
2-14
2-14
2-14
2-2, 2-14
2-14
2-5, 2-7
2-14
2-14, 2-27
2-14
2-7
2-2, 2-14
2-5, 2-7, 2-14, 2-22, 2-27
2-5, 2-14, 2-27
2-14
2-3
2-10, 2-14
2-3, 2-14
2-25
2-13
2-8, 2-14
2-14, 2-22
2-14
2-14
2-26
TWO - 13
Revision 2
November 1990

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                                TABLE 2-1.
                                (Continued)
Compound
Table(s)
Disperse Blue 14
Disperse Brown 1
Disperse Orange 3
Disperse Orange 30
Disperse Red 1
Disperse Red 5
Disperse Red 13
Disperse Red 60
Disperse Yellow 5
Disulfoton
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
Epichlorohydrin
EPN
Ethanol
Ethion
Ethoprop
Ethyl benzene
Ethyl carbamate
Ethyl methacrylate
Ethyl methanesulfonate
Ethylene dibromide
Ethyl ene oxide
Famphur
Fensulfothion
Fenthion
Fluchloralin
Fluoranthene
Fluorene
Fluorescent Brightener 61
Fluorescent Brightener 236
2-Fluorobiphenyl
2-Fluorophenol
Formaldehyde
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachloroethane
Hexachl orophene
Hexachl oropropene
Hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX)
2-26
2-26
2-26
2-26
2-26
2-26
2-26
2-26
2-26
2-8, 2-14, 2-26
2-9, 2-14
2-9, 2-14
2-9, 2-14
2-9, 2-14
2-9, 2-14
2-14
2-11, 2-13
2-8, 2-14
2-13, 2-15
2-8, 2-14
2-8
2-12, 2-13, 2-17
2-14
2-13
2-14
2-11
2-13
2-8, 2-14, 2-26
2-8, 2-14, 2-26
2-8, 2-14
2-14
2-14, 2-19
2-14, 2-19, 2-22
2-26
2-26
2-14
2-14
2-23
2-7, 2-9, 2-14
2-9, 2-14
2-7, 2-14, 2-18, 2-22
2-7, 2-12, 2-13, 2-14, 2-18
2-7, 2-14, 2-18
2-7, 2-14, 2-18
2-14
2-14
2-27
                                 TWO -  14
                  Revision 2
                  November 1990

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TABLE 2-1.
(Continued)
Compound
Hexamethyl phosphoramide
2-Hexanone
Hexyl 2-ethylhexyl phthalate (HEHP)
HMPA
1,2,3,4,6,7,8-HpCDD
1,2,3,4,7,8-HxCDD
1,2,3,4,7,8-HxCDF
3-Hydroxycarbofuran
5-Hydroxydicamba
Hydroquinone
2-Hydroxypropi oni tri 1 e
Indeno(l,2,3-cd)pyrene
lodomethane
Isobutyl alcohol
Isodrin
Isophorone
Isopropyl benzene
p- 1 sopropyl toluene
Isosafrole
Leptophos
Malathion
Malononitrile
MCPA
MCPP
Merphos
Mestranol
Methacrylonitrile
Methapyrilene
Methiocarb (Mesurol)
Methomyl (Lannate)
Methoxychlor
3-Methylcholanthrene
2-Methyl -4,6-dinitrophenol
4,4'-Methylenebis(2-chloroaniline)
4, 4' -Methyl enebis(N,N-dimethyl aniline)
Methyl ethyl ketone (MEK)
Methyl iodide
Methyl isobutyl ketone (MIBK)
Methyl methacrylate
Methyl methanesulfonate
2-Methyl naphthalene
2-Methyl -5-nitroaniline
Methyl Parathion
4-Methyl -2-pentanone
4-Methyl phenol
2-Methyl pyridine
Methyl -2,4,6-trinitrophenylnitramine (Tetryl )
Table(s)
2-14
2-13
2-3
2-8
2-20
2-20
2-20
2-25
2-10
2-14
2-13
2-14, 2-19
2-13
2-13
2-14
2-5, 2-14
2-12, 2-13
2-12, 2-13
2-14
2-8, 2-14
2-8, 2-14
2-13
2-10
2-10
2-8, 2-26
2-14
2-13
2-14
2-25
2-25, 2-26
2-9, 2-14
2-14, 2-19
2-2
2-14
2-14
2-15
2-11, 2-13
2-15
2-13
2-14
2-14
2-14
2-14, 2-26
2-13
2-22
2-14
2-27
TWO - 15
Revision 2
November 1990

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                                        TABLE 2-1.
                                        (Continued)
         Compound
Table(s)
Mevinphos                                              2-8,
Mexacarbate                             '               2-14
Mirex                                                  2-14
Monochrotophos                                         2-8,
Naled                                                  2-8,
Naphthalene                                            2-7,
Naphthoquinone                                         2-5
1,4-Naphthoquinone                                     2-14
1-Naphthylamine                                        2-14
2-Naphthylamine                                        2-14
Nicotine                                               2-14
5-Nitroacenaphthene                                    2-14
2-Nitroaniline                                         2-14
3-Nitroaniline                                         2-14
4-Nitroaniline                                         2-14
5-Nitro-o-anisidine                                    2-14
Nitrobenzene (NB)                                      2-5,
4-Nitrobiphenyl                                        2-14
Nitrofen                                               2-14
2-Nitrophenol                                          2-2,
4-Nitrophenol                                          2-2,
Nitroquinoline-1-oxide                                 2-14
N-Nitrosodibutylamine                                  2-14
N-Nitrosodiethylamine                                  2-14
N-Nitrosodimethylamine                                 2-4,
N-Nitrosodiphenylamine                                 2-4,
N-Nitrosodi-n-propylamine                              2-4,
N-Nitrosomethylethyl amine                              2-14
N-Nitrosomorpholine                                    2-14
N-Nitrosopiperidine                                    2-14
N-Nitrosopyrrolidine                                   2-14
o-Nitrotoluene (2NT)                                   2-27
m-Nitrotoluene (3NT)                                   2-27
p-Nitrotoluene (4NT)                                   2-27
5-Nitro-o-toluidine                                    2-14
OCDF                                                   2-20
Octamethyl pyrophosphoramide                           2-14
Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine (HMX) 2-27
4,4'-Oxydianiline                                      2-14
Parathion                                              2-14
Parathion ethyl                                        2-8
Parathion methyl                                       2-8
PCB-1016 (Aroclor-1016)                                2-9
PCB-1221 (Aroclor-1221)                                2-9
PCB-1232 (Aroclor-1232)                                2-9
PCB-1242 (Aroclor-1242)                                2-9
PCB-1248 (Aroclor-1248)                                2-9

                                         TWO - 16
     2-14
     2-14, 2-26
     2-14, 2-26
     2-12, 2-13, 2-14, 2-19, 2-22
     2-7, 2-14, 2-27
     2-14
     2-10, 2-14
     2-14
     2-14
     2-14
                 Revision 2
                 November 1990

-------
                                        TABLE 2-1.
                                        (Continued)
         Compound
Table(s)
PCB-1254 (Aroclor-1254)
PCB-1260 (Aroclor-1260)
1,2,3,4,7-PeCDD
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
Pentachlorobenzene
Pentachloroethane
Pentachlorohexane
Pentachloronitrobenzene
Pentachlorophenol
Phenacetin
Phenanthrene
Phenobarbital
Phenol
Phenylenediamine
Phorate
Phosalone
Phosmet
Phosphamidion
Phthalic anhydride
2-Picoline
Picloram
Piperonyl sulfoxide
B-Priopiolactone
Promecarb
Pronamide
Propargyl alcohol
Propionitrile
Propoxur (Baygon)
n-Propylamine
n-Propylbenzene
Propylthiouracil
Pyrene
Pyridine
Resorcinol
Ronnel
Safrole
Solvent Red 3
Solvent Red 23
Strychnine
Styrene
Sulfall ate
Sulfotep
2,4,5-T
2X7.8-TCDD
1,2,3,4-TCDD
2-9
2-9
2-20
2-20
2-20
2-14, 2-18
2-13
2-18
2-14
2-2, 2-10, 2-14
2-14
2-14, 2-19, 2-22
2-14
2-2, 2-14
2-14
2-7, 2-8, 2-14
2-14, 2-26
2-8, 2-14
2-8, 2-14
2-14
2-7, 2-13, 2-14, 2-17
2-10
2-14
2-13
2-25
2-14
2-13
2-13
2-25
2-13
2-12, 2-13
2-14
2-14, 2-19, 2-22
2-7, 2-13, 2-14, 2-17
2-14
2-8
2-14
2-26
2-26
2-14, 2-26
2-12, 2-13, 2-17
2-14
2-8
2-10
2-20
2-20
                                         TWO - 17
                 Revision 2
                 November 1990

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                                        TABLE 2-1.
                                        (Continued)
         Compound
Table(s)
1,3,6,8-TCDD
1,3,7,9-TCDD
1,3,7,8-TCDD
1,2,7,8-TCDD
1,2,8,9-TCDD
1,2,7,8-TCDF
TEPP
Terbuphos
Terphenyl
Tetrachlorobenzene(s)
1,2,3,4-Tetrachlorobenzene
1,2,3,5-Tetrachlorobenzene
1,2,4,5-Tetrachlorobenzene
1,1,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
Tetrachloroethene
2,3,4,6-Tetrachlorophenol
Tetrachlorophenol (s)
Tetrachlorvinphos (Stirophos)
Tetraethyl dithiopyrophosphate
Tetraethyl pyrophosphate
Tetrazene
Thiofanox
Thionazine
Thiophenol (Benzenethiol)
TOCP
Tokuthion (Prothiofos)
Toluene
Toluene diisocyanate
o-Toluidine
Toxaphene
2,4,5-TP (Silvex)
2,4,6-Tri bromophenol
1,2,3-Trichlorobenzene
1,2,4-Tri chlorobenzene
1,3,5-Trichlorobenzene
1,1,1-Tri chloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chlorof1uoromethane
Trichlorfon
Trichloronate
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Trichlorophenol(s)
1,2,3-Tri chloropropane
Trichloropropane(s)
2-20
2-20
2-20
2-20
2-20
2-20
2-8
2-8, 2-14
2-14
2-7, 2-18
2-18
2-18
2-14, 2-18
2-11, 2-12, 2-13
2-11, 2-12, 2-13
2-11, 2-12, 2-13
2-14
2-2
2-8, 2-14
2-14
2-14
2-28
2-26
2-14
2-14, 2-17
2-8
2-8
2-12, 2-13, 2-17
2-14
2-14
2-7, 2-9, 2-14
2-7, 2-10
2-14
2-12, 2-13, 2-18
2-12, 2-13, 2-14, 2-18
2-18
2-11, 2-12, 2-13
2-11, 2-12, 2-13
2-11, 2-12, 2-13
2-11, 2-12, 2-13
2-26
2-8
2-14
2-2, 2-14
2-2
2-12, 2-13
2-11
                                         TWO - 18
                 Revision  2
                 November 1990

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                                        TABLE 2-1.
                                        (Continued)
         Compound                                      Table(s)
Trifluralin                                            2-14
2,4,5-Trimethylaniline                                 2-14
1,2,4-Trimethylbenzene                                 2-12, 2-13
1,3,5-Trimethylbenzene                                 2-12, 2-13
Trimethyl phosphate                                    2-14
1,3,5-Trinitrobenzene (TNB)                            2-14, 2-27
2,4,6-Trinitrotoluene (TNT)                            2-27
Tris(2,3-dibromopropyl) phosphate  (Tris-BP)            2-14, 2-26
Tri-p-tolyl phosphate                                  2-14
0,0,0-Triethyl phosphorothioate                        2-14
Vinyl acetate                                          2-13
Vinyl chloride                                         2-11, 2-12, 2-13
o-Xylene                                               2-12, 2-17
m-Xylene                                               2-12, 2-17
p-Xylene                                               2-12, 2-17
Xylene(s)                                              2-13
                                        TABLE 2-2.
                                  METHOD 8040 - PHENOLS

      2-sec-Butyl-4,6-dinitrophenol  (DNBP)            2,4-Dimethylphenol
      4-Chloro-3-methylphenol                         2,4-Dinitrophenol
      2-Chlorophenol                                  2-Methyl-4,6-dinitrophenol
      Cresol(s) (methyl phenols)                      2-Nitrophenol
      2-Cyclohexyl-4,6-dinitrophenol                  4-Nitrophenol
      2,4-Dichlorophenol                              Pentachlorophenol
      2,6-Dichlorophenol                              Phenol
      Trichlorophenol(s)                              2,4,6-Trichlorophenol
                                                      Tetrachlorophenol(s)
                                         TWO - 19                       Revision 2
                                                                        November 1990

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            TABLE 2-3.                                 TABLE 2-4.
   METHODS 8060/8061 - PHTHALATE ESTERS         METHOD 8070 - NITROSAMINES

      Benzyl benzoate*                          N-Nitrosodimethyl amine
      Benzyl butyl phthalate                    N-Nitrosodiphenylamine
      Bis(2-n-butoxyethyl) phthalate (BBEP)"    N-Nitrosodi-n-propylamine
      Bis(2-ethylhexyl) phthalate
      Bis(2-ethoxyethyl) phthalate (BEEP)*
      Bis(4-methyl-2-pentyl) phthalate (BMPP)*
      Bis(2-methoxyethyl) phthalate (BMEP)*
      Diamyl phthalate (DAP)*
      Di-n-butyl phthalate
      Dicyclohexyl phthalate (DCP)*
      Diethyl phthalate
      Dihexyl phthalate (DHP)"
      Diisobutyl phthalate (DIBP)*
      Dimethyl phthalate
      Dinonyl phthalate*
      Di-n-octyl phthalate
      Hexyl 2-ethylhexyl  phthalate (HEHP)*

   Target  analyte  of  Method  8061  only.
          TABLE 2-5.
METHOD 8090 - NITROAROMATICS AND                       TABLE 2-6.
        CYCLIC KETONES                           METHOD 8110 - HALOETHERS

      Dinitrobenzene                            Bis(2-chloroethyl) ether
      2,4-Dinitrotoluene                        Bis(2-chloroethoxy)methane
      2,6-Dinitrotoluene                        Bis(2-chloroisopropyl) ether
      Isophorone                                4-Bromophenyl phenyl ether
      Naphthoquinone                            4-Chlorophenyl phenyl ether
      Nitrobenzene
                                  TABLE  2-7a.
                      METHOD 3650  -  BASE/NEUTRAL  FRACTION


Benz(a)anthracene                               Hexachlorobenzene
Benzo(a)pyrene                                  Hexachlorobutadiene
Benzo(b)fluoranthene                            Hexachloroethane
Chlordane                                       Hexachlorocyclopentadiene
Chlorinated dibenzodioxins                      Naphthalene
Chrysene                                        Nitrobenzene
Creosote                                        Phorate
Dichlorobenzene(s)                              2-Picoline
Dinitrobenzene                                  Pyridine
2,4-Dinitrotoluene                              Tetrachlorobenzene(s)
Heptachlor                                      Toxaphene

                                   TWO - 20                       Revision 2
                                                                  November 1990

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                                  TABLE 2-7b.
                          METHOD 3650 - ACID FRACTION
2-Chlorophenol
Cresol(s)
Dichlorophenoxyacetic acid
2,4-Dimethylphenol
4,6-Dinitro-o-cresol
                        4-Nitrophenol
                        Pentachlorophenol
                        Phenol
                        Tetrachlorophenol(s)
                        Trichlorophenol(s)
                        2,4,5-TP  (Silvex)
                                  TABLE 2-8.
                METHODS 8140/8141 - ORGANOPHOSPHORUS COMPOUNDS
                        (PACKED AND CAPILLARY COLUMNS)
Azinphos methyl
Bolstar (Sulprofos)
Chlorpyrifos
Coumaphos
Demeton, o,s
Diazinon
Dichlorvos^
Dimethoate*
Disulfoton
EPN*
Ethoprop
Fensulfothion
Fenthion
Trichloronate

   Target  analyte of Method 8141 only.
                        Malathion*
                        Merphos
                        Mevinphos
                        Monochrotophos"
                        Naled
                        Parathion ethyl"
                        Parathion methyl
                        Phorate
                        Ronnel
                        Stirophos (Tetrachlorvinphos)
                        Sulfotep*
                        TEPP"
                        TOCP*
                        Tokuthion (Prothiofos)
                                  TABLE 2-9.
            METHODS 8080/8081 - ORGANOCHLORINE PESTICIDES AND PCBs
Aldrin
a-BHC
0-BHC
6-BHC
•y-BHC (Lindane)
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Methoxychlor
Toxaphene
PCB-1016 (Arocl
PCB-1221 (Arocl
PCB-1232 (Arocl
PCB-1242 (Arocl
PCB-1248 (Arocl
PCB-1254 (Arocl
PCB-1260 (Arocl
or-1016)
or-1221)
or-1232)
or-1242)
or-1248)
or-1254)
or-1260)
                                   TWO - 21
                                          Revision 2
                                          November 1990

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                                TABLE 2-10.
                METHODS 8150/8151  - CHLORINATED HERBICIDES
 Acifluorfen*
 Bentazon*
 Chloramben"
 2,4-D
 Dalapon
 2,4-DB
 DCPA diacid*
Dicamba
3,5-Dichlorobenzoic acid"
Dichlorprop
Dinoseb
5-Hydroxydicamba*
    Target  analyte of Method 8151  only.
MCPA
MCPP
4-Nitrophenol*
Pentachlprophenol"
Picloram"
2,4,5-TP (Silvex)
2,4,5-T
                                TABLE 2-11.
                    METHOD 8010 - HALOGENATED VOLATILES
Allyl chloride
Benzyl chloride
Bromoacetone
Bromobenzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chloroacetaldehyde
Chlorobenzene
Chloroethane
Bis(2-chloroethoxy)methane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane
Bis(2-chloroisopropyl) ether
Chloromethane
Chloromethyl methyl ether
Chloroprene
4-Chlorotoluene
Di bromochloromethane
1,2-Di bromo-3-chloropropane
Dibromomethane
1,2-Dichlorobenzene
             1,3-Dichlorobenzene
             1,4-Dichlorobenzene
             l,4-Dichloro-2-butene
             Di chlorodi f1uoromethane
             1,1-Dichloroethane
             1,2-Dichloroethane
             1,1-Dichloroethene (Vinylidene chloride)
             trans-1,2-Dichloroethene
             Dichloromethane  (Methylene Chloride)
             1,2-Dichloropropane
             1,3-Dichloro-2-propanol
             cis-l,3-Dichloropropene
             trans-1,3-Dichloropropene
             Epichlorohydrin
             Ethylene dibromide
             Methyl  iodide
             1,1,2,2-Tetrachloroethane
             1,1,1,2-Tetrachloroethane
             Tetrachloroethene
             1,1,1-Tri chloroethane
             1,1,2-Trichloroethane
             Trichloroethene
             Trichlorofluoromethane
             Trichloropropane
             Vinyl chloride
                                 TWO - 22
                                          Revision 2
                                          November 1990

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                                     TABLE 2-12.
           METHOD  8021  (METHOD  8011") - HALOGENATED AND AROMATIC VOLATILES
      Benzene
      Bromobenzene
      Bromochloromethane
      Bromodi chloromethane
      Bromoform
      Bromomethane
      n-Butylbenzene
      sec-Butyl benzene
      tert-Butylbenzene
      Carbon tetrachloride
      Chlorobenzene
      Chloroethane
      Chloroform
      Chloromethane
      2-Chlorotoluene
      4-Chlorotoluene
      Di bromochloromethane
      1,2-Di bromo-3-chlpropropane*
      1,2-Dibromoethane*
      Dlbromomethane
      1,2-Dichlorobenzene
      1,3-Dichlorobenzene
      1,4-Di chlorobenzene
      Di chlorodi f1uoromethane
      1,1-Dichloroethane
      1,2-Dichloroethane
      1,1,-Dichloroethene
      cis-1,2-Dichloroethene
      trans-1,2-Dichloroethene

Target analyte of Method 8011
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Di chloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachlorobutadi ene
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-Tri chloroethane
Trichloroethene
Tri chlorof1uoromethane
1,2,3-Trichloropropane
1,2,4-Tri methyl benzene
1,3,5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
                                       TWO  -  23
                  Revision 2
                  November 1990

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                                        TABLE 2-13.
                               METHODS 8240/8260 - VOLATILES
Acetone"
Acetonitrile*
Acrolein (Propenal)*
Acrylonitrile
Allyl alcohol".
Allyl chloride*
Benzene
Benzyl chloride*
Bromobenzene*
Bromoacetone*
Bromochloromethane
Bromodi chloromethane
l-Bromo-4-fluorobenzene
Bromoform
Bromomethane
2-Butanone (Methyl ethyl  ketone)*
n-Butylbenzene*
sec-Butyl benzene*
tert-Butylbenzene*
Carbon disulfide"
Carbon tetrachloride
Chlorobenzene
Chlorodi bromomethane*
Chloroethane
2-Chloroethanol*
Bis(2-chloroethyl) sulfide*
2-Chloroethyl vinyl ether*
Chloroform
Chloromethane
Chloroprene*
3-Chloropropionitrile*
2-Chlorotoluene*
4-Chlorotoluene*
Di bromochloromethane*
1,2-Di bromo-3-chloropropane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene*
1,3-Di chlorobenzene*
1,4-Dichlorobenzene*
l,4-Dichloro-2-butene*
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-1,2-Dichloroethene*
trans-1,2-Dichloroethene
1,2-Dichloropropane
1,3-Dichloropropane*
2,2-Dichloropropane*
1,3-Dichloro-2-propanol*
1,1-Dichloropropene*
cis-1,3-Dichloropropene*
trans-1,3-Di chloropropene*
1,2:3,4-Di epoxybutane
1,4-Difluorpbenzene*
1,4-Dioxane"
Epichlorohydrin*
Ethanol*
Ethyl benzene
Ethylene oxide*
Ethyl methacrylate*
Hexachlorobutadi ene*
2-Hexanone*
2-Hydroxyprppionitrile*
lodomethane"
Isobutyl alcohol*
Isopropylbenzene*
p-Isopropylto]uene*
Malononitrile*
Methacrylonitrile*
Methylene chloride
Methyl iodide"
Methyl methacrylate*^
4-Methyl-2-pentanone*
Naphthalene*
Pentachlorpethane*
2-Picoline*
Propargyl alcohol*
b-Propiolactone"
Propionitrile]
n-Propylamine*
n-Propylbenzene*
Pyridine*
Styrene
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene*
1,2,4-Trichlorobenzene*
1,1,1-Trichloroethane
1,1,2-Tri chloroethane
Trichloroethene
Tri chlorof1uoromethane
1,2,3-Trichloropropane
1,2,4-Trimethylbenzene*
1,3,5-Trimethylbenzene*
Vinyl acetate
Vinyl chloride
Xylene(s)
*  Target  analyte  of Method 8240.  All Method 8240 analytes  should  be  analyzable by Method
  8260.

* Target  analyte  of Method 8260 only.
                                          TWO -  24
                                      Revision 2
                                      November 1990

-------
                                        TABLE 2-14.
                             METHODS 8250/8270 - SEMIVOLATILES
Acenaphthene
Acenaphthylene
Acetophenone
2-Acetylami nof1uorene"
1-Acetyl-2-thiourea"
Aldrin
2-Aminoanthraquinone"
Aminoazobenzene*
4-Aminobiphenyl
3-Ami no-9-ethylcarbazole*
Anilazine"
Aniline
o-Anisidine*
Anthracene
Aramite*
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Azinphps-methyl*
Barban"
Benz(a)anthracene
Benzidine
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzoic acid
Benzo(g,h,i)perylene
Benzo(a)pyrenet
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
2-sec-Butyl-4,6-dinitrophenoV
Captafpl*
Captan*
Carbaryl*
Carbofuran"
Carbofenthion*
Chlordane
Chlorfenvinphos"
4-Chloroaniline
Chiorobenzilate*
5-Chloro-2-methylani1i ne"
4-Chloro-3-methylphenol
3-(Chloromethyl)  pyridine hydrochloride"
1-Chloronaphthalene
2-Chloronaphthalene
2-Chlorophenol
4-Chloro-l,2-phenylenediamine]
4-Chloro-l,3-phenylenediamine*
4-Chlorophenyl  phenyl ether
5-Chloro-o-toluidine"
Chrysene
Coumaphos"
p-Cresidine]
Crotoxyphos"
2-Cyclohexyl-4,6-dinitrophenol*
4,4'-DDD
4,4'-DDE*
4,4'-DDT
Demeton-o]
Demeton-s*
Diallate (cis or trans)"
2,4-Diaminotoluene*
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
Dibenzofuran
Dibenzo(a,e)pyrene*
1,2-Di bromo-3-chloropropane*
Di-n-butyl  phthalate
Dichlone
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorpphenol
Dichlorovos]
Dicrotophos"
Dieldrin
Diethyl phthalate
Diethylstilbestrol*
Diethyl sulfate"
Dihydrosaffrole"
Dimethoate"
3,3'-Dimethoxybenzidine*
                                         TWO - 25
                        Revision 2
                        November 1990

-------
                                        TABLE 2-14.
                       METHODS 8250/8270 - SEMIVOLATILES (CONTINUED)
p-Dimethylaminoazobenzene
7,12-Dimethylbenz(a)anthracene
3,3'-Dimethylbenzidine*
a-,a-Dimethylphenethylamine
2,4-Dimethylphenol
Dimethyl phthalate
1,2-Dinitrobenzene*
1,3-Dinitrobenzene*
1,4-Dinitrobenzene*
4,6-Dinitro-2-methylphenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap*
Dinoseb*
Dioxathion"
Diphenylamine
5,5-Diphenylhydantoin*
1,2-Di phenylhydrazi ne
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*
Fluchloralin"
Fluoranthene
Fluorene
2-Fluorobiphenyl
2-Fluorophenol
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadi ene
Hexachloroethane
Hexachlorophene*
Hexachloropropene*
Hexamethyl phosphoramide*
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-dimethylaniline)"
Methyl methanesulfonate
2-Methylnaphthalene
2-Methyl-5-nitroaniline"
Methyl parathion*
2-Methylphenol (o-cresol)
3-Methylphenol (m-cresol)*
4-Methylphenol (p-cresol)
2-Methylpyridine
Mevinphos
Mexacarbate*
Mi rex*
Monocrotophos*
Naled*
Naphthalene
1,4-Naphthoquinone"
1-Naphthylamine
2-Naphthylamine
Nicotine
5-Nitroacenaphthene*
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
5-Nitroanisidine*
Nitrobenzene
4-Nitrobiphenyl*
Nitrofen*
2-Nitrophenol
4-Nitrophenol
Nitroquinoline-1-oxide*
N-Ni trosodi butyl ami ne^
N-Nitrosodiethyl amine"
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
N-Ni trosomethylethyl ami ne*
N-Nitrosomorpholine*
N-Nitrosopiperidine
                                         TWO  - 26
                        Revision 2
                        November 1990

-------
                                        TABLE 2-14.
                       METHODS 8250/8270 - SEMIVOLATILES (CONTINUED)
N-Nitrosopyrrolidine*
5-Nitro-o-toluidine*
Octamethyl pyrophpsphoramide*
4,4'-Oxydianiline*
Parathion*
Pentachlorobenzene
Pentachloron i trobenzene
Pentachlorophenol
Phenacetin
Phenanthrene
Phenobarbital*
Phenol
Phenylenediamine*
Phorate"
Phosalone*
Phosmet*
Phosphamidion*
Phthalic anhydride*
2-Picoline
Piperonyl sulfoxide"
Pronamide
Propylthiouracil"
Pyrene
Pyridine"
Resorcinol*
   Target  analyte of Method 8270 only.
      Safrole*
      Strychnine*
      Sulfal1 ate*
      Terbuphos*
      Terphenyl
      1,2,4,5-Tetrachlorobenzene
      2,3,4,6-Tetrachlorophenol
      Tetrachlorvinphos (Stirophos)*
      Tetraethyl  dithiopyrophosphate*
      Tetraethyl^ pyrophosphate*
      Thionazine*
      Thiophenol  (Benzenethiol)*
      Toluene  diisocyanate*
      o-Toluidine*
      Toxaphene
      2,4,6-Tri bromophenol
      1,2,4-Tri chlorobenzene
      2,4,5-Trichlorophenol
      2,4,6-Trichlorophenol
      Trifluralin"
      2,4,5-Trimethylaniline*
      Trimethyl  phosphate*
      1,3,5-Trinitrobenzene*
      Tris(2,3-dibromopropyl)  phosphate"
      Tri-p-tolyl  phosphate*
      0,0,0-Triethyl  phosphorothioate*
            TABLE 2-15.
METHOD 8015 - NON-HALOGENATED VOLATILES

        Diethyl ether
        Ethanol
        Methyl ethyl ketone (MEK)
        Methyl isobutyl ketone (MIBK)
       TABLE 2-16.
METHODS 8030/8031 - ACETONITRILE,
       ACROLEIN,  ACRYLONITRILE

    Acetonitrile*
    Acrolein  (Propenal)"
    Acrylonitrile

  Target  analyte  of Method 8030 only.
                                         TWO  - 27
                              Revision 2
                              November 1990

-------
         TABLE 2-17.
METHOD 8020 - AROMATIC VOLATILES

Benzene
Chlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Ethyl benzene
2-Picoline
Pyridine
Styrene
Toluene
Thiophenol (Benzenethiol)
o-Xylene
m-Xylene
p-Xylene
                    TABLE  2-18.
METHODS 8120/8121 - CHLORINATED HYDROCARBONS

      Benzal  chloride*<
      Benzotrichloride"
      Benzyl  chloride*
      2-Chloronaphthalene
      Dichlorobenzene(s)*
      1,2-Dichlorobenzene"
      1,3-Dichlorobenzene]
      1,4-Di chlorobenzene*
      Hexachlorobenzene
      Hexachlorobutadiene
      Hexachlorocyclohexane*
      alpha-Hexachlorocyclohexane  (alpha-BHC)*
      beta-Hexachlorocyclohexane  (beta-BHC)*
      gamma-Hexachlorocyclohexane  (gamma-BHC)]
      delta-Hexachlorocyclohexane  (delta-BHC)*
      Hexachlorocyclopentadi ene
      Hexachloroethane
      Pentachlorobenzene*
      Pentachlorohexane*
      Tetrachlorobenzenets)*
      1,2,3,4-Tetrachlorobenzene"
      1,2,3,5-Tetrachlorobenzene]
      1,2,4,5-Tetrachlorobenzene*
      1,2,3-Tri chlorobenzene"
      1,2,4-Tri chlorobenzene^
      1,3,5-Tri chlorobenzene"

        Target analyte of Method 8121 only.
      *  Target analyte of Method 8121 only.
                                        TABLE 2-19.
                   METHODS 8100/8310 - POLYNUCLEAR AROMATIC HYDROCARBONS
                  Acenaphthene
                  Acenaphthylene
                  Anthracene
                  Benz(a)anthracene
                  Benzo(a)pyrene
                  Benzo(b)fl uoranthene
                  Benzo(g,h,i)perylene
                  Benzo(k)f1uoranthene
                 Chrysene
                 Dibenz(a,h)acridine
                 Fluoranthene
                 Fluorene
                 Indeno(l,2,3-cd)pyrene
                 Naphthalene
                 Phenanthrene
                 Pyrene
                                         TWO - 28
                                   Revision 2
                                   November  1990

-------
                                TABLE 2-20.
               METHODS 8280/8290 - DIOXINS AND DIBENZOFURANS
     2,3,7,8-TCDD
     1,2,3,4-TCDD
     1,3,6,8-TCDD
     1,3,7,9-TCDD
     1,3,7,8-TCDD
     1,2,7,8-TCDD
     1,2,8,9-TCDD
1,2,3,4,7-PeCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,4,6,7,8-HpCDD
1,2,7,8-TCDF
1,2,3,7,8-PeCDF
1,2,3,4,7,8-HxCDF
OCDF
       TABLE 2-21.
METHOD 8032 - ACRYLAMIDE

     Acrylamide
       TABLE 2-23.
METHOD 8315 - FORMALDEHYDE

     Formaldehyde
     Acetaldehyde
                      TABLE 2-22.
          METHOD  8275  -  SEMIVOLATILES  (SCREENING)

               2-Chlorophenol
               4-Methylphenol
               2,4-Dichlorophenol
               Naphthalene
               4-Chloro-3-methyl-phenol
               1-Chioronaphthalene
               2,4-Dinitrotoluene
               Fluorene
               Diphenylamine
               Hexachlorobenzene
               Dibenzothiophene
               Phenanthrene
               Carbazole
               Aldrin
               Pyrene
               Benzo(k)fluoranthene
               Benzo(a)pyrene
    TABLE  2-24.
METHOD 8316 - ACRYLAMIDE,
ACRYLONITRILE AND ACROLEIN
    Acrylamide
    Acrylonitrile
    Acrolein
                 TABLE 2-25.
         METHOD  8318  - N-METHYL CARBAMATES

               Aldicarb (Temik)
               Carbaryl  (Sevin)
               Carbofuran  (Furadan)
               Dioxacarb
               3-Hydroxycarbofuran
               Methiocarb  (Mesurol)
               Methomyl  (Lannate)
               Promecarb
               Propoxur (Baygon)
                                 TWO - 29
                                       Revision 2
                                       November 1990

-------
                                TABLE 2-26.
                        MEfriOD 8321  - NONVOLATILES
    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 Dves
Disperse Blue 3
Disperse Blue 14
Disperse Red 60
Coumarin Dyes

(Fluorescent Brighteners)
Fluorescent Brightener 61
Fluorescent Brightener 236
Alkaloids
Caffeine
Strychnine

Orqanophosphorus Compounds
Methomyl
Thiofanox
Famphur
Asulam
Dichlorvos
Dimethoate
Disulfoton
Fensulfothion
Merphos
Methyl parathion
Monocrotophos
Naled
Phorate
Trichlorfon
Tris-(2,3-Dibromopropyl) phosphate, (Tris-BP)
                                TABLE 2-27.
                METHOD 8330 -  NITROAROMATICS AND NITRAMINES

Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine (HMX)
Hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX)
1,3,5-Trinitrobenzene (TNB)
1,3-Dinitrobenzene (DNB)
Methyl -2,4,6-tri ni trophenylni trami ne (Tetryl)
Nitrobenzene (NB)
2,4,6-Trinitrotoluene (TNT)
2,4-Dinitrotoluene (24DNT)
2,6-Dinitrotoluene (26DNT)
o-Nitrotoluene (2NT)
m-Nitrotoluene (3NT)
p-Nitrotoluene (4NT)
                                TABLE 2-28.
                          METHOD 8331 -  TETRAZENE

                                   Tetrazene
                                 TWO - 30
                              Revision  2
                              November 1990

-------
                                                       TABLE 2-29.
                    REQUIRED  CONTAINERS. PRESERVATION TECHNIQUES, AND HOLDING TIMES  FOR AQUEOUS MATRICES
Name
Bacterial Tests:
Collform, total
Inorganic Tests:
Chloride
Cyanide, total and amenable
to chlorlnation



Hydrogen Ion (pH)
Nitrate
Sulfate
Sulfide
Metals:
Chromium VI
Mercury
Metals, except chromium VI
and mercury
Organic Tests:
Oil and grease
Organic carbon, total (TOC)
Purgeable Halocarbons

Purgeable aromatic
hydrocarbons
Acrolein and acrylonitrile

Phenol s

Benzi dines

Phthalate esters

Nitrosamines

PCBs

Nitroaromatics and
cyclic ketones
Polynuclear aromatic
hydrocarbons
Haloethers

Chlorinated hydrocarbons

Dioxins and Furans

Total organic halides (TOX)
Pesticides

Radiological Tests:
Alpha, beta and radium
Container1

P, 6

P, 6
P, 6




P. G
P, G
P, G
P, G

P, G
P, 6
P, G


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

G, Teflon-lined cap

G, Teflon-lined cap

G, Teflon-lined cap

G, Teflon-lined cap
G, Teflon-lined cap


P, G
Preservation

Cool, 4°C. 0.008% Na2S20,

None required
Cool, 4°C; if oxidizing
agents present add 5 ml
0.1N NaAsO, per L or 0.06 g
of ascorbic acid per L;
adjust pH>12 with 50% NaOH.
None required
Cool, 4°C
Cool, 4°C
Cool, 4°C, add zinc acetate

Cool, 4°C
HNO, to pH<2
HNO, to pH<2


Cool. 4°C2
Cool, 4°C2
Cool, 4°C3

Cool, 4°C, 0.008% Na2S2032'3

Cool, 4°C, 0.008% Na2S20,.
Adjust pH to 4-5
Cool, 4°C, 0.008% Na2S203

Cool, 4°C. 0.008% Na,S203

Cool. 4°C

Cool , 4"C, store in dark.
0.008% Na2S203
Cool, 4°C

Cool. 4°C. 0.008% Na,S20,
store in dark
Cool. 4°C. 0.008% Na2S203
store in dark
Cool, 4"C. 0.008% Na8S203

Cool. 4°C, 0.008% Na2S203

Cool, 4°C, 0.008% Na.SA

Cool, 4°C2
Cool, 4°C, pH 5-9


HN03 to pH<2
Maximum holding time

6 hours

28 days
14 days




Analyze immediately
48 hours
28 days
7 days

24 hours
28 days
6 months


28 days
28 days
14 days

14 days

14 days

7 days until extraction,
after extraction
7 days until extraction.
after extraction
7 days until extraction,
after extraction
7 days until extraction,
40 days after extraction
7 days until extraction,
40 days after extraction
7 days until extraction,
40 days after extraction
7 days until extraction,
40 days after extraction
7 days until extraction,
40 days after extraction
7 days until extraction,
40 days after extraction
7 days until extraction,
40 days after extraction
8 days
7 days until extraction,
40 days after extraction

6 months




























40 days

40 days

40 days




















1 Polyethylene  (P) or Glass (G)
2Adjust  to pH<2 with H2SO,. HC1 or solid NaHSO,
3Free chlorine must be removed prior to addition of HC1 by exact  addition of Na2S203
                                                       TWO  -  31
Revision  2
November 1990

-------
  co
  ro
Z 30
O*
                                                                                                                                                                      o
                                                                                                                                                                      ?o
                                                                                                                                                                      C7>
                                                                                                                                                                         -
vo
o

-------
                                                      FIGURE 2-2.
                                            DETERMINATION OF ORGANIC ANALYTES
                                         Semi volatile Organic Compounds

GC/MS
Determination
Methods
Specific
Detection
Methods
HPLC
Phenol s
8270
8250
8040

Acids
8270
8250


Phthalate
Esters
8270
8250
8060
8061

Nitro-
soami nes
8270
8250
8070

Nitro-
& Cyclic
Ketones
8270
8250
8090

Poly-
nuclear
Hydro-
carbons
8270
8250
8100
8310
Haloethers
8270
8250
8110

                        Semi volatile Organic Compounds (Continued)

GC/MS
Determination
Methods
Specific GC
Detection
Methods
HPLC
Chlorinated
Hydro-
carbons
8270
8250
8120
8121

Base/
Neutral
8270
8250


Organo-
phosphorus
Pesticides
8270'
8140
8141
8321
Organo-
chlorine
Pesticides
& PCBs
8270*
8080
8081

Chlorinated
Herbicides
8270'
8150
8151

Carbamates


8318
Explosives


8330
8331
'This method is an alternative confirmation method.  It is not the method of choice.
                                                      TWO  -  33
Revision  2
November 1990

-------
                      FIGURE 2-2.
                      (Continued)
Volatile Organic  Compounds

GC/MS
Determination
Methods
Specific GC
Detection
Methods
HPLC
Halogenated
Volatiles
8240
8260
8010
8011
8021

Non-
halogenated
Volatiles
8240
8015

Aromatic
Volatiles
8240
8260
8020
8021

Acrolein
Acryl o-
nitrile
Acetonitrile
8240
8030
8031
8316
Volatile
Organics
8240
8260
8021

Formal dehyde


8315
Acryl amide

8032
8316
                      FIGURE 2-3.
           CLEANUP OF ORGANIC ANALYTE  EXTRACTS



Phenols
3630
3640
3650



Acids
3650




Phthalate
Esters
3610
3620
3640
Nitro-
aromatics
& Cyclic
Ketones
3620
3640


Polynuclear
Aromatic
Hydrocarbons
3611
3630
3640
Chlorinated
Hydrocarbons
3620
3640
Base/Neutral
3650
Organo-
phosphorus
Pesticides
3620
Organo-
chlorine
Pesticides
& PCBs
3620
3640
3660
3665
Chlorinated
Herbicides
8150
                      TWO  - 34
Revision 2
November  1990

-------
                                                     FIGURE  2-4.
                                       PREPARATION METHODS FOR ORGANIC ANALYTES

Aqueous
PH3
Solids
Aqueous
Sludges
Emulsions'
PH3
Solids
Oils
Phenols
3510
3520
<2
3540
3550
35802


3520
<2


3650
35802
Acids
3510
3520
<2
3540
3550
35801


3520
<2


3650
35802
Phthalate
Esters
3510
3520
Neutral
3540
3550
35802
Sec

3520
Neutral
Sec

35802
Nitro-
aromatics
& Cyclic
Ketones
3510
3520
5-9
3540
3550
35802
Aqueous Ai
3520
5-9
Solids Abe
35802
Poly-
nuclear
Aromatic
Hydro-
carbons
3510
3520
Neutral
3540
3550
35802


3520
Neutral


3560
35802
Chlori-
nated
Hydro-
carbons
3510
3520
Neutral
3540
3550
35802


3520
Neutral


35802
Base/
Neutral
3510
3520
>11
3540
3550
35802


3520
>11


3650
35802
'If attempts to break up emulsions are unsuccessful, this method may be used.
2Waste dilution. Method 3580,  is only appropriate  if the sample is soluble in the
 specified  solvent.
3pH at which extraction should be performed.
                                                    TWO  - 35
Revision  2
November 1990

-------
                                                     FIGURE 2-4.
                                                     (Continued)






Aqueous

PH3

Solids



Aqueous
Sludges
Emulsions'
PH'
Sol ids

Oils
Organo-
phosph-
orus
Pesti-
cides
3510
3520

6-8
3540
3550
35802





3520
6-8


35801
Organo-
chlorine
Pesti-
cides
& PCBs
3510
3520
3665
5-9
3540
3550
35802
3665
3541*



3520
5-9


3580*

Chlori-
nated
Herbi-
cides
8150


<2
8150
3580'






8150
<2
See

35801


Halo-
genated
Volatiles
5030




5030



Aqueous Al

5030


Non-
halo-
genated
Volatiles
5030



5030







5030




Aromatic
Volatiles
5030



5030







5030

Acrolein
Acrylo-
nitrlle
Aceto-
nitrile
5030



5030







5030




Volatile
Organics
5030



5030






5030



5030

5030

5030

5030

5030
'If attempts to break up emulsions are unsuccessful,  this method may be used.
'Waste dilution. Method 3580,  is only appropriate if  the sample is soluble in  the
 specified solvent.
3pH at which extraction should be performed.
'Method 3541 Is appropriate if the sample is to be analyzed for PCBs only.
                                                     TWO -  36
Revision  2
November 1990

-------
(
                 FIGURE 2-5.
SCHEMATIC OF  SEQUENCE OF TESTING TO DETERMINE
  IF A WASTE  IS HAZARDOUS  BY CHARACTERISTICS
        Method 1020
        DOT 149 CFR 173 131)
A
• i r «r
«* ti
\
No

ir? / V

No

C~* ~"
lonhaurdout by
ignitibility
.
                                               (N*nh«t«rd*u*   \  f
                                              (•r CP tonoilf  I  (
                                              °h
-------
                              FIGURE 2-5.
                              (Continued)
                                                             DOT (49  CFR 173 30C;
at \
ical \
does J >
s te /
ve' /

Solid



Mixture






/ \
/ Is uaste >v Yes /^~ ' *

No

Paint
Filter Test
— ' I Nonhazardous \
•* 1 for ignitability 1

1

Liquid

           Methods 1113  and  8240
 Nonhaza rdous
for  corrosivity
 chrac teris tic
                                                     Method 1010, Method 1020


                                                                     Yei
                                                 [  Hazardous   V-
      Nonhazardous
    for ignitability
     characteristic
                            TWO -  38
Revision  2
November 1990

-------
                                            FIGURE 2-6A.
                                                EP
Cr
Ag 	
                                            TWO - 39
Revision 2
November 1990

-------
                                               FIGURE 2-6B.
                                                  TCLP
Ba
Cr
Ag
         As
         Cd
         Pb
         Se
                                               TWO  -  40
Revision 2
November  1990

-------
                                                FIGURE 2-7A.
                                            GROUND WATER ANALYSIS
                                     (Found In Easyflow, titled:  ch2f1g7a)




VOA


8240
8260



Semivolatile




Org.


inie
lie

Pes ticides

3510 or 3S20


8270
82SO




Herbicides Oioxini

3510 or 3520
Neutral


1
3620, 3640,
and/or 3660


8080 or 8081
81SO or 81S1 8280 or 8290

Optional: Cleanup required only if interference* prevent analytia.
                                                 TWO -  41
Revision  2
November  1990

-------
                                 METHOD 3051

               MICROWAVE ASSISTED ACID DIGESTION OF SEDIMENTS.
                           SLUDGES.  SOILS.  AND OILS
1.0   SCOPE AND APPLICATION

      1.1  This method is applicable to the microwave assisted acid digestion
of sludges, sediments, soils, and oils for the following elements:

      Aluminum    Cadmium        Iron          Molybdenum         Sodium
      Antimony    Calcium        Lead          Nickel             Strontium
      Arsenic     Chromium       Magnesium     Potassium          Thallium
      Boron       Cobalt         Manganese     Selenium           Vanadium
      Barium      Copper         Mercury       Silver             Zinc
      Beryllium

      1.2  This method is provided as an alternative to Method 3050A.   It is
intended to provide a rapid multielement acid leach digestion prior to
analysis so that decisions can be made about site cleanup levels,  the  need for
TCLP testing of a waste and whether a BOAT process is providing acceptable
performance.  If a decomposition including hydrochloric acid is required for
certain elements, it is recommended that Method 3050A be used.  Digests
produced by the method are suitable for analysis by flame atomic absorption
(FLAA), graphite furnace atomic absorption (GFAA), inductively coupled plasma
emission spectroscopy (ICP-ES) and inductively coupled plasma mass
spectrometry (ICP-MS).


2.0  SUMMARY OF METHOD

      2.1  A representative sample of up to 0.5 g is digested in 10 mL of
concentrated nitric acid for 10 min using microwave heating with a suitable
laboratory microwave unit.  The sample is placed in a Teflon PFA vessel with
10 mL of concentrated nitric acid.  The vessel is capped and heated in the
microwave unit.  After cooling, the vessel contents are diluted to volume and
analyzed by the appropriate SW-846 method (Ref. 1).


3.0  INTERFERENCES

      3.1  Very reactive or volatile materials that may create high pressures
when heated may cause venting of the vessels with potential loss of sample and
analytes.  The complete decomposition of either carbonates, or carbon based
samples, may cause enough pressure to vent the vessel if the sample size is
greater than 0.25 g when used in the 120 mL vessels with a pressure relief
device that has an upper limit of 7.5+  0.7  atm (110  ±  10 psi).


                                   3051 - 1                      Revision 0
                                                                 November 1990

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4.0  APPARATUS AND MATERIALS

      4.1  Microwave apparatus requirements.

            4.1.1  The microwave unit provides programmable power with a
      minimum of 574 W and can be programmed to within ± 10 W of the required
      power.

            4.1.2  The microwave unit cavity is corrosion resistant as well as
      ventilated.
            4.1.3
      operation.
All electronics are protected against corrosion for safe
            4.1.4  The system requires Teflon PFA digestion vessels (120 ml
      capacity) capable of withstanding pressures up to 7.5 ± 0.7 atm (110 ±
      10 psi) and capable of controlled pressure relief at pressures exceeding
      7.5 ± 0.7 atm (110 ± 10 psi).

            4.1.5  A rotating turntable is employed to insure homogeneous
      distribution of microwave radiation within the unit.  The speed of the
      turntable should be a minimum of 3 rpm.

            4.1.6  Those laboratories now using or contemplating the use of
      kitchen type microwave ovens for this method should be aware of several
      significant safety issues.  First, when an acid such as nitric is used
      to assist sample digestion in microwave units in open vessels, or sealed
      vessels equipped with venting features, there is the potential for the
      acid gases released to corrode the safety devices that prevent the
      microwave magnetron from shutting off when the door is opened.  This can
      result in operator exposure to microwave energy.  Use of a unit with
      corrosion resistant safety devices prevents this from occurring.

      The second safety concern relates to the use of sealed containers
      without pressure relief valves in the unit.  Temperature is the
      important variable controlling the reaction.  Pressure is needed to
      attain elevated temperatures but must be safely contained.  However,
      many digestion vessels constructed from certain Teflons may crack,
      burst, or explode in the unit under certain pressures.  Only unlined PFA
      Teflon containers with pressure relief mechanisms are considered
      acceptable at present.

      Users are therefore advised not to use kitchen type microwave ovens or
      to use sealed containers without pressure relief valves for microwave
      acid digestions by this method.  Use of laboratory-grade microwave
      equipment is required to prevent safety hazards.  For further details
      consult reference 2.
                                   3051 - 2
                                              Revision 0
                                              November 1990

-------
      4.2  Polymeric volumetric ware in plastic (Teflon or polyethylene)
50 or 100 ml capacity.

      4.3  Whatman No. 41 filter paper (or equivalent).

      4.4  Disposable polypropylene filter funnel.

      4.5  Analytical balance, 300 g capacity, and minimum ± 0.001 g.


5.0  REAGENTS

      5.1  All acids should be sub-boiling distilled where possible to
minimize the blank levels due to metallic contamination.  Other grades may be
used, provided it is first ascertained that the reagent is of sufficient
purity to permit its use without lessening the accuracy of the determination.

            5.1.1  Concentrated nitric acid, HN03.   Acid should  be analyzed  to
      determine levels of impurity.

      5.2  Reagent Water.  Reagent water shall be interference free.  All
references to water in the method refer to reagent water unless otherwise
specified (Ref. 3).


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

      6.2  All sample containers must be prewashed with detergents, acids and
water.  Plastic and glass containers are both suitable.  See Chapter Three,
Step 3.1.3 of this manual, for further information.

      6.3  Samples must be refrigerated upon receipt and analyzed as soon as
possible.


7.0  PROCEDURE

      7.1  Calibration of Microwave Equipment

            7.1.1  Measurement of the available power for heating is evaluated
      so that absolute power in watts may be transferred from one microwave
      unit to another.  For cavity type microwave equipment, this is
      accomplished by measuring the temperature rise in 1 kg of water exposed
      to microwave radiation for a fixed period of time.  The analyst can
      relate power in watts to the partial power setting of the unit.  The
      calibration format required for laboratory microwave units depends on
      the type of electronic system used by the manufacturer to provide

                                   3051 - 3                      Revision 0
                                                                 November 1990

-------
partial microwave power.  Few units have an accurate and precise linear
relationship between percent power settings and absorbed power.  Where
linear circuits have been utilized, the calibration curve can be
determined by a three-point calibration method (7.1.3), otherwise, the
analyst must use the multiple point calibration method (7.1.2).

      7.1.2  The multiple point calibration involves the measurement of
absorbed power over a large range of power settings.  Typically, for a
600 W unit, the following power settings are measured;
100,99,98,97,95,90,80,70,60,50, and 40%using the procedure described in
section 7.1.4.  This data is clustered about the customary working power
ranges.  Nonlinearity has been commonly encountered at the upper end of
the calibration.  If the unit's electronics are known to have nonlinear
deviations in any region of proportional power control, it will be
necessary to make a set of measurements that bracket the power to be
used.  The final calibration point should be at the partial power
setting that will be used in the test.  This setting should be checked
periodically to evaluate the integrity of the calibration.  If a
significant change is detected (±10 W), then the entire calibration
should be reevaluated.

      7.1.3  The three-point calibration involves the measurement of
absorbed power at three different power settings.  Measure the power at
100% and 50% using athe procedure described in section 7.1.4.   From the
2-point line calculate the power setting corresponding to the required
power in watts specified in the procedure.  Measure the absorbed power
at that partial power setting.  If the measured absorbed power does not
correspond to the specified power within ±10 W, use the multiple point
calibration in 7.1.2.  This point should also be used to periodically
verify the integrity of the calibration.

      7.1.4  Equilibrate a large volume of water to room temperature
(23 ± 2eC).  One kg of reagent water is weighed (1,000.0 g + 0.1 g) into
a Teflon 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 unit's exhaust
fan on maximum (as it will be during normal operation).  The beaker is
removed and the water vigorously stirred.  Use a magnetic stirring bar
inserted immediately after microwave irradiation and record the maximum
temperature within the first 30 seconds to ± 0.05 8C.  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.
                             3051 - 4                      Revision 0
                                                           November 1990

-------
      The absorbed power is determined by the following relationship

                             P = (K)  (Cp) (m) (AT)
      Eq. 1                  	
      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).

      AT = the final temperature minus the initial tempera  ture (°C), and

      t = the time  in seconds (s).


      Using the experimental conditions of 2 minutes and 1 kg of distilled
      water (heat capacity at 25 °C is 0.9997 cal g"1 °C"1) the calibration
      equation simplifies to:

      Eq. 2                    P = (AT) (34.85)

      NOTE:  Stable line voltage is necessary for accurate and reproducible
      calibration and operation.  The line voltage should be within
      manufacturer's specification, and during measurement and operation
      should not vary by more than ±2 V.  A constant power supply may be
      necessary for microwave use if the source of the      line voltage is
      unstable.

      Electronic components in most microwave units are matched to
      the units' function and output.  When any part of the high  voltage
      circuit, power source, or control components in the unit have been
      serviced or replaced, it will be necessary to recheck the units'
      calibration.  If the power output has changed significantly (±10 W),
      then the entire calibration should be reevaluated.

      7.2  All digestion vessels and volumetric ware must be carefully acid
washed and rinsed with reagent water.  When switching between high concen-
tration samples and low concentration samples, all digestion vessels should be
cleaned by leaching with hot (1:1) hydrochloric acid for a minimum of two
hours followed with hot (1:1) nitric acid 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

                                   3051 - 5                      Revision 0
                                                                 November 1990

-------
volumetric ware and storage containers should be cleaned by leaching with more
dilute acids appropriate for the specific plastics used and then rinsed with
reagent water and dried in a clean environment.

      7.3  Sample Digestion

            7.3.1  Weigh the Teflon PFA digestion vessel, valve and cap
      assembly to 0.001 g prior to use.

            7.3.2  Weigh a well-mixed sample to the nearest 0.001 g into the
      Teflon PFA sample vessel equipped with a single-ported cap and a
      pressure relief valve.  For soils, sediments, and sludges use no more
      than 0.500 g.  For oils use no more than 0.250 g.

            7.3.3  Add 10 ± 0.1 ml concentrated nitric acid in a fume hood.
      If a vigorous reaction occurs, allow the reaction to stop before capping
      the vessel.  Cap the vessel and torque the cap to 12 ft-lb (16 N-m)
      according to the unit manufacturer's directions.  The sample vessel may
      be connected to an overflow vessel using Teflon PFA connecting tubes.
      Weigh the vessels to the nearest 0.001 g.  Place the vessels in the
      microwave carousel.  Connect the overflow vessels to the center well of
      the unit.

      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.

            7.3.4  Place the vessels evenly distributed in the turntable of
      the microwave unit using groups of 2 sample vessels or 6 sample vessels.
      Any vessels containing 10 ml of nitric acid for analytical blank
      purposes are counted as sample vessels.  When fewer than the recommended
      number of samples are to be digested, i.e., 3 samples plus 1 blank, the
      remaining vessels should be filled with 10 mL of nitric acid to achieve
      the full complement of vessels.  This provides an energy balance since
      the microwave power absorbed is proportional to the total mass in the
      cavity (Ref. 4).  Irradiate each group of 2 sample vessels at 344 W for
      10 minutes and each group of 6 sample vessels at 574 W for 10 minutes.
      The temperature of each sample should rise to 175 °C in less than 5.5
      minutes and remain between 170-180 CC for the balance of the 10 minute
      irradiation period.  The pressure should peak at less than 6 atm for
      most soil, sludge, and sediment samples (Ref. 5).  The pressure will
      exceed these limits in the case of high concentrations of carbonate or
      organic compounds.  In these cases the pressure will be limited by the
      relief pressure of the vessel  to 7.5 ± 0.7 atm (110 ± 10 psi).

                  7.3.4.1  Newer microwave units may be capable of higher
            power (W) that permits digestion of a larger number of samples per


                                   3051 - 6                      Revision 0
                                                                 November 1990

-------
      batch.  If the analyst wishes to digest other that two or six
      samples at a time, the analyst may use different values of power
      as long as they result in the same time and temperature conditions
      defined in 7.3.4.  That is, any sequence of power that brings the
      samples to 175°C  in 5.5 minutes and  permits a slow rise to 175  -
      180°C during the  remaining 4.5 minutes (Ref.  5).

      Issues of safety, structural integrity (both temperature and
      pressure limitations), heat loss, chemical  compatibility,
      microwave absorption of vessel material, and energy transport will
      be considerations made in choosing alternative vessels.  If all of
      the considerations are met and the appropriate power settings
      provided to reproduce the reaction conditions defined in 7.3.4,
      then these alternative vessels may be used (Ref. 1,2).

      7.3.5  At the end of the microwave program, allow the vessels to
cool for a minimum of 5 minutes before removing them from the microwave
unit.  When the vessels have cooled to room temperature, weigh and
record the weight of each vessel assembly. If the weight of acid plus
sample has decreased by more than 10 percent from the original
weight, discard the sample.  Determine the reason for the weight loss.
These are typically attributed to loss of vessel  seal integrity, use of
a digestion time longer than 10 minutes, too large a sample, or improper
heating conditions.  Once the source of the loss has been   corrected,
prepare a new sample or set of samples for digestion beginning at 7.3.1.

      7.3.6  Complete the preparation of the sample by carefully
uncapping and venting each vessel in a fume hood.  Transfer the sample
to an acid-cleaned polyethylene 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.

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

            7.3.6.2  Settling:  Allow the sample to stand until the
      supernatant is clear.  Allowing a sample to stand overnight will
      usually accomplish this.  If it does not, centrifuge or filter the
      sample.

            7.3.6.3  Filtering:  The filtering apparatus must be
      thoroughly cleaned and prerinsed with dilute nitric acid.  Filter
      the sample through quantitative filter paper into a second
      acid-cleaned container.

      7.3.7  The diluted digest has an approximate acid concentration
of 20 percent (v/v) HN03.  The digest is now ready for analysis for
elements of interest using the appropriate SW-846 method.


                             3051 - 7                      Revision 0
                                                           November 1990

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


8.0  QUALITY CONTROL

      8.1  All quality control data must be maintained and available for
reference or inspection for a period of three years.  This method is
restricted to use by, or under supervision of, experienced analysts.  Refer to
the appropriate section of Chapter One for additional quality control
requirements.

      8.2  Replicate samples should be processed on a routine basis.  A
replicate sample is a sample brought through the whole sample preparation and
analytical process.  A replicate sample should be processed with each
analytical batch or every 20 samples, whichever is the greater number.  A
replicate sample should be prepared for each matrix type (i.e., soil, sludge,
etc.).

      8.3  Spiked samples or standard reference materials should be included
with each group of samples processed or every 20 samples, whichever is the
greater number.  A spiked sample should also be included whenever a new sample
matrix is being analyzed.


9.0  METHOD PERFORMANCE

      9.1  Precision:  The precision of Method 3051, as determined by the
statistical examination of interlaboratory test results is as follows:

      9.2  Repeatability:  If successive results are obtained by the same
analyst with the same apparatus under constant operating conditions on
identical test material, then the difference between these successive results
will not, with 95% probability, exceed the repeatability value.  For example,
in the case of lead, an average of only 1 case in 20 would exceed

                                    0.206  x

in the long run, where x is one result in  g/g (Ref. 6).

      9.3  Reproducibility: If two successive measurements are made indepen-
dently by each of two different analysts working in different laboratories on
identical test material, then the difference between the average result for
each analyst will not, with 95% probability, exceed the reproducibility value.
For example, in the case of lead, an average of only 1 case in 20 would exceed

                                    0.303  x

in the long run, where x is the average of two successive measurements in  g/g
(Ref. 2).

                                   3051 - 8                      Revision 0
                                                                 November 1990

-------
      As can be seen in Table 1, repeatability and reproducibility differ
between elements, and usually depend on that element's concentration.  Table 2
provides an example of how users of the method can determine expected values
for repeatability and reproducibility; nominal values of lead have been used
for this model (Ref. 6).

      9.4  Bias:  In the case of SRM 1085 - Wear Metals in Oil, the bias of
this test method is different for each element.  An estimate of bias, as shown
in Table 3, is:

                    Bias = Amount found - Amount expected.

      However, the bias estimate inherits both the uncertainty in the
measurements made using Method 3051 and the uncertainty on the certificate, so
whether the bias is real or only due to measurement error must also be con-
sidered.  The concentrations found for Al,  Cr, and Cu using Method 3051 fall
within their certified ranges on SRM 1085,  and 95% confidence intervals for Fe
and Ni overlap with their respective certified ranges; therefore, the observed
biases for these elements are probably due to chance and should be considered
insignificant.  Biases should not be estimated at all for Ag and Pb because
these elements were not certified.  Therefore, the only two elements
considered in this table for which the bias estimates are significant are Mg
and Mo.
10.0  REFERENCES

1.    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.

2.    Kingston, H. M. and L. B. Jassie, "Safety Guidelines for Microwave
      Systems in the Analytical Laboratory".  In Introduction to Microwave
      Acid Decomposition;  Theory and Practice; Kingston, H. M. and Jassie, L.
      B., eds.; ACS Professional Reference Book Series; American Chemical
      Society: Washington, DC, 1988.

3.    1985 Annual Book of ASTM Standards. Vol. 11.01; "Standard Specification
      for Reagent Water  ; ASTM, Philadelphia, PA, 1985, D1193-77.

4.    Introduction to Microwave Sample Preparation: Theory and Practice.
      Kingston, H. M. and Jassie, L. B., Eds.; ACS Professional Reference Book
      Series; American Chemical Society:  Washington, DC, 1988.
                                   3051 - 9                      Revision 0
                                                                 November 1990

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

Binstock, D. A., Yeager, W. M., Grohse, P. M. and Gaskill, A.  Valida-
tion of a Method for Determining Elements in Solid Waste by Microwave
Digestion. Research Triangle Institute Technical Report Draft, RTI
Project Number 321U-3579-24, November, 1989, prepared for the Office of
Solid Waste, U.S. Environmental Protection Agency, Washington, DC 20460.
                             3051  -  10
Revision
November
0
1990

-------
                                  TABLE 1.
         EQUATIONS RELATING REPEATABILITY AND REPRODUCIBILITY TO MEAN
     CONCENTRATION OF DUPLICATE DETERMINATION WITH 95 PERCENT CONFIDENCE

            Element          Repeatability          Reproducibilitv

               Ag               0.195X*                  0.314X
               Al                0.232X                   0.444X
               B               12.9b                     22.6b
               Ba               0.238X                   0.421X
               Be               0.082b                   0.082b
               Ca               0.356X                   1.27X
               Cd               0.385X                   0.571X
               Co               0.291X                   0.529X
               Cr               0.187X                   0.195X
               Cu               0.212X                   0.322X
               Fe               0.257X                   0.348X
               Mg               0.238X                   0.399X
               Mn               1.96X1/2°                4.02X1/2
               Mo               0.701X                   0.857X
               Ni                0.212X                   0.390X
               Pb               0.206X                   0.303X
               Sr               0.283X                   0.368X
               V                1.03X1/2                 2.23X1/2
               Zn               3.82X1/2                 7.69X1/2

aLog  transformed variable based on  one-way analysis  of variance.
"Repeatability and reproducibility  were independent  of concentratio .
cSquare  root transformed variable  based on  one-way analysis  of variance.
                                   TABLE 2.
                  REPEATABILITY AND REPRODUCIBILITY  FOR LEAD
                                BY METHOD 3051

            Average Value      Repeatability      Reproducibility

                  50                 10.3                15.2
                  100                 20.6                30.3
                  200                 41.2                60.6
                  300                 61.8                90.9
                  400                 82.4               121
                  500                103                 152

 all  results  are in  mg/Kg
                                  3051 - 11                      Revision 0
                                                                 November 1990

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                                  TABLE 3.
          RECOVERY AND BIAS DATA FOR SRM 1085 - WEAR METALS IN OIL
    Element

      Ag
      Al
      Cr
      Cu
      Fe
      Mg
      Mo
      N1
      Pb
 Amount
 Expected
(Certified
  Range)

  (291)**
  296+4
  298±5
  295+10
  300+4
  297±3
  292±11
  303±7
  (305)**
all values in mg/Kg
 Amount
  Found*
(95% Conf
Interval)

 234±16
 295±12
 293110
 289±9
 311±14
 270±11
 238±11
 293+9
 27918
Absolute
  Bias
 ( g/g)
   -1
   -5
   -6
   +11
   -27
   -54
   -10
 Relative
  Bias
(Percent)
    0
   -2
   -2
   +4
   -9
   -18
   -3
Significant
(due to more
than chance)
    No
    No
    No
    No
    Yes
    Yes
    No
*Results taken from table 4-7, Ref. 2.
**Value not certified, so should not be used in bias detection and
estimation.
                                 3051  -  12
                                                  Revision  0
                                                  November  1990

-------
Start
                                           METHOD  3051
                      MICROWAVE ASSISTED ACID DIGESTION OF  SEDIMENTS
                                   SLUDGES,  SOILS,  AND  OILS
                7.3.1 W.igh
               aliquot into
               the digestion
                  ve*»el
                 7.3.2 Add
               concentrated
              HNO.,cap after
                 reaction
                  •topped
               7.3.3 Place 6
              •ample veaaeli
               in oven, heat
               according to
               power program
                7.3.4 Allow
                •ample* to
               cool  to room
                temperature
                7.3.S Heigh
                each venel
                 a»»embly
                                                                      7.3.7 Uie the
                                                                       appropriate
                                                                      SH-846 method
                                                                       to analyze
7.4 Calculate
concontration*
ba*ad on
original »ac
apl«
weight


                                                                         Stop
                                          3051 -  13
Revision  0
November  1990

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                                 METHOD 3015

                MICROWAVE ASSISTED ACID DIGESTION OF AQUEOUS
                            SAMPLES AND EXTRACTS
1.0  SCOPE AND APPLICATION

        1.1  This digestion procedure is used for the preparation of aqueous
samples, mobility-procedure extracts,  and wastes  that contain  suspended  solids
for analysis, by flame atomic absorption spectroscopy (FLAA),  graphite furnace
absorption spectroscopy (GFAA),  inductively coupled  argon  plasma  spectroscopy
(ICP), or inductively coupled argon plasma mass  spectrometry  (ICP-MS).   The
procedure is a hot acid leach for determining available  metals.

        1.2  Samples prepared by Method 3015 using nitric acid digestion may
be analyzed by FLAA, GFAA, ICP,  or ICP-MS for the following:

                          Aluminum             Lead
                          Antimony             Magnesium
                          *Arsenic             Manganese
                          Barium               Molybdenum
                          Beryllium            Nickel
                          Cadmium              Potassium
                          Calcium              *Selenium
                          Chromium             Silver
                          Cobalt               Sodium
                          Copper               Thallium
                          Iron                 Vanadium
                          Zinc
                          ''Cannot be analyzed by FLAA
2.0  SUMMARY OF METHOD
        2.1  Nitric acid is added to an aqueous sample in a 120 mL Teflon
digestion vessel.  The vessel  is capped and heated in  a microwave  unit.   After
cooling, the vessel contents are filtered,  centrifuged,  or allowed to  settle
in a clean sample bottle for analysis.


3.0  INTERFERENCES

        3.1  Very  reactive or volatile materials that may create high pres-
sures when heated may cause venting of the  vessels with potential  loss of
sample and analytes.  Samples that contain  carbonates  or other carbon  dioxide
generating compounds may cause enough pressure to vent the vessel.   If this
situation is anticipated the analyst may wish to use a smaller sample.

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4.0  APPARATUS AND MATERIALS

        4.1  Microwave apparatus requirements

              4.1.1  The microwave unit provides programmable power with a
        minimum of 574 W and can be programmed to within ± 10 W of the
        required power.

              4.1.2  The microwave unit cavity is corrosion resistant and
        well ventilated.

              4.1.3  All electronics are protected against corrosion for safe
        operation.

              4.1.4  The system requires Teflon PFA digestion vessels (120 ml
        capacity) capable of withstanding pressures up to 7.5 ± 0.7 atm (110
        + 10 psi) and capable of controlled pressure relief at pressures
        exceeding 7.5 + 0.7 atm (110 ± 10 psi).

              4.1.5  A rotating turntable is employed to insure homogeneous
        distribution of microwave radiation within the unit.  The speed of
        the turntable should be a minimum of 3 rpm.

              4.1.6  Those laboratories now using or contemplating the use of
        kitchen type microwave ovens for this method should be aware of
        several significant safety issues.  First, when an acid such as
        nitric is used to assist sample digestion in microwave units in open
        vessels, or sealed vessels equipped with venting features, there is
        the potential for the acid gases released to corrode the safety
        devices that prevent the microwave magnetron from shutting off when
        the door is opened.  This can result in operator exposure to micro-
        wave energy. Use of a unit with corrosion resistant safety devices
        prevents this from occurring.

        The second safety concern relates to the use of sealed containers
        without pressure relief valves in the unit.  Temperature is the
        important variable controlling the reaction.  Pressure is needed to
        attain elevated temperatures but must be safely contained.  However,
        many digestion vessels constructed from certain Teflons may crack,
        burst, or explode in the oven under certain pressures.  Only unlined
        PFA Teflon containers with pressure relief mechanisms are considered
        acceptable at present.

        Users are therefore advised not to use kitchen type microwave ovens
        or to use sealed containers without pressure relief valves for
        microwave acid digestions by this method.  Use of laboratory grade
        microwave equipment is required to prevent safety hazards.  For
        further information consult reference 1.

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        4.2  Plastic ware graduated cylinder, 50 or 100 ml capacity.

        4.3  Quantitative filter paper, Whatman No. 41 or S&S White label or
equivalent.

        4.4  Analytical balance, 300 g capacity, minimum ± 0.01 g.

        4.5  Disposable polypropylene filter funnel.

        4.6  Polyethylene bottles, 125 ml, with caps


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.   All  acids  should
be sub-boiling distilled where possible to minimize the blank levels due to
metallic contamination. Other grades may be used,  provided it is first
ascertained that the reagent is of sufficiently high purity  to permit  its use
without lessening the accuracy of the determination.

        5.2  Reagent Water.  Reagent water shall be interference free.  All
references to water in the method refer to reagent water unless  otherwise
specified (Ref. 2).

        5.3  Concentrated Nitric acid, HN03.   Acid should be analyzed  to
determine levels of impurities.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

        6.2  All  sample containers must be prewashed with detergents,  acids,
and water.  Plastic containers are preferable.   See Chapter  Three,  Step 3.1.3
of this manual, for further information.

        6.3  Aqueous waste waters must be acidified to a pH of < 2 with HN03.


7.0  PROCEDURE

        7.1  Calibration of Microwave Equipment

               7.1.1  Measurement of the available power for heating is
        evaluated  so that absolute power in watts may be transferred  from one

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microwave unit to another.  For cavity type microwave equipment, this
is accomplished by measuring the temperature rise in 1 kg of water
exposed to microwave radiation for a fixed period of time.  The
analyst can relate power in watts to the partial  power setting of the
unit.  The calibration format required for laboratory microwave units
depends on the type of electronic system used by the manufacturer to
provide partial microwave power.  Few units have an accurate and
precise linear relationship between percent power settings and
absorbed power.  Where linear circuits have been utilized, the
calibration curve can be determined by a three-point calibration
method (7.1.3), otherwise, the analyst must use the multiple point
calibration method (7.1.2).

      7.1.2  The multiple point calibration involves the measurement
of absorbed power over a large range of power settings.   Typically,
for a 600 W unit, the following power settings are measured; 100,99,-
98,97,95,90,80,70,60,50, and 40% using the procedure described in
section 7.1.4.  This data is clustered about the customary working
power ranges.  Nonlinearity has been commonly encountered at the
upper end of the calibration.  If the unit's electronics are known to
have nonlinear deviations in any region of proportional  power
control, it will be necessary to make a set of measurements that
bracket the power to be used.  The final calibration point should be
at the partial power setting that will be used in the test.  This
setting should be checked periodically to evaluate the integrity of
the calibration.  If a significant change is detected (±10 W), then
the entire calibration should be reevaluated.

      7.1.3  The three-point calibration involves the measurement of
absorbed power at three different power settings.  Measure the power
at 100% and 50% using the procedure described in section 7.1.4, and
calculate the power setting corresponding to the required power in
watts specified in the procedure from the (2-point) line.  Measure
the absorbed power at that partial power setting.  If the measured
absorbed power does not correspond to the specified power within ±10
W, use the multiple point calibration in 7.1.2.  This point should
also be used to periodically verify the integrity of the calibration.

      7.1.4  Equilibrate a large volume of water to room temperature
(23 ± 2 °C).  One kg of reagent water is weighed (1,000.0 g ± 0.1 g)
into a Teflon 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 unit's exhaust fan on maximum (as it will be during
normal operation).  The beaker is removed and the water vigorously
stirred.  Use a magnetic stirring bar inserted immediately after
microwave irradiation and record the maximum temperature within the

                          3015 - 4                 Revision  0
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         first 30  seconds  to  ± 0.05  °C.  Use a new sample for each additional
         measurement.   If  the water  is reused both the water and the beaker
         must have returned to 23 ±  2 °C.  Three measurements at each power
         setting should  be made.

         The absorbed  power is determined by the following relationship

                             P - (K) (Cp)  (m)  (AT)

        Eq. 1
         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),

         AT = the final  temperature minus  the  initial temperature  ( °C), and

         t = the  time in seconds (s).

         Using the experimental conditions of  2 minutes and 1 kg of distilled
         water (heat capacity  at 25 "C is  0.9997 cal g"1 °C"1) the calibration
         equation simplifies to:

                               P = (AT)  (34.86)                           Eq.  2

         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
         not vary by more than ±2 V.  A constant power supply may  be necessary
         for microwave use if  the source of the line voltage is unstable.

              Electronic components in most microwave units are matched to
              the units' function  and output.  When any part of the high
              voltage circuit, power source,  or control components in the
              unit have been  serviced or  replaced, it will be necessary to
              recheck the units' calibration  power.  If the power output has
              changed significantly (±10  W),  then the entire calibration
              should be reevaluated.

         7.2  All  digestion  vessels and volumetric ware must be carefully acid
washed and rinsed with reagent water.   When switching between  high solids

                                   3015  -  5                 Revision  0
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(concentrated) samples and low solids (low concentration) samples all  diges-
tion vessels should be cleaned by leaching with hot (1:1) hydrochloric acid
for a minimum of two hours followed with hot (1:1)  nitric acid 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 volumetric ware and storage containers should be cleaned by leaching
with more dilute acids appropriate for the specific plastics used and then
rinsed with reagent water and dried in a clean environment.

         7.3  Sample Digestion

              7.3.1  Weigh the Teflon PFA digestion vessel, valve and cap
         assembly to 0.01 g prior to use.

              7.3.2  A 45 ml aliquot of a well shaken sample  is measured in a
         graduated cylinder.  This aliquot is poured into the  Teflon digestion
         vessel with the number of the vessel recorded on the  preparation
         sheet.

              7.3.3  A blank sample of reagent water is treated in the same
         manner along with spikes and duplicates.

              7.3.4  Add 5 ml of concentrated nitric acid to  each vessel that
         will be used.  Check to make sure the pressure relief disks are in
         the caps with the smooth side toward the sample and start the caps a
         few turns on the vessels. Finish tightening the caps  in the capping
         station which will tighten them to a uniform torque pressure of 12
         ft.lbs. (16-N m).  Weigh each capped vessel to the nearest 0.01 g.

              7.3.5  Place five vessels evenly distributed in the carousel.
         Blanks are treated as samples for the purpose of balancing the power
         input.  When fewer than the recommended number of samples are
         digested, the remaining vessels should be filled with 45 ml of
         reagent water and 5 mL of nitric acid to achieve the  full compliment
         of vessels.  This provides an energy balance since the microwave
         power absorbed is proportional to the total mass in the cavity (Ref.
         1).

              7.3.6  Place the carousel in the unit; be sure  to seat it
         carefully on the turntable.  Program the microwave unit for the
         first-stage of the power program to give 545 W for 10 minutes and the
         second-stage program to give 344 W for 10 minutes.  This sequence
         brings the samples to 160°C ± 4"C in 10 minutes and permits a slow
         rise to 165-170 °C during the second 10 minutes (Ref. 3).  Start the
         turntable motor and be sure the vent fan is running on high and the
         turntable is turning.  Start the microwave generator.

                       7.3.6.1   Newer  microwave  units may  be  capable of  higher
              power that permit digestion of a larger number of samples per

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                                                            November 1990

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      batch.  If the analyst wishes to digest more than 5 samples at
      a time, the analyst may use different power settings as long as
      they result in the same time and temperature conditions defined
      in 7.3.6.  That is, any sequence of power that brings the
      samples to 160*C ± 4"C in 10 minutes and permits a slow rise to
      165-170°C during the second 10 minutes (Ref. 2).

      Issues of safety, structural integrity (both temperature and
      pressure limitations), heat loss, chemical  compatibility,
      microwave absorption of vessel material, and energy transport
      will be considerations made in choosing alternative vessels.
      If all of the considerations are met and the appropriate power
      settings are provided to reproduce the reaction conditions
      defined in 7.3.6, then these alternative vessels may be used
      (Ref. 1,2)

      7.3.7  At the end of the microwave program, allow the vessels
to cool for at least 5 minutes in the unit before removal to avoid
possible injury if a vessel vents immediately after microwave
heating.  The samples may be cooled outside the unit by removing the
carousel and allowing the samples to cool on the bench or in a water
bath.  When the vessels have cooled to room temperature, weigh and
record the weight of each vessel  assembly.  If the weight of the
sample plus acid has decreased by more than 10% discard the sample.

      7.3.8  Rinse virgin or acid-cleaned polyethylene 125 ml bottles
(or other suitable size) and caps with reagent water and shake out
the large water drops. Label the  bottles.

      7.3.9  Complete the preparation of the sample by carefully
uncapping and venting each vessel in a fume hood.  Transfer the
sample to an acid-cleaned polyethylene 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.

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

          7.3.9.2   Settling:   Allow the sample to stand  until  the
      supernatant is clear.  Allowing a sample to stand overnight
      will usually accomplish this.  If it does not, centrifuge or
      filter the sample.

          7.3.9.3   Filtering:  The filtering apparatus  must  be
      thoroughly cleaned and prerinsed with dilute nitric acid.
      Filter the sample through quantitative filter paper into a
      second acid-cleaned container.
                          3015  - 7                Revision 0
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              7.3.10  The concentration values obtained from analysis must be
        corrected for the dilution factor from the acid addition.  If the
        sample will be analyzed by ICP-MS additional dilution will generally
        be necessary.  For example, the sample may be diluted by a factor of
        20 with reagent water and the acid strength adjusted back to 10%
        prior to analysis.  The dilutions used should be recorded and the
        measured concentrations adjusted accordingly.


8.0  QUALITY CONTROL

        8.1  All quality control measures described in Chapter One, of this
Manual, should be followed.

        8.2  For each analytical batch of samples processed, analytical
reagent blanks (also field blanks if they were taken)  should be carried
throughout the entire sample preparation and analytical  process.   These blanks
will be useful  in determining if samples are being contaminated.

        8.3  Replicate samples should be processed on a routine basis.  A
replicate sample is a real  sample brought through the whole sample preparation
and analytical  process.   A replicate sample should be processed with  each
analytical batch or every 20 samples,  whichever is the greater number.

        8.4  Spiked samples or standard reference materials should be
employed to determine accuracy.   A spiked sample should be included with each
group of samples processed and whenever a new sample matrix is being  analyzed.

        8.5  The method of standard addition shall be used for the analysis
of all EP extracts (see Method 7000,  Step 8.7).


9.0  METHOD PERFORMANCE

        9.1  Refer to Reference 4.
                                  3015 -  8                Revision  0
                                                            November  1990

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10.0  REFERENCES

1.      Introduction to Microwave Sample Preparation:  Theory and Practice.
        Kingston, H. M.; Jassie, L. B., Eds.; ACS Professional  Reference  Book
        Series: American Chemical Society,  Washington,  DC,  1988; Ch  6 & 11.

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

3.      Kingston, H. M., Final Report EPA IAG #DWI3932541-01-I, September 30,
        1988, Appendix A.

4.      Shannon, M., Alternate Test Procedure Application,  USEPA Region Y,
        Central Regional Laboratory, 536 S. Clark Street,  Chicago,  IL 60606,
        1989.
                                  3015  - 9                Revision 0
                                                           November 1990

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                          METHOD 3015
             MICROWAVE ASSISTED ACID DIGESTION
              OF AQUEOUS  SAMPLES  AND EXTRACTS
7.1 Calibrate
th* microwav*
  •quipnant
7.2 Acid waah
and HtO rinaa
7.3.1 Moa.ur.
45 ml aliquot
 into th«
 digavtion
  vmmmml
all dis* tion
     gs*
  enal* and
  glaiaware
 7.3.7 Rin..
  virgin
bottU. with
rvagvnt water
                           3015  - 10
                                       Revision  0
                                       November  1990

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                                  METHOD  6020

                INDUCTIVELY COUPLED PLASMA - MASS SPECTROMETRY
1.0  SCOPE AND APPLICATION

      1.1  Inductively coupled plasma-mass  spectrometry  (ICP-MS) is a technique
which is  applicable  to jxg/L  concentrations  of a large number  of elements in
water and wastes  after appropriate sample preparation  steps  are  taken [1,2].
When dissolved  constituents  are required,  samples must be  filtered  and acid-
preserved prior to analysis.   No further digestion is  required  prior to analysis
for dissolved  elements.   Acid-digestion prior to filtration and analysis is
required for groundwater, aqueous  samples,  industrial  wastes, soils, sludges,
sediments, and other solid wastes for which total  (acid-leachable) elements are
required.

      1.2  Elements for which Method 6020 has  shown acceptable performance  in a
multi-laboratory study are listed in TABLE 1.  Acceptability of the method for
an element was  based  upon the multi-laboratory performance  compared with that of
either furnace  atomic absorption  spectroscopy or  inductively coupled plasma-
atomic emission spectroscopy.   Other elements  may be added  to Table  1 as more
information becomes available. Multi-laboratory performance data for  the listed
elements (and others) are provided  in Section 9.  Instrument detection limits,
sensitivities, and linear ranges for these elements will  vary with  the matrices,
instrumentation, and operating conditions.

      1.3    Use of  this method   is  restricted  to   spectroscopists who  are
knowledgeable in the recognition and the correction of spectral, chemical, and
physical interferences in ICP-MS.

      1.4   An  appropriate   internal  standard  is required  for  each  analyte
determined by ICP-MS.  Recommended  internal standards are  Li,  Sc,   Y,   Rh,
mln,  159Tb,  1<5Ho,  and 209Bi.   The lithium  internal  standard  should  have an
enriched abundance of Li, so that interference  from lithium native  to  the sample
is minimized.   Other elements may   need to be  used as  internal  standards when
samples contain significant amounts of the recommended internal  standards.


2.0  SUMMARY OF METHOD

      2.1 Prior to analysis,  samples which require total  values must be digested
using appropriate sample preparation methods (such  as Methods 3005  - 3051).

      2.2  Method 6020 describes the multi-elemental  determination of analytes
by ICP-MS.  The method measures ions produced by a radio-frequency inductively
coupled plasma.  Analyte species originating in a liquid are nebulized and the
resulting aerosol  transported by  argon gas  into the plasma  torch.   The  ions
produced are entrained  in the plasma gas and introduced,  by means of a water-
cooled interface,  into a quadrupole mass spectrometer.  The ions  produced in the

                                    6020-1                         Revision  0
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plasma are sorted according to their mass-to-charge ratios and quantified with
a  channel  electron  multiplier.    Interferences  must  be  assessed  and  valid
corrections applied  or the data  flagged  to indicate problems.   Interference
correction must  include compensation for  background ions contributed  by the
plasma gas, reagents, and constituents of the sample matrix.


3.0  INTERFERENCES

      3.1  Isobaric elemental  interferences in  ICP-MS are caused by isotopes of
different elements forming atomic ions with the same nominal mass-to-charge ratio
(m/z). A data  system must be used  to  correct for these  interferences.   This
involves determining the signal  for another isotope of the interfering element
and subtracting the appropriate signal  from the analyte isotope signal.   Since
commercial  ICP-MS  instruments nominally provide  unit resolution  at 10%  of the
peak height, very  high ion currents at adjacent masses can also contribute to ion
signals at  the mass of interest.  Although this type of interference is uncommon,
it is not easily corrected, and samples exhibiting a significant problem of this
type could require resolution  improvement,  matrix separation,  or use of another
method.

      3.2  Isobaric molecular and doubly-charged ion interferences in  ICP-MS are
caused by ions consisting of more than one atom or charge, respectively.  Most
isobaric  interferences  that  could  affect  ICP-MS  determinations   have  been
identified in  the literature  [3,4].  Examples  include  ArCl* ions  on the   As
signal and MoO* on the  cadmium  isotopes.   Since the   Cl  natural  abundance of
75.8 percent  is  3.13  times  the   Cl  abundance  of 24.2 percent,  the  choride
corrections can be calculated as follows (where the  Ar  Cl* contribution at m/z
75 is a negligible 0.06 percent of the 40Ar35cr signal):

      corrected arsenic  signal  =  (m/z 75  signal)  -  (3.13)  (m/z 77  signal)  +
      (2.53)  (m/z  82  signal),  (where the final  term adjusts for  any selenium
      contribution at 77 m/z),

Similarly,

      corrected cadmium signal =  (m/z 114  signal)  -  (0.027)(m/z  118 signal)  -
      (1.63)(m/z   108  signal),  (where last 2 terms adjust  for any  tin or MoO*
      contributions at m/z 114).

The above equations are based upon the constancy  of the isotopic ratios for the
interfering species.  Corrections that presume a constant fraction of a molecular
ion relative to the "parent" ion have not been found  [5] to be reliable, e.g.,
oxide levels can vary.   If a correction for an  oxide ion  is based upon the ratio
of parent-to-oxide  ion intensities, the  correction  must be  adjusted for the
degree of oxide formation by the use of an appropriate  oxide internal standard
previously demonstrated to  form  a similar level of oxide  as the  interferant.
This type of correction has been  reported [5]  for oxide-ion  corrections using
ThO*/Th*  for the determination of  rare earth elements.


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      3.3  Physical interferences are associated with the sample nebulization and
transport processes as well as with ion-transmission efficiencies.  Nebulization
and transport processes  can be affected if a matrix component causes a change in
surface  tension  or  viscosity.    Changes  in matrix   composition  can  cause
significant signal suppression or enhancement [6]. Dissolved solids can deposit
on the  nebulizer  tip of a pneumatic nebulizer  and  on  the  interface  skimmers
(reducing the orifice size  and the  instrument performance).  Total solid levels
below 0.2% (2,000  mg/L)  have  been recommended  [7] to minimize solid deposition.
An internal standard  can be used to correct for physical  interferences, if it is
carefully matched  to  the analyte so that the two elements are similarly affected
by matrix changes  [8].   When the intensity level of an internal standard is less
than 30  percent  or  greater  than  120  percent of the  intensity of the  first
standard used during  calibration, the sample must  be reanalyzed after a fivefold
(1+4) dilution has been performed.

      3.4   Memory interferences can occur  when  there  are large concentration
differences between samples or standards which are analyzed  sequentially.  Sample
deposition on the  sampler and skimmer cones, spray chamber design, and the type
of nebulizer affect the extent of the memory interferences which are observed.
The rinse  period  between samples must  be  long enough  to eliminate significant
memory interference.


4.0  APPARATUS AND MATERIALS

      4.1  Inductively coupled plasma-mass spectrometer:

            4.1.1   A system capable of  providing resolution,   better  than  or
      equal to  1  amu at 10%  peak height is required.   The system must  have a
      mass range  from  at least  6  to  240  amu and a  data system  that  allows
      corrections  for isobaric interferences and the application  of the internal
      standard technique. Use of a mass-flow controller for the nebulizer argon
      and a peristaltic pump for the sample solution  are recommended.

            4.1.2   Argon gas supply:  high-purity grade (99.99%).


5.0  REAGENTS

      5.1  Acids used in the  preparation of  standards and for sample processing
must be of high purity.   Redistilled acids are recommended because of the high
sensitivity of ICP-MS.  Nitric acid at less than 2 per  cent  (v/v)  is required for
ICP-MS to minimize damage to the interface and to minimize isobaric molecular-ion
interferences with the  analytes.   Many  more  molecular-ion  interferences  are
observed on the analytes when hydrochloric  and sulfuric acids  are used [3,4].
Concentrations of antimony and silver  above 300  /xg/L  require  1% (v/v)  HC1  for
stability.  If HC1 is added as a stabilizer, then corrections for the chloride
molecular-ion interferences must be applied to all data generated.
                                    6020-3                        Revision 0
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      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  Standard stock solutions may be purchased or prepared from ultra-high
purity grade chemicals or metals (99.99 to  99.999%  pure).   See Method 6010A,
Section 5.3, for instructions on preparing standard solutions  from solids.

            5.3.1  Bismuth internal  standard  solution,  stock,  1 mL = 100 /xg Bi:
      Dissolve 0.1115 g  Bi203 in  a  minimum amount of  dilute  HN03.   Add  10 ml
      cone. HN03 and dilute to 1,000 ml with  reagent water.

            5.3.2  Holmium internal  standard  solution,  stock,  1 mL = 100 jug Ho:
      Dissolve 0.1757 g  Ho2(C03)2-5H20  in 10 ml reagent  water and 10 mL  HN03.
      After dissolution  is complete, warm the solution to degas.   Add  10 mL
      cone. HN03 and dilute to 1,000 mL with  reagent water.

            5.3.3  Indium internal standard solution, stock, 1 mL = 100 M9 In:
      Dissolve 0.1000 g  indium metal  in  10 mL cone.  HN03.   Dilute to 1,000 mL
      with reagent water.

            5.3.4  Lithium internal  standard  solution, stock, 1 mL = 100 jug 6Li:
      Dissolve 0.6312 g 95-atom-% Li, Li2C03  in 10 mL of reagent water and  10 mL
      HN03.  After dissolution  is  complete,  warm the  solution to degas.   Add
      10 mL cone. HN03 and dilute to 1,000 mL with reagent water.

            5.3.5  Rhodium internal  standard  solution,  stock,  1 mL = 100 jug Rh:
      Dissolve 0.3593 g  ammonium hexachlororhodate  (III)  (NH,)3RhCl,  in  10 mL
      reagent water.  Add 100 mL cone. HC1 and dilute to 1,000 mL with reagent
      water.

            5.3.6  Scandium internal  standard solution, stock,  1 mL = 100 jug Sc:
      Dissolve 0.15343 g Sc203 in 10  mL (1+1) hot HN03.  Add 5  ml cone. HN03 and
      dilute to 1,000 mL with reagent water.

            5.3.7  Terbium internal  standard  solution,  stock,  1 mL = 100 M9 Tb:
    .  Dissolve 0.1828 g Tb2(CO,)3-5H20 in  10 mL  (1+1) HN03.  After dissolution is
      complete, warm the  solution to degas.  Add  5 ml  cone. HN03 and dilute to
      1,000 mL with reagent water.

            5.3.8  Yttrium internal standard solution, stock,  1 mL = 100  /xg Y:
      Dissolve 0.2316 g  Y2(C03),.3H20 in 10 mL  (1+1) HN03.  Add 5 ml cone. HN03
      and dilute to 1,000 mL with reagent water.

            5.3.9  Titanium solution, stock,  1 mL = 100 ng Ti:  Dissolve 0.4133  g
      (NH,)2TiF6 in reagent water.  Add 2 drops cone. HF  and dilute to 1,000 mL
      with reagent water.
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            5.3.10   Molybdenum solution,  stock, 1 ml  =  100 M9  Mo:   Dissolve
      0.2043 g  (NH4)2Mo04  in reagent water.   Dilute to  1,000 ml with reagent
      water.

      5.4   Mixed  calibration standard solutions --  Dilute  the  stock-standard
solutions  to  levels  in the  linear  range  for  the instrument  in  a solvent
consisting of 1 percent (v/v) HNO, in reagent water.  The calibration standard
solutions  must  contain a  suitable concentration  of an  appropriate internal
standard for each analyte.   Generally,  an  internal  standard should be no more
than 50 amu removed  from the analyte.   Recommended internal standards include
*Li,  45Sc, ®Y,  1(53Rh,  115In,  159Te, 1*9Ho, and 209Bi.  Prior to preparing  the mixed
standards, each stock solution must be analyzed separately to determine possible
spectral interferences or the presence of impurities.  Care must be taken when
preparing  the  mixed  standards  that  the elements  are  compatible  and stable.
Transfer the mixed standard solutions to freshly acid-cleaned FEP fluorocarbon
bottles for storage.  Fresh mixed standards  must be  prepared as needed with the
realization that concentrations can change on aging.  Calibration  standards must
be initially  verified using  a quality control  sample (see Section  5.8)  and
monitored weekly for  stability.

      5.5   Blanks:  Three types of blanks are  required for  the  analysis.   The
calibration blank is  used  in  establishing  the calibration curve.  The reagent
blank is used to monitor for possible contamination resulting  from the sample
preparation procedure.  The rinse blank is  used to  flush the system between all
samples and standards.

            5.5.1   The calibration blank consists  of  1  percent HN03 (v/v) in
      reagent water along with  the selected concentrations of internal  standards
      such that there is an appropriate  internal  standard element for each of
      the analytes.

            5.5.2  The reagent blank must contain all the reagents in the same
      volumes as  used in  processing  the  samples.   The reagent  blank must be
      carried  through  the  complete  procedure and  contain  the   same  acid
      concentration  in the  final  solution as  the sample  solutions  used  for
      analysis.

            5.5.3   The rinse  blank  consists  of 1  to  2  percent  HN03 (v/v) in
      reagent water.  Prepare a sufficient  quantity to  flush the  system between
      standards and  samples.

      5.6  The instrument check standard is prepared by  the analyst  by combining
compatible  elements  at  concentrations equivalent  to  the  midpoint  of their
respective calibration ranges.

      5.7  The interference  check solution(s)  (ICS)  is prepared to contain known
concentrations  of  interfering  elements that will  demonstrate the magnitude of
interferences and provide an adequate test  of any corrections.  Chloride in the
ICS  provides  a  means to  evaluate  software  corrections  for chloride-related
interferences  such  as 35ClV on 3V  and  "Ar^Cl*  on  ^As*.  Iron  is used to

                                    6020-5                        Revision  0
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demonstrate adequate  resolution  of the spectrometer  for  the determination of
manganese.  Molybdenum serves to indicate oxide effects on cadmium isotopes.  The
other components are present to evaluate the ability of the measurement system
to correct for various molecular-ion isobaric interferences.  The ICS is used to
verify that the interference levels  are  corrected by the  data system within
quality control limits.

            5.7.1  The final  concentrations of elements  in ICS A and  ICS AB are
      shown in Table  2. These  solutions  must be  prepared from ultra-pure
      reagents.  They can be  obtained  commercially  or  prepared by the following
      procedure.

                  5.7.1.1   Mixed  ICS solution  I  may  be prepared  by  adding
            13.903 g A1(NO,)3-9H,0,  2.498  g CaCO, (dried at 180 C for 1 h before
            weighing), 1.000  g Fe,  1.658 g MgO, 2.305 g Na2C03, and 1.767 g K2C03
            to 25 ml of reagent water.  Slowly add 40 ml  of  (1+1)  HN03.  After
            dissolution  is  complete,  warm  the  solution  to  degas.   Cool  and
            dilute to 1,000 ml with reagent water.

                  5.7.1.2   Mixed  ICS  solution  II may  be prepared  by slowly
            adding 7.444 g 85 % H,P04,  6.373 g 96%  H,S04, 40.024  g 37% HC1, and
            10.664 g citric acid t60,H8  to  100 mL of  reagent water.  Dilute to
            1,000 ml with reagent water.

                  5.7.1.3  Mixed  ICS solution III may be prepared by adding 5 ml
            each of 100 M9/ml arsenic stock solution, chromium  stock solution,
            copper  stock solution, manganese  stock   solution,  selenium  stock
            solution, silver  stock solution, and zinc  stock solution,  10 ml each
            of  100  /K|/ml  cobalt  stock solution,  nickel   stock solution,  and
            vanadium  stock  solution,  and  2.5  ml  of  100  ng/m\  cadmium  stock
            solution.  Dilute to 100 ml with 2% HN03.

                  5.7.1.4  Working ICS Solutions

                        5.7.1.4.1   ICS A may be  prepared by adding 50 mL of
                  mixed  ICS  solution  I  (5.7.1.1),  10 ml each of  100  /zg/ml
                  titanium stock solution  (5.3.9) and  molybdenum stock solution
                  (5.3.10),  and   25 ml  of  mixed   ICS  solution  II   (5.7.1.2).
                  Dilute to 100 ml with reagent water.  ICS  solution A must be
                  prepared fresh weekly.

                        5.7.1.4.2   ICS  AB may be  prepared  by  adding 50 ml of
                  mixed  ICS  solution  I  (5.7.1.1),  10 ml each of  100  /ug/ml
                  titanium stock solution  (5.3.9) and  molybdenum stock solution
                  (5.3.10), 25 ml of mixed  ICS solution II (5.7.1.2), and 2 ml
                  of  Mixed ICS solution III (5.7.1.3).   Dilute  to 100 mL with
                  reagent water.   ICS  solution AB must be prepared fresh weekly.

      5.8   The  quality  control  sample is  the initial  calibration verification
solution,  which  must be prepared  in  the  same acid matrix as  the calibration

                                    6020-6                        Revision  0
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standards.  This solution must be an independent standard near the midpoint of
the  linear range  at  a  concentration  other than  that  used for  instrument
calibration.  An independent standard is defined as a standard composed of the
analytes from a source different from those used  in the standards for instrument
calibration.
6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   Sample  collection  procedures  should  address the  considerations
described in Chapter Nine of this Manual.

      6.2  See the introductory material in Chapter Three, Inorganic Analytes,
Sections  3.1.3  for  information on  sample  handling and  preservation.   Only
polyethylene or Teflon containers are recommended for use in Method 6020.


7.0   PROCEDURE

      7.1  Solubilization and digestion procedures are presented in the Sample
Preparation Methods (e.g. Methods 3005 - 3050).

      7.2   Initiate  appropriate  operating configuration  of the   instrument
computer.

      7.3  Set up the instrument with the proper operating parameters.

      7.4   Operating  conditions:    In  general,  the analyst  should  follow the
instructions  provided by  the  instrument manufacturer.    The  following  is  a
suggested listing of operating conditions which may be useful.

                  Perkin-Elmer  Sciex
                       Elan  500         VG Plasmaauad
Plasma Gas (1pm)           12                   13
Aux. Gas  (1pm)            1.2                 0.65
Neb. Gas  (1pm)           0.95                0.69
Forward power (kW)        1.2                 1.30
Reflected power (W)       < 5                 <  5
Sampling Height            18                   12
  (mm above load coil)

     Note:  Addition of nitrogen to the  plasma  argon has  been      reported to
decrease many molecular interferences [9].

    Allow at least 30 minutes  for the instrument to equilibrate before analyzing
any samples.  This must be  verified by  analyzing  a tuning  solution (such as 100
jiig/L Li,  Co,  In, and Tl)  at least four times with relative standard deviations
of less than 10% for the  analytes contained in the tuning solution.
                                    6020-7                        Revision  0
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      Note:  Precautions must be taken to protect the channel electron multiplier
from high  ion currents.   The  channel  electron multiplier suffers from fatigue
after being exposed to high ion  currents.   This fatigue can  last from several
seconds to hours depending on  the extent of exposure.  During this time period,
response  factors  are constantly  changing,  which  invalidates  the calibration
curve, causes instability, and invalidates sample analyses.

      7.5  Conduct mass calibration and resolution checks in the mass regions of
interest.  The mass calibration and resolution parameters are required criteria
which must be met prior to any samples being analyzed.   If the mass calibration
exceeds a difference of more than 0.1 amu from the actual value,  then the mass
calibration must be adjusted to the correct values.  The  resolution must also be
verified to be less than 1.0 amu full width at 10 percent peak height.

      7.6  Calibrate the instrument for the analytes of interest for the isotopes
shown in  Table  3 using the calibration blank and at least  a  single standard
according to the manufacturer's recommended procedure.  Flush the system with the
rinse blank  (5.5.3)  between  each standard  solution.   Use the average  of the
multiple integrations for both standardization and sample analysis.

      7.7  Some elements  (such  as Hg,  W, and Mo)  require  extended flushing times
which need to be determined for each   instrumental system.

      7.8  All masses  which  could affect data quality  should  be monitored to
determine potential effects from matrix components on the analyte  peaks.  These
masses must be monitored  either simultaneously in a separate scan  or at the same
time quantification occurs.

      7.9    Immediately  after  the   calibration   has   been  established,  the
 ••libration must be verified and documented for every analyte  by the analysis of
tne initial calibration verification  solution  (Section 5.8).  When measurements
exceed ± 10% of the accepted value the analysis must be  terminated, the problem
corrected, the  instrument  recalibrated,  and the  calibration  reverified.   Any
samples analyzed under an out-of-control  calibration must be reanalyzed.

      7.10  Flush the system with the  rinse  blank  solution (5.5.3) for at least
30 seconds before the analysis of each sample  (see Section 7.7).  Aspirate each
sample for at least 30 seconds before collecting data.   Analyze the instrument
check standard  (Section  5.6)  and the calibration blank (Section 5.5.1)  at a
frequency of at least once every 10 analytical samples.

      7.11   Dilute  and  reanalyze samples  that are  more concentrated than the
linear range for an analyte (or species needed for a correction)  or measure an
alternate less-abundant isotope.

      7.12  Calculations:  The quantitative values shall  be reported in units of
micrograms per  liter (M9/L) for  aqueous  samples and milligrams  per kilogram
(mg/kg)  for solid  samples.    If dilutions were  performed,  the appropriate
corrections must be applied to the sample values.


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            7.12.1  Results for solids must be reported on a dry-weight  basis as
      follows:

                  (1)  A  separate  determination  of  percent  solids   must  be
                       performed.

                  (2)  The concentrations determined  in  the digest are  to be
                       reported on  the basis  of  the  dry weight  of the sample.

                  Concentration (dry weight)(mg/kg) =  {* x ^
                                                       H A O

                       Where,

                  C = Digest Concentration (mg/L)
                  V = Final volume in liters after sample preparation
                  W = Weight in kg of wet sample

                        % Sol ids
                           100

      Calculations  should include  appropriate interference  corrections (see
      Section  3.2  for  examples),  internal  standard  normalization,  and  the
      summation of  signals at 206, 207, and 208 m/z for lead to compensate for
      any differences in  the  abundances  of these  isotopes between samples and
      standards.
8.0  QUALITY CONTROL

      8.1  All quality  control  data  should  be maintained and be available for
easy reference or inspection.

      8.2  Instrument Detection Limits (IDL's) (in M9/L)  can  be estimated by
multiplying by three the  average  of  the standard  deviations obtained on three
nonconsecutive days from  the  analysis  of a  standard solution (each analyte in
reagent water)  at a concentration 3x-25x IDL, with seven consecutive measurements
per day.   Each measurement must be  performed as  though  it were  a separate
analytical sample (i.e., each  measurement must be followed by a rinse and/or any
other procedure normally  performed between  the analysis of separate samples).
IDL's must be determined at least every three months and kept with  the instrument
log book.

      8.3  The  intensities of  all internal standards must be monitored for every
analysis.  When the intensity of any  internal  standard fails to fall between 30
and 120  percent of  the  intensity of that internal  standard  in  the  initial
calibration standard, the following procedure is followed.  The sample must be
diluted fivefold (1+4)  and reanalyzed with the addition of appropriate amounts
of  internal  standard.   This procedure  must  be  repeated  until the  internal


                                    6020-9                        Revision 0
                                                                  November 1990

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standard intensities fall within the prescribed window.  The intensity levels of
the internal  standards for  the calibration blank (Section 5.5.1) and instrument
check standard  (Section 5.6) must  agree within ± 20 percent  of  the intensity
level of the internal standard of the original calibration blank solution.  If
they do not agree, terminate the analysis,  correct the problem, recalibrate, and
reanalyze the affected samples.

      8.4  To obtain analyte data of known quality,  it  is necessary to measure
more than the analytes of  interest  in  order  to determine whether interference
corrections are necessary.   If the concentrations of interference sources (such
as C, Cl, Mo, Zr, W) are  below the levels that show an  effect  on  the analyte
level, uncorrected equations may be used provided all  QC criteria  are met.  Note
that monitoring  the  interference sources does  not necessarily require monitoring
the interferant  itself, but that a molecular species may  be monitored to indicate
the  presence of the interferent.   When  corrected  equations are used,  all  QC
criteria must  also   be  met.   Extensive QC  for  interference corrections  are
required at all  times.  The monitored masses  must include those elements whose
hydrogen, oxygen, hydroxyl,  chlorine, nitrogen, carbon and sulfur molecular ions
could impact  the analytes of interest.  Unsuspected interferences may be detected
by adding pure major matrix components  to  a sample to observe any impact on the
analyte signals.  When an  interference  source is present,  the sample elements
impacted must be flagged to indicate  (a) the percentage interference correction
applied to the data or (b) an uncorrected interference by virtue of the elemental
equation used  for quantitation.   The  isotope proportions  for  an  element  or
molecular-ion cluster provide information useful  for quality assurance.

      NOTE:   Only isobaric elemental, molecular, and doubly charged interference
corrections which use  established  isotopic response  ratios  or parent-to-oxide
ratios (provided an  oxide internal standard is used  as described in Section 3.2)
are acceptable corrections for use in Method  6020.

      8.5  Serial dilution:  If the analyte concentration is within the linear
dynamic range of the  instrument and  sufficiently high (minimally,  a factor of 100
above the instrumental  detection limit), an analysis of  a  fivefold dilution must
agree within ± 10% of the original determination.  If not,  an interference effect
must be suspected.  One serial dilution must be analyzed for each twenty samples
or less of each matrix in a batch.

      8.6  Matrix spike  addition:   An  analyte spike added to a portion  of a
prepared sample, or  its dilution, should be recovered to within 75  to 125 percent
of the known value.   The spike addition should produce a minimum signal 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.   The  use of a standard-addition  analysis procedure  can usually
compensate for this  effect.  See Section 8.5.3 of Method 6010 for  information on
standard additions.

      8.7  A Laboratory Control Sample (LCS) should  be analyzed for each analyte
using  the  same  sample preparations,  analytical  methods and  QA/QC procedures


                                    6020-10                        Revision  0
                                                                  November 1990

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employed for the test samples.  One LCS  should be prepared and analyzed for each
sample batch at a frequency of one LCS for each 20 samples or less.

      8.8  Check the  instrument standardization  by  analyzing appropriate quality
control solutions as follows:

            8.8.1    Check  instrument  calibration using  a calibration  blank
      (Section  5.5.1)  and  the  initial  calibration  verification  solution
      (Sections 5.8 and 7.9).

            8.8.2   Verify  calibration at  a  frequency of every  10 analytical
      samples  with  the  instrument   check standard   (Section  5.6)  and  the
      calibration blank (Section 5.5.1).   These solutions must also be analyzed
      for  each  analyte at the  beginning of the  analysis  and after  the last
      sample.

            8.8.3  The results  of the  initial calibration verification solution
      and the instrument check  standard must agree within ± 10% of the expected
      value.    If  not,  terminate  the  analysis,  correct  the  problem,  and
      recalibrate the instrument.  Any sample analyzed under an out-of-control
      calibration must be reanalyzed at no additional  cost to the government.

            8.8.4   The results of the calibration  blank must be  less  than 3
      times the current  IDL  for each  element.   If this is not  the  case,  the
      reason for the out-of-control condition must be found and corrected,  and
      affected samples must be reanalyzed.

      8.9    Verify  the  magnitude  of elemental   and  molecular-ion  isobaric
interferences  and the  adequacy of  any   corrections  at the  beginning  of  an
analytical run or once every 12 hours, whichever  is more frequent.  Do this by
analyzing the interference check solutions A and AB
      8.10   Analyze one  duplicate sample for  every matrix
frequency of one matrix duplicate for every 20 samples.
in a  batch  at a
            8.10.1   The relative  percent  difference  (RPD)  between duplicate
      determinations must be calculated as follows:
                                 ID, - D2 |
                   RPD =      	     x 100
                               (D, + D2)/2

            where:

            RPD = relative percent difference.
            D1 = first sample value.
            D2 = second sample value (duplicate)

      A  control  limit of 20% RPD should  not  be exceeded  for  analyte values
      greater than 100 times  the  instrumental detection limit.  If this  limit is
      exceeded, the reason for the out-of-control  situation must be found and

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                                                                  November 1990

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      corrected, and any  samples  analyzed during the out-of-control condition
      must be reanalyzed.

9.0  METHOD PERFORMANCE
      9.1  In an EPA multi-laboratory study, 10 laboratories applied the
ICP-MS technique to both aqueous and  solid samples.  TABLE  5 summarizes the
method performance  data for aqueous samples.  Performance data  for solid samples
is provided in TABLE 6.

10.0  REFERENCES
1. Horlick, G., et  al., Spectrochim. Acta  40B,  1555  (1985).
2. Gray, A.L., Spectrochim. Acta  40B, 1525 (1985); 41B,  151 (1986).
3. Tan, S.H., and Horlick, G., Appl. Spectrosc. 40,  445  (1986).
4. Vaughan, M.A., and  Horlick, G., Appl.  Spectrosc.  40,  434 (1986).
5.  Lichte, F.E., et al., Anal. Chem. 59,  1150  (1987).
6. Beauchemin, D.,  et  al., Spectrochim. Acta 42B, 467  (1987).
7. Houk, R.S., Anal. Chem. 58, 97A (1986).
8. Thompson, J.J.,  and Houk, R.S., Appl.  Spectrosc.  41,  801 (1987).
9. Evans,  E.H., and Ebdon, L., J. Anal. At. Spectrom.  4,  299  (1989).
                                    6020-12                       Revision  0
                                                                 • November 1990

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TABLE 1. ELEMENTS APPROVED FOR ICP-MS DETERMINATION
            Element
  CAS* *
Estimated Detection
   Limit (/ig/L)
            Aluminum
            Antimony
            Arsenic
            Barium
            Beryl 1i urn
            Cadmium
            Chromium
            Cobalt
            Copper
            Lead
            Manganese
            Nickel
            Silver
            Thallium
            Zinc
7429-90-5
7440-36-0
7440-38-2
7440-39-3
7440-41-7
7440-43-9
7440-47-3
7440-48-4
7440-50-8
7439-92-1
7439-96-5
7440-02-0
7440-22-4
7440-28-0
7440-66-6
         ,1
   0.1
   0.02
   0.4
   0.02
   0.
0.07
0.02
0.01
0.03
0.02
0.04
0.03
0.04
0.05
0.08
                                    6020-13
                           Revision  0
                           November 1990

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TABLE 2.  RECOMMENDED INTERFERENCE CHECK SAMPLE COMPONENTS AND CONCENTRATIONS.
   Interference                          Solution A              Solution AB
    component                  Concentration  (mg/L)         Concentration  (mg/L)
Al
Ca
Fe
Mg
Na
P
K
S
C
Cl
Mo
Ti
As
Cd
Cr
Co
Cu
Mn
Ni
Ag
Zn
500.0
500.0
500.0
500.0
500.0
500.0
500.0
500.0
1000.0
3600.0
10.0
10.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
500.0
500.0
500.0
500.0
500.0
500.0
500.0
500.0
1000.0
3600.0
10.0
10.0
0.100
0.050
0.100
0.200
0.100
0.100
0.200
0.100
0.100
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TABLE 3.  RECOMMENDED ISOTOPES FOR SELECTED ELEMENTS
Mass                                           Element of interest


27                                                   Aluminum
121. 123                                             Antimony
75                                                   Arsenic
138, 137, 136, 135. 134                              Barium
9                                                    Beryl 1i urn
209                                                  Bismuth (IS)
114. 112, 111. 110, 113, 116, 106                    Cadmium
42, 43, 44, 46, 48                                   Calcium (I)
35, 37, (77, 82)a                                    Chlorine (I)
52, 53, 50, 54                                       Chromium
59                                                   Cobalt
63, 65                                               Copper
165                                                  Hoi mi urn (IS)
115. 113                                             Indium (IS)
56, 54, 57, 58                                       Iron (I)
139                                                  Lanthanum (I)
208, 207. 206. 204                                   Lead
6^7                                                Lithium (IS)
24, 25, 26                                           Magnesium (I)
55                                                   Manganese
98, 96, 92, 97, 94, (108)a                           Molybdenum (I)
58, 60, 62, 61, 64                                   Nickel
39                                                   Potassium (I)
103                                                  Rhodium (IS)
45                                                   Scandium (IS)
107. 109                                             Silver
23                                                   Sodium (I)
159                                                  Terbium (IS)
205. 203                                             Thallium
120, 118                                             Tin  (I)
89                                                   Yttrium (IS)
64, 66, 68, 67, 70                                   Zinc

       NOTE:  Method 6020 is recommended for only  those analytes listed in Table
1.   Other  elements  are  included  in  this table  because  they  are  potential
interferents (labeled  I) in the determination of recommended analytes, or because
they are commonly used internal  standards  (labeled  IS).   Isotopes  are listed in
descending order of natural abundance.  The most generally useful isotopes are
underlined and in  boldface,  although certain matrices may  require  the  use of
alternative isotopes.  a These masses are also useful for interference correction
(Section 3.2).    Internal  standard must be enriched in the  Li isotope.   This
minimizes interference from indigenous lithium.
                                    6020-15                        Revision  0
                                                                  November 1990

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TABLE 4.  SPIKING LEVELS FOR  ICP-MS ANALYSIS  (/zg/L)
             Element        Water      Soil
            Aluminum           500        *
            Antimony           100       100
            Arsenic            100       100
            Barium             200       200
            Beryl 1i urn           50        50
            Cadmium             50        50
            Chromium            50        50
            Cobalt             100       100
            Copper              50        50
            Lead                50        50
            Manganese           50        50
            Nickel             100       100
            Silver              50        50
            Thallium            50        50
            Vanadium           100       100
            Zinc               100       100
* No spike required.
                                    6020-16                        Revision  0
                                                                   November 1990

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TABLE  5.    ICP-MS  MULTI-LABORATORY  PRECISION  AND ACCURACY  DATA FOR  AQUEOUS
SOLUTIONS
Element
Comparability8
Range
%RSD
Range
Nb Sc
Aluminum           95 - 100              11  -  14         14-14         4
Antimony              d                 5.0  -  7.6        16-16         3
Arsenic            97 - 114             7.1  -  48         12-14         4
Barium             91 - 99              4.3  -  9.0        16-16         5
Beryllium         103 - 107             8.6  -  14         13-14         3
Cadmium            98 - 102             4.6  -  7.2        18-20         3
Calcium            99 - 107             5.7  -  23         17-18         5
Chromium           95 - 105              13  -  27         16-18         4
Cobalt            101 - 104             8.2  -  8.5        18-18         3
Copper             85 - 101             6.1-27         17-18         5
Iron               91 - 900              11  -  150        10-12         5
Lead               71 - 137              11  -  23         17-18         6
Magnesium          98 - 102              10  -  15         16-16         5
Manganese          95 - 101             8.8  -  15         18-18         4
Nickel             98 - 101             6.1  -  6.7        18-18         2
Potassium         101 - 114             9.9  -  19         11-12         5
Selenium          102 - 107              15  -  25         12-12         3
Silver            104 - 105             5.2  -  7.7        13-16         2
Sodium             82 - 104              24-43          9-10         5
Thallium           88 - 97              9.7  -  12         18-18         3
Vanadium          107 - 142              23-68          8-13         3
Zinc               93 - 102             6.8  -  17         16-18         5
8 Comparability refers to  the percent agreement of mean ICP-MS values to those
of  the reference  technique.      N  is  the  range of  the  number  of  ICP-MS
measurements where the analyte values exceed  the limit of quantitation  (3.3 times
the average IDL value).      c S is the number of samples  with results greater
than  the  limit of quantitation.     No comparability values  are  provided for
antimony  because of evidence  that  the reference  data   is  affected  by  an
interference.
                                    6020-17                        Revision  0
                                                                  November 1990

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TABLE 6.   ICP-MS MULT I-LABORATORY PRECISION AND ACCURACY DATA FOR SOLID MATRICES
Element
Comparability8
Range
%RSD
Range Nb
Sc
Aluminum           83 - 101              11  - 39         13-14         7
Antimony              d                  12-21         15-16         2
Arsenic            79 - 102              12  - 23         16-16         7
Barium            100 - 102             4.3  - 17         15-16         7
Beryllium          50 - 87               19  - 34         12 - 14         5
Cadmium            93 - 100             6.2  - 25         19-20         5
Calcium            95 - 109             4.1  - 27         15-17         7
Chromium           77 - 98               11  - 32         17-18         7
Cobalt             43 - 102              15  - 30         17-18         6
Copper             90 - 109             9.0  - 25         18-18         7
Iron               87 - 99              6.7  - 21         12-12         7
Lead               90 - 104             5.9  - 28         15-18         7
Magnesium          89 - 111             7.6  - 37         15-16         7
Manganese          80 - 108              11  - 40         16-18         7
Nickel             87 - 117             9.2  - 29         16-18         7
Potassium          97 - 137              11  - 62         10-12         5
Selenium             81                   39              12            1
Silver             43 - 112              12  - 33         15-15         3
Sodium            100 - 146              14-77          8-10         5
Thallium             91                   33              18            1
Vanadium           83 - 147              20-70          6-14         7
Zinc               84 - 124              14  - 42         18-18         7
a Comparability refers  to the percent agreement of mean ICP-MS  values to those
of  the reference  technique.      N  is  the range of  the  number of  ICP-MS
measurements where the analyte values exceed  the limit of quantitation (3.3 times
the average IDL value).      c S is the number  of samples  with  results greater
than  the  limit of quantitation.     No comparability values are  provided  for
antimony  because of evidence  that  the reference  data  is  affected  by  an
interference.
                                    6020-18                       Revision  0
                                                                  November 1990

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                              METHOD  6020
          INDUCTIVELY  COUPLED PLASMA MASS SPECTROMETRY
                       Start
                               J
7 . 1 Analyia
by Mothod
7000 or
Method 6010


7.1 U..
Method 3040
                     !• aanpla
                    oil«,graa*a«
                      waxa«?
                                                        tha invtruamnt
   I* H,0
 acidified,
pr«-filt«r«d?
 !•  •anpla
  vat«r?
    I.
   ••mpla
 •nalyiad by
 FLAA/ICP or
    CFAA?
                                   7.8 Monitor all
 !•  ••nplv
•quaoui or
  •olid?
instrument par
                                                        data quality a*
                                                                           raooamandation*
                   calibration and
                             6020-19
                                              Revision   0
                                              November 1990

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                                 METHOD 7062

         ANTIMONY  AND ARSENIC  (ATOMIC  ABSORPTION.  GASEOUS  BOROHYDRIDE1


1.0  SCOPE AND APPLICATION

      1.1  Method 7062 is an atomic  absorption procedure for determining 1 jig/L
to 400 ng/L concentrations of antimony and arsenic in wastes, mobility procedure
extracts, soils, and ground  water.   Method  7062  is approved for sample matrices
that contain up to 4000 mg/L  concentrations  of cobalt,  copper,  iron, mercury, and
nickel.  A solid  sample can contain  up  to 40% by weight  of the interferents
before exceeding 4000 mg/L in  a digested  sample.  All samples including aqueous
matrices must be subjected to an appropriate dissolution step  prior to analysis.
Spiked samples and relevant standard reference materials are used to determine
the applicability of the method to a given waste.


2.0  SUMMARY OF METHOD

      2.1  Samples are prepared according to the  nitric  acid digestion procedure
described   in   Method   3010   for   aqueous  and   extract   samples   and   the
nitric/peroxide/hydrochloric acid digestion procedure described in Method 3050
(furnace AA option) for  sediments,  soils, and  sludges.   Excess  peroxide  is
removed  by evaporating  samples to  near  dryness  at  the end of  the digestion
followed by degassing the samples upon addition of urea.  L-cystine is then added
as a masking agent.   Next, the antimony and arsenic in the digest are reduced to
the trivalent forms with potassium iodide.  The trivalent antimony and arsenic
are then converted to volatile hydrides using hydrogen produced from the reaction
of the  acidified  sample with  sodium  borohydride  in  a  continuous-flow hydride
generator.

      2.2   The volatile  hydrides are  swept into an  air-acetylene flame heated
quartz  absorption cell   located  in  the optical  path  of an  atomic  absorption
spectrophotometer.    The  resulting  absorption  of  the  lamp  radiation  is
proportional to the arsenic or antimony concentration.

      2.3  The typical detection limit for this method is 1.0 [ig/L.


3.0  INTERFERENCES

      3.1   Very  high (>4000  mg/L)  concentrations of cobalt,  copper,  iron,
mercury, and nickel can cause  analytical  interferences  through precipitation as
reduced metals and associated blockage of transfer lines and fittings.

      3.2  Traces of peroxides left following the sample work-up can result in
analytical  interferences.  Peroxides must be removed by evaporating each sample
to near dryness followed by  reaction with urea and allowing sufficient time for
degassing before analysis (see Sections 7.1 and 7.2).

                                    7062-1                        Revision 0
                                                                  November 1990

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4.0  APPARATUS AND MATERIALS

      4.1  Electric  hot  plate:   Large enough to hold at  least  several  100 mL
Pyrex digestion beakers.

      4.2   A  continuous-flow hydride  generator:    A commercially  available
continuous-flow  sodium  borohydride/HCl  hydride  generator  or  a  generator
constructed similarly to that shown in Figure 1 (P. S.  Analytical or equivalent).

            4.2.1  Peristaltic Pump:  A four-channel, variable-speed peristaltic
      pump to permit regulation of liquid-stream flow rates (Ismatec Reglo-100
      or equivalent).  Pump  speed and tubing diameters should  be  adjusted to
      provide  the  following  flow rates:    sample/blank  flow  = 4.2  mL/min;
      borohydride flow =2.1 mL/min;  and potassium iodide  flow = 0.5 mL/min.

            4.2.2  Sampling Valve (optional):    A sampling valve (found in the
      P. S.  Analytical  Hydride Generation System  or equivalent)  that  allows
      switching between samples and blanks (rinse solution) without introduction
      of air into the system will provide more signal stability.

            4.2.3  Transfer Tubing and Connectors: Transfer tubing (1 mm I.D.),
      mixing T's, and connectors  are  made  of teflon and are of compatible sizes
      to form  tight, leak-proof  connections  (Latchat,  Technicon,  etc.  flow
      injection apparatus accessories or equivalent).

            4.2.4  Mixing Coil:  A 20-turn coil  made by wrapping transfer tubing
      around a 1-cm diameter by 5-cm long plastic or  glass rod (see Figure 1).

            4.2.5  Mixing Coil Heater:  A 250-mL Erlenmeyer flask containing 100
      mL of water heated  to boiling on  a dedicated one-beaker hotplate (Corning
      PC-35 or equivalent). The mixing coil in 4.2.4  is immersed in the boiling
      water to  speed kinetics of the  hydride forming reactions and  increase
      solubility of interfering reduced metal  precipitates.

            4.2.6   Gas-Liquid Separator:   A  glass  apparatus  for  collecting
      liquid and  gaseous  products (P.T.  Analytical  accessory  or  equivalent)
      which allows the liquid fraction  to  drain  to waste  and  gaseous  products
      above the liquid to be swept by a regulated carrier gas (argon) out of the
      cell  for analysis.    To avoid undue  carrier gas  dilution,  the  gas  volume
      above the liquid should  not  exceed 20 mL.  See Figure 1 for an acceptable
      separator shape.

            4.2.7  Condenser:  Moisture picked up by the carrier gas must be
      removed before encountering the  hot  absorbance  cell.  The moist carrier
      gas with the  hydrides is dried by passing the gasses through a small (< 25
      mL) volume condenser  coil  (Ace  Glass  Model 6020-02 or equivalent) that is
      cooled to 5°C by a water chiller (Neslab RTE-110  or equivalent).  Cool tap-
      water in place of a chiller is  acceptable.


                                    7062-2                        Revision 0
                                                                  November 1990

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            4.2.8  Flow Meter:  A meter capable of regulating up to 1 L/min of
      argon carrier gas is recommended.

      4.3  Absorbance Cell:  A 17 cm or longer quartz tube T-cell (windowless is
strongly suggested)  is recommended,  as  shown in  Figure 1  (Varian  Model VGA-76
accessory or equivalent).   The cell  is held  in place by a holder that positions
the cell  about 1  cm over a  conventional  AA air-acetylene  burner head.   In
operation, the cell is heated to around 900°C by  an air-acetylene  flame.

      4.4  Atomic  absorption spectrophotometer:  Single or dual channel, single-
or  double-beam instrument  having  a  grating monochromator,  photomultiplier
detector, adjustable slits,  a wavelength range of 190  to 800 nm, and provisions
for interfacing with a strip-chart recorder.

      4.5  Burner: As recommended by the particular instrument manufacturer for
an air-acetylene flame.  An  appropriate mounting  bracket attached to the burner
that suspends the  quartz absorbance cell between 1  and 2 cm above the burner slot
is required.

      4.6   Antimony  and  arsenic hollow cathode  lamps  or antimony  and arsenic
electrodeless discharge lamps and power supply.   Super-charged hollow-cathode
lamps or EDL lamps are recommended for maximum sensitivity.

      4.7    Strip-chart  recorder   (optional):         Connect  to  output  of
spectrophotometer.


5.0  REAGENTS

      5.1   Reagent water:   Water must be monitored for impurities.   Refer to
Chapter 1 for definition of Reagent water.

      5.2  Concentrated nitric acid  (HN03):   Acid must be analyzed to determine
levels of impurities.  If a method blank is 
-------
                                 QUARTZ  CELL


                                 A A  OURNER
    '»0 ISCOHHECTEff
    UIIRINO S*/Sn
      ftHALVStS
                         20 TURN COIL
                           (TEFLON)
                           HOTPLATE
                            VALUE
                           (•LANK)
Figure 1.  Continuous-flow sodium borohydride/hydride  generator apparatus set-
up and an AAS sample introduction system.
                                    7062-4
Revision 0
November 1990

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      5.5  Diluent  solution:  A 3% HC1 solution in reagent water must be prepared
as a diluent solution if excessive levels of analytes or  interfering metals are
found in the undiluted samples.

      5.6  Urea (H2NCONH2):  A 5.00-g portion of reagent grade urea must be added
to  a  25-mL  aliquot  of  each sample for  removal  of  excess  peroxide  through
degassing (see Section 7.2).

      5.7  L-cystine (C6H12N204S2):  A 1.00-g portion of reagent grade L-cystine
must be  added  to a  25-mL aliquot of each  sample  for masking the  effects of
suppressing transition metals (see Section 7.2).

      5.8  20% Potassium iodide (KI):  A 20% KI  solution  (20 g reagent-grade KI
dissolved and  brought to  volume  in  100 ml  reagent  water) must be prepared for
reduction of antimony and arsenic to their +3 valence states.

      5.9  4% Sodium borohydride (NaBHJ:  A 4%  sodium borohydride solution (20
g reagent-grade NaBH4 plus 2 g sodium hydroxide dissolved in 500 ml of reagent
water)  must  be prepared  for  conversion of  the antimony and  arsenic  to their
hydrides.

      5.10 Analyte solutions:

            5.10.1  Antimony and arsenic stock standard solution (1,000 mg/L):
      Either  procure  certified  aqueous  standards  from   a  supplier  (Spex,
      Inorganic Ventures, or equivalent) and verify by comparison with a second
      standard, or dissolve  1.197  g  of  antimony trioxide Sbp03  and  1.320  g of
      arsenic  trioxide  As203  in  100 ml  of reagent water containing 4  g NaOH.
      Acidify the solution with 20 ml concentrated HN03 and dilute  to  1  liter.

            5.10.2   Intermediate antimony and  arsenic  solution:   Pipet  1 ml
      stock antimony  and  arsenic solution into a  100-mL volumetric  flask and
      bring  to  volume  with  reagent  water  containing  1.5  mL  concentrated
      HN03/liter (1 ml = 10 ^g each of  Sb  and  As).

            5.10.3   Standard  antimony and  arsenic  solution:    Pipet  10 ml
      intermediate antimony and arsenic solution into a  100-mL volumetric flask
      and  bring  to volume with  reagent water containing  1.5 ml  concentrated
      HN03/liter (1 ml = 1 jig each of Sb and As).


6.0  SAMPLE COLLECTION,  PRESERVATION, AND  HANDLING

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

      6.2  All  sample containers must be prewashed with detergents,  acids, and
reagent water.   Plastic and glass containers are both suitable.


                                    7062-5                        Revision 0
                                                                  November  1990

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      6.3   Special  containers  (e.g.,  containers  used  for volatile  organic
analysis) may have to be used if very volatile antimony and arsenic compounds are
suspected to be present in the samples.

      6.4  Aqueous samples must be acidified to a pH of <2 with nitric acid.

      6.5  Nonaqueous samples shall be refrigerated, when possible, and analyzed
as soon as possible.


7.0  PROCEDURE

      7.1  Place a 100-mL portion  of  an aqueous sample or extract or 1.000 g of
a dried solid sample in a 250-mL digestion beaker.   Digest aqueous samples and
extracts according to Method 3010.   Digest solid samples according to Method 3050
(furnace AA option) with the following modifications:  add 5 ml of concentrated
hydrochloric  acid  just prior to  the final volume reduction  stage to  aid  in
antimony recovery;  the  final volume reduction should be to less than 5 ml but not
to dryness  to adequately remove  excess hydrogen peroxide (see note).   After
dilution to volume, further dilution with  diluent may be necessary if analytes
are known to exceed 400 ng/L or if interferents are expected to exceed 5000 mg/L
in the digest.

Note:  For  solid digestions, the  volume reduction stage  is  critical  to obtain
accurate data,  especially for arsenic.   Close  monitoring  of each  sample  is
necessary when this critical stage is reached.

      7.2  Prepare samples for hydride analysis by adding  5.00 g  urea, 1.00 g L-
cystine, and 20 ml concentrated HC1 to a 25-mL aliquot of digested sample in a
50-mL volumetric flask.  Heat in a water bath  until the L-cystine has dissolved
and  effervescence  has  subsided   (At  least  30  minutes  is  suggested.    If
effervescense is still  seen, repeat step 7.1 with more volume reduction.).  Bring
flask to volume with reagent water before analyzing.  A 1:1 dilution correction
must be made in the final concentration calculations.

      7.3   Prepare working standards  from the  standard antimony  and  arsenic
solution.   Transfer 0, 0.5, 1.0,   1.5,  2.0,  and  2.5 ml of standard  to 100-mL
volumetric flasks and bring to volume with diluent.   These concentrations will
be 0, 5, 10, 15, 20, and 25 jig Sb and As/liter.

      7.4   If EP extracts  (Method  1310)  are being  analyzed for  arsenic,  the
method  of  standard  additions  must  be used.    Spike  appropriate amounts  of
intermediate or standard antimony and arsenic solution to three 25 mL aliquots
of each  unknown.   Spiking volumes should  be  kept less than 0.250 ml to avoid
excessive spiking dilution errors.

      7.5   Set up  instrumentation  and hydride  generation apparatus  and fill
reagent containers.  The sample and blank flows should be set around 4.2 mL/min,
the borohydride flow around  2.1 mL/min, and the potassium iodide  flow around 0.5
mL/min.  The argon  carrier gas flow is adjusted to about 200 mL/min. For the AA,

                                    7062-6                        Revision 0
                                                                  November 1990

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use the 217.6-nm wavelength and 0.7-nm  slit width without background correction
if analyzing for antimony.   Use the  193.7-nm wavelength and 0.7-nm slit width
without background correction for the analysis of arsenic.   Begin all flows and
allow 10 minutes for warm-up.

      7.6  Place sample  feed  line into a prepared sample  solution and start pump
to begin  hydride  generation.   Wait  for  a maximum steady-state signal  on the
strip-chart recorder  or output meter.    Switch to  blank sample and  watch for
signal to decline to baseline before  switching to the next sample and beginning
the next analysis.  Run standards first  (low to high),  then unknowns.  Include
appropriate QA/QC solutions,  as required.  Prepare calibration curves and convert
absorbances to concentration.  See following analytical  flowchart.

        CAUTION:  The  hydrides  of  antimony  and  arsenic  are  very  toxic.
                  Precautions must be taken to avoid inhaling the gas.

      7.7  If the method of  standard additions was employed, plot the measured
concentration  of the  spiked samples  and  unspiked  sample  versus the  spiked
concentrations.  The spiked  concentration axis intercept will be the method of
standard additions  concentration.   If  the plot does not result  in a straight
line,  a  nonlinear  interference is  present.   This  problem can sometimes  be
overcome by dilution or addition of  other  reagents  if there is some knowledge
about the waste.  If the method of standard additions  was not required, then the
concentration is determined  from a standard calibration  curve.
8.0  QUALITY CONTROL

      8.1  See section 8.0 of Method 7000A.


9.0  METHOD PERFORMANCE

      9.1  The relative standard deviations obtained by a single laboratory for
7 replicates of a contaminated soil were 18% for antimony at 9.1  ug/L in solution
and 4.6% for arsenic at 68 ug/L in solution.


10.0  REFERENCES

1.    Methods  for  Chemical  Analysis  of Water  and Wastes,  EPA-600/4-82-055,
      December 1982, Method 206.3.

2.    "Evaluation of Hydride Atomic Absorption  Methods  for Antimony, Arsenic,
      Selenium, and Tin",  an  EMSL-LV internal report under Contract 68-03-3249,
      Job Order  70.16,  prepared for T.  A. Hinners by D.  E.  Dobb,  and  J.  D.
      Lindner of Lockheed Engineering and Sciences Co.,  and L.  V.  Beach of the
      Varian Corporation.
                                    7062-7                        Revision 0
                                                                  November 1990

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                                METHOD  7062
ANTIMONY AND ARSENIC  (ATOMIC ABSORPTION, GASEOUS BOROHYDRIDE)
     7.1 U». M.thod
      3050 (furnace
      AA option)  to
      dig..t 1.0  9
        (ample
         7.1-7.4
       Digeat with
         H.O. .>
      deaoribed in
       Method 3050
7.5 Add
concentrated
HC1


7.6 Do final
volume
reduction and
dilution, aa
described


                    No
       7.1 Further
       dilute with
         diluent
                           7.1  Uae
                         Method 3010
                        to digeat 100
                          •1  «ample
  7.2 Add to
 aliquot urea,
L-cyatine, HC1;
heet H.O bath;
bring to volume
                              7.3 Prepare
                            itandarda from
                            itandard atook
                            •olutiona of Sb
                                and Aa
                                                      7.4 U.. the
                                                      method of
                                                      atandard
                                                     additiona on
                                                    •xtracti,  only
                             7062-8
                                      Revision 0
                                      November 1990

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                                  METHOD 7742

               SELENIUM (ATOMIC ABSORPTION.  GASEOUS  BOROHYDRIDE)
1.0  SCOPE AND APPLICATION

      1.1  Method 7742 is an atomic absorption procedure for determining 3 |ig/L
to 750 ng/L concentrations of selenium in wastes, mobility procedure extracts,
soils, and  ground water.   Method 7742  is  approved for  sample  matrices  that
contain up  to  1000 mg/L concentrations of cobalt,  copper,  iron,  mercury, and
nickel. A solid sample can contain up to 10% by weight of the interferents before
exceeding 1000 mg/L in a digested sample.  All samples including aqueous matrices
must be subjected to an  appropriate dissolution  step prior to analysis.  Spiked
samples and relevant standard reference materials are employed to determine the
applicability of the method to a given waste.


2.0  SUMMARY OF METHOD

      2.1  Samples are prepared according to the  nitric  acid digestion procedure
described   in   Method  3010   for  aqueous  and  extract  samples   and   the
nitric/peroxide/hydrochloric acid digestion procedure described in Method 3050
(furnace  AA option) for  sediments,  soils,  and  sludges.   Excess  peroxide  is
removed by  evaporating  samples  to near-dryness  at  the  end of  the digestion
followed by dilution to  volume and degassing the  samples upon addition of urea.
The selenium is  converted  to the +4 oxidation  state during digestion in  HC1.
After a 1:10 dilution,  selenium is then converted to its volatile hydride using
hydrogen  produced  from the  reaction of  the  acidified  sample  with  sodium
borohydride in a continuous-flow hydride generator.

      2.2   The volatile hydride  is  swept  into   an  air-acetylene  flame heated
quartz absorption  cell  located  in the optical   path of  an atomic  absorption
spectrophotometer.    The  resulting  absorption  of  the  lamp  radiation  is
proportional to the selenium concentration.

      2.3  The typical detection limit for this  method is 3 ng/L.


3.0  INTERFERENCES

      3.1   Very  high   (>1000  mg/L)  concentrations  of cobalt,  copper,  iron,
mercury,  and, nickel can cause analytical  interferences  through precipitation as
reduced metals and associated blockage of transfer lines and fittings.

      3.2  Traces of peroxides left following the sample work-up can result in
analytical interferences.  Peroxides must be removed by evaporating each sample
to  near-dryness  followed  by  reacting each  sample  with urea  and  allowing
sufficient time for degassing before analysis (see Sections 7.1  and 7.2).
                                    7742-1                        Revision 0
                                                                  November 1990

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4.0  APPARATUS AND MATERIALS

      4.1  Electric  hot  plate:   Large enough to hold at  least  several  100 mL
Pyrex digestion beakers.

      4.2   A  continuous-flow hydride  generator:    A commercially  available
continuous-flow  sodium  borohydride/HCl  hydride  generator  or  a  generator
constructed similarly to that shown in Figure 1 (P. S.  Analytical or equivalent).

            4.2.1  Peristaltic Pump:  A four-channel, variable-speed peristaltic
      pump to permit regulation of liquid-stream flow rates (Ismatec Reglo-100
      or equivalent).  Pump  speed and tubing diameters should  be  adjusted to
      provide  the  following  flow rates:    sample/blank  flow  = 4.2  mL/min;
      borohydride flow = 2.1 mL/min.

            4.2.2  Sampling Valve (optional):    A sampling valve (found in the
      P. S.  Analytical  Hydride Generation System  or equivalent) that  allows
      switching between samples and blanks (rinse solution) without introduction
      of air into the system will provide more signal stability.

            4.2.3  Transfer Tubing and Connectors: Transfer tubing (1 mm I.D.),
      mixing T's, and connectors  are  made of teflon and are of compatible sizes
      to form  tight, leak-proof  connections (Latchat,  Technicon,  etc.  flow
      injection apparatus accessories or equivalent).

            4.2.4  Mixing Coil:  A 20-turn coil made by wrapping transfer tubing
      around a 1-cm diameter by 5-cm long plastic or glass rod (see Figure 1).

            4.2.5  Mixing Coil Heater: A 250-mL  Erlenmeyer flask containing 100
      mL of water heated  to boiling on a dedicated one-beaker hotplate (Corning
      PC-35 or equivalent). The mixing coil  in 4.2.4  is immersed in the boiling
      water to  speed kinetics of the hydride forming reactions and  increase
      solubility of interfering reduced  metal  precipitates.

            4.2.6   Gas-Liquid Separator:   A glass  apparatus  for  collecting
      liquid and gaseous products  (P.  S.  Analytical accessory  or  equivalent)
      which allows the liquid fraction to drain  to waste  and  gaseous  products
      above the liquid to be swept by a regulated carrier gas (argon) out of the
      cell  for analysis.    To avoid undue carrier gas dilution,  the  gas  volume
      above the liquid should not  exceed 20 mL.  See Figure 1 for an acceptable
      separator shape.

            4.2.7  Condenser:  Moisture  picked  up by the carrier gas must be
      removed before encountering the hot absorbance cell.  The moist  carrier
      gas with the  hydrides is dried by passing the gasses through a small (< 25
      mL) volume condenser  coil  (Ace  Glass Model 6020-02 or equivalent)  that is
      cooled to 5°C by a water chiller (Neslab RTE-110 or equivalent).  Cool tap-
      water in place of a chiller is  acceptable.

            4.2.8  Flow Meter:   A meter  capable  of regulating  up to  1  L/min of
      argon carrier gas  is  recommended.

                                    7742-2                        Revision 0
                                                                  November 1990

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      4.3  Absorbance Cell:  A 17-cm or longer quartz tube T-cell (windowless is
strongly suggested)  is recommended, as  shown  in  Figure  1  (Varian  Model  VGA-76
accessory or equivalent).   The  cell  is  held  in place by a holder that positions
the cell  about 1  cm over a conventional  AA air-acetylene  burner head.   In
operation, the cell  is heated to around 900°C by  an air-acetylene  flame.

      4.4   Atomic absorption  spectrophotometer:   Single-  or  dual-  channel,
single- or double-beam instrument having a grating  monochromator, photomultiplier
detector, adjustable slits, a wavelength range of 190 to 800 nm, and provisions
for interfacing with a strip-chart recorder.

      4.5  Burner:  As recommended by the particular instrument manufacturer for
an air-acetylene flame.  An appropriate mounting  bracket attached to the burner
that suspends the quartz absorbance cell between 1 and 2 cm above  the burner slot
is required.

      4.6  Selenium hollow cathode lamp or selenium electrodeless discharge lamp
and  power  supply.   Super-charged  hollow-cathode  lamps or   EDL  lamps  are
recommended for maximum sensitivity.

      4.7     Strip-chart   recorder   (optional):       Connect   to   output  of
spectrophotometer.


5.0  REAGENTS

      5.1  Reagent water  :   Water must be monitored  for impurities.   Refer to
Chapter 1 for definition of Reagent water.

      5.2  Concentrated nitric  acid  (HN03):  Acid must be analyzed to determine
levels of impurities.  If a method blank is 
-------
                                 QUARTZ CELL


                                 A A  OURNCR
                                                                      TO
                                                                    CHILLER
   •OISCONNECTE
   UIIRINO S*XSn
     ANALYSIS
                        20 TURN COIL
                          (TEFLON)
                                                                __—Ą DRAIN
                          VALVC
                         (BLANK)
Figure 1.  Continuous-flow sodium  borohydride/hydride generator apparatus
setup and an AAS sample  introduction  system
                                     7742-4
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November 1990

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      5.7  4% Sodium Borohydride  (NaBHJ:  A 4 % sodium borohydride solution (20
g reagent-grade NaBH4 plus 2 g sodium hydroxide dissolved in 500 mL of reagent
water) must be prepared for conversion of the selenium to its hydride.

      5.8  Selenium solutions:

            5.8.1   Selenium  standard stock  solution  (1,000  mg/L):   Either
      procure  certified  aqueous  standards  from  a  supplier  (Spex,  Inorganic
      Ventures, or equivalent) and verify by comparison with a second standard,
      or dissolve 0.3453 g  of  selenious  acid (assay 96.6% of H2Se03) in 200 ml
      of reagent water (1 mL = 1 mg Se).

            5.8.2   Selenium  working  stock solution:   Pipet  1 ml  selenium
      standard stock solution  into  all volumetric  flask and bring to volume
      with  reagent  water   containing  1.5  ml   concentrated  HNOj/liter.    The
      concentration of this solution is  1 mg Se/L (1 ml = 1 \ig Se).


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

      6.2  All sample containers must be prewashed with detergents, acids, and
reagent water.  Plastic and glass containers are both suitable.

      6.3   Special  containers  (e.g.,  containers used  for volatile  organic
analysis) may have to be used  if very  volatile  selenium compounds are suspected
to be present  in the samples.

      6.4  Aqueous  samples must be acidified to a pH of <2 with nitric acid.

      6.5  Nonaqueous samples  shall be refrigerated, when possible, and analyzed
as soon as possible.


7.0  PROCEDURE

      7.1  Place a 100-mL portion of an aqueous sample or extract or 1.000 g of
a dried solid  sample in a 250-mL digestion  beaker.  Digest aqueous samples and
extracts according to Method 3010.  Digest solid  samples according to Method 3050
(furnace AA option) with the following modifications:  add 5 mL of concentrated
hydrochloric  acid  just prior  to  the final  volume  reduction  stage  to  aid in
conversion of selenium to  its  plus four state; the final  volume reduction should
be to less  than  5 mL but not  to  dryness to adequately  remove excess hydrogen
peroxide (see note). After dilution to volume, further dilution with diluent may
be necessary  if the analyte is known to  exceed  750 \ig/l or if interferents are
expected to exceed  1000 mg/L  in the digestate.
                                    7742-5                        Revision 0
                                                                  November 1990

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Note:For solid digestions, the volume reduction stage is critical to obtain
     accurate data.  Close monitoring of each sample is necessary when this
     critical stage in the digestion is reached.

      7.2  Prepare samples for hydride analysis by adding 1.00 g  urea, and 20 ml
concentrated HC1 to a 5.00 ml aliquot of digested sample in a 50-mL volumetric
flask.  Heat in a water bath  to dissolve salts and reduce selenium (at least 30
minutes  is  suggested).    Bring  flask  to  volume  with  reagent water  before
analyzing.    A  ten-fold  dilution  correction  must  be  made   in  the  final
concentration calculations.

      7.3  Prepare working standards  from  the standard stock selenium solution.
Transfer 0,  0.5,  1.0,  1.5, 2.0, and  2.5  ml of standard to  100-mL  volumetric
flasks and bring to volume with diluent.  These concentrations will be 0, 5, 10,
15, 20, and 25 jig Se/L.

      7.4   If  EP extracts (Method  1310) are being  analyzed  for selenium,  the
method of standard additions must be used.   Spike appropriate  amounts of working
standard selenium  solution to three  25 ml aliquots of  each  unknown.   Spiking
volumes should be  kept less than 0.250  ml to  avoid  excessive spiking dilution
errors.

      7.5   Set up  instrumentation and  hydride generation apparatus  and  fill
reagent containers. The  sample and blank flows should  be set  around 4.2 mL/min,
and the  borohydride flow around 2.1  mL/min.    The  argon  carrier gas  flow is
adjusted to about 200 mL/min.   For the AA, use the 196.0-nm wavelength and 2.0-nm
slit width without background correction.   Begin all flows and allow 10 minutes
for warm-up.

      7.6  Place sample feed line into a prepared sample  solution  and start pump
to begin  hydride generation.   Wait  for  a maximum steady-state  signal  on  the
strip-chart recorder.   Switch to blank sample and watch for signal to decline to
baseline before  switching to the next  sample  and  beginning  the  next analysis.
Run standards  first  (low to  high), then unknowns.  Include  appropriate QA/QC
solutions, as required.  Prepare calibration curves  and convert  absorbances to
concentration.   See following analytical flowchart.

        CAUTION:  The hydride of selenium  1s very toxic.   Precautions  must be
                  taken to avoid Inhaling the gas.

      7.7  If the method of standard  additions was employed,  plot the measured
concentration  of the  spiked  samples  and  unspiked  sample  versus  the  spiked
concentrations.  The spiked concentration axis intercept will be the method of
standard additions  concentration.  If the plot does not result  in  a straight
line,   a  nonlinear  interference  is present.   This problem  can  sometimes  be
overcome by dilution or  addition of other  reagents  if there  is  some knowledge
about the waste.   If the method of standard additions was not required, then the
concentration is determined from a standard calibration curve.
                                    7742-6                        Revision 0
                                                                  November 1990

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8.0  QUALITY CONTROL

      8.1  Refer to Section 8.0 of Method 7000A.


9.0  METHOD PERFORMANCE

      9.1  The relative standard deviation obtained by a single laboratory for
7 replicates of a contaminated soil was 18% for selenium at 8.2 ug/L  in solution.


10.0  REFERENCES

1.    Methods  for  Chemical  Analysis  of  Water  and Wastes,  EPA-600/4-82-055,
      December 1982, Method 206.3.

2.    "Evaluation of Hydride Atomic Absorption  Methods  for Antimony, Arsenic,
      Selenium, and Tin",  an EMSL-LV internal report under Contract 68-03-3249,
      Job Order  70.16,  prepared for  T.  A.  Hinners by  D.  E. Dobb,  and  J.  D.
      Lindner of Lockheed Engineering and Sciences Co.,  and L. V. Beach of the
      Varian Corporation.
                                    7742-7                        Revision 0
                                                                  November 1990

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                    METHOD 7742
SELENIUM (ATOMIC ABSORPTION, GASEOUS BOROHYDRIDE)
                   7742-8
Revision 0
November 1990

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                                 METHOD 3510B

                  SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
1.0  SCOPE AND APPLICATION

      1.1  This method describes a procedure for isolating organic compounds from
aqueous samples.   The method also describes concentration techniques suitable
for preparing the  extract  for the appropriate determinative methods described
in 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.


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.  The extract  is dried, concentrated, and, as necessary, exchanged into
a solvent compatible  with the cleanup or determinative method  to be used (see
Table 1 for appropriate exchange solvents).


3.0  INTERFERENCES

      3.1  Refer to Method 3500.

      3.2  Under basic extraction conditions required to separate analytes for
the packed columns of Method 8250, the decomposition of some analytes has been
demonstrated.  Organochlorine pesticides may dechlorinate, phthalate esters may
exchange, and phenols may react to form tannates.   These reactions increase with
increasing pH,  and are decreased by  the shorter reaction times  available  in
Method 3510.   Methods 3520/8270, 3510/8270,  and  3510/8250,  respectively,  are
preferred over Method 3520/8250 for  the analysis  of these classes of compounds.


4.0  APPARATUS AND MATERIALS

      4.1  Separatory funnel  - 2 liter, with Teflon stopcock.

      4.2  Drying  column  -  20 mm  ID  Pyrex chromatographic column  with  Pyrex
glass wool at bottom and a Teflon stopcock.

NOTE; Fritted  glass   discs   are  difficult  to   decontaminate  after   highly
      contaminated extracts  have  been  passed through.   Columns without frits may
      be purchased. Use a small pad  of Pyrex glass wool to retain the adsorbent.
      Prewash the  glass wool  pad with 50  ml  of  acetone followed by 50  mL  of
      elution solvent prior to packing the column with adsorbent.

      4.3  Kuderna-Danish (K-D) apparatus (Kontes K-570025-0500).


                                  3510B  -  1                       Revision 2
                                                                  November 1990

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            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).

      4.4  Boiling chips - Solvent extracted,  approximately 10/40 mesh (silicon
carbide or equivalent).

      4.5  Water  bath  - Heated,  with concentric  ring  cover,  capable  of
temperature control (±5°C).   The bath  should be used  in a  hood.

      4.6  Vials - 2 ml, glass with Teflon lined screw-caps or crimp tops.

      4.7  pH indicator paper - pH range including the  desired extraction pH.

      4.8  Erlenmeyer flask - 250 ml.

      4.9  Syringe - 5 ml.

      4.10  Graduated cylinder -  1 liter.


5.0  REAGENTS

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

      5.2  Organic-free reagent water - All references  to water in this method
refer to.organic-free reagent water, as defined in Chapter One.

      5.3  Sodium hydroxide  solution (ION), NaOH.  Dissolve 40 g NaOH in organic-
free reagent water and dilute to  100 ml.

      5.4  Sodium sulfate (granular,  anhydrous), Na2S04.   Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning  the sodium sulfate with
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.

                                   3510B -  2                       Revision 2
                                                                  November 1990

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      5.5  Sulfuric acid solution  (1:1  v/v),  H2S04.  Slowly add  50  ml  of H2S04
(sp. gr. 1.84) to 50 mL of organic-free reagent water.

      5.6  Extraction/exchange solvents

            5.6.1 Methylene chloride, CH2C12 - Pesticide quality or equivalent.

            5.6.2 Hexane, C6H14 - Pesticide quality or equivalent.

            5.6.3 2-Propanol, CH3CH(OH)CH3 - Pesticide quality or equivalent.

            5.6.4 Cyclohexane, C6H12 - Pesticide quality or equivalent.

            5.6.5 Acetonitrile, CH3CN -  Pesticide quality or equivalent.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See the  introductory material to  this chapter,  Organic Analytes,
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.    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).  For the  sample in each analytical  batch  selected
for spiking, add  1.0 mL of the matrix spiking standard.   For base/neutral-acid
analysis, the amount added of  the surrogates and matrix spiking compounds  should
result  in  a final concentration of 100  ng//iL  of each base/neutral  analyte and
200 ng//uL  of  each acid  analyte in  the  extract  to be  analyzed (assuming a 1 ^L
injection).   If  Method  3640,  Gel-Permeation Cleanup,  is to be used, add twice
the volume of surrogates and matrix spiking compounds  since half  the extract is
lost due to loading of the GPC column.

      7.2  Check the pH of the sample with wide-range pH paper and, if necessary,
adjust the pH to  that  indicated  in Table 1 for  the specific determinative  method
that will  be used to analyze  the extract.

      7.3  Add 60 mL of methylene chloride to the separatory funnel.

      7.4  Seal and shake the separatory funnel vigorously for 1-2 minutes with
periodic venting  to release excess  pressure.

NOTE: Methylene  chloride  creates  excessive pressure  very rapidly;  therefore,
      initial venting  should be done immediately after the separatory funnel has
      been sealed and shaken  once.   Venting of the separatory funnel should be
      into a hood to avoid needless  exposure of the analyst to solvent vapors.
                                   3510B -  3
Revision 2
November 1990

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      7.5  Allow the organic layer to separate from the water phase for a minimum
of 10 minutes.  If the emulsion  interface  between layers is more than one-third
the size of the solvent layer, the analyst must employ mechanical techniques to
complete the  phase  separation.   The  optimum  technique  depends upon the sample
and  may include  stirring, filtration  of the  emulsion  through  glass  wool,
centrifugation, or  other physical methods.   Collect  the  solvent extract in an
Erlenmeyer flask.   If  the  emulsion cannot be broken  (recovery of < 80% of the
methylene chloride, corrected for the water solubility of methylene chloride),
transfer the  sample,  solvent,  and emulsion  into  the extraction  chamber  of a
continuous extractor and proceed  as described  in Method 3520, Continuous Liquid-
Liquid Extraction.

      7.6  Repeat the extraction two  more  times using fresh portions of solvent
(Sections 7.3 through 7.5).  Combine the three solvent extracts.
                    •
      7.7  If further  pH adjustment  and extraction  is  required, adjust the pH
of the aqueous phase to the desired pH indicated in Table 1.  Serially extract
three times  with 60  mL of methylene  chloride,  as  outlined in  Sections 7.3
through 7.5.  Collect  and  combine the  extracts and  label  the combined extract
appropriately.

      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  or base compounds  at  low concentrations must be determined,
separate extract analyses may be warranted).

      7.9  Perform  the  concentration using the Kuderna-Danish (K-D) Technique
(Sections 7.10.1 through 7.10.4).

      7.10 K-D Technique

            7.10.1  Assemble a Kuderna-Danish (K-D)  concentrator by attaching
      a 10 mL concentrator tube  to a  500 mL evaporation flask.  Dry the extract
      by passing it through a drying  column containing about 10 cm of anhydrous
      sodium sulfate.  Collect the dried extract in a K-D concentrator.  Rinse
      the Erlenmeyer flask, which contained the solvent extract, with 20-30 mL
      of methylene chloride and add it to the column to complete the quantitative
      transfer.

            7.10.2  Add one or two clean boiling chips to the flask and attach
      a three ball  Snyder  column.  Prewet the Snyder column by adding about 1
      mL of methylene chloride to the top of the column.  Place  the K-D apparatus
      on a hot water  bath  (15-20°C above  the boiling  point of the solvent) so
      that the concentrator tube is partially immersed  in  the  hot water and the
      entire lower rounded  surface of the  flask is bathed with hot vapor.  Adjust
      the  vertical  position of  the apparatus  and  the  water  temperature as
      required to complete the concentration  in 10-20  minutes.   At the proper
      rate of distillation the balls of the  column  will  actively chatter, but
      the chambers will not flood.   When the  apparent volume of liquid reaches
      1 mL, remove the K-D apparatus from the water bath and allow it to drain
      and cool for at least 10 minutes.
                                   3510B -  4                       Revision 2
                                                                  November 1990

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            7.10.3  If a solvent exchange is required (as indicated in Table 1),
      momentarily remove the Snyder column, add 50 mL of the exchange solvent,
      a new  boiling chip,  and  reattach the  Snyder column.   Concentrate  the
      extract, as described  in Section 7.11, raising the temperature of the water
      bath, if necessary, to maintain proper distillation.

            7.10.4  Remove the Snyder column and rinse the flask and its lower
      joints  into the  concentrator  tube with 1-2 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  Section  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
                                                             e

                  7.11.1.1  If further  concentration is indicated  in  Table 1,
            add another clean boiling chip to the concentrator tube and attach
            a two ball  micro-Snyder column.   Prewet  the  column by adding 0.5 ml
            of methylene chloride or exchange solvent to the top of the column.
            Place the K-D apparatus  in a hot water bath  so that the concentrator
            tube  is partially immersed  in the  hot  water.  Adjust the vertical
            position of  the apparatus and the  water temperature,  as required,
            to complete the concentration in 5-10 minutes.  At the proper rate
            of distillation the balls of the column will actively chatter,  but
            the chambers will not flood.   When the  apparent volume of liquid
            reaches 0.5  ml, remove  the  K-D apparatus from  the water  bath  and
            allow it  to drain and cool for  at least 10  minutes.   Remove  the
            Snyder  column  and rinse the flask  and its  lower joints  into  the
            concentrator tube with  0.2  ml  of extraction  solvent.   Adjust  the
            final volume to 1.0-2.0 ml,  as indicated in Table 1,  with solvent.

            7.11.2  Nitrogen Blowdown Technique

                  7.11.2.1  Place the concentrator tube in a warm bath (35°C) and
            evaporate  the  solvent volume to 0.5  mL using a gentle  stream of
            clean, dry nitrogen (filtered through a column of activated carbon).

CAUTION:   New plastic tubing must not be used between the carbon trap and the
           sample, since it may introduce interferences.

                  7.11.2.2  The internal wall of the tube must  be  rinsed down
            several  times with methylene chloride or appropriate solvent during
            the operation.  During evaporation, the tube solvent level  must be
            positioned to avoid water condensation.   Under normal  procedures,
            the extract must not be allowed to become dry.

CAUTION:   When  the volume of  solvent  is  reduced  below 1 ml,  semi volatile
           analytes may be lost.
                                   3510B  -  5
Revision 2
November 1990

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      7.12  The extract may now  be  analyzed  for the target analytes using the
appropriate determinative technique(s)  (see  Section 4.3  of this Chapter).  If
analysis  of  the   extract  will  not  be  performed  immediately,  stopper  the
concentrator tube and store refrigerated.   If the extract will be stored longer
than 2 days it should be transferred to  a  vial with  a Teflon lined screw-cap or
crimp top, and labeled appropriately.


8.0  QUALITY CONTROL

      8.1  Refer to  Chapter One for  specific  quality control  procedures and
Method 3500 for extraction and sample preparation procedures.


9.0  METHOD PERFORMANCE

      9.1  Refer to the determinative methods for performance data.


10.0  REFERENCES

1.   U.S. EPA 40 CFR Part 136,  "Guidelines Establishing Test Procedures for the
     Analysis of Pollutants Under the Clean  Water  Act;  Final  Rule and Interim
     Final Rule and Proposed Rule," October 26,  1984.
                                   3510B -  6                      Revision 2
                                                                  November  1990

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                                                          TABLE 1.
                              SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8140
8141
8250bc
8270bd
8310
8321
8410
Initial
extraction
PH
<2
as received
as received
as received
5-9
5-9
5-9
as received
as received
as received
as received
6-8
as received
>11
>11
as received
as received
as received
Secondary
extraction
PH
none
none
none
none
none
none
none
none
none
none
none
none
none
<2
<2
none
none
none
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
hexane
hexane
none
none
acetonitrile
methanol
methyl ene chloride
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
methyl ene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
hexane
_
-
-
-
methyl ene chloride
Vol ume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
10.0
10.0
-
-
-
-
10.0
Final
extract
vol ume
for
analysis
1.0, 10
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
10.0
10.0
1.0
1.0
1.0
1.0
(ml)
.Oa
















0.0 (dry)
a  Phenols may be analyzed, by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID.  Method 8040 also contains an optional
   derivatization procedure for  phenols which  results  in  a 10 ml  hexane extract to be analyzed by GC/ECD.

b  The  specificity  of GC/MS may make cleanup  of the extracts unnecessary.   Refer to Method 3600 for guidance  on the cleanup
   procedures available  if required.

c  Loss of phthalate esters, organochlorine pesticides and phenols  can occur under these extraction conditions (see Section 3.2).

d  Extraction pH sequence may  be reversed  to  better separate  acid and  neutral  waste  components.   Excessive pH adjustments may
   result in the loss  of some  analytes  (see Section 3.2).
                                                          3510B -  7
Revision 2
November 1990

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                               METHOD 3510B
               SEPARATORY FUNNEL LIQUID-LIQUID  EXTRACTION
Yes
           7.1  Add
          surrogate
       slands .  to al 1
       samples,  spikes
         and blanks
                         7.7 Collect
                         and combine
                        extracts and
                           label
                                      7.8
                                    CC/MS
                                  analysis
                                 (Method 8250
                                  8270) being
                                  performed?
                                                 7.8 Combine
                                                base/neutral
                                                  extracts
                                                  prior to
                                                concentration
 7.2.  Check
and adjust pH
           7.3-7.6
          Extract 3
            times
                          7.9-7.11
                         Concentrate
                           extract
                                     7.12
                                   Ready for
7.7 Further
extractions
 required?
                                 3510B - 8
                                                         Revision 2
                                                         November 1990

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                                 METHOD 3520B

                      CONTINUOUS  LIQUID-LIQUID  EXTRACTION
1.0  SCOPE AND APPLICATION

      1.1  This method  describes  a procedure for  isolating  organic compounds
from  aqueous  samples.   The  method also  describes concentration  techniques
suitable  for  preparing the  extract for  the appropriate  determinative  steps
described in 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.


2.0  SUMMARY OF METHOD

      2.1  A  measured  volume of  sample, usually  1 liter,  is  placed into  a
continuous liquid-liquid extractor,  adjusted,  if necessary, to  a  specific pH
(see Table 1), and extracted with  organic solvent for 18-24 hours.  The extract
is dried, concentrated, and, as necessary, exchanged into a solvent compatible
with  the cleanup  or  determinative  method   being  employed  (see  Table  1  for
appropriate exchange solvents).


3.0  INTERFERENCES

      3.1  Refer to Method 3500.

      3.2  Under basic extraction conditions required to separate analytes for
the packed columns of Method 8250, the decomposition of some analytes has been
demonstrated.  Organochlorine pesticides may dechlorinate, phthalate esters may
exchange, and phenols  may react to form tannates.  These  reactions increase with
increasing pH,  and are decreased  by the shorter reaction times  available in
Method 3510.   Methods 3520/8270,  3510/8270, and 3510/8250,  respectively,  are
preferred over Method  3520/8250  for the analysis of  these classes of compounds.


4.0  APPARATUS AND MATERIALS

      4.1  Continuous liquid-liquid extractor - Equipped with  Teflon  or  glass
connecting joints  and  stopcocks requiring no lubrication  (Kontes 584200-0000,
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.

                                   3520B - 1                       Revision 2
                                                                  November 1990

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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).

      4.4  Boiling chips - Solvent extracted, approximately  10/40 mesh (silicon
carbide or equivalent).

      4.5  Water  bath  -  Heated,  with   concentric  ring   cover,  capable  of
temperature control (± 5°C).   The bath  should be  used  in a hood.

      4.6  Vials - 2 ml, glass with Teflon lined screw-caps or crimp tops.

      4.7  pH indicator paper - pH range  including the desired extraction pH.

      4.8  Heating mantle - Rheostat controlled.

      4.9  Syringe - 5 ml.


5.0  REAGENTS

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

      5.2  Organic-free reagent water  - All   references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3  Sodium hydroxide solution (ION), NaOH.  Dissolve 40 g NaOH in organic-
free reagent water and dilute to  100 ml.

                                   3520B - 2                       Revision 2
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      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

            5.6.1  Methylene chloride, CH2C12 - Pesticide  quality  or equivalent.

            5.6.2  Hexane, C6H14 - Pesticide quality or equivalent.

            5.6.3  2-Propanol, (CH3)2CHOH - Pesticide quality or  equivalent.

            5.6.4  Cyclohexane, C6H12 - Pesticide quality or equivalent.

            5.6.5  Acetonitrile, CH3CN - Pesticide quality or equivalent.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See  the  introductory material  to this  chapter,  Organic Analytes,
Section 4.1.


7.0  PROCEDURE

      7.1  Using a 1 liter graduated cylinder, measure  out 1  liter (nominal) of
sample  and  transfer it quantitatively  to  the continuous  extractor.   If high
concentrations are anticipated,  a  smaller  volume  may be  used and then diluted
with organic-free  reagent water to  1 liter.  Check the pH of the sample with
wide-range pH paper and adjust the pH, if necessary,  to the pH indicated in Table
1 using 1:1 (V/V) sulfuric acid or  10 N sodium hydroxide.  Pipet 1.0 mL  of the
surrogate standard spiking solution into each sample into the extractor and mix
well.  (See Method 3500 and the determinative method to be used,  for details on
the surrogate standard solution and the  matrix spike solution.)   For the  sample
in each analytical batch selected for spiking, add 1.0  mL of  the  matrix spiking
standard.   For base/neutral-acid  analysis,  the amount  of  the  surrogates and
matrix  spiking  compounds  added  to the  sample  should  result in   a  final
concentration of 100 ng//iL of each base/neutral  analyte  and 200 ng/juL of each
acid analyte  in  the extract to  be  analyzed  (assuming  a  1 pi injection).   If
Method  3640,  Gel-Permeation Cleanup, is to  be used, add  twice  the volume of
surrogates and matrix spiking  compounds since half the extract is lost  due to
loading of the GPC column.

      7.2  Add 300-500 mL  of  methylene  chloride to the distilling flask.  Add
several boiling chips to the flask.

      7.3  Add sufficient water to the extractor to ensure proper operation and
extract for 18-24 hours.


                                   3520B -  3                       Revision 2
                                                                  November 1990

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      7.4  Allow to cool;  then  detach the boiling flask.   If  extraction at a
secondary pH is not required (see Table 1), the extract is dried and concentrated
using one of the techniques referred to in Section 7.7.

      7.5  Carefully,  while stirring,  adjust the  pH of  the aqueous phase to the
second pH  indicated  in Table 1.   Attach a clean distilling  flask containing
500 mL of methylene chloride  to the continuous  extractor.   Extract  for 18-24
hours, allow to cool,  and detach the distilling flask.

      7.6  If performing GC/MS analysis (Method 8270), the acid/neutral and base
extracts may be combined prior to concentration.   However,  in some situations,
separate concentration  and analysis of the  acid/neutral  and base extracts may
be  preferable  (e.g.   if for  regulatory  purposes the  presence  or absence  of
specific  acid/neutral  and  base  compounds at  low  concentrations  must  be
determined, separate extract analyses may be warranted).

      7.7  Perform  concentration  using   the  Kuderna-Danish  (K-D)  Technique
(Sections 7.8.1 through 7.8.4).

      7.8  K-D Technique

            7.8.1  Assemble a Kuderna-Danish (K-D) concentrator by attaching a
      10 mL concentrator tube to a  500 mL evaporation  flask.   Dry the extract
      by passing it through a  drying column  containing  about 10 cm of anhydrous
      sodium sulfate.   Collect the dried extract  in a K-D concentrator.   Rinse
      the flask which contained the solvent extract with 20-30 mL of methylene
      chloride and add  it to the column to complete the quantitative transfer.

            7.8.2  Add one or two clean  boiling  chips  to the  flask and  attach
      a three ball  Snyder column.  Prewet the Snyder column by adding about 1 mL
      of methylene chloride to the top of the column.  Place the K-D apparatus
      on a hot water  bath  (15-20°C  above  the boiling point  of  the solvent)  so
      that the concentrator tube is  partially immersed  in the hot water and the
      entire lower rounded  surface of the  flask is bathed with hot  vapor.  Adjust
      the vertical  position of  the apparatus  and  the water temperature,  as
      required, to complete the concentration in  10-20 minutes.   At the  proper
      rate of distillation the  balls  of  the column will  actively chatter,  but
      the chambers will not flood.   When the apparent volume of liquid reaches
      1 mL, remove the K-D apparatus from the water bath and allow it to drain
      and cool  for at  least 10 minutes.   Remove the Snyder column and rinse the
      flask and  its  lower joints  into  the concentrator tube  with 1-2  mL  of
      extraction solvent.

            7.8.3  If a solvent  exchange  is  required  (as  indicated in Table 1),
      momentarily remove the Snyder column, add 50 mL of the exchange solvent,
      a new  boiling  chip, and  reattach  the Snyder  column.  Concentrate  the
      extract,  as described in Section 7.9, raising the  temperature of the water
      bath, if necessary, to maintain proper distillation.

            7.8.4  Remove the Snyder  column and  rinse  the flask  and  its lower
      joints into the  concentrator  tube  with 1-2 mL of  methylene  chloride  or
      exchange solvent.   If  sulfur crystals are  a problem, proceed  to  Method
      3660 for cleanup.  The  extract  may  be further  concentrated by  using the


                                  3520B  -  4                      Revision 2
                                                                  November 1990

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      techniques outlined In Section  7.9 or adjusted to 10.0 ml with the solvent
      last used.

      7.9  If further concentration  is indicated in Table 1, either the micro-
Snyder column technique (7.9.1) or nitrogen blowdown technique (7.9.2) is used
to adjust the extract to the final volume required.

            7.9.1  Micro-Snyder Column Technique

                  7.9.1.1   Add  another one or two clean  boiling  chips  to the
            concentrator tube and  attach a two ball  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,  rinse the flask and its
            lower joints  into  the concentrator tube with 0.2 ml  of methylene
            chloride or exchange solvent,  and  adjust  the final volume to 1.0 to
            2.0 ml, as indicated  in Table 1, with solvent.

            7.9.2  Nitrogen Blowdown Technique

                  7.9.2.1    Place the concentrator tube  in a warm bath  (35°C)
            and evaporate the solvent volume to 0.5 ml using a gentle stream of
            clean, dry nitrogen  (filtered through a column  of activated carbon).

CAUTION:   New plastic tubing must not be used between the carbon trap and the
           sample, since it may introduce interferences.

                  7.9.2.2    The internal  wall of the tube must  be rinsed down
            several times with methylene chloride or appropriate solvent during
            the operation.  During evaporation, the tube solvent level must be
            positioned to  avoid water  condensation.   Under normal  procedures,
            the extract must not be allowed to become dry.

CAUTION:   When  the  volume  of  solvent is  reduced  below 1 ml,  semi volatile
           analytes may be lost.

      7.10  The extract may  now be analyzed for  the  target  analytes using the
appropriate determinative  technique(s)  (see Section  4.3 of  this  Chapter).   If
analysis  of  the extract  will  not   be  performed  immediately,  stopper  the
concentrator tube and store refrigerated.   If  the extract  will be stored longer
than 2 days it should be transferred  to a vial with a Teflon lined screw-cap or
crimp top, and labeled appropriately.
                                   3520B  -  5
Revision 2
November 1990

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8.0  QUALITY CONTROL

      8.1  Refer  to  Chapter One  for  specific quality  control  procedures and
Method 3500 for extraction and sample-preparation procedures.


9.0  METHOD PERFORMANCE

      9.1  Refer to the determinative methods for performance data.


10.0  REFERENCES

1.   U.S. EPA 40 CFR Part 136,  "Guidelines  Establishing  Test  Procedures for the
     Analysis of  Pollutants Under the  Clean  Water Act;  Final Rule and Interim
     Final Rule and Proposed Rule," October 26, 1984.
                                   3520B - 6                      Revision 2
                                                                  November 1990

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                                                          TABLE 1.
                              SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8140
8141
8250b'c
8270b'd
8310
8321
8410
Initial
extraction
pH
<2
as received
as received
as received
5-9
5-9
5-9
as received
as received
as received
as received
6-8
as received
>11
<2
as received
as received
as received
Secondary
extraction
PH
none
none
none
none
none
none
none
none
none
none
none
none
none
<2
>11
none
none
none
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
hexane
hexane
none
none
acetonitrile
methanol
methyl ene chloride
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
methyl ene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
hexane
-
-
-
-
methyl ene chloride
Vol ume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
10.0
10.0
-
-
-
-
10.0
Final
extract
vol ume
for
analysis (mL)
1.0,10.0"
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
10.0
10.0
1.0
1.0
1.0
1.0
0.0 (dry)
a  Phenols may be analyzed, by Method 8040, using a 1.0 mL 2-propanol extract by GC/FID.  Method 8040 also contains an optional
   derivatization procedure for phenols which  results  in  a 10 mL  hexane extract to be analyzed by GC/ECD.

b  The  specificity  of GC/MS may make cleanup  of the extracts unnecessary.   Refer to Method 3600 for guidance  on the cleanup
   procedures available  if  required.

c  Loss of phthalate esters, organochlorine pesticides and  phenols  can occur under these extraction conditions (see Section 3.2).

d  If  further separation  of  major  acid  and  neutral  components  is required, Method  3650, Acid-Base  Partition  Cleanup,  is
   recommended.   Reversal  of  the  Method  8270 pH sequence  is not  recommended as analyte losses are more  severe  under the base
   first continuous  extraction  (see  Section  3.2).
                                                          3520B -  7
Revision 2
November 1990

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                                    METHOD  3520B
                     CONTINUOUS LIQUID-LIQUID EXTRACTION
  c
      Start
7.1  Add appropriate
   surrogate and
  matrix spiking
     solutions
 7 . 2  Add methylene
    chloride to
 distilling flask
  7 . 3  Add reagent
Hater  to extractor;
 extract for 18-24
       hours
7.5 Adjust pH of
 aqueous phase;
extract for 18-24
hours  with clean
      flask
         Yes
 7.6 Combine acid
 and base/neutral
 extracts  prior to
   concentration
                                                7.7-7.8 Concentrate
                                                     extract
                                                                    Yes
                                                                        7.8.3 Add exchange
                                                                            solvent:
                                                                        concentrate extract
                                                   7 9 Further
                                                concentrate extract
                                                  if necessary;
                                                adjust final volume
                                                 7.10 Analyze using
                                                 organic techniques
                                                       8000
                                                      Series
                                                      Methods
                                      3520B  - 8
                                                                              Revision 2
                                                                              November  1990

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                                 METHOD 3540B

                              SOXHLET EXTRACTION
1.0  SCOPE AND APPLICATION

      1.1  Method 3540 Is a procedure for extracting nonvolatile and semi-
volatile organic compounds from solids such as soils, sludges, and wastes.
The Soxhlet extraction process ensures intimate contact of the sample matrix
with the extraction solvent.

      1.2  This method is applicable to the isolation and concentration of
water insoluble and slightly water soluble organics in preparation for a
variety of chromatographic procedures.


2.0  SUMMARY OF METHOD

      2.1  The solid sample is mixed with anhydrous sodium sulfate, placed in
an extraction thimble or between two plugs of glass wool, and extracted using
an appropriate solvent in a Soxhlet extractor.  The extract is then dried,
concentrated, and, as necessary, exchanged into a solvent compatible with the
cleanup or determinative step being employed.


3.0  INTERFERENCES

      3.1  Refer to Method 3500.
4.0  APPARATUS AND MATERIALS

      4.1  Soxhlet extractor - 40 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.

      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.


                                   3540B  -  1                      Revision  2
                                                                 November  1990

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            4.3.3  Snyder column - Three ball macro (Kontes K-503000-0121 or
      equivalent).

            4.3.4  Snyder column - Two ball micro (Kontes K-569001-0219 or
      equivalent).

            4.3.5  Springs - 1/2 inch (Kontes K-662750 or equivalent).

      4.4  Boiling chips - Solvent extracted, approximately 10/40 mesh
(silicon carbide or equivalent).

      4.5  Water bath - Heated, with concentric ring cover, capable of
temperature control (+ 5°C).   The bath should be used  in a hood.

      4.6  Vials - Glass, 2 ml capacity, with Teflon lined screw or crimp top.

      4.7  Glass or paper thimble or glass wool - Contaminant free.

      4.8  Heating mantle - Rheostat controlled.

      4.9  Disposable glass pasteur pipet and bulb.

      4.10  Apparatus for determining percent dry weight.

            4.10.1 Oven - Drying.

            4.10.2 Desiccator.

            4.10.3 Crucibles - Porcelain or disposable aluminum.

      4.11  Apparatus for grinding

      4.12  Analytical balance - 0.0001 g.


5.0  REAGENTS

      5.1  Reagent grade 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), Na?S04.  Purify by heating at
400°C for 4  hours in a shallow tray,  or by precleaning the sodium  sulfate with
methylene chloride.  If the sodium sulfate is precleaned with methylene
chloride, a method blank must be analyzed, demonstrating that there is no
interference from the sodium sulfate.
                                   3540B  -  2                      Revision 2
                                                                 November 1990

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      5.4  Extraction solvents
            5.4.1  Soil/sediment and aqueous sludge samples  shall  be  extracted
      using either of the following solvent systems:
                  5.4.1.1  Acetone/Hexane  (1:1)  (v/v), CH3COCH3/CH6H14.
            Pesticide quality or equivalent.
NOTE:  This solvent system has lower disposal cost and lower toxicity.
                  5.4.1.2  Methylene chloride/Acetone (1:1 v/v),
            CH2C12/CH3COCH3.  Pesticide  quality  or equivalent.
            5.4.2  Other samples shall be  extracted using the  following:
                  5.4.2.1  Methylene chloride,  CH2C12.  Pesticide  quality or
            equivalent.
                  5.4.2.2  Toluene/Methanol (10:1) (v/v), C6H5CH3/CH3OH.
            Pesticide quality or equivalent.
      5.5  Exchange solvents
            5.5.1  Hexane, C6H14.  Pesticide quality or equivalent.
            5.5.2  2-Propanol, (CH3)2CHOH.   Pesticide quality or equivalent.
            5.5.3  Cyclohexane, C6H12.   Pesticide quality or  equivalent.
            5.5.4  Acetonitrile, CH3CN.  Pesticide quality or equivalent.
6.0  SAMPLE COLLECTION, PRESERVATION,  AND  HANDLING
     6.1   See the introductory material to this chapter, Organic  Analysis,
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 multiphases must  be
      prepared by the phase separation method in Chapter Two before
      extraction.  This procedure is for solids only.
            7.1.3  Dry waste samples amenable to grinding  - Grind or otherwise
      subdivide the waste so that it either passes through a 1 mm sieve  or can
      be extruded through a 1 mm hole.  Introduce sufficient sample into the
      grinding apparatus to yield at least 10 g after grinding.
                                   3540B -  3                      Revision 2
                                                                 November 1990

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            7.1.4  Gummy, fibrous or oily materials not amenable to grinding
      should be cut, shredded, or otherwise broken up to allow mixing, and
      maximum exposure of the sample surfaces for extraction.  The
      professional judgment of the analyst is required for handling these
      difficult matrixes.

      7.2  Determination of sample % dry weight - In certain cases, sample
results are desired based on dry weight basis.  When such data is desired, a
portion of sample for this determination should be weighed out at the same
time as the portion used for analytical determination.

WARNING:   The drying oven should be contained in a hood or vented.
           Significant laboratory contamination may result from a heavily
           contaminated hazardous waste sample.

            7.2.1  Immediately after weighing the sample for extraction, weigh
      5-10 g of the sample into a tared crucible.  Determine the % dry weight
      of the sample by drying overnight at 105°C.   Allow to cool  in a
      desiccator before weighing:

            % dry weight = q of dry sample x 100
                              g of sample

      7.3  Blend 10 g of the solid sample with 10 g of anhydrous sodium
sulfate and place in an extraction thimble.  The extraction thimble must drain
freely for the duration of the extraction period.  A glass wool plug above and
below the sample in the Soxhlet extractor is an acceptable alternative for the
thimble.  Add 1.0 mL of the surrogate standard spiking solution onto the
sample (see Method 3500 for details on the surrogate standard and matrix
spiking solutions).  For the sample in each analytical batch selected for
spiking, add 1.0 mL of the matrix spiking standard.  For base/neutral-acid
analysis, the amount added of the surrogates and matrix spiking compounds
should result in a final concentration of 100 ng//iL of each base/neutral
analyte and 200 ng//zL of each acid analyte in the extract to be analyzed
(assuming a 1 nl  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 (Section 5.4)
into a 500 mL round bottom flask containing one or two clean boiling chips.
Attach the flask to the extractor and extract the sample for 16-24 hours at
4-6 cycles/hr.

      7.5  Allow the extract to cool after the extraction is complete.

      7.6  Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10 mL
concentrator tube to a 500 mL evaporation flask.

      7.7  Dry the extract by passing it through a drying column containing
about 10 cm of anhydrous sodium sulfate.  Collect the dried extract in a K-D
concentrator.  Wash the extractor flask and sodium sulfate column with 100 to
125 mL of extraction solvent to complete the quantitative transfer.
                                   3540B -  4                     Revision 2
                                                                 November 1990

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      7.8  Add one or two clean boiling chips to the flask and attach a three
ball Snyder column.  Prewet the Snyder column by adding about 1 ml of
methylene chloride to the top of the column.  Place the K-D apparatus on a hot
water bath (15-20°C above the boiling point of the solvent)  so that  the
concentrator tube is partially immersed in the hot water and the entire lower
rounded surface of the flask is bathed with hot vapor.  Adjust the vertical
position of the apparatus and the water temperature, as required, to complete
the concentration in 10-20 minutes.  At the proper rate of distillation the
balls of the column will actively chatter, but the chambers will not flood.
When the apparent volume of liquid reaches 1-2 ml, remove the K-D apparatus
from the water bath and allow it to drain and cool for at least 10 minutes.

      7.9  If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add approximately 50 mL of the exchange
solvent and a new boiling chip, and reattach the Snyder column.  Concentrate
the extract as described in Section 7.8, raising the temperature of the water
bath, if necessary, to maintain proper distillation.  When the apparent volume
again reaches 1-2 ml, remove the K-D apparatus from the water batch and allow
it to drain and cool for at least 10 minutes.

      7.10  Remove the Snyder column and rinse the flask and its lower joints
into the concentrator tube with 1-2 ml of methylene chloride or exchange
solvent.  If sulfur crystals are a problem, proceed to Method 3660 for
cleanup.  The extract may be further concentrated by using the techniques
described in Section 7.11 or adjusted to 10.0 ml with the solvent last used.

      7.11  If further concentration is indicated in Table 1, either micro
Snyder column technique (Section 7.11.1) or nitrogen blowdown technique
(Section 7.11.2) is used to adjust the extract to the final volume required.

            7.11.1  Micro Snyder Column Technique

                   7.11.1.1  Add another one or two clean boiling chips to
            the concentrator tube and attach a two ball micro Snyder column.
            Prewet the column by adding about 0.5 ml of methylene chloride or
            exchange solvent to the top of the column.  Place the K-D
            apparatus in a hot water bath so that the concentrator tube is
            partially immersed in the hot water.  Adjust the vertical position
            of the apparatus and the water temperature, as required, to
            complete the concentration in 5-10 minutes.  At the proper rate of
            distillation the balls of the column will actively chatter, but
            the chambers will not flood.  When the apparent volume of liquid
            reaches 0.5 ml, remove the K-D apparatus from the water bath and
            allow it to drain and cool for at least 10 minutes.  Remove the
            Snyder column and rinse the flask and its lower joints with about
            0.2 ml of solvent and add to the concentrator tube.  Adjust the
            final volume to 1.0-2.0 ml, as indicated in Table 1, with solvent.

            7.11.2  Nitrogen Blowdown Technique

                  7.11.2.1   Place the concentrator tube  in a warm 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).

                                   3540B -  5                     Revision  2
                                                                 November  1990

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CAUTION;   Do not use plasticized tubing between the carbon trap and the
           sample.

                  7.11.2.2  The  internal wall of the tube must be rinsed down
            several times with the appropriate solvent during the operation.
            During evaporation, the solvent level  in the tube must be
            positioned to prevent water from condensing into the sample (i.e.,
            the solvent level  should be below the level of the water bath).
            Under normal operating conditions, the extract should not be
            allowed to become dry.

CAUTION;   When the volume of solvent is reduced below 1 ml, semivolatile
           analytes may be lost.

      7.12  The extracts obtained may now be analyzed for the target analytes
using the appropriate organic technique(s) (see Section 4.3 of this Chapter).
If analysis of the extract will not be performed immediately, stopper the
concentrator tube and store in a refrigerator.  If the extract will be stored
longer than 2 days, it should be transferred to a vial  with a Teflon lined
screw cap or crimp top, and labeled appropriately.


8.0  QUALITY CONTROL

      8.1  Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.


9.0  METHOD PERFORMANCE

      9.1  Refer to the determinative methods for performance data.


10.0 REFERENCES

1.   U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for
     the Analysis of Pollutants Under the Clean Water Act; Final Rule and
     Interim Final Rule and Proposed Rule," October 26, 1984.
                                   3540B -  6                     Revision 2
                                                                 November 1990

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                                                  TABLE 1.
                      SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040a
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8140
8141
8250a'c
8270C
8310
8321
8410
Extraction
PH
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
hexane
hexane
none
none
acetonitrile
methanol
methyl ene chloride
Exchange Volume
solvent of extract
required required
for for
cleanup cleanup (ml)
hexane
hexane
hexane
methyl ene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
hexane
--
--
--
--
methylene chloride
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
10.0
10.0
--
--
--
--
10.0
Final
extract
vol ume
for
analysis (ml)
1.0, 10.0"
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
10.0
10.0
1.0
1.0
1.0
1.0
0.0 (dry)
a To obtain separate acid and base/neutral extracts, Method 3650 should be performed following
  concentration of the extract to 10.0 mL.

b Phenols may be analyzed by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID.  Method 8040 also
  contains an optical derivatization procedure for phenols which results in a 10 mL hexane extract to be
  analyzed by GC/ECD.

  The specificity of GC/MS may make cleanup of the extracts unnecessary.
  on the cleanup procedures available if required.

                                                  3540B  -  7
Refer to Method 3600 for guidance
                  Revision 2
                  November 1990

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                                    METHOD 3540B
                                SOXHLET  EXTRACTION
  c
Start
7.1  Use appropriate
  sample handling
     technique
   7.2  Determine
sample  % dry weight
7.3 Add appropriate
   surrogate and
  matrix spiking
     s tandards
7.4 Add  extraction
 solvent to flask:
 extract for 16-24
      hours
 7.5 Cool extract
                   7.6  Assemble K-D
                     concent rator
                  7.7  Dry and collect
                    extract in K-D
                    concentrator
                    7.8 Concentrate
                  using Snyder column
                   and K-D apparatus
7.12  Analyze using
organic  techniques
      8000
      Series
      Methods
                   7.9  Add exchang
                       solvent,
                     reconcentrate
                        extract
                                      3540B -  8
                                                                       Revision 2
                                                                       November 1990

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                                  METHOD 3541

                         AUTOMATED SOXHLET EXTRACTION
1.0  SCOPE AND APPLICATION

      1.1  This  method extracts  polychlorinated  biphenyls  (PCBs)  from soil,
sediment, sludges, and waste solids.   The method uses a commercially available,
unique,  three  stage extraction system  to achieve PCB recovery comparable to
Method 3540,  but in a much shorter  time.   The two differences  between this
extraction method and  Method 3540 are Sections  7.10  and  7.11.  In the initial
extraction  stage,  the sample-loaded  extraction  thimble  is  immersed  into the
boiling solvent.  This ensures  very rapid intimate  contact  between the specimen
and solvent and rapid  recovery of the PCB.  In the second  stage the thimble is
elevated above the  solvent, and is rinse-extracted as  in Method 3540.   In the
third stage, the  solvent is evaporated,  as would  occur  in the Kuderna-Danish
(K-D) concentration step in  Method 3540.  The concentrated extract  is then ready
for measurement of the PCB concentrations using Method 8080 or 8081.

      1.2  The method is applicable to the extraction  and  concentration of water
insoluble or slightly water soluble PCBs in preparation for gas chromatographic
measurement of the PCB concentration of the sample.


2.0  SUMMARY OF METHOD

      2.1  After  air drying of the samples  (EPA  Method  600/4-81-055,  Interim
Methods for the Sampling  and Analysis of Priority Pollutants in Sediments and
Fish Tissue, Section 3.1.3), the  sample is  ground to 100-200 mesh  (150  /im to
75  /itm).  The  powdered  sample  is  extracted  using 1:1  acetonerhexane  as  the
extraction solvent,  as detailed  below.    The extract is  then concentrated and
exchanged into pure hexane prior,  to final gas chromatographic PCB measurement.

      2.2  This  method is  applicable  to soils,  clays,  wastes  and sediments
containing from 1 to 50 /ug of PCB  per gram of sample.  It  has been statistically
evaluated at 5  and 50 /Ltg/g of Aroclors 1254 and 1260,  and  found to be equivalent
to Method 3540 (Soxhlet Extraction).   Higher concentrations of PCB are measured
following volumetric dilution with hexane.


3.0  INTERFERENCES

      3.1  Refer to Method 3500.

      3.2  If cleanup  is  necessary, the Florisil  and/or  sulfur procedures may
be employed.  In such cases,  proceed with Method 3620,  followed by, if necessary,
Method 3660, using the 10 ml hexane extracts obtained from Section 7.14.
                                   3541 - 1                       Revision 0
                                                                  November 1990

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4.0  APPARATUS AND MATERIALS

      4.1  Automated Soxhlet  Extraction  System - With  controlled,  heated oil
bath (Soxtec, or equivalent).  See Figure 1.  Apparatus is used in a hood.

      4.2  Cellulose  extraction  thimbles  -  Contamination  free   (Fisher  No.
1522-0018, or equivalent).

      4.3  Syringe - 5 ml.

      4.4  Apparatus for Determining Percent Dry Weight

           4.4.1   Drying Oven.

           4.4.2   Desiccator.

           4.4.3   Crucibles, porcelain.

           4.4.4   Balance, analytical.

      4.5  Apparatus for Grinding - If the sample will not pass through a 1 mm
standard  sieve  or cannot  be extruded through  a 1  mm  opening,  it  should  be
processed  into  a homogeneous  sample  that meets  these requirements.   Gummy,
fibrous, or oily materials may be mixed with anhydrous sodium  sulfate to improve
grinding  efficiency.    Disassemble  grinder  between  samples,   according  to
manufacturer's instructions, and clean with  soap and  water, followed by acetone
and hexane rinses.


5.0  REAGENTS

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

      5.2  Organic-free reagent water.  All  references to water in this method
refer to organic-free  reagent water, as defined in Chapter One.

      5.3  Sodium sulfate  (granular,  anhydrous), Na2S04.  Purify  by heating at
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  Acetone/hexane  (1:1  (v/v)),  CH3COCH3/C6H14.   Pesticide  quality  or
equivalent.

      5.5  Hexane, C6H14.  Pesticide quality or equivalent.
                                   3541  - 2                       Revision 0
                                                                  November 1990

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6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See the  introductory material to  this chapter,  Organic  Analytes,
Section 4.1.
7.0  PROCEDURE

      7.1  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.   Air dry
      the sample at room temperature for 48 hours in a glass tray or on hexane
      cleaned aluminum foil, or dry the sample by mixing with anhydrous sodium
      sulfate until a free-flowing powder is obtained.

            7.1.2 Dry waste  samples amenable  to  grinding  - Grind or otherwise
      subdivide the waste so that it either passes through a 1 mm sieve or can
      be extruded through a 1 mm hole.   Introduce  sufficient sample  into the
      grinding apparatus to yield at least 20 g after grinding.

                  7.1.2.1  Gummy,  fibrous  or oily  materials  not  amenable  to
            grinding should  be cut, shredded, or otherwise broken up  to allow
            mixing, and maximum exposure of the  sample surfaces for extraction.
            The professional judgment of  the  analyst  is required for  handling
            these difficult matrices.

            7.1.3 Waste samples - Samples consisting of  multiple phases must be
      prepared by the phase separation in Chapter Two before extraction.  This
      procedure is for solids gnly.

      7.2  Determination of sample percent dry weight - In certain cases, sample
results are desired  based on dry weight basis.   When such data  is desired,  a
portion of sample for this determination should  be weighed  out at the same time
as the portion used for analytical determination.

WARNING; The drying oven should be contained in a hood or vented.  Significant
         laboratory  contamination  may  result   from  a heavily  contaminated
         hazardous waste sample.

            7.2.1 Immediately after weighing  the sample for extraction, weigh
      5-10 g of the  sample  into  a  tared crucible.   Determine  the % dry weight
      of the sample by drying overnight  at 105°C.  Allow  to  cool in a desiccator
      before weighing:

           % dry weight = q of dry sample x 100
                            g of sample

      7.3  Grind sufficient  dried  sample  from Section 7.1.2 or 7.1.3  to yield
20 g of powder.  After grinding,  samples  should pass  through  a 10 mesh sieve.

      7.4  Weigh 10 g of sample into extraction thimbles.


                                   3541 - 3                       Revision 0
                                                                  November 1990

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      7.5  Check the  oil  level  in the  automated  Soxhlet unit and  add  oil  if
needed.  See service manual for details.

      7.6  Press the "MAINS" button,  observe that the switch lamp is now "ON".

      7.7  Open the cold water tap for the reflux condensers.  Adjust the flow
to 2 L/min to prevent solvent loss through the condensers.

      7.8  Transfer weighed samples into the condensers.   Raise the knob to the
"BOILING" position.  The magnet  will  now fasten to the thimble.  Lower the knob
to the "RINSING" position.  The thimble will now hang just below the condenser
valve.

      7.9  Insert the extraction  cups containing  boiling chips,  and load each
with 50 mL of solvent (1:1 (v/v) hexaneracetone).  Using the cup holder, lower
the locking handle, ensuring that  the safety catch  engages.   The cups are now
clamped into position.

      7.10  Move the extraction knobs to the "BOILING" position.  The thimbles
are now immersed in solvent.  Set the  timer for 60 minutes. The condenser valves
must be in the "OPEN" position.   Run for the preset time.

      7.11  Move the extraction knobs to the "RINSING" position.  The thimbles
will now hang above the solvent surface.  Set timer for 60 minutes.  Condenser
valves are still open.  Run for the preset time.

      7.12  After rinse time has elapsed, close the  condenser valves by turning
each a quarter-turn, clockwise.

      7.13  When all  but  1 or 2  mL  of  solvent  have been collected,  open the
system and remove the cups.  Let the solvent air-evaporate from this point.

      7.14  Quantitatively transfer contents of cups to 10 mL collection vials
using hexane.  Dilute to volume.

NOTE: The recovery solvent volume can be adjusted by adding solvent at the top
      of the condensers.  For more details concerning use  of the extractor, see
      the operating manual for the automated extraction system.

      7.15  Shutdown

            7.15.1 Turn "OFF" main switch.

            7.15.2 Turn "OFF" cold water tap.

            7.15.3 Check to ensure that all  condensers are free of solvent.

      7.16  The extract is now ready for cleanup or analysis, depending on the
extent of interfering co-extractives.
                                   3541 - 4                       Revision 0
                                                                  November  1990

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8.0  QUALITY CONTROL

      8.1  Any reagent  blanks  or matrix spike samples  should  be subjected to
exactly the same analytical procedures as those used on actual samples.

      8.2  Refer to  Chapter One  for  specific quality  control  procedures and
Method 3500 for extraction and sample preparation procedures.

      8.3  The  analyst  must  prepare  method  blanks  to  check  for  cross-
contamination and routinely check the integrity of the  instrument seals.


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.   Stewart, J.   "EPA Verification Experiment for  Validation of the SOXTEC"
     PCB Extraction Procedure";  Oak Ridge National  Laboratory, Oak Ridge, TN,
     37831-6138; October 1988.
                                   3541 - 5                       Revision 0
                                                                  November 1990

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             Figure 1
Automated Soxhlet Extraction  System
             Condenser
              Thimble

           Glass Wool Plug

              Sample


      Aluminum beaker (cup)


              Hot plate
             3541 - 6
Revision 0
November 1990

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                              METHOD 3541
                     AUTOMATED SOXHLET EXTRACTION
 7.3 Grind
   dried
  sample.
 7.5 Check
 oil level in
Soxhlet unit.
 7.8 Transfer
 samples into
 condensers.
Adjust position
of  magnet and
   thimble.
                                                              Stop
                               3541  -  7
                                      Revision 0
                                      November 1990

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                                  METHOD  3550B

                             ULTRASONIC EXTRACTION


See DISCLAIMER-1.  See manufacturer's specifications for operational  settings.


1.0  SCOPE AND APPLICATION

      1.1  Method 3550 is a procedure for extracting nonvolatile and semi-
volatile organic compounds from solids such as soils, sludges, and wastes.
The ultrasonic process ensures intimate contact of the sample matrix with the
extraction solvent.

      1.2  The method is divided into two sections, based on the expected
concentration of organics in the sample.   The low concentration method
(individual organic components of < 20 mg/Kg) uses a larger sample size and a
more rigorous extraction procedure (lower concentrations are more difficult to
extract).  The medium/high concentration method (individual organic components
of > 20 mg/Kg) is much simpler and therefore faster.

      1.3  It is highly recommended that the extracts be cleaned up prior to
analysis.  See Chapter Four  (Cleanup), Section 4.2.2, for applicable methods.


2.0  SUMMARY OF METHOD

      2.1  Low concentration method - A 30 g sample is mixed with anhydrous
sodium sulfate to form a free flowing powder.  This is solvent extracted three
times using ultrasonic extraction.  A portion of the extract is removed for
cleanup and/or analysis.

      2.2  Medium/high concentration method - A 2 g sample is mixed with
anhydrous sodium sulfate to form a free flowing powder.  This mixture 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.


3.0  INTERFERENCES

      3.1  Refer to Method 3500.


4.0  APPARATUS AND MATERIALS

      4.1  Apparatus for grinding dry waste samples.

      4.2  Ultrasonic preparation - A horn type device equipped with a
titanium tip, or a device that will give equivalent performance, shall be
used.
                                   3550B -  1                      Revision  2
                                                                 November  1990

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            4.2.1  Ultrasonic Disrupter - The disrupter must have a minimum
      power wattage of 300 watts, with pulsing capability.  A device designed
      to reduce the cavitation sound is recommended.  Follow the manufacturers
      instructions for preparing the disrupter for extraction of samples with
      low and medium/high concentration.
      Use a 3/4" horn for the low concentration method and a 1/8" tapered
      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  Oven - Drying.
            4.4.2  Desiccator.
            4.4.3  Crucibles - Porcelain or disposable aluminum.
      4.5  Pasteur glass pipets - 1 ml, disposable.
      4.6  Beakers - 400 ml.
      4.7  Vacuum or pressure filtration apparatus.
            4.7.1  Buchner funnel.
            4.7.2  Filter paper - Whatman No. 41 or equivalent.
      4.8  Kuderna-Danish (K-D) apparatus.
            4.8.1  Concentrator tube - 10 ml, graduated (Kontes K-570050-1025
      or equivalent).  A ground glass stopper is used to prevent evaporation
      of extracts.
            4.8.2  Evaporation flask - 500 ml (Kontes K-570001-500 or
      equivalent). Attach to concentrator tube with springs, clamps, or
      equivalent.
            4.8.3  Snyder column -  Three ball macro (Kontes K-503000-0121 or
      equivalent).
            4.8.4  Snyder column -  Two ball micro (Kontes  K-569001-0219 or
      equivalent).
            4.8.5  Springs - 1/2 inch (Kontes K-662750 or  equivalent).
      4.9  Boiling chips - Solvent  extracted, approximately 10/40 mesh
(silicon carbide or equivalent).
      4.10  Water bath - Heated, with concentric ring cover, capable of
temperature control (+ 5°C).   The batch should be used in  a hood.
                                   3550B -  2                      Revision 2
                                                                 November 1990

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      4.11  Balance - Top loading, capable of accurately weighing to the
nearest 0.01 g.

      4.12  Vials - 2 ml, for GC autosampler, with Teflon lined screw caps or
crimp tops.

      4.13  Glass scintillation vials - 20 ml, with Teflon lined screw caps.

      4.14  Spatula - Stainless steel or Teflon.

      4.15  Drying column - 20 mm ID Pyrex 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.

      4.16  Syringe - 5 ml.


5.0  REAGENTS

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

      5.2  Organic-free reagent water.  All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3  Sodium sulfate (granular, anhydrous), Na?S04.  Purify by heating at
400°C for 4 hours in a shallow tray,  or by precleaning the  sodium sulfate with
methylene chloride.   If the sodium sulfate is precleaned with methylene
chloride, a method blank must be analyzed, demonstrating that there is no
interference from the sodium sulfate.

      5.4  Extraction solvents.

            5.4.1  Low concentration soil/sediment and aqueous sludge samples
      shall be extracted using a solvent system that gives optimum,
      reproducible recovery for the matrix/analyte combination to be measured.
      Suitable solvent choices are given in Table 1.

            5.4.2  Methylene chloriderAcetone, CH2C12:CH3COCH3 (1:1, v:v).
      Pesticide quality or equivalent.

            5.4.3  Methylene chloride, CH2C12.  Pesticide quality or
      equivalent.


                                   3550B -  3                      Revision 2
                                                                 November 1990

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            5.4.4  Hexane, C6H14.  Pesticide quality or equivalent.

      5.5  Exchange solvents.

            5.5.1  Hexane, C6H14.  Pesticide quality or equivalent.

            5.5.2  2-Propanol,  (CH3)2CHOH.  Pesticide quality or equivalent.

            5.5.3  Cyclohexane, C6H12.  Pesticide quality or equivalent.

            5.5.4  Acetonitrile, CH3CN.   Pesticide quality or equivalent.

            5.5.5  Methanol, CH3OH.   Pesticide quality or equivalent.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See the introductory material to this Chapter, Organic Analytes,
Section 4.1.


7.0  PROCEDURE

      7.1  Sample handling

            7.1.1  Sediment/soil samples - Decant and discard any water layer
      on a sediment sample.  Mix sample thoroughly, especially composited
      samples.  Discard any foreign objects such as sticks, leaves, and rocks.

                  7.1.1.2  Determine the dry weight of the sample (Section
            7.2) remaining after decanting.  Measurement of soil pH may be
            required.

            7.1.2  Waste samples - Samples consisting of multiphases must be
      prepared by the phase separation method in Chapter Two before
      extraction.  This procedure is for solids only.

            7.1.3  Dry waste samples amenable to grinding - Grind or otherwise
      subdivide the waste so that it either passes through a 1 mm sieve or can
      be extruded through a 1 mm hole.  Introduce sufficient sample into the
      grinder to yield at least 100 g after grinding.

            7.1.4  Gummy, fibrous or oily materials not amenable to grinding
      should be cut, shredded,  or otherwise broken up to allow mixing, and
      maximum exposure of the sample surfaces for extraction.  The
      professional judgment of  the analyst is required for handling of these
      difficult matrices.

      7.2  Determination of percent dry weight - In certain cases, sample
results are desired based on a  dry weight basis.  When such data is desired,
or required, a portion of sample for this determination should be weighed out
at the same time as the portion used for analytical determination.
                                   3550B -  4                     Revision 2
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WARNING;   The drying oven should be contained in a hood or vented.
           Significant laboratory contamination may result from drying a
           heavily contaminated hazardous waste sample.

            7.2.1  Immediately after weighing the sample for extraction, weigh
      5-10 g of the sample into a tared crucible.  Determine the % dry weight
      of the sample by drying overnight at 105°C.   Allow to cool  in a
      desiccator before weighing:

           % dry weight = g of dry sample x 100
                              g of sample

      7.3  Extraction method for samples expected to contain low
concentrations of organics and pesticides (< 20 mg/Kg):

            7.3.1  The following step should be performed rapidly to avoid
      loss of the more volatile extractables.  Weigh approximately 30 g of
      sample into a 400 ml beaker.  Record the weigh to the nearest 0.1 g.
      Nonporous or wet samples (gummy or clay type) that do not have a free-
      flowing sandy texture must be mixed with 60 g of anhydrous sodium
      sulfate, using a spatula.  If required, more sodium sulfate may be
      added.  After addition of sodium sulfate, the sample should be free
      flowing.  Add 1 ml of surrogate standards to all samples, spikes,
      standards, and blanks (see Method 3500 for details on the surrogate
      standard solution and the matrix spike solution).  For the sample in
      each analytical batch selected for spiking, add 1.0 ml of the matrix
      spiking standard.  For base/neutral-acid analysis, the amount added of
      the surrogates and matrix spiking compounds should result in a final
      concentration of 100 ng//iL of each base/neutral analyte and 200 ng//iL
      of each acid analyte in the extract to be analyzed (assuming a 1 p.1
      injection).  If Method 3640, Gel-Permeation Cleanup, is to be used, add
      twice the volume of surrogates and matrix spiking compounds since half
      of the extract is lost due to loading of the GPC column.  Immediately
      add 100 ml of 1:1 methylene chloride:acetone.

            7.3.2  Place the bottom surface of the tip of the #207 3/4 in.
      disrupter horn about 1/2 in. below the surface of the solvent, but above
      the sediment layer.

            7.3.3  Extract ultrasonically for 3 minutes, with output control
      knob set at 10 (full power) and with mode switch on Pulse (pulsing
      energy 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 and filter extracts through Whatman No. 41
      filter paper using vacuum filtration or centrifuge, and decant
      extraction solvent.

            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.


                                   3550B  -  5                      Revision 2
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      7.3.6  Assemble a Kuderna-Danish (K-D) concentrator by attaching a
10 ml concentrator tube to a 500 ml evaporator flask.

      7.3.7 Dry the extract by passing it through a drying column
containing about 10 cm of anhydrous sodium sulfate.  Collect the dried
extract in the K-D concentrator.  Wash the extractor flask and sodium
sulfate column with 100-125 ml of extraction solvent to complete the
quantitative transfer.

      7.3.8  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.

      7.3.9  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 Section 7.3.8, raising
the temperature of the water bath, if necessary, to maintain proper
distillation.  When the apparent volume again reaches 1-2 ml, remove the
K-D apparatus and allow it to drain and cool for at least 10 minutes.

      7.3.10      Remove the Snyder column and rinse the flask and its
lower joints into the concentrator tube with 1-2 ml of methylene
chloride or exchange solvent.  If sulfur crystals are a problem, proceed
to Method 3660 for cleanup.  The extract may be further concentrated by
using the technique outlined in Section 7.3.11 or adjusted to 10.0 ml
with the solvent last used.

      7.3.11      If further concentration is indicated in Table 1,
either micro Snyder column technique (Section 7.3.11.1) or nitrogen blow
down technique (Section 7.3.11.2) is used to adjust the extract to the
final volume required.

            7.3.11.1  Micro Snyder Column Technique

                  7.3.11.1.1  Add a clean boiling chip and attach a two
            ball micro Snyder column to the concentrator tube.  Prewet
            the column by adding approximately 0.5 ml of methylene
            chloride or exchange solvent through the top.  Place the
            apparatus in the hot water bath.  Adjust the vertical
            position and the water temperature, as required, to complete
            the concentration in 5-10 minutes.  At the proper rate of
            distillation the balls of the column will actively chatter,
            but the chambers will not flood.  When the liquid reaches an
            apparent volume of approximately 0.5 ml, remove the

                             3550B -  6                      Revision 2
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                  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).

                  7.3.11.2  Nitrogen Blowdown Technique

                        7.3.11.2.1  Place the concentrator tube in a warm
                  water bath (approximately 35°C)  and evaporate the solvent
                  volume to the required level using a gentle stream of clean,
                  dry nitrogen (filtered through a column of activated
                  carbon).

CAUTION;   Do not use plasticized tubing between the carbon trap and the
           sample.

                        7.3.11.2.2  The internal wall of the tube must be
                  rinsed down several times with the appropriate solvent
                  during the operation.  During evaporation, the solvent level
                  in the tube must be positioned to prevent water from
                  condensing into the sample (i.e., the solvent level should
                  be below the level of the water bath).  Under normal
                  operating conditions, the extract should not be allowed to
                  become dry.

CAUTION;   When the volume of solvent is reduced below 1 ml, semivolatile
           analytes may be lost.

      7.4  If analysis of the extract will not be performed immediately,
stopper the concentrator tube and store refrigerated.  If the extract will be
stored longer than 2 days, it should be transferred to a vial with a Teflon
lined cap and labeled appropriately.

      7.5  Extraction method for samples expected to contain high
concentrations of organics (> 20 mg/Kg):

            7.5.1  Transfer approximately 2 g (record weight to the nearest
      0.1 g) of sample to a 20 ml vial.  Wipe the mouth of the vial with a
      tissue to remove any sample material.  Record the exact weight of sample
      taken.  Cap the vial before proceeding with the next sample to avoid any
      cross contamination.

            7.5.2  Add 2 g of anhydrous sodium sulfate to sample in the 20 ml
      vial and mix well.

            7.5.3  Surrogate standards are added to all samples, spikes, and
      blanks (see Method 3500 for details on the surrogate standard solution
      and on the matrix spike solution).  Add 2.0 mL of surrogate spiking
      solution to sample mixture.  For the sample in each analytical batch
      selected for spiking, add 2.0 ml of the matrix spiking standard.  For
      base/neutral-acid analysis, the amount added of the surrogates and
      matrix spiking compounds should result in a final concentration of

                                   3550B - 7                      Revision 2
                                                                 November 1990

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      200 ng/juL of each base/neutral analyte and 400 ng//il_ of each  acid
      analyte in the extract to be analyzed (assuming a 1 /uL injection).  If
      Method 3640, Gel-Permeation Cleanup, is to be used, add twice the volume
      of surrogates and matrix spiking compounds since half the extract is
      lost due to loading of the GPC column.

            7.5.4  Immediately add whatever volume of solvent is necessary to
      bring the final volume to 10.0 ml considering the added volume of
      surrogates and matrix spikes.  Disrupt the sample with the 1/8 in.
      tapered microtip ultrasonic probe for 2 minutes at output control
      setting 5 and with mode switch on pulse and percent duty cycle at 50%.
      Extraction solvents are:

               1. Nonpolar compounds (i.e., organochlorine pesticides and
                  PCBs), hexane or appropriate solvent.

               2. Extractable priority pollutants, methylene chloride.

            7.5.5  Loosely pack disposable Pasteur pipets with 2 to 3 cm Pyrex
      glass wool plugs.  Filter the extract through the glass wool and collect
      5.0 ml in a concentrator tube if further concentration is required.
      Follow Section 7.3.11 for details on concentration.  Normally, the
      5.0 ml extract is concentrated to approximately 1.0 ml  or less.

            7.5.6  The extract is ready for cleanup or analysis, depending on
      the extent of interfering co-extractives.


8.0  QUALITY CONTROL

      8.1  Refer to Chapter One for specific quality control  procedures and
Method 3500 for extraction and sample preparation procedures.

      8.2  Horn tip and tuning criteria are critical elements in achieving
good method performance.  Refer to the manufacturer's specifications.


9.0  METHOD PERFORMANCE

      9.1  Refer to the determinative method for performance data.


10.0 REFERENCES

1.   U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for
     the Analysis of Pollutants Under the Clean Water Act; Final Rule and
     Interim Final Rule and Proposed Rule," October 26, 1984.

2.   U.S. EPA, Interlaboratory 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.
                                   3550B -  8                     Revision 2
                                                                 November 1990

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3.   Christopher S. Hein, Paul J. Marsden, Arthur S. Shurtleff, "Evaluation of
     Methods 3540 (Soxhlet) and 3550 (Sonicatlon) for Evaluation of Appendix
     IX Analytes form Solid Samples", S-CUBED, Report for EPA Contract 68-03-
     33-75, Work Assignment No. 03, Document No. SSS-R-88-9436, October 1988.
                                   3550B  -  9                      Revision  2
                                                                 November  1990

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                                                  TABLE 1.
                                  EFFICIENCY OF EXTRACTION SOLVENT SYSTEMS3
Solvent Svstem°
Compound
4-Bromophenyl phenyl ether
4-Chl oro-3-methyl phenol
bi s(2-Chl oroethoxy)methane
bis(2-Chloroethyl) ether
2-Chl oronaphthal ene
4-Chlorophenyl phenyl ether
1 , 2-Di chl oro benzene
1,3-Di chl orobenzene
Diethyl phthalate
4,6-Dinitro-o-cresol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Heptachlor epoxide
Hexachl orobenzene
Hexachl orobutadi ene
Hexachl orocyclopentadi ene
Hexachl oroethane
5-Nitro-o-toluidine
Nitrobenzene
Phenol
1 , 2 , 4-Tr i chl orobenzene
CAS No.b
101-55-3
59-50-7
111-91-1
111-44-4
91-58-7
7005-72-3
95-50-1
541-73-1
84-66-2
534-52-1
121-14-2
606-20-2
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
99-55-8
98-95-3
108-95-2
120-82-1
ABNC
N
A
N
N
N
N
N
N
N
A
N
N
N
N
N
N
N
B
N
A
N
A
%R
64.2
66.7
71.2
42.0
86.4
68.2
33.3
29.3
24.8
66.1
68.9
70.0
65.5
62.1
55.8
26.8
28.4
52.6
59.8
51.6
66.7
B
SD
6.5
6.4
4.5
4.8
8.8
8.1
4.5
4.8
1.6
8.0
1.6
7.6
7.8
8.8
8.3
3.3
3.8
26.7
7.0
2.4
5.5
%R
56.4
74.3
58.3
17.2
78.9
63.0
15.8
12.7
23.3
63.8
65.6
68.3
58.7
56.5
41.0
19.3
15.5
64.6
38.7
52.0
49.9
SD
0.5
2.8
5.4
3.1
3.2
2.5
2.0
1.7
0.3
2.5
4.9
0.7
1.0
1.2
2.7
1.8
1.6
4.7
5.5
3.3
4.0
C
%R
86.7
97.4
69.3
41.2
100.8
96.6
27.8
20.5
121.1
74.2
85.6
88.3
86.7
95.8
63.4
35.5
31.1
74.7
46.9
65.6
73.4

SD
1.9
3.4
2.4
8.4
3.2
2.5
6.5
6.2
3.3
3.5
1.7
4.0
1.0
2.5
4.1
6.5
7.4
4.7
6.3
3.4
3.6
D
%R
84.5
89.4
74.8
61.3
83.0
80.7
53.2
46.8
99.0
55.2
68.4
65.2
84.8
89.3
76.9
46.6
57.9
27.9
60.6
65.5
84.0

SD
0.4
3.8
4.3
11.7
4.6
1.0
10.1
10.5
4.5
5.6
3.0
2.0
2.5
1.2
8.4
4.7
10.4
4.0
6.3
2.1
7.0
E
%R
73.4
84.1
37.5
4.8
57.0
67.8
2.0
0.6
94.8
63.4
64.9
59.8
77.0
78.1
12.5
9.2
1.4
34.0
13.6
50.0
20.0

SD
1.0
1.6
5.8
1.0
2.2
1.0
1.2
0.6
2.9
2.0
2.3
0.8
0.7
4.4
4.6
1.7
1.2
4.0
3.2
8.1
3.2
a Percent  recovery  of analytes  spiked  at  200  mg/Kg  into NIST sediment SRM 1645
b Chemical  Abstracts  Service Registry  Number
c Compound  Type:  A = Acid,  B = Base,  N = neutral
d A = Methylene  chloride
  B = Methylene chloride/Acetone (1/1)
  C = Hexane/Acetone (1/1)
  D = Methyl t-butyl  ether
  E = Methyl t-butyl  ether/Methanol (2/1)
                                                 3550B - 10
Revision 2
November 1990

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                                                  TABLE 2.
                      SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040a
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8140
8141
8250"-c
8270C
8310
8321
8410
Extraction
PH
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
hexane
hexane
none
none
acetonitrile
methanol
methyl ene chloride
Exchange Volume
solvent of extract
required required
for for
cleanup cleanup (ml)
hexane
hexane
hexane
methyl ene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
hexane
_.
--
--
--
methyl ene chloride
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
10.0
10.0
-.
--
--
--
10.0
Final
extract
vol ume
for
analysis (ml)
1.0, 10. Ob
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
10.0
10.0
1.0
1.0
1.0
1.0
0.0 (dry)
a To obtain separate acid and base/neutral extracts, Method 3650 should be performed following
  concentration of the extract to 10.0 ml.

b Phenols may be analyzed, by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID.  Method 8040 also
  contains an optical derivatization procedure for phenols which results in a 10 ml hexane extract to be
  analyzed by GC/ECD.

c The specificity of GC/MS may make cleanup of the extracts unnecessary.  Refer to Method 3600 for guidance
  on the cleanup procedures available if required.
                                                 3550B - 11
Revision 2
November 1990

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                         METHOD  3550B
                   ULTRASONIC  EXTRACTION
                              START
                        7  1 Prepare tample*
                        using appropriate
                          method for the
                          wa*te matriit
                         7.2 Determine the
                        percent dry weight
                           of the sample
752 Add anhydrous
 sodium sulfate  to
     •ample
                    No
7 5.3 Add surrogate
 standard* to all
 samples. spikes,
    and  blanks
7.3.1 Add surrogate
 standards to al1
 samples. spikes,
    and blanks
   7.3 2 - 7.3.5
Sonicate sample at
   least 3 times
   754 Adjust
  volume; disrupt
sample with tapered
microtip ultrasonic
      probe
7.5.5
through
filter
glass wool
   7.3.7 Dry and
collect extract in
 K-D  concentrator
                                                7.3.8 Concentrate
                                                extract and collect
                                                in K-D concentrator
                          3550B  -  12
                      Revision 2
                      November 1990

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               METHOD 3550B
                 continued
                             73.9  Is
                             a solvent
                             exchange
                             required?
73.9 Add  exchange
     solvent;
concentrate  extract
7.3.10  Use  Method
3660 for  cleanup
                              7.3.10 Do
                           sulfur crystals
                                form?
                          7.3.11 Further
                        concentrate and/or
                           adjust volume
                     »[ Cleanup or analyze
                 3550B -  13
                                                     Revision 2
                                                     November 1990

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                                 METHOD 3600B

                                   CLEANUP
1.0   SCOPE AND APPLICATION

      1.1   General

            1.1.1    Injection  of sample extracts, without  further  cleanup  or
      isolation  of analytes,  into  a gas  or liquid  chromatograph can  cause
      extraneous peaks,  deterioration of peak resolution and column efficiency,
      and loss of detector sensitivity and can greatly shorten the lifetime of
      expensive columns.  The following  techniques have been applied to extract
      purification:   partitioning   between  immiscible  solvents;  adsorption
      chromatography; gel  permeation chromatography;  chemical  destruction  of
      interfering  substances  with  acid,  alkali,  or oxidizing  agents;  and
      distillation.  These  techniques may be used  individually or  in various
      combinations, depending on the extent and nature of the co-extractives.

            1.1.2    It  is  an unusual  situation  (e.g.  with  some water  samples)
      when extracts can  be directly  determined without further treatment.  Soil
      and waste extracts often  require  a combination  of  cleanup methods.   For
      example, when analyzing for organochlorine pesticides  and PCBs,  it may be
      necessary to  use gel permeation chromatography  (GPC), to eliminate the high
      boiling material  and  a  micro alumina or  Florisil  column  to eliminate
      interferences with the analyte peaks on the GC/ECD.

      1.2   Specific

            1.2.1    Adsorption column chromatography - Alumina (Methods 3610 and
      3611), Florisil (Method 3620), and silica gel (Method 3630) are useful for
      separating analytes  of  a relatively  narrow  polarity  range away  from
      extraneous, interfering peaks  of a different polarity.

            1.2.2    Acid-base partitioning (Method 3650) - Useful for separating
      acidic or basic organics  from  neutral organics.   It  has  been applied to
      analytes such as the chlorophenoxy herbicides  and phenols.

            1.2.3    Gel permeation chromatography  (GPC) (Method 3640) - The most
      universal  cleanup  technique for a broad range of  semivolatile organics and
      pesticides.  It is  capable of separating  high molecular-weight  material
      from  the  sample  analytes.  It has been  used successfully  for all  the
      semivolatile base,  neutral, and  acid compounds  associated  with the EPA
      Priority  Pollutant  and  the  Superfund  Target Compound  list for  GC/MS
      analysis for semivolatiles and pesticides.  GPC is usually not applicable
      for eliminating extraneous peaks  on  a chromatogram which interfere with
      the analytes of interest.

            1.2.4    Sulfur cleanup (Method 3660)  - Useful in eliminating sulfur
      from sample extracts,  which may cause chromatographic interference with
      analytes of interest.
                                  3600B  -  1                       Revision 2
                                                                  November 1990

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            1.2.5    Table 1 indicates the recommended cleanup techniques for the
      indicated groups  of compounds.   This information  can also be used  as
      guidance for compounds  that are not listed.  Compounds  that are chemically
      similar  to  these groups  of  compounds should  follow  a  similar  elution
      pattern.


2.0   SUMMARY OF METHOD

      2.1   Refer to the specific cleanup method for a summary of the procedure.


3.0   INTERFERENCES

      3.1   Analytical interferences may be caused by contaminants in solvents,
reagents,  glassware, and  other sample  processing  hardware.    All  of  these
materials must be routinely demonstrated  to be free of interferences, under the
conditions of the analysis, by running laboratory reagent blanks.

      3.2   More extensive procedures than  those outlined  in  the methods may be
necessary for reagent purification.


4.0   APPARATUS AND MATERIALS

      4.1   Refer to  the  specific  cleanup method  for apparatus  and materials
needed.


5.0   REAGENTS

      5.1   Refer to the specific cleanup method for the reagents needed.


6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1   See the  introductory material  to this  chapter,  Organic Analytes,
Section 4.1.


7.0  PROCEDURE

      7.1   Prior to using the cleanup procedures, samples should undergo solvent
extraction.  Chapter Two,  Section 2.3.3, may be used as a guide  for choosing the
appropriate extraction procedure based on the physical composition of the waste
and on the analytes of interest in the matrix (see also Method 3500 for a general
description of the extraction technique).   For some organic liquids, extraction
prior to cleanup may not be necessary.

      7.2   In most cases, the extracted sample is then  analyzed by one of the
determinative methods available in  Section  4.3 of this chapter.  If the analytes
of  interest  are not  able  to be determined  due to  interferences,  cleanup  is
performed.


                                   3600B  -  2                       Revision 2
                                                                  November 1990

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      7.3   Many of the determinative methods specify cleanup methods that should
be  used  when   determining  particular  analytes  (e.g.   Method   8060,   gas
chromatography of phthalate esters, recommends using either Method 3610 (Alumina
column cleanup) or Method 3620 (Florisil column cleanup) if interferences prevent
analysis).   However,  the  experience of the  analyst  may prove  invaluable  in
determining which cleanup  methods are needed.   As  indicated in Section 1.0 of
this method, many matrices may  require  a  combination  of cleanup procedures in
order to ensure proper analytical determinations.

      7.4   Guidance for cleanup is specified in  each of the methods that follow.
The amount of extract cleanup required prior to  the final determination depends
on the selectivity of both  the extraction procedure  and the determinative method
and the required detection limit.

      7.5   Following cleanup, the sample  is concentrated  to whatever volume is
required  in  the  determinative method.  Analysis follows as  specified  in the
determinative procedure  (Section 4.3 of this Chapter).


8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control procedures.

      8.2   The analyst  must demonstrate that the compounds of interest are being
quantitatively recovered by the  cleanup  technique before the cleanup is applied
to actual  samples.   For sample  extracts  that are cleaned  up,  the  associated
quality control samples  (e.g. spikes, blanks,  replicates, and duplicates)  must
also be processed through  the same cleanup procedure.

      8.3   The  analysis  using  each determinative method  (GC, GC/MS,  HPLC)
specifies  instrument  calibration  procedures  using  stock  standards.   It  is
recommended that  cleanup also  be performed on  a  series  of the same  type  of
standards to  validate chromatographic elution  patterns for  the compounds  of
interest and to verify the absence of interferences from reagents.


9.0   METHOD PERFORMANCE

      9.1   Refer to the specific cleanup method for performance data.


10.0  REFERENCES

     10.1   Refer to the specific cleanup method.
                                   3600B  -  3                       Revision 2
                                                                  November 1990

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                                         TABLE 1.
             RECOMMENDED CLEANUP TECHNIQUES FOR INDICATED GROUPS OF COMPOUNDS
                                       Determinative8              Cleanup Method
Analyte Group                              Method                      Option


Phenols                                  8040                     3630",  3640,  3650,  8040C
Phthalate esters                         8060, 8061               3610, 3620, 3640
Nitrosamines                             8070                     3610, 3620, 3640
Organochlorine pesticides & PCBs         8080, 8081               3620, 3640, 3660
Nitroaromatics and cyclic ketones        8090                     3620, 3640
Polynuclear aromatic hydrocarbons        8100                     3611, 3630, 3640
Chlorinated hydrocarbons                 8120, 8121               3620, 3640
Organophosphorus pesticides              8140, 8141               3620
Chlorinated herbicides                   8150, 8151               8150d
Priority pollutant semivolatiles         8250, 8270               3640, 3650, 3660
Priority pollutant semivolatiles         8410                     3640
Petroleum waste                          8250, 8270               3611, 3650


a          The  GC/MS Methods,  8250 and 8270, are also appropriate determinative methods for
          all  analyte groups,  unless lower detection limits  are  required.

b          Cleanup applicable  to derivatized phenols.

c          Method  8040 includes a derivatization  technique followed  by GC/ECD analysis,  if
          interferences  are encountered using GC/FID.

d          Methods 8150 and 8151 incorporate  an acid-base cleanup  step as an integral part
          of the  method.
                                         3600B -  4                       Revision 2
                                                                        November 1990

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              METHOD 3600B
                CLEANUP
     START
      I
    7.1 Do
    solvent
  extraction
      1
  7.2 Analyze
 analyte by a
 determinative
  method from
   Sec. 4.3
   analyte.-
undeterminabl
7.3 Use cleanup
    method
 specified for
the determina-
  tive method
                                7.5
                           Concentrate
                            sample  to
                            required
                             volume
               3600B - 5
                   Revision 2
                   November 1990

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                                 METHOD 3630B

                              SILICA GEL CLEANUP
1.0  SCOPE AND APPLICATION
      1.1  Silica gel is a regenerative adsorbent of amorphous silica with weakly
acidic properties.   It  is  produced from  sodium  silicate  and  sulfuric  acid.
Silica gel  can be  used  for column chromatography  and  is  for  separating  the
analytes from interfering compounds of a different chemical polarity.

      1.2  General applications (Gordon and Ford):

            1.2.1  Activated:  Heated at 150-160°C for several  hours.   USES:
      Separation of hydrocarbons.

            1.2.2  Deactivated:  Containing 10-20% water.  USES:  An adsorbent
      for most functionalities with ionic or nonionic characteristics, including
      alkaloids, sugar esters, glycosides, dyes, alkali  metal cations, lipids,
      glycerides, steroids, terpenoids and plasticizers.  The disadvantages of
      deactivated silica gel  are that the solvents  methanol  and ethanol decrease
      adsorbent activity.

      1.3  Specific applications:   This method  includes guidance for cleanup of
sample  extracts  containing  polynuclear   aromatic  hydrocarbons,  derivatized
phenolic  compounds, polychlorinated  biphenyls  (PCBs)   and single  component
pesticides.   When only PCBs  are  to be measured,  this  method  can  be  used in
conjunction with sulfuric acid/permanganate cleanup (Method 3665).


2.0  SUMMARY OF METHOD

      2.1  The  column  is  packed  with  the  required amount of adsorbent, topped
with a water adsorbent,  and  then loaded with the sample to be analyzed.  Elution
of the analytes is effected with a suitable solvent(s) leaving the interfering
compounds on the column.  The eluate is then concentrated.


3.0  INTERFERENCES

      3.1   A reagent blank  should  be  analyzed for the  compounds of interest
prior to the use of this method.  The level of interferences must be below the
method detection limit before this method  is performed on actual samples.

      3.2  More extensive procedures than those outlined in this method may be
necessary for reagent purification.


4.0  APPARATUS AND MATERIALS

      4.1  Chromatographic column - 250 mm long  x 10 mm ID; with  Pyrex glass wool
at bottom and a Teflon stopcock.


                                   3630B  -  1                      Revision 2
                                                                  November  1990

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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.

      4.2  Beakers - 500 ml.

      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-570001-0500  or
      equivalent).   Attach  to  concentrator  tube  with  springs,  clamps,  or
      equivalent.

            4.3.3   Snyder  column  - Three ball macro  (Kontes K-503000-0121 or
      equivalent).

            4.3.4   Snyder column  -  Two  ball  micro (Kontes  K-569001-0219 or
      equivalent).

            4.3.5  Springs - 1/2 inch (Kontes K-662750 or equivalent).

      4.4  Vials - 10,  25 ml, glass with Teflon lined screw-caps or crimp tops.

      4.5  Muffle furnace.

      4.6  Reagent bottle - 500 ml.

      4.7    Water bath  -  Heated,  with concentric  ring cover,  capable  of
temperature control (±5°C).   The bath should be used in a hood.

      4.8  Boiling chips -  Solvent  extracted, approximately 10/40 mesh (silicon
carbide or equivalent).

      4.9  Erlenmeyer flasks - 50  and 250 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.

      5.2  Organic-free reagent water.   All references to water in this method
refer to organic-free reagent water, as  defined in Chapter One.
                                   3630B - 2                      Revision 2
                                                                  November 1990

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      5.3  Silica gel.   100/200 mesh desiccant (Davison Chemical grade 923 or
equivalent).   Before  use,  activate for at least  16  hr.  at 130°C in a shallow
glass tray, loosely covered with foil.

      5.4  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  Eluting solvents

            5.5.1  Cyclohexane,  C6H12 - Pesticide quality or equivalent.

            5.5.2  Hexane, C6H14 - Pesticide quality or equivalent.

            5.5.3  2-Propanol,  (CH3)2CHOH  - Pesticide  quality  or equivalent.

            5.5.4  Toluene, C6H5CH3 - Pesticide quality or equivalent.

            5.5.5  Methylene chloride, CH2C12 - Pesticide quality or  equivalent.

            5.5.6  Pentane, C5H12 - Pesticide quality or equivalent.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the introductory  material to  this  chapter,  Organic Analytes,
Section 4.1.


7.0  PROCEDURE

      7.1  Polynuclear aromatic hydrocarbons

            7.1.1  Before the silica gel  cleanup technique can be utilized, the
      extract solvent  must be exchanged to cyclohexane. The exchange is performed
      as follows:

                  7.1.1.1  Following K-D concentration of the  extract to 1-2 mL
            using the macro-Snyder column, allow the apparatus to cool and drain
            for at least 10 minutes.  Add one or two clean boiling chips to the
            K-D flask. Add 4 mL of exchange solvent and attach a two  ball micro-
            Snyder column.  Prewet the Snyder  column by adding  about 0.5 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  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 0.5-1 mL, remove the K-D apparatus


                                   3630B  - 3                       Revision 2
                                                                  November  1990

-------
            from the water bath and allow it to drain and cool for at least 10
            minutes.

Caution:   When  the volume  of solvent  is  reduced  below  1  ml,  semivolatile
           analytes may be lost.

                  7.1.1.2  Remove the micro-Snyder  column  and rinse its lower
            joint into the concentrator tube with a minimum amount of exchange
            solvent.  Adjust the extract volume to about 2 ml.

            7.1.2  Prepare a  slurry of 10 g of activated  silica gel in methylene
      chloride and place this into a 10 mm ID chromatographic column.  Tap the
      column to settle the silica gel and elute the methylene chloride.  Add 1
      to 2 cm of anhydrous sodium sulfate to the top of the silica gel.

            7.1.3  Preelute the column with  40 ml of pentane.  The rate for all
      elutions should be about 2 mL/min.  Discard the eluate and just prior to
      exposure  of the  sodium sulfate  layer to the air,   transfer the  2  ml
      cyclohexane  sample  extract onto  the  column  using  an  additional  2  mL
      cyclohexane to complete the transfer.  Just prior to exposure of the sodium
      sulfate layer to the air, add  25  mL of pentane and continue the elution
      of the column.  Discard this pentane eluate.

            7.1.4   Next,  elute the  column  with  25 ml  of  methylene chloride/
      pentane  (2:3)(v/v)   into  a  500   ml  K-D  flask equipped  with  a 10  ml
      concentrator tube.  Concentrate the collected  fraction to whatever volume
      is required (1-10 ml).   Proceed with HPLC or GC analysis.  Components that
      elute in this fraction are:

                  Acenaphthene
                  Acenaphthylene
                  Anthracene
                  6enzo(a)anthracene
                  Benzo(a)pyrene
                  Benzo(b)fluoranthene
                  Benzo(g,h,i)perylene
                  Benzo(k)fl uoranthene
                  Chrysene
                  Dibenzo(a,h)anthracene
                  Fluoranthene
                  Fluorene
                  Indeno(l,2,3-cd)pyrene
                  Naphthalene
                  Phenanthrene
                  Pyrene

      7.2  Derivatized phenols

            7.2.1   This silica gel  cleanup procedure  is  performed on sample
     extracts that  have  undergone  pentafluorobenzyl bromide derivatization as
     described in Method 8040.
                                   3630B -  4                       Revision 2
                                                                  November 1990

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            7.2.2    Place  4.0  g of  activated  silica  gel  into  a  10 mm  ID
      chromatographic column.  Tap the column to settle the silica gel and add
      about 2 g of anhydrous sodium sulfate to the top of the silica gel.

            7.2.3  Preelute the  column with 6  ml of  hexane.   The  rate for all
      elutions should be about 2 mL/min.  Discard the eluate and just prior to
      exposure of the sodium sulfate layer to the  air, pipet onto the column 2 mL
      of the hexane  solution that contains the derivatized sample or standard.
      Elute the column with 10.0 ml of hexane and discard the eluate.

            7.2.4  Elute the column,  in  order, with  10.0  ml  of 15% toluene in
      hexane (Fraction 1);  10.0 mL of 40%  toluene  in hexane  (Fraction 2); 10.0 ml
      of 75% toluene  in hexane  (Fraction 3);  and 10.0 ml  of  15% 2-propanol  in
      toluene (Fraction 4).  All  elution'mixtures  are prepared  on  a volume:volume
      basis.  Elution patterns for the  phenolic derivatives are shown in Table 1.
      Fractions may be combined,  as desired, depending upon the specific phenols
      of interest or level of interferences.   Proceed with GC analysis (Method
      8040).

      7.3  PCBs and  single component pesticides:

            7.3.1  Place a portion of  activated silica gel  (normally 20 g)  into
      a glass jar and deactivate  it with organic-free  reagent  water to bring the
      moisture content  to 3.3  percent.    Mix  the contents  of the  glass  jar
      thoroughly and equilibrate for 6 hours.  Store  the deactivated silica gel
      in a sealed glass jar  inside  a  desiccator.  Transfer a 3 g  portion  into
      a  10  mm ID glass chromatographic  column  and top it with 2 to  3 cm  of
      anhydrous sodium sulfate.

            7.3.2  Add 10  ml  of hexane to the top  of the column to wet and rinse
      the sodium sulfate and silica gel.   Just prior to exposure of the sodium
      sulfate layer to air, stop the hexane eluate  flow by closing the stopcock
      on the chromatographic column.  Discard the eluate.

            7.3.3  Transfer the  sample extract (2  ml)  onto the column.  Rinse
      the extract vial twice with 1  to 2  ml of hexane and add each rinse to the
      column.  Elute the column with 80 ml of hexane (Fraction I)  at a rate of
      about 5 mL/min.   Remove the collection  flask and set it aside for later
      concentration.  Elute the  column with 50 mL  of hexane  (Fraction II)  and
      collect the  eluate.    Perform a third elution  with 15 mL  of  methylene
      chloride (Fraction  III).   The  elution  patterns for the  organochlorine
      pesticides, Aroclor-1016,  and Aroclor-1260  are shown in Table 2.

            7.3.4  Prior to gas chromatographic analysis, the extraction solvent
      must be exchanged to hexane (Sections 7.1.1.1 and 7.1.1.2).  Proceed  with
      GC analysis.


8.0  QUALITY CONTROL

      8.1   Refer to Chapter One  for  specific quality control  procedures  and
Method 3600 for cleanup procedures.
                                   3630B  -  5                       Revision 2
                                                                  November 1990

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      8.2  The  analyst should demonstrate that the  compounds  of Interest are
being quantitatively recovered before applying this method to actual samples.

      8.3   For sample  extracts  that  are  cleaned up  using this  method,  the
associated quality control samples must also be processed through this cleanup
method.
9.0  METHOD PERFORMANCE

      9.1   Table 1 provides  performance information on  the  fractionation of
phenolic derivatives using this method.

      9.2  Table 2 provides performance information on the  fractionation of PCBs
and single component pesticides using this method.


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.
                                   3630B -  6                       Revision 2
                                                                  November 1990

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                                    TABLE 1
                 SILICA GEL FRACTIONATION OF PFBB DERIVATIVES
                                        Percent Recovery by Fraction8

Parameter                           123
2-Chlorophenol
2-Nitrophenol
Phenol
2, 4 -Dimethyl phenol
2,4-Dichlorophenol
2 , 4 , 6-Tri chl orophenol
4-Chloro-3-methyl phenol
Pentachl orophenol
4-Nitrophenol
90

90
95
95
50 50
84
75 20

1
9
10
7
1

14

1

90






90
   Eluant composition:

    Fraction 1 - 15% toluene in hexane.
    Fraction 2 - 40% toluene in hexane.
    Fraction 3 - 75% toluene in hexane.
    Fraction 4 - 15% 2-propanol in toluene.
                                   3630B - 7                       Revision  2
                                                                   November 1990

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                              TABLE 2
       DISTRIBUTION AND PERCENT RECOVERIES  OF  ORGANOCHLORINE
PESTICIDES AND PCBs AS AROCLORS  IN  SILICA GEL COLUMN FRACTIONS8-"-0'"'6
Compound
alpha-BHCf
beta-BHC
gamma -BHC
delta-BHC
Heptachlor
Aldrin
Heptachlor
Technical
Endosulfan
4,4'-DDE
Dieldrin
Endrin
Endosulfan
4,4'-DDDf
Fraction I
Cone. Cone.
1 2






epoxide
chlordane
I



II





109(4.
97(5.

14(5.

86(5.








1)
6)

5)

4)








118(8.7)
104(1.6)

22(5.3)

94(2.8)




Endrin aldehyde
Endosulfan
4,4'-DDTf
sulfate







4,4'-Methoxychlor
Toxaphene'

Aroclor-1016
Aroclor-1260

86(4.
91(4.

0)
1)

87(6.1)
95(5.0)
Fraction II Fraction I
Cone. Cone. Cone.
1 2 1
82(1.
107(2.
91(3.
92(3.


95(4.
19(6.8) 39(3.6) 29(5.
95(5.

96(6.
85(10
97(4.
102(4.
81(1.
93(4.
86(13.4) 73(9.1) 15(17
99(9.
15(2.4) 17(1.4) 73(9.



7)
1)
6)
5)


7)
0)
1)

0)
.5)
4)
6)
9)
9)
•7)
9)
4)


II
Cone.
2
74(8.0)
98(12.5)
85(10.7)
83(10.6)


88(10.2)
37(5.1)
87(10.2)

87(10.6)
71(12.3)
86(10.4)
92(10.2)
76(9.5)
82(9.2)
8.7(15.0)
82(10.7)
84(10.7)


Total
Cone.
1
82(1.
107(2.
91(3.
92(3.
109(4.
97(5.
95(4.
62(3.
95(5.
86(5.
96(6.
Recovery
Cone.
2
7)
1)
6)
5)
1)
6)
7)
3)
1)
4)
0)
85(10.5)
97(4.
102(4.
81(1.
93(4.
4)
6)
9)
9)
101(5.3)
99(9.
88(12
86(4.
91(4.
9)
.0)
0)
1)
74(8.
98(12
85(10
83(10
118(8.
104(1.
88(10
98(1.
87(10
94(2.
87(10
0)
.5)
.7)
.6)
7)
6)-
.2)
9)
.2)
8)
.6)
71(12.3)
86(10
92(10
76(9.
82(9.
82(23
82(10
101(10
87(6.
95(5.
•4)
.2)
5)
2)
•7)
.7)
•1)
1)
0)
                             3630B - 8
Revision 2
November 1990

-------
                                             TABLE  2
                                           (Continued)
Effluent composition:   Fraction  I, 80 ml hexane;  Fraction  II, 50 ml hexane;  Fraction III,  15 ml methylene
chloride.
Concentration 1 is 0.5 /Ltg  per column  for BHCs,  heptachlor,  aldrin,  heptachlor epoxide,  and endosulfan
I; 1.0 /ig per column for dieldrin, endosulfan II, 4,4'-DDD,  4,4'-DDE, 4,4'-DDT, endrin, endrin aldehyde,
and endosulfan sulfate; 5  /zg per column for 4,4'-methoxychlor  and technical chlordane; 10 ug per column
for toxaphene, Aroclor-1016, and Aroclor-1260.
For Concentration 2,  the amounts spiked are 10 times as high as those for Concentration 1.
Values given  represent the average recovery  of three  determinations;  numbers in  parentheses  are the
standard deviation; recovery cutoff point is 5 percent.
Data obtained with standards, as indicated in footnotes b and c, dissolved in 2 ml hexane.
It has been found that because of batch-to-batch variation in the silica gel  material, these compounds
cross over in two fractions and the amounts recovered in each fraction are difficult to reproduce.
                                           3630B  -  9                                      Revision 2
                                                                                          November 1990

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                           METHOD 3630B
                       ililCA GEL CLEANUP
                                Start
  7.1.1 Exchange
extract «olv«nt to
eyclohexana during
   K-D procedure
   7.1.2 Prepare
 tlurry activated
•ilica gel,  prepare
      column
                                   Derivatixed
                                   Phenol*
                          7.3.1 Deactivate
                         •ilica gel,  prepare
                               column
   7.2.1 Do  PFBB
 derivatixation on
  •ample extract
      (8040)
7.3.2 Elute the  CC
column with hexane
  7.1.3 Preelute
    column with
 pentane,  transfer
extract unto  column
  and elute with
      pentane
7.1.4 Elute column
       with
  CHiCli/pentane;
    concentrate
collected fraction;
   adjuit volume
    7.2.2 Place
 activated liliea
      gel in
  chromatographio
    column;  add
 anhydrou* tU|SO(
  7.3.3 Transfer
extract unto column
  and elute with
      hexane
  7.2.3 Preelute
column with  hexane;
   pipet hexane
•olution on  column;
       elute
7.3.4 Exchange  the
extraction solvent
to hexane (Section*
    7.1.1.1 and
     7.1.1.2)
                         7.2.4 Elute column
                             with hexane
                              •olution
                               Aaalyie
                                by CC
                               (Method
                                8040)
                           3630B  -  10
                                             Revision  2
                                             November  1990

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                                 METHOD 3640A

                            GEL-PERMEATION CLEANUP
1.0  SCOPE AND APPLICATION

      1.1   Gel-permeation  chromatography  (GPC)  is  a size  exclusion  cleanup
procedure  using  organic solvents  and hydrophobic gels  in the  separation  of
synthetic macromolecules (1).  The  packing  gel  is  porous and is characterized
by the range or uniformity  (exclusion range) of that pore size.  In the choice
of gels,  the exclusion range  must  be larger than  the molecular  size  of the
molecules to be separated  (2).  A cross linked divinyl benzene-styrene copolymer
(SX-3 Bio Beads or equivalent) is specified for this method.

      1.2  General  cleanup  application -  GPC is recommended for the elimination
from the sample of lipids,  polymers,  copolymers,  proteins,  natural resins and
polymers, cellular components,  viruses, steroids, and dispersed high-molecular-
weight compounds (2).   GPC is appropriate for both polar and non-polar analytes,
therefore, it  can  be  effectively used to cleanup extracts  containing  a broad
range of analytes.

      1.3  Specific application - This method includes guidance for cleanup of
sample extracts containing  the following analytes  from the RCRA Appendix VIII
and Appendix IX lists:
      Compound Name                                         CAS  No.*
      Acenaphthene                                             83-32-9
      Acenaphthylene                                           208-96-8
      Acetophenone                                             98-86-2
      2-Acetylaminofluorene                                    53-96-3
      Aldrin                                                   309-00-2
      4-Aminobiphenyl                                          92-67-1
      Aniline                                                  62-53-3
      Anthracene                                               120-12-7
      Benomyl                                                17804-35-2
      Benzenethiol                                             108-98-5
      Benzidine                                                92-87-5
      Benz(a)anthracene                                        56-55-3
      Benzo(b)fluoranthene                                     205-99-2
      Benzo(a)pyrene                                           50-32-8
      Benzo(ghi)perylene                                       191-24-2
      Benzo(k)fluoranthene                                     207-08-9
      Benzoic acid                                             65-85-0
      Benzotrichloride                                         98-07-7
      Benzyl alcohol                                           100-51-6
      Benzyl chloride                                          100-44-7
      alpha-BHC                                                319-84-6
      beta-BHC                                                 319-85-7
      gamma-BHC                                                58-89-9

                                    3640A - 1                    Revision 1
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Compound Name
CAS No.'
delta-BHC
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-butyl-4,6-dinitrophenol (Dinoseb)
Carbazole
Carbendazim
alpha-Chlordane
gamma-Chlordane
4-Chloro-3-methylphenol
4-Chloroaniline
Chiorobenzilate
Bi s(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenol
3-Chlorophenol
4-Chlorophenyl phenyl ether
3-Chloropropionitrile
Chrysene
2-Cresol
3-Cresol
4-Cresol
Cyclophosphamide
ODD
DDE
DDT
Di-n-butyl phthalate
Dial late
Dibenzo(a,e)pyrene
Dibenzo(a,i)pyrene
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
Dibenzofuran
Dibenzothiophene
1,2-Di bromo-3-chloropropane
1,2-Dlbromoethane
trans-l,4-Dichloro-2-butene
cis-l,4-Dichloro-2-butene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dlchlorobenzene
3,3'-Dichlorobenzidine
2,6-Dichlorophenol
2,4-Dichlorophenoxyacetic acid (2,4-D)
2,4-Dichlorophenol
2,4-Dichlorotoluene
l,3-Dichloro-2-propanol
  319-86-8
  101-55-3
   85-68-7
   88-85-7
   86-74-8
10605-21-7
 5103-71-9
 5566-34-7
   59-50-7
  106-47-8
  510-15-6
  111-91-1
  111-44-4
  108-60-1
   91-58-7
   95-57-8
  106-48-9
  108-43-0
 7005-72-3
  542-76-7
  218-01-9
   95-48-7
  108-39-4
  106-44-5
   50-18-0
   72-54-8
   72-55-9
   50-29-3
   84-74-2
 2303-16-4
  192-65-4
  189-55-9
  224-42-0
   53-70-3
  132-64-9
  132-65-0
   96-12-8
  106-93-4
  110-57-6
 1476-11-5
   95-50-1
  106-46-7
  541-73-1
   91-94-1
   87-65-0
   94-75-7
  120-83-2
   95-73-8
   96-23-1
                              3640A - 2
    Revision  1
    November  1990

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Compound Name
Dieldrin
Di ethyl phthalate
Dimethoate
Dimethyl phthalate
p-Dimethylaminoazobenzene
7,12-Dimethyl-benz(a)anthracene
2,4-Dimethylphenol
3,3-Dimethylbenzidine
4,6-Dinitro-o-cresol
1,3-Dinitrobenzene
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
Diphenyl ether
1 , 2-Diphenyl hydrazi ne
Disulfoton
Endosulfan sulfate
Endosulfan I
Endosulfan II
Endrin
Endrin aldehyde
Endrin ketone
Ethyl methane sulfonate
Ethyl methacrylate
Bis(2-ethylhexyl) phthalate
Famphur
Fluorene
Fluoranthene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachl orobutadi ene
Hexachl orocycl opentadi ene
Hexachl oroethane
Hexachl oropropene
Indeno( 1 , 2 , 3-cd) pyrene
Isodrin
Isophorone
cis-Isosafrole
trans-Isosafrole
Kepone
Malononitrile
Merphos
Methoxychlor
3-Methyl chol anthrene
2-Methyl naphthalene
Methyl parathion
4,4'-Methylene-bis(2-chloroaniline)
CAS No.a
60-57-1
84-66-2
60-51-5
131-11-3
60-11-7
57-97-6
105-67-9
119-93-7
534-52-1
99-65-0
51-28-5
121-14-2
606-20-2
122-39-4
101-84-8
122-66-7
298-04-4
1031-07-8
959-98-8
33213-65-9
72-20-8
7421-93-4
53494-70-5
62-50-0
97-63-2
117-81-7
52-85-7
86-73-7
206-44-0
76-44-8
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
1888-71-7
193-39-5
465-73-6
78-59-1
17627-76-8
4043-71-4
143-50-0
109-77-3
150-50-5
72-43-5
56-49-5
91-57-6
298-00-0
101-14-4
3640A - 3
Revision 1
November 1990

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Compound Name
Naphthalene
1,4-Naphthoqulnone
2-Naphthylamine
1-Naphthylamine
5-Nitro-o-toluidine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
N-Nitrosodi-n-butylamine
N-Nitrosodiethanolamine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
N-Ni trosomethyl ethyl ami ne
N-Nitrosomorphol ine
N-Nitrosopiperidine
N-Nitrosopyrolidine
Di-n-octyl phthalate
Parathion
Pentachl orobenzene
Pentachl oroethane
Pentachl oronitrobenzene (PCNB)
Pentachl orophenol
Phenacetin
Phenanthrene
Phenol
1,2-Phenylenediamine
Phorate
2-Picoline
Pronamide
Pyrene
Resorcinol
Safrole
1,2,4, 5-Tetrachl orobenzene
2,3,5 , 6-Tetrachl oroni trobenzene
2,3,5,6-Tetrachlorophenol
2,3,4 , 6-Tetrachl orophenol
Tetraethyl dithiopyrophosphate (Sulfotep)
Thiosemicarbazide
2-Toluidine
4-Toluidine
Thiourea, l-(o-chlorophenyl)
Toluene-2,4-diamine
1 , 2 , 3-Tri chl orobenzene
1, 2, 4-Trichl orobenzene
CAS No."
91-20-3
130-15-4
91-59-8
134-32-7
99-55-8
88-74-4
99-09-2
100-01-6
98-95-3
79-46-9
100-02-7
924-16-3
1116-54-7
55-18-5
62-75-9
86-30-6
621-64-7
10595-95-6
59-89-2
100-75-4
930-55-2
117-84-0
56-38-2
608-93-5
76-01-7
82-68-8
87-86-5
62-44-2
85-01-8
108-95-2
95-54-5
298-02-2
109-06-8
23950-58-5
129-00-0
108-46-3
94-59-7
95-94-3
117-18-0
935-95-5
58-90-2
3689-24-5
79-19-6
106-49-0
95-53-4
5344-82-1
95-80-7
87-61-6
120-82-1
3640A - 4
Revision 1
November 1990

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      Compound Name                                         CAS No."


      2,4,6-Trichlorophenol                                    88-06-2
      2,4,5-Trichlorophenol                                    95-95-4
      2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)              93-76-5
      2,4,5-Trichlorophenoxypropionic acid (2,4,5-TP)          93-72-1
      Warfarin                                                 81-81-2


      8   Chemical  Abstract  Services  Registry  Number.


      Table 1 presents average percent recovery and percent RSD data for these
analytes, as  well  as the  retention volumes  of  each  analyte  on a  single 6PC
system.    Retention volumes vary  from  column to  column.   Figure  1  provides
additional information on  retention  volumes  for  certain  classes  of compounds.
The data for the semivolatiles was determined by GC/MS, whereas,  the pesticide
data was  determined  by  GC/ECD or GC/FPD.   Compounds not amenable  to  GC were
determined by HPLC.   Other analytes may also be appropriate  for  this  cleanup
technique, however, recovery through the GPC should be >70%.

      1.4  Normally,  this  method  is  most  efficient for removing  high  boiling
materials that condense in the injection port area of a gas chromatograph (GC)
or  the  front of  the  GC   column.    This  residue  will  ultimately  reduce the
chromatographic separation efficiency or column capacity because of adsorption
of the target analytes on  the  active sites.   Pentachlorophenol  is especially
susceptible to this problem.  GPC, operating on the  principal of size exclusion,
will not usually remove interference  peaks that appear in the chromatogram since
the molecular size  of these compounds is relative similar to the target analytes.
Separation cleanup techniques, based on other molecular characteristics (i.e.,
polarity), must be used to eliminate this type of interference.


2.0  SUMMARY OF METHOD

      2.1 The column  is packed with  the required amount of preswelled absorbent,
and is flushed with  solvent for  an  extended  period.   The column  is calibrated
and then loaded with the sample extract to be cleaned up.  Elution is  effected
with a suitable solvent(s) and the product is then concentrated.


3.0  INTERFERENCES

      3.1  A reagent  blank  should be analyzed for the  compound of interest prior
to  the  use of  this  method.   The  level  of  interferences  must  be below the
estimated quantitation limits  (EQLs) of the analytes  of  interest  before this
method is performed on actual  samples.

      3.2  More extensive procedures than those outlined in this method may be
necessary for reagent purification.


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4.0  APPARATUS

      4.1  Gel-permeation chromatography system - GPC Autoprep Model  1002 A or B,
or equivalent, Analytical Biochemical Laboratories, Inc.  Systems that perform
very satisfactorily have also been assembled  from the following components - an
HPLC pump, an auto sampler or a valving system with  sample  loops, and a fraction
collector.  All systems, whether automated  or manual, must meet the calibration
requirements of Section 7.2.2.

             4.1.1  Chromatographic column -  700 mm x 25 mm  ID  glass column.
      Flow is  upward.   (Optional)   To  simplify switching  from the UV detector
      during calibration to the  GPC collection device  during extract cleanup,
      attach a double 3-way valve (Rheodyne Type 50 Teflon Rotary Valve #10-262
      or equivalent) so that the column exit flow can be shunted either to the
      UV flow-through cell  or to the GPC collection device.

             4.1.2  Guard column - (Optional)  5 cm,  with  appropriate fittings
      to connect  to the inlet side of the analytical  column (Supelco 5-8319 or
      equivalent).

             4.1.3 Bio Beads (S-X3)  - 200-400 mesh,  70 gm (Bio-Rad Laboratories,
      Richmond, CA, Catalog 152-2750 or equivalent).  An additional 5 gm of Bio
      Beads is required if the optional guard column is employed.  The quality
      of Bio Beads may vary from lot to lot because of excessive fines in some
      lots.   The UV chromatogram of  the Calibration solution should  be very
      similar  to  that in Figure  2,  and  the backpressure should be within 6-10
      psi.  Also,  the gel  swell ratio in methylene  chloride  should  be  in the
      range of 4.4 - 4.8 mL/gm.  In addition to fines having a detrimental effect
      on chromatography, they can also pass  through the column screens and damage
      the valve.

             4.1.4 Ultraviolet detector - Fixed wavelength  (254 nm) with a semi-
      prep flow-through cell.

             4.1.5  Strip chart  recorder,  recording integrator  or laboratory
      data system.

             4.1.6  Syringe  -  10 mL  with  Luerlok fitting.

             4.1.7  Syringe filter  assembly, disposable -  Bio-Rad  "Prep Disc"
      sample  filter  assembly  #343-0005, 25  mm,  and  5 micron  filter  discs or
      equivalent.  Check each batch for contaminants.  Rinse each filter assembly
      (prior to use) with methylene chloride if necessary.

      4.2    Analytical  balance  - 0.0001  g.

      4.3    Volumetric  flasks,  Class  A  - 10  mL to  1000 mL

      4.4    Graduated cylinders


5.0  REAGENTS

      5.1  Methylene chloride, CH2C12.  Pesticide quality or equivalent.

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             5.1.1   Some brands of methyl ene chloride may contain unacceptably
      high levels  of  acid (HC1).   Check  the pH by  shaking  equal  portions of
      methylene chloride and water, then check the pH of the water layer.

                   5.1.1.1   If the  pH  of the water  layer  is <  5,  filter the
             entire supply of  solvent  through a 2  in.  x 15  in.  glass column
             containing   activated  basic  alumina.    This  column  should  be
             sufficient  for processing approximately  20-30  liters  of solvent.
             Alternatively,  a  different supply of methylene chloride should be
             found.

      5.2  Cyclohexane,  C6H12.   Pesticide quality or equivalent.

      5.3  n-Butyl chloride, CH3CH2CH2CH2C1 .   Pesticide quality or equivalent.

      5.4  GPC Calibration Solution. Prepare a calibration solution  in methylene
chloride containing the following analytes (in elution order):

             Compound                            mq/L
             corn  oil                            25,000
             bis(2-ethylhexyl)  phthalate           1000
             methoxychlor                          200
             perylene                                20
             sulfur                                 80

Note: Sulfur is not very soluble  in methylene chloride,  however, it is soluble
      in warm corn oil.   Therefore, one approach is to weigh out the corn oil,
      warm it and transfer the weighed  amount of sulfur  into the warm corn oil.
      Mix it and then  transfer into a volumetric flask with methylene chloride,
      along with the other calibration compounds.

      Store  the  calibration solution   in  an  amber  glass bottle  with  a Teflon
lined screw-cap at  4°C,  and protect from  light.   (Refrigeration may cause the
corn oil to  precipitate.   Before use,  allow the calibration solution to stand
at room  temperature until the corn oil  dissolves.)  Replace the calibration
standard solution every 6 months, or more frequently  if necessary.

      5.5  Corn Oil Spike  for  Gravimetric Screen.   Prepare a solution of corn
oil in methylene chloride (5 mg/100
6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the introductory  material  to this chapter,  Organic Analytes,
Section 4.1.
7.0  PROCEDURE

      7.1  It is very important to have consistent laboratory temperatures during
an entire GPC  run,  which  could  be 24 hours or more.   If temperatures are not
consistent, retention times will shift, and the dump and collect times determined
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by the calibration standard will no longer be appropriate.  The ideal laboratory
temperature to prevent outgassing of the methylene chloride is 72°F.

      7.2  GPC Setup and Calibration

             7.2.1  Column  Preparation

                   7.2.1.1  Weigh out 70 gm of Bio Beads (SX-3).  Transfer them
             to  a quart bottle with a Teflon lined cap  or  a 500 ml separatory
             funnel  with  a  large bore stopcock, and add approximately 300 ml of
             methylene  chloride.   Swirl  the container to ensure the wetting of
             all  beads.  Allow  the beads to swell  for  a minimum  of  2 hours.
             Maintain  enough  solvent  to sufficiently cover the beads  at  all
             times.  If a guard column is to be  used,  repeat  the above with 5 gm
             of  Bio Beads  in a  125 ml  bottle or  a beaker,  using  25 ml  of
             methylene  chloride.

                   7.2.1.2  Turn  the column upside down from its normal position,
             and  remove the  inlet  bed support plunger  (the inlet plunger  is
             longer than  the  outlet plunger).   Position  and tighten the outlet
             bed  support plunger as near the end as possible, but no closer than
             5 cm (measured from the gel  packing to the  collar).

                   7.2.1.3  Raise the end of the outlet tube  to keep the solvent
             in  the GPC column,  or close the column  outlet  stopcock  if one  is
             attached.  Place a small amount of solvent in the column to minimize
             the  formation  of air bubbles at the base of poured column packing.


                   7.2.1.4  Swirl the  bead/solvent slurry to get a homogeneous
             mixture and,  if  the wetting was  done in a quart  bottle,  quickly
             transfer   it  to   a  500 ml  separatory  funnel  with  a large  bore
             stopcock.   Drain the excess methylene chloride directly  into  the
             waste beaker,  and then start draining the  slurry  into the column
             by placing the separatory funnel tip  against the column wall.  This
             will  help  to minimize bubble formation.   Swirl occasionally to keep
             the  slurry homogeneous. Drain enough to fill the column.  Place the
             tubing from the column outlet into  a waste beaker below the column,
             open the   stopcock (if attached)  and  allow the excess  solvent  to
             drain.  Raise the tube to  stop  the  flow and close the stopcock when
             the  top of the gel  begins to look dry.   Add  additional  methylene
             chloride to  just rewet the gel.

                   7.2.1.5  Wipe any remaining beads and solvent from the inner
             walls of the top of the column with a  laboratory tissue.  Loosen the
             seal  slightly on the  other plunger  assembly   (long  plunger)  and
             insert it  into the column.  Make the seal just tight enough so that
             any  beads  on the glass surface will  be  pushed  forward,  but loose
             enough so  that the plunger can  be  pushed forward.

CAUTION:  Do  not tighten  the seal  if beads are between  the  seal  and  the glass
          surface because this can  damage the seal and cause leakage.
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      7.2.1.6   Compress the  column as  much  as  possible  without
applying excessive force.  Loosen  the  seal  and  gradually pull  out
the plunger.  Rinse and wipe off the plunger.  Slurry any remaining
beads and transfer them into the column.  Repeat Section 7.2.1.5 and
reinsert the plunger.   If the  plunger cannot be inserted and pushed
in without  allowing  beads  to  escape  around  the seal,  continue
compression of the beads without tightening the seal, and loosen and
remove the plunger as  described.   Repeat this procedure until  the
plunger is successfully inserted.

      7.2.1.7  Push the plunger until it meets the gel, then compress
the column bed about four centimeters.

      7.2.1.8  Pack the optional 5 cm column with approximately 5 gm
of preswelled beads (different guard columns may require different
amounts).  Connect the guard column to  the inlet of the analytical
column.

      7.2.1.9  Connect the  column inlet to the  solvent reservoir
(reservoir should be placed higher than the top of the column)  and
place  the  column  outlet  tube in  a waste  container.    Placing  a
restrictor in the outlet tube  will  force  air out of the column more
quickly.   A  restrictor can  be  made  from a  piece  of  capillary
stainless steel  tubing  of  1/16"  OD  x  10/1000"  ID x  2".   Pump
methylene chloride through  the column at  a rate of 5 mL/min for one
hour.

      7.2.1.10   After washing the  column  for at least  one hour,
connect the  column outlet tube, without  the restrictor, to the inlet
side of the UV detector.  Connect  the  system  outlet  to the outlet
side of  the UV detector.  A  restrictor  (same size as  in  Section
7.2.1.9) in  the outlet  tube from the UV  detector will prevent bubble
formation which causes a noisy UV baseline.   The restrictor will  not
effect  flow rate.  After  pumping  methylene  chloride  through  the
column for  an  additional  1-2  hours, adjust the  inlet  bed  support
plunger until  approximately 6-10 psi backpressure is achieved.  Push
the plunger  in to increase pressure or slowly pull outward to reduce
pressure.

      7.2.1.11   When  the GPC  column is not  to be used  for several
days, connect the column outlet line to the column inlet to prevent
column drying and/or channeling.  If channeling occurs, the gel must
be removed  from  the  column,  reswelled,  and repoured  as described
above.  If drying occurs, methylene  chloride should be pumped through
the column  until  the  observed  column pressure is  constant  and  the
column  appears wet.    Always  recalibrate after column  drying  has
occurred to verify retention volumes have not changed.

7.2.2  Calibration of the GPC Column

      7.2.2.1   Using  a  10  ml syringe,  load  sample  loop  #1  with
calibration solution (Section  5.6). With the ABC automated system,
the 5 ml sample loop requires a minimum of 8 ml of the calibration
solution.  Use a firm,  continuous pressure to push the sample onto

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the loop.  Switch the valve so that GPC flow is  through the UV flow-
through cell.

      7.2.2.2  Inject the calibration solution and obtain a UV trace
showing  a  discrete  peak for each component.   Adjust  the detector
and/or recorder sensitivity to produce a UV trace similar to Figure
2  that   meets  the  following  requirements.    Differences  between
manufacturers' cell volumes and detector sensitivities may require
a dilution of the calibration solution to achieve similar results.
An analytical flow-through detector  cell will  require  a much less
concentrated solution  than  the semi-prep cell,  and  therefore the
analytical cell  is not acceptable for use.

      7.2.2.3    Following   are  criteria  for  evaluating  the  UV
chromatogram for column condition.

            7.2.2.3.1   Peaks  must  be observed,  and  should  be
      symmetrical, for all  compounds in the calibration solution.

            7.2.2.3.2   Corn oil  and  phthalate peaks  must exhibit
      >85% resolution.

            7.2.2.3.3   Phthalate and methoxychlor peaks must exhibit
      >85% resolution.

            7.2.2.3.4   Methoxychlor and perylene peaks must exhibit
      >85% resolution.

            7.2.2.3.5   Perylene  and  sulfur  peaks  must  not  be
      saturated  and must exhibit >90% baseline resolution.

      7.2.2.4  Calibration for Semivolatiles - Using the information
from  the UV trace,  establish appropriate  collect  and  dump  time
periods to ensure collection of all target analytes. Initiate column
eluate collection just  before elution of bis(2-ethylhexyl) phthalate
and  after  the elution  of  the corn  oil.   Stop  eluate collection
shortly after the elution of perylene.  Collection should be stopped
before sulfur elutes.   Use a "wash" time of 10  minutes after the
elution  of  sulfur.   Each laboratory  is required  to  establish its
specific  time  sequences.    See Figure 2  for  general  guidance  on
retention time.   Figure 1 illustrates retention volumes for different
classes of compounds.

      7.2.2.5    Calibration  for  Organochlorine  Pesticides/PCBs  -
Determine  the  elution  times  for  the  phthalate,  methoxychlor,
perylene, and sulfur.   Choose a dump  time which removes >85% of the
phthalate, but collects >95%  of  the  methoxychlor.  Stop collection
after the elution of perylene, but before sulfur elutes.

      7.2.2.6  Verify the flow rate by collecting column eluate for
10 minutes  in  a  graduated  cylinder and measure  the  volume,  which
should be 45-55  ml  (4.5-5.5 mL/min).   If the flow rate is outside
of this range,  corrective action  must  be taken, as described above.
Once the flow rate is within the range of 4.5-5.5 mL/min, record the

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      column pressure (should be 6-10 psi)  and room temperature.  Changes
      in pressure,  solvent flow rate,  and temperature conditions can affect
      analyte retention times,  and must  be monitored.   If the flow rate
      and/or column pressure do  not  fall within  the  above ranges,  a new
      column  should  be prepared.   A  UV trace  that  does not  meet the
      criteria in  Section 7.2.2.3 would  also  indicate that a new column
      should be prepared.   It may be  necessary to obtain a  new  lot of Bio
      Beads if the column fails all  the criteria.

            7.2.2.7  Reinject the calibration solution after appropriate
      collect and  dump cycles have  been  set,  and the  solvent flow and
      column pressure have been established.

                   7.2.2.7.1  Measure  and record  the  volume of collected
            GPC eluate in  a graduated cylinder.   The volume of  GPC eluate
            collected  for each  sample extract processed may  be used to
            indicate problems with the system during sample processing.

                   7.2.2.7.2   The retention times  for bis(2-ethylhexyl)
            phthalate  and perylene must  not vary more  than  ±5% between
            calibrations.    If  the  retention  time shift  is  >5%,  take
            corrective action.   Excessive retention time shifts  are caused
            by:

                        7.2.2.7.2.1  Poor laboratory  temperature control
                   or system leaks.

                        7.2.2.7.2.2 An unstabilized column that requires
                   pumping methylene chloride through it for several more
                   hours or overnight.

                        7.2.2.7.2.3 Excessive  laboratory  temperatures,
                   causing outgassing of the methylene chloride.

            7.2.2.8   Analyze  a GPC  blank  by  loading 5 ml of methylene
      chloride into  the GPC.   Concentrate the  methylene  chloride that
      passes through the system during the  collect cycle using  a Kuderna-
      Danish  (KD)   evaporator.    Analyze  the concentrate by whatever
      detectors will  be used for the analysis of future samples.  Exchange
      the  solvent  if  necessary.   If the  blank exceeds  the  estimated
      quantitation  limit  of  the  analytes,  pump  additional  methylene
      chloride through the system for  1-2  hours. Analyze another GPC blank
      to ensure the system  is  sufficiently clean.   Repeat the methylene
      chloride pumping if necessary.

7.3  Extract Preparation

      7.3.1  Adjust the extract  volume to  10.0 ml.   The solvent extract
must  be  primarily methylene  chloride.   All  other  solvents,  e.g.  1:1
methylene chloride/acetone, must  be  concentrated to 1 ml  (or  as  low as
possible if a  precipitate  forms) and diluted to 10.0  mL  with methylene
chloride.  Thoroughly mix the sample before proceeding.
                              3640A - 11                   Revision 1
                                                           November 1990

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            7.3.2  Filter the extract through a 5 micron filter disc by attaching
      a syringe filter assembly containing the filter disc to a 10 ml syringe.
      Draw the sample  extract  through  the filter assembly and  into  the  10 mL
      syringe.  Disconnect the filter  assembly  before transferring  the sample
      extract into a small glass  container, e.g. a 15 ml culture tube with a
      Teflon lined screw cap.   Alternatively, draw the extract into the syringe
      without the  filter assembly.   Attach the  filter assembly  and  force the
      extract through the filter and into  the glass container.   The  latter is
      the preferred technique  for  viscous extracts or extracts with  a lot of
      solids.  Particulate larger than 5  microns may  scratch the valve,  which
      may result in a system leak and cross-contamination of sample extracts in
      the sample loops.  Repair of the damaged valve is quite expensive.

NOTE; Viscosity of a  sample extract  should not exceed  the viscosity of 1:1
      water/glycerol.   Dilute samples that exceed this viscosity.

      7.4  Screening the Extract

            7.4.1  Screen the extract to determine the concentration of dissolved
      residue by  evaporating   a  100 /iL  aliquot to dryness  and weighing the
      residue.  The concentration of dissolved residue loaded on the GPC column
      cannot exceed 0.500 g.  Concentrations exceeding 0.500 g will very likely
      result in incomplete extract cleanup and contamination of the GPC switching
      valve (which results  in cross-contamination of sample extracts).

                  7.4.1.1  Transfer 100 /nL of the filtered extract from Section
            7.3.2 to a tared aluminum weighing dish.

                  7.4.1.2  A suggested evaporation  technique  is  to  use a heat
            lamp.  Set  up a 250 watt heat  lamp in  a hood so that  it  is 8 + 0.5 cm
            from a surface covered with a clean sheet of aluminum foil.  Surface
            temperature  should be  80-100°C  (check temperature  by  placing  a
            thermometer on the  foil and under the  lamp).  Place the weighing dish
            under the lamp  using tongs.  Allow it to stay under the  lamp for 1
            min.   Transfer the  weighing dish to an analytical  balance or a micro
            balance and weigh to the nearest 0.1 mg.  If the residue weight is
            less than 10 mg/100 /*L, then  further weighings  are not  necessary.
            If the residue  weight is greater than 10 mg/100 pi, then determine
            if constant weight has  been  achieved by placing  the weighing dish
            and residue back under  the heat lamp for  2  or more additional 0.5
            min.  intervals.  Reweigh after each  interval.   Constant  weight is
            achieved when three weights agree within ±10%.

                  7.4.1.3  Repeat the  above residue analysis on  a blank and a
            spike.  Add 100 n\.  of the  same methylene  chloride used  for the
            sample extraction,  to a weighing dish  and determine residue as above.
            Add 100 jil_  of  a  corn oil  spike  (5 mg/100 pi)  to another weighing
            dish and repeat the residue determination.

            7.4.2  A residue weight of 10  mg/100  pi  of  extract represents 500 mg
      in 5 mL of extract.   Any sample extracts  that  exceed the  10  mg/100 /xL
      residue weight must be diluted so that the 5 mL loaded on the GPC column
      does not exceed 0.500 g.  When making the  dilution,  keep in mind that a

                                    3640A  -  12                   Revision 1
                                                                 November 1990

-------
      minimum  volume of  8 ml  is  required  when  loading  the  ABC GPC  unit.
      Following is a calculation that may  be used to determine what dilution is
      necessary if the residue exceeds 10 mg.

            Y ml taken  =     10 ml final    x    10 ma maximum
            for dilution        volume          X mg of residue

      Example:

            Y mL taken  =     10 ml final    x    10 ma maximum
            for dilution        volume          15 mg of residue

                        Y mL taken for dilution  =  6.7 ml

            Therefore, taking 6.7 mL of sample extract from Section 7.3.2,  and
      diluting to 10 mL with methylene chloride, will result in 5 mL of diluted
      extract loaded on the GPC column that contains 0.500 g of residue.

NOTE; This dilution factor must be included in the final calculation of analyte
      concentrations.  In the above example,  the dilution factor is 1.5.

      7.5  GPC Cleanup

            7.5.1   Calibrate the  GPC at  least once  per  week following  the
      procedure outlined  in Sections 7.2.2 through  7.2.2.6.   Ensure  that  UV
      trace requirements,  flow rate and column  pressure  criteria are acceptable.
      Also, the retention time shift must be <5% when compared to retention times
      in the last calibration UV trace.

                  7.5.1.1  If these criteria are  not met, try cleaning the column
            by loading one or more 5 mL portions of butyl chloride and running
            it through the  column.  Butyl  chloride removes the discoloration and
            particulate that may have precipitated out of the methylene chloride
            extracts.  If  a guard column  is being  used,  replace  it with  a  new
            one.  This may correct the problem.  If column maintenance does  not
            restore acceptable performance, the column must  be repacked with new
            Bio Beads and calibrated.

            7.5.2  Draw  a  minimum of 8 mL of extract  (diluted,  if necessary,
      and filtered) into a 10 mL syringe.

            7.5.3  Attach  the syringe  to  the  turn  lock on  the  injection  port.
      Use firm,  continuous pressure to push  the  sample onto the  5-mL sample
      loop.  If the sample is  difficult to load, some part of the system may be
      blocked.  Take  appropriate  corrective  action.    If the back  pressure  is
      normal (6-10 psi), the blockage  is  probably  in the valve.   Blockage  may
      be flushed out of the valve by  reversing  the  inlet and outlet tubes  and
      pumping solvent through  the tubes.   (This should be  done  before sample
      loading.)

NOTE; Approximately  2  mL  of  the  extract remains  in  the  lines   between  the
      injection port and the sample  loop;  excess sample also passes through  the
      sample loop to waste.


                                    3640A - 13                   Revision 1
                                                                 November 1990

-------
            7.5.4  After  loading  a  loop,  and before removing the syringe from
      the injection  port,  index  the 6PC to the next loop.   This will prevent
      loss of sample caused by unequal pressure in the loops.

            7.5.5  After  loading  each  sample loop,  wash  the loading port with
      methylene chloride in a PTFE wash bottle to minimize cross-contamination.
      Inject approximately 10 ml of methylene chloride to rinse the common tubes.

            7.5.6  After loading all the sample loops,  index the GPC to the 00
      position,  switch  to the  "RUN"  mode  and  start the  automated sequence.
      Process each sample using the  collect and dump cycle times established in
      Section 7.2.2.

            7.5.7  Collect  each  sample in a 250 ml  Erlenmeyer flask, covered
      with aluminum  foil  to  reduce solvent evaporation,  or directly  into  a
      Kuderna-Danish evaporator.   Monitor sample volumes collected.  Changes in
      sample  volumes collected  may  indicate  one  or  more  of  the  following
      problems:

                  7.5.7.1     Change in solvent flow rate, caused by channeling
            in the column or changes in column pressure.

                  7.5.7.2     Increase in column  operating pressure due to the
            absorption of particles or gel  fines onto  either the guard column
            or the analytical column gel, if a guard column is not used.

                  7.5.7.3     Leaks  in  the  system or significant variances in
            room temperature.

      7.6  Concentrate  the  extract  by the standard K-D technique  (see any of
the extraction methods, Section  4.2 of this chapter).   See the determinative
methods (Chapter Four, Section 4.3)  for the final  volume.

      7.7   It should be  remembered that only half  of the  sample  extract is
processed by the GPC (5  ml of the  10 ml extract is loaded onto the GPC column),
and thus, a  dilution factor of 2 (or  2 multiplied  by any  dilution  factor in
Section 7.4.2) must be used  for quantitation  of the sample in the determinative
method.
8.0  QUALITY CONTROL

      8.1  Refer  to  Chapter One and Method 3600  for  specific  quality control
procedures.

      8.2  The analyst should demonstrate that the compound(s)  of interest are
being quantitatively recovered before applying this method to actual samples.

      8.3   For sample  extracts that are  cleaned up  using this method,  the
associated quality control samples must also be processed through this cleanup
method.
                                    3640A - 14                   Revision 1
                                                                 November 1990

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9.0  METHOD PERFORMANCE

      9.1  Refer to Table 1 for single laboratory performance data.


10.0  REFERENCES

1.  Wise, R.H.; Bishop,  D.F.;  Williams,  R.T.; Austern, B.M.   "Gel Permeation
    Chromatography  in  the GC/MS  Analysis  of Organics  in Sludges";  U.S.  EPA
    Municipal  Environmental  Research Laboratory:   Cincinnati, Ohio 45268.

2.  Czuczwa,  J.; Alford-Stevens, A.  "Optimized Gel Permeation Chromatographic
    Cleanup for Soil, Sediment, Waste  and  Waste  Oil  Sample Extracts for GC/MS
    Determination  of  Semivolatile Organic  Pollutants, JAOAC,  submitted April
    1989.

3.  Marsden,  P.J.;  Taylor, V.;  Kennedy,  M.R.  "Evaluation of  Method  3640 Gel
    Permeation Cleanup";  Contract  No. 68-03-3375, U.S. Environmental Protection
    Agency, Cincinnati, Ohio,  pp.  100,  1987.
                                    3640A - 15                   Revision 1
                                                                 November 1990

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                  TABLE 1
GPC RECOVERY AND RETENTION VOLUMES FOR RCRA
          APPENDIX  VIII ANALYTES
Compound
Acenaphthene
Acenaphthylene
Acetophenone
2-Acetylaminofluorene
Aldrin
4-Aminobiphenyl
Aniline
Anthracene
Benomyl
Benzenethiol
Benzidine
Benz(a)anthracene
Benzo(b)fl uoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Benzo(k)fl uoranthene
Benzoic acid
Benzotrichloride
Benzyl alcohol
Benzyl chloride
alpha-BHC
beta-BHC
gamma- BHC
delta-BHC
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-butyl-4,6-dinitrophenol (Dinoseb)
Carbazole
Carbendazim
alpha-Chlordane
gamma-Chlordane
4-Chl oro-3-methyl phenol
4-Chloroaniline
Chi orobenzi late
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
2 -Chi oronaphthal ene
2-Chlorophenol
3-Chlorophenol
4-Chlorophenol
4-Chlorophenyl phenyl ether
3-Chloropropionitrile
Chrysene
2-Cresol
3-Cresol
% Rec1
97
72
94
97
99
96
93
89
131
92
95
100
93
93
90
91
66
93
95
99
84
94
93
102
93
104
103
99
131
97
93
87
88
92
89
76
83
89
90
86
87
98
80
102
91
70
% RSD2
2
10
7
2
9
7
4
2
8
11
5
3
5
3
6
4
7
7
17
4
13
9
4
7
1
3
18
5
8
2
2
1
3
5
1
2
2
1
1
3
2
2
5
1
1
3
Ret. Vol.3 (ml
196-235
196-235
176-215
156-195
196-215
176-215
196-235
196-235
146-195
196-235
176-215
196-235
196-235
196-235
196-235
196-235
176-195
176-215
176-215
176-215
196-215
196-215
196-215
216-255
176-215
136-175
176-195
196-255
146-195
196-235
196-215
196-255
196-235
176-235
156-195
156-215
156-195
196-235
196-215
196-215
196-215
176-215
176-215
196-235
196-215
196-215
                   3640A - 16
Revision 1
November 1990

-------
TABLE 1 (continued)
Compound
4-Cresol
Cyclophosphamide
ODD
DDE
DDT
Di-n-butyl phthalate
Dial late
Dibenzo(a,e)pyrene
Dibenzo(a,i)pyrene
Dibenz(a,j)acridine
Dibenz (a, h) anthracene
Dibenzofuran
Dibenzothiophene
1 , 2-Di bromo-3-chl oropropane
1,2-Dibromoethane
trans- l,4-Dichloro-2-butene
cis-l,4-Dichloro-2-butene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
2,6-Dichlorophenol
2,4-Dichlorophenoxyacetic acid (2,4-D)
2,4-Dichlorophenol
2,4-Dichlorotoluene
l,3-Dichloro-2-propanol
Dieldrin
Di ethyl phthalate
Dimethoate
3,3'-Dimethoxybenzidinea
Dimethyl phthalate
p-Dimethylaminoazobenzene
7,12-Dimethyl-benz(a)anthracene
2,4-Dimethylphenol
3, 3' -Dimethyl benzi dine
4,6-Dinitro-o-cresol
1,3-Dinitrobenzene
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
Diphenyl ether
1 , 2-Di phenyl hydrazi ne
Disulfoton
Endosulfan sulfate
Endosulfan I
Endosulfan II
Endrin
% Rec1
88
114
94
94
96
104
97
94
99
117
92
94
94
83
121
107
106
81
81
81
98
86
80
87
70
73
100
103
79
15
100
96
77
93
93
100
99
118
93
101
95
67
92
81
94
99
92
95
%RSD2
2
10
4
2
6
3
6
10
8
9
5
1
3
2
8
6
6
1
1
1
3
3
NA
2
9
13
5
3
15
11
1
1
1
2
2
1
2
7
4
2
6
12
1
15
2
8
6
6
Ret. Vol.3 (ml
196-215
146-185
196-235
196-235
176-215
136-175
156-175
216-235
216-235
176-195
196-235
176-235
196-235
176-215
196-215
176-195
176-215
196-235
196-235
196-235
176-215
196-215
76-215
96-215
196-235
176-215
196-215
136-195
146-185
156-195
156-195
176-215
176-215
176-215
156-215
156-195
156-195
176-195
156-195
156-175
176-235
196-215
176-215
146-165
176-195
176-215
196-215
196-215
       3640A -  17
Revision 1
November 1990

-------
TABLE 1 (continued)
Compound
Endrin aldehyde
Endrin ketone
Ethyl methane sulfonate
Ethyl methacrylate
Bis(2-ethylhexyl) phthalate
Famphur
Fluorene
Fluoranthene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachl orobutadl ene
Hexachl orocycl opentadi ene
Hexachl oroethane
Hexachl oropropene
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
cis-Isosafrole
trans- Isosaf role
Kepone
Malononitrile
Merphos
Methoxychlor
3-Methyl chol anthrene
2 -Methyl naphthal ene
Methyl parathion
4,4'-Methylene-bis(2-chloroaniline)
Naphthalene
1,4-Naphthoqulnone
2-Naphthylamine
1-Naphthylamine
5-Nitro-o-toluidine
2-Nitroanillne
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
N-Nitroso-di -n-butyl amine
N-Nitrosodiethanolamine
N-Nitrosodiethyl amine
N-Ni trosodimethyl ami ne
N-Nitrosodiphenyl amine
N-Nitrosodi-n-propyl amine
N-Ni trosomethyl ethyl amine
N-Nitrosomorpholine
N-Nitrosopiperidine
% Rec1
97
94
62
126
101
99
95
94
85
91
108
86
89
85
91
79
98
68
90
88
102
111
93
94
74
67
84
96
95
73
94
96
77
96
96
103
86
95
77
89
104
94
86
99
85
83
86
84
%RSD2
1
4
7
7
1
NA
1
1
2
11
2
2
3
1
2
13
5
7
4
16
NA
9
12
6
12
6
13
1
7
7
8
6
2
8
2
8
2
3
3
4
3
2
13
2
4
7
4
4
Ret. Vol.3 (ml
176-215
176-215
176-235
176-195
120-145
126-165
176-235
196-235
195-215
156-195
196-235
176-215
176-215
196-235
196-235
216-255
196-235
156-195
176-215
156-195
196-235
156-195
126-165
156-195
176-195
196-215
146-185
176-215
196-215
176-215
196-235
196-235
176-195
176-215
176-215
176-215
176-195
176-195
196-215
156-175
146-185
156-175
156-195
156-195
156-175
156-175
156-195
156-195
       3640A  -  18
Revision 1
November 1990

-------
                                 TABLE 1 (continued)
Compound                                     % Rec1    %RSD2      Ret. Vol.3 (ml)
N-Nitrosopyrolidine
Di-n-octyl phthalate
Parathion
Pentachlorobenzene
Pentachloroethane
Pentachloronitrobenzene (PCNB)
Pentachlorophenol
Phenacetin
Phenanthrene
Phenol
1 , 2-Phenyl enedi ami ne
Phorate
2-Picoline
Pronamide
Pyrene
Resorcinol
Safrole
Streptozotocin"
1,2,4,5-Tetrachlorobenzene
2,3,5 , 6-Tetrachl oro-ni trobenzene
2,3,4,6-Tetrachlorophenol
2,3,5 , 6-Tetrachl orophenol
Tetraethyl dithiopyrophosphate (Sulfotep)
Thiosemicarbazide
2-Toluidine
4-Toluidine
Thiourea, l-(o-chlorophenyl)
Toluene- 2, 4-di ami ne
1 , 2 , 3-Tri chl orobenzene
1,2,4-Trichlorobenzene
2, 4, 5-Tri chl orophenol
2, 4, 6-Tri chl orophenol
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)
2,4,5-Trichlorophenoxypropionic acid
Warfarin
92
83
109
95
74
91
102
100
94
83
91
74
99
105
98
70
93
6
96
85
95
96
89
74
92
87
75
69
87
89
77
95
71
67
94
1
4
14
2
1
8
1
3
2
2
1
NA
14
15
2
6
1
48
2
9
1
7
14
3
3
8
11
7
1
1
1
1
23
NA
2
156-175
120-156
146-170
196-235
196-235
156-195
196-215
156-195
196-235
156-195
196-215
116-135
156-215
156-195
215-235
196-215
176-215
225-245
196-235
176-215
196-215
196-215
116-135
146-185
176-235
176-235
166-185
176-215
196-235
196-235
216-235
216-235
156-235
216-215
166-185
NA = Not applicable, recovery presented as the average of two determinations.
a  Not an appropriate analyte for this method.
1  The percent recovery is based on an average of three recovery values.
2  The % relative standard deviation is determined from three recovery values.
3  These Retention Volumes are  for  guidance  only as  they will  differ from column to
   column and from system to system.
                                       3640A - 19                   Revision 1
                                                                    November 1990

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                        Figure 1
        GPC RETENTION VOLUME OF CLASSES OF ANALYTES
                                  W//////////////,
                                  PAH1!

                                  CHLOROBENZENES
        PHTHALAT8
OROANOPHOSPHATE
    PESTICIDES
   CORN OIL —
                       NITROSAMINE3, NITROAROMATICS

                                  AROMATIC AMINES

                           NITROPHENOLS

                               CHLOROPHENOLS

                                  ORQANOCHIORINE
                                  PESTICIOES/PCB't

                   W///////W////A HERBICIDES (6 160)
                                        — PCP
                                                       C-Collect
 10
20
30        40
TIME (minutes)
50
60
70
                         3640A - 20
                                       Revision  1
                                       November  1990

-------
                               Figure  2
             UV CHROMATOGRAM OF  THE CALIBRATION SOLUTION
Injection
5 fflLs
on column
                                                                — 0 minutes
Corn oil
25 mg/nL
Bis(2-ethylheayl) .pbthtiate
1.0 mg/nL
Methoxychlor
0.2 ng/mL
Perylene
0.02 mg/mL  .
Sulfur
0.08 rng/oL :—
                                                               IS minuces
                                                            .""'  30  minutes
                                                        	~,_.^,;	;  45 minutes
700 mm X25 am
70 g Bio-Beads  SX
Bed length - 490
CH,C12  at 5.0  uL
254 nu
         col iiw^0i._."0^—o«;
             1?I_..T._!"_::.':—ILT-— ,"  ' '..m.-J.i:	~1_ "im_"..'....."JlJ  60 minutes
                                 3640A - 21
                                                                    Revision  1
                                                                    November  1990

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                                      METHOD 3640A
                                GEL-PERMEATION CLEANUP
                                         (START)
7.1 Ensure ambient temp, consistent
throughout GPC run.
i
i
                             7.2 GPC Setup and Calibration
 7.2.1  Column Preparation
7.2.1.1 Place Bio Beads and MeCI
       in a container.  Swirl and
       allow beads to swell.
7.2.1.2 Remove column inlet  bed
       support plunger.  Position
       and tighten outlet bed
       support plunger to column
       end.
 7.2.1.3  Ensure GPC column  outlet
        contains  solvent.  Place
        small amt. solvent in
        column to minimize  bubble
        formation.
7.2.1.4 Transfer bead  mixture into
       sep. funnel. Drain excess
       solvent; drain beads Into
       column.  Keep beads wet
       throughout.
7.2.1.5 Loosen seal on opposite
       plunger assembly, insert
       into column.
7.2.1.6 Compress column. Slurry
       remaining beads  and  repeat
       Section 7.2.1.5 and column
       compression.
                                                          7.2.1.7 Compress column bed
                                                                 approximately four cm.
7.2.1.8 Pack option 5 cm. guard
       column w/roughly 5 gm.
       preswellea beads.
7.2.1.9 Connect column inlet to
       solvent reservoir.  Pump
       MeCI at 5 ml./min. for
       1 hr.
 7.2.1.10 Connect column  outlet to
         UV-Vis detector.   Place
         restrictor at detector outlet.
         Run  MeCI for additional
         1-2 hrs.  Compress column
         bed  to provide 6-10 psi
         backpressure.
 7.2.1.11 Connect outlet line to column
          inlet when column not in
          use.  Repack column when
          channeling is observed.
          Assure consistent
          backpressure when  beads are
          rewefted after drying.
                                           3640A  -  22
                       Revision 1
                       November 1990

-------
METHOD 3640A
  continued
7.2.2 Calibration of tht GPC Column

7.2.2.1
i
i
Load sample loop with
calibration solution.
1
7.2.2.2
!
Inject calibration soln.; adjust
recorder or detector sensitivity
to produce similar UV trace as
Fig. 2 .
1
7.2.2.3
1
Evaluation criteria for UV
chromatogrom.
I
7.2.2.4
r
Calibration for Semivolatiles
Use information from UV
trace to obtain collect and
dump times. Initiate collection
before bis(2-ethylhexyl) phthalate.
stop after perylene. Stop run
before sulfur elutes.
1
7.2.2.5
r
Calibration for Organochlorine
Pesticides/PCBs
Choose dump time which removes
> 85% phthalate. but collects at
times > 95% methoxychlor. Stop
collection between perylene and
sulfur elution.
i
7.2.2.6
t
Verify column flow rate and
backpressure. Correct
inconsistencies when criteria
are not met.
                 7.2.2.7 Reinject calibration soln. when
                        collect and dump cycles are set.
                 	and column criteria are  met.
                  7.2.2.7.1 Measure and record volume
                          of GPC eluate.
                  7.2.2.7.2 Correct for retention time
                          shifts of > +/- 5% for
                          bis(2-e»hylhexyl) phthalate
                 	and perylene.	
                  7.2.2.8  Inject and analyze GPC blank
                         for column cleanliness.  Pump
                 	through MeCI as column wash.
     3640A  - 23
Revision  1
November  1990

-------
                                      METHOD  3640A
                                         continued
7.3 Extract Preparation
7.3.1  Adjust extract volume to 10 ml.
      Primary solvent should be MeCI.
7.3.2 Filter extract through  5 micron
     filter disc/syringe assembly into
     small gloss container.	
 7.4 Screening the  Extract
7.4.1  Screen  extract by determining
      residue wt. of 100 ul aliquot.
7.4.1.1 Transfer 100 ul of filtered
       extract from Section 7.3.2
       to tared  aluminum weighing
       dish.
                   1
7.4.1.2 Evaporate extract solvent
       under heating lamp.  Weigh
       residue  to nearest 0.1 mg.
                   I
7.4.1.3 Repeat residue analysis of
       Section  7.4.1.2 w/blonk
       and spike sample.
                   I
7.4.2 Use dilution example to
      determine neccessory dilution
      when residue wts. > 10 mg.
  7.5 GPC Cleanup

7.5.1
i
P
Calibrate GPC weekly. Assure
column criteria, UV trace, retention
time shift criteria are met.
7.5.1.1
Clean column w/butyl chloride
loadings, or replacement of guard
column.
1
i
                                                       |  7.5.2 Draw 8 ml. extract into syringe.     |
|  7.5.3 Load sample Into injection  loop
  7.5.4 Index GPC to next loop to
        prevent sample loss.
  7.5.5 Wash sample port w/MeCI
        between sample loadings.
  7.5.6 At end of loadings, index GPC to
        00, switch to "RUN" mode, start
        automated sequence.	
  7.5.7 Collect sample into aluminum  foil
        covered Erlenmeyer flask or into
        Kuderno-Donish evaporator.
                                                         7.6 Concentrate extract by std.
                                                             Kuderno-Donish technique.
                                                         7.7 Note dilution factor of GPC method
                                                             Into final determinations.
                                                                          STOP
                                            3640A  - 24
                            Revision  1
                            November  1990

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                                  METHOD  3665

                      SULFURIC ACID/PERMANGANATE CLEANUP
1.0  SCOPE AND APPLICATION

      1.1  This method is suitable for the rigorous cleanup of sample extracts
prior to  analysis  for polychlorinated biphenyls.   This method  should  be used
whenever  elevated  baselines  or overly complex  chromatograms  prevent accurate
quantitation of PCBs.  This method cannot  be used to cleanup extracts for other
target  analytes,   as  it will  destroy most  organic  chemicals  including  the
pesticides  aldrin,  dieldrin,  endrin,  endosulfan   (I  and  II),  and  endosulfan
sulfate.
2.0  SUMMARY OF METHOD

      2.1  An  extract is  solvent exchanged  to  hexane,  then  the hexane  is
sequentially treated  with  (1) concentrated sulfuric  acid and  (2)  5% aqueous
potassium permanganate.  Appropriate  caution must  be taken with these corrosive
reagents.

      2.2  Blanks and replicate analysis samples must be subjected to the same
cleanup as the samples associated with them.

      2.3  It is important that all the extracts be exchanged to hexane before
initiating the following treatments.


3.0  INTERFERENCES

      3.1  This technique  will  not destroy chlorinated  benzenes,  chlorinated
naphthalenes (Halowaxes), and a number of chlorinated pesticides.


4.0  APPARATUS

      4.1  Syringe or Class A volumetric pipet, glass; 1.0,  2.0 and 5.0 mL.

      4.2  Vials - 1, 2 and 10 mL, glass with Teflon lined screw caps or crimp
tops.

      4.3  Kuderna-Danish (K-D) apparatus.

            4.3.1  Concentrator tube  - 10 mL graduated (Kontes K-570050-1025 or
      equivalent).  A ground  glass stopper is used to  prevent  evaporation  of
      extracts.

            4.3.2  Evaporation   flask  -  500  mL  (Kontes   K-570001-500   or
      equivalent).    Attach  to  concentrator  tube  with  springs,  clamps,  or
      equivalent.
                                   3665 - 1                      Revision 0
                                                                 November 1990

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            4.3.3  Snyder  column  - Three ball macro  (Kontes K-503000-0121 or
      equivalent).

            4.3.4  Snyder  column   -  Two ball  micro (Kontes  K-569001-0219 or
      equivalent).

            4.3.5  Springs - 1/2 inch (Kontes K-662750 or equivalent).

      4.4  Vortex mixer.
5.0  REAGENTS

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

      5.2  Organic-free reagent water.  All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3  Sulfuric acid/Water, H2SOyH20, (1:1,  v/v).

      5.4  Hexane, C6H14 - Pesticide grade or equivalent.

      5.5  Potassium permanganate, KMn04,  5 percent aqueous  solution (w/v).


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1   See  the  introductory material  to  this  chapter,  Organic Analytes,
Section 4.1.


7.0  PROCEDURE

      7.1  Sulfuric acid cleanup

            7.1.1  Using a syringe  or a volumetric pipet, transfer  1.0 or 2.0 mL
      of the hexane extract to a 10 mL vial and,  in a fume  hood, carefully add
      5 mL of the 1:1 sulfuric acid/water solution.

            7.1.2  The volume of hexane extract used depends  on the requirements
      of the GC  autosampler used by the laboratory.  If the autosampler functions
      reliably with 1  mL  of sample volume, 1.0 mL of extract  should  be used.
      If the autosampler  requires  more than 1  mL of sample  volume, 2.0 mL of
      extract should be used.

CAUTION:   Make sure that there is no exothermic reaction  nor evolution of gas
           prior to proceeding.
                                   3665 - 2                      Revision  0
                                                                 November  1990

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            7.1.3  Cap the vial  tightly  and vortex for one minute.   A vortex
      must be visible in the vial.

CAUTION:   Stop the vortexing immediately if the vial  leaks, AVOID SKIN CONTACT,
           SULFURIC ACID BURNS.

            7.1.4  Allow the phases to separate for at least 1 minute.  Examine
      the top (hexane)  layer; it  should not be highly  colored nor should it have
      a visible emulsion or cloudiness.

            7.1.5  If  a  clean  phase  separation  is  achieved,   proceed  to
      Section 7.1.8.

            7.1.6  If the hexane layer is colored or the emulsion  persists for
      several minutes,  remove the sulfuric  acid layer from the vial and dispose
      of it properly.  Add another 5 ml of the clean 1:1 sulfuric  acid/water.

NOTE: Do not remove any hexane at this stage of the procedure.

            7.1.7  Vortex the  sample  for one  minute  and  allow the  phases  to
      separate.

            7.1.8  Transfer the hexane layer to a clean 10 ml vial.

            7.1.9  Add an additional 1 ml of hexane to the sulfuric acid layer,
      cap and  shake.   This  second  extraction is done  to  ensure  quantitative
      transfer of the PCBs and Toxaphene.

            7.1.10   Remove the second hexane layer and combine with the hexane
      from Section 7.1.8.

      7.2  Permanganate cleanup

            7.2.1  Add 5  ml  of  the  5 percent  aqueous  potassium  permanganate
      solution to the combined hexane fractions from 7.1.10.

CAUTION:   Make sure that there is no exothermic reaction  nor evolution of gas
           prior to proceeding.

            7.2.2  Cap the vial  tightly and vortex  for 1 minute.  A vortex must
      be visible in the vial.

CAUTION:   Stop the vortexing immediately if the vial leaks. AVOID SKIN CONTACT,
           POTASSIUM PERMANGANATE BURNS.

            7.2.3  Allow the phases to separate for at least 1 minute.  Examine
      the top (hexane)  layer,  it  should not be highly  colored nor should it have
      a visible emulsion or cloudiness.

            7.2.4  If  a  clean  phase  separation  is  achieved,   proceed  to
      Section 7.2.7.

            7.2.5  If the hexane layer is colored or the emulsion  persists for
      several minutes,  remove the permanganate  solution  from  the vial  via a

                                   3665 -  3                     Revision 0
                                                                November 1990

-------
      glass pipette and dispose of it properly.  Add another 5 ml of the clean
      aqueous permanganate solution.

NOTE:  Do not remove any hexane at this stage of the procedure.

            7.2.6  Vortex the sample and allow the phases to separate.

            7.2.7  Transfer the hexane layer to a clean 10 ml vial.

            7.2.8  Add an additional 1 ml of hexane to the permanganate layer,
      cap the vial  securely and shake.  This second extraction is done to ensure
      quantitative transfer of the PCBs and Toxaphene.

            7.2.9  Remove the second hexane  layer and combine with the hexane
      from Section 7.2.7.

      7.3  Final preparation

            7.3.1  Reduce  the volume  of the  combined hexane  layers  to  the
      original  volume   (1  or   2   ml)   using  the  Kuderna-Danish  Technique
      (Section 7.3.1.1).

                  7.3.1.1  Add one or two clean boiling chips to the flask and
            attach a  three ball  Snyder  column.   Prewet the  Snyder  column by
            adding about 1 ml  of  hexane to the top of the column.  Place the K-D
            apparatus on  a  hot water  bath  (15-20°C  above  the boiling point of
            the solvent) so that  the concentrator tube is partially immersed in
            the hot water and the entire lower rounded surface of the flask is
            bathed with hot vapor.  Adjust the vertical position of the apparatus
            and the water temperature,  as required, to complete the concentration
            in 10-20 minutes.  At the proper rate of distillation the balls of
            the column will actively chatter, but the chambers will not flood.
            When the apparent volume of  liquid reaches 1-2 ml,  remove the K-D
            apparatus from the water bath and allow it to drain and cool for at
            least 10 minutes.

                  7.3.1.2   Remove the Snyder column and rinse the flask and its
            lower joints into the concentrator tube with 1-2 ml of hexane.  The
            extract may be further concentrated by using either the micro Snyder
            column  technique  (Section  7.3.2)  or nitrogen  blowdown  technique
            (Section 7.3.3).

            7.3.2  Micro Snyder Column Technique

                  7.3.2.1   Add another  one  or two  clean  boiling  chips to the
            concentrator tube and attach a two ball micro Snyder column.  Prewet
            the column by adding  about 0.5 ml of hexane to the top  of the column.
            Place the K-D apparatus  in a  hot water bath so  that the concentrator
            tube is partially immersed  in  the hot water.   Adjust the vertical
            position of  the apparatus  and  the water temperature, as required,
            to complete  the concentration in 5-10 minutes.  At the 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

                                    3665  - 4                      Revision 0 „
                                                                 November 1990

-------
            allow It  to  drain and cool for  at  least 10 minutes.   Remove the
            Snyder column and rinse the flask and  Its  lower joints with about
            0.2 ml of hexane  and add to the concentrator tube.  Adjust the final
            volume to 1.0-2.0 ml, as required,  with hexane.

            7.3.3  Nitrogen Slowdown Technique

                  7.3.3.1  Place the  concentrator  tube  in  a warm  water bath
            (approximately 35°C) and evaporate the solvent volume to the required
            level using a gentle stream of clean, dry  nitrogen (filtered through
            a column of activated carbon).

CAUTION;  Do not use plasticized tubing between the  carbon trap  and the sample.

                  7.3.3.2  The internal wall of the tube must  be  rinsed down
            several times  with  the appropriate solvent  during  the operation.
            During evaporation,  the solvent level in the tube must be positioned
            to prevent water from condensing  into the sample (i.e., the solvent
            level should be  below  the  level  of  the water bath).  Under normal
            operating conditions, the  extract should not be allowed to become
            dry.

            7.3.4  Remove  any remaining  organochlorine pesticides from the
      extracts using Florisil Column Cleanup (Method 3620) or Silica Gel Cleanup
      (Method 3630).

            7.3.5  The extracts  obtained  may now  be analyzed  for  the target
      analytes  using  the appropriate  organic technique(s)  (see Section 4.3 of
      this  Chapter).     If  analysis  of  the  extract  will   not be  performed
      immediately, stopper the concentrator  tube and store  in  a refrigerator.
      If the extract will be  stored longer than 2 days,  it should be transferred
      to  a  vial  with a Teflon lined  screw cap  or  crimp  top,   and  labeled
      appropriately.


8.0  QUALITY CONTROL

     8.2   Refer to Chapter One for specific quality control procedures.


9.0  METHOD PERFORMANCE

     9.1   No performance data are currently available.


10.0 REFERENCES

     None required.
                                   3665 - 5                      Revision 0
                                                                 November 1990

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            METHOD 3665
SULFURIC ACID/PERMANGANATF CLEANUP
7 1 1 Carefully
combine hexane
with 1: 1
H,SO,/H,0
solution


7.1.2
Transfer the
appropriate
volume to
vial


7.1.3-714
Cap , vortex.
and allow
phase
separation
/I . 1 . <
f phi
separi
^ clea
.
7.]
Tram
hexane
to clei
,
> Is N.
ise
ition
in? .
Yes
8
fer
layer
in vial

7.1.9 Add
hexane to
H.SO, layer,
cap and shake


7.1.10
Combine two
hexane layer*

716 Remove
\ No and dispose
J > HiSO. solution.
/ add clean H.SO.
solution

7.1.7 Cap.
vortex, and
separation


^^i
<
7.2.1 Add
KMnO,
solution
1
72.2-723
Cap, vortex,
and allow
phase
separation
/T1H l*^
' phase N
. clean? .
Yes
72.7
Transfer
hexane layer
to clean vial

728 Add
hexane to
KMnO. layer,
cap and shake
1
72.9 Combine
two hexane
layers


\ No
• >


7.2.5 Remove
and dispose
KMnO. solution,
add clean KMnO.
solution

7.2.6 Cap.
vortex , and
allow phase
separation

7.3.1-7.3.3
Reduce volume
using K-D
and/or nitrogen
blowdown tech.
I
7.3.4 Use
Method 3620 or
Method 3630 to
further remove
contaminants
1
7 . 3 . 5 Stopper
and
refrigerate
for further
analysis
                                       *

                                (     Stop      J
             3665 - 6
Revision 0
November 1990

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                                 METHOD 5040A

  ANALYSIS  OF SORBENT CARTRIDGES FROM VOLATILE  ORGANIC  SAMPLING  TRAIN  fVOSTh
                GAS CHROMATOGRAPHY/MASS SPECTROMETRY TECHNIQUE
1.0  SCOPE AND APPLICATION

      1.1  Method 5040 was  formerly Method  3720  In  the Second Edition of this
manual.

      1.2  This method covers  the  determination  of  volatile principal organic
hazardous constituents (POHCs),  collected on  Tenax  and Tenax/charcoal sorbent
cartridges using  a  volatile organic  sampling train,  VOST  (1).   Much  of the
description for purge-and-trap GC/MS  analysis is described  in Method 8240 of
this  chapter.   Because  the majority  of gas  streams sampled using  VOST will
contain a high  concentration of water,  the analytical method is  based on the
quantitative  thermal  desorption  of   volatile   POHCs  from the  Tenax  and
Tenax/charcoal traps and analysis by purge-and-trap  GC/MS.  For the purposes of
definition, volatile POHCs are those  POHCs with boiling points less than  100°C.

      1.3  This method is applicable to the analysis of Tenax and Tenax/ charcoal
cartridges used to  collect  volatile POHCs  from wet stack gas effluents from
hazardous waste incinerators.

      1.4  The sensitivity  of  the  analytical  method for a particular volatile
POHC depends on  the  level of interferences and the presence of detectable levels
of  volatile  POHCs  1n blanks.    The  desired  target  detection  limit of the
analytical method  is 0.1  ng/L (20 ng on a single pair of traps) for a particular
volatile POHC desorbed  from either a single  pair of Tenax and  Tenax/charcoal
cartridges or by thermal desorption of  up to  six pairs of traps  onto a single
pair of Tenax and Tenax/charcoal traps.  The resulting single pair of traps is
then thermally desorbed and  analyzed by purge-and-trap GC/MS.

      1.5  This  method  is  recommended for   use   only  by  experienced  mass
spectroscopists or under the close supervision of such qualified  persons.


2.0  SUMMARY OF METHOD

      2.1  A schematic diagram of  the analytical  system  is shown  in  Figure 1.
The contents of the  sorbent cartridges are spiked with  an internal  standard and
thermally desorbed for 10 min at 180°C with  organic-free nitrogen or helium gas
(at a  flow  rate of 40 mL/min),  bubbled through 5  ml  of organic-free reagent
water,  and  trapped  on  an  analytical  adsorbent trap.    After   the  10  min.
desorption, the analytical  adsorbent trap is  rapidly heated to 180°C, with the
carrier gas flow reversed so that the effluent flow  from the analytical trap is
directed  into  the  GC/MS.    The  volatile POHCs  are separated by  temperature
programmed gas chromatography and detected by  low-resolution mass spectrometry.
The concentrations of volatile POHCs are calculated  using the internal standard
technique.
                                   5040A  -  1                       Revision 1
                                                                  November 1990

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3.0  INTERFERENCES

      3.1  Refer to Methods 3500 and 8240.


4.0  APPARATUS AND MATERIALS

      4.1  Thermal desorption unit:

            4.1.1  The   thermal   desorption  unit   (for   Inside/Inside  VOST
      cartridges,  use  Supelco  "clamshell"  heater;  for   Inside/Outside  VOST
      cartridges,  user-fabricated  unit  Is  required)  should  be capable  of
      thermally desorblng the sorbent  resin  tubes.   It should also be capable
      of heating the tubes to 180 ± 10°C with flow of organic-free nitrogen or
      helium through the tubes.

      4.2  Purge-and-trap unit:

            4.2.1  The purge-and-trap unit consists  of three separate pieces of
      equipment:   the sample purger,  trap,  and the  desorber.    It  should be
      capable  of meeting  all  requirements  of  Method 5030  for  analysis  of
      purgeable organic compounds from water.

      4.3  GC/MS system:  As described In Method 8240.


5.0  REAGENTS

      5.1  Organic-free reagent water.  All references to water 1n this method
refer to organic-free reagent water, as defined 1n Chapter One.

      5.2  Methanol, CH3OH  -  Pesticide grade,  or equivalent.

      5.3  Analytical trap reagents:

            5.3.1  2,6-Diphenylene oxide polymer:  Tenax (60/80 mesh), chromato-
      graphic grade or equivalent.

            5.3.2  Methyl silicone  packing:   3%  OV-1 on Chromosorb  W (60/80
      mesh) or equivalent.

            5.3.3  Silica gel:   Davison  Chemical  (35/00  mesh), Grade  15,  or
      equivalent.

            5.3.4 Charcoal:  Petroleum-based (SKC Lot 104 or equivalent).

      5.4  Stock standard solution:

            5.4.1  Stock standard solutions will  be  prepared from pure standard
      materials or purchased as certified solutions.   The stock standards should
      be prepared in methanol using assayed  liquids or gases, as appropriate.
      Because of the toxicity of  some  of  the organohalides,  primary dilutions
      of these materials should be prepared  in  a  hood.  A NIOSH/MESA approved


                                   5040A - 2                       Revision 1
                                                                  November 1990

-------
      toxic  gas  respirator  should  be  used  when  the  analyst handles  high
      concentrations of such materials.

            5.4.2  Fresh stock standards should  be prepared weekly for volatile
      POHCs with boiling points of <35°C.  All other standards must be replaced
      monthly, or sooner if comparison with check standards indicates a problem.

      5.5  Secondary dilution standards:

            5.5.1  Using  stock  standard  solutions,  prepare,  in  methanol,
      secondary dilution standards that contain the compounds of interest, either
      singly  or mixed  together.   The  secondary dilution standards  should be
      prepared  at concentrations  such  that  the  desorbed calibration standards
      will bracket the working range of the analytical system.

      5.6  4-Bromofluorobenzene (BFB) standard:

            5.6.1 Prepare a 25 ng//xL solution of BFB  in methanol.

      5.7  Deuterated benzene:

            5.7.1  Prepare a 25 ng//iL solution  of benzene-d6 in methanol.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  Refer to Method 0030, Chapter Ten.

      6.2  Sample trains obtained  from  the  VOST should be  analyzed within 2-6
weeks of sample collection.


7.0  PROCEDURE

      7.1  Assembly of  PTD device:

            7.1.1  Assemble a purge-and-trap desorption device (PTD) that meets
      all the requirements of Method 5030 (refer to Figure 1).

            7.1.2  Connect  the thermal desorption  device  to  the  PTD device.
      Calibrate the PTD-GC/MS system using the  internal standard technique.

      7.2  Internal standard calibration procedure:

            7.2.1  This approach requires the use of deuterated benzene as the
      internal  standard for these analyses.  Other  internal  standards may be
      proposed  for use  in  certain  situations.   The  important  criteria for
      choosing  a  particular compound as  an  internal  standard  are  that it be
      similar in  analytical  behavior to the  compounds of interest and that it
      can  be  demonstrated  that  the measurement  of ,the internal  standard be
      unaffected  by method  or  matrix  interferences.   Other internal standards
      that have been  used  are d10-ethylbenzene  and d4-l,2-dichloroethane.   One
      adds 50 ng  of BFB to  all  sorbent cartridges (in addition to one or more


                                   5040A - 3                      Revision 1
                                                                  November 1990

-------
 internal  standards)  to  provide  continuous  monitoring  of  the  GC/MS
 performance relative to BFB.

       7.2.2  Prepare  calibration  standards  at   a  minimum  of  three
 concentration levels for each analyte of interest.

       7.2.3  The calibration  standards  are prepared  by  spiking  a blank
 Tenax or Tenax/charcoal  trap with a methanolic solution of the calibration
 standards (including 50 ng of the  internal  standard,  such as deuterated
 benzene), using the  flash evaporation technique.   The flash evaporation
 technique requires  filling  the  needle  of a  5.0  juL  syringe  with clean
 methanol and drawing air  into the  syringe to the 1.0  /uL  mark.   This is
 followed by  drawing a  methanolic solution of the calibration standards
 (containing 25 /xg/ML of the  internal  standard)  to the 2.0 ML mark.  The
 glass traps  should be attached to the injection port of a gas chromatograph
 while maintaining the injector temperature at  160°C.  The carrier gas flow
 through the traps should be maintained at about 50 mL/min.

       7.2.4  After directing the gas flow through the trap, the contents
 of the  syringe  should  be  slowly expelled through the gas chromatograph
 injection port over about  15 sec.  After 25 sec have  elapsed, the gas flow
 through the  trap  should be  shut off, the syringe removed,  and  the trap
 analyzed by the PTD-GC/MS procedure outlined  in Method 8240.   The total
 flow of gas  through the  traps  during addition  of calibration standards to
 blank cartridges, or internal  standards  to  sample cartridges, should be
 25 mL or less.

       7.2.5  Analyze each calibration standard  for both Tenax and Tenax/
 charcoal cartridges according to Section  7.3.  Tabulate the area response
 of the  characteristic ions of each  analyte  against  the concentration of
 the  internal  standard  and calculate  the response factor  (RF)  for each
 compound, using Equation 1.

      RF - ASC|S/A|SCS                                                 (1)

where:

 As   =Area of the characteristic ion for the analyte to be measured.

 A,s  =Area of the characteristic ion for the internal standard.

 Cls  =Amount (ng) of the internal standard.

 Cs   =Amount (ng) of the volatile POHC in calibration  standard.

       If the  RF  value  over  the working  range is  a  constant (<10% RSD),
 the RF can be assumed to be  invariant, and the average  RF can be used for
 calculations. Alternatively,  the results can  be  used to plot  a calibration
 curve of response ratios,  As/A,,, versus RF.

       7.2.6  The working calibration curve or RF must  be verified on each
 working day by the measurement of one or more of the calibration standards.
                              5040A -  4                      Revision 1
                                                             November 1990

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      If the response varies by more than ±25% for any analyte, a new calibration
      standard must be prepared and analyzed for that analyte.

      7.3  The schematic  of  the PTD-GC/MS system  is  shown in Figure  1.   The
sample cartridge  is placed in  the thermal  desorption apparatus  (for Inside/
Inside VOST cartridges, use Supelco "clamshell" heater; for Inside/Outside VOST
cartridges, user fabricated unit is required) and  desorbed  in the purge-and-trap
system by heating to 180°C  for 10 min at a flow  rate of 40 mL/min.  The desorbed
components pass into the bottom of  the  water column, are purged from the water,
and collected  on  the  analytical  adsorbent trap.    After the  10  min desorption
period, the compounds are desorbed from the analytical  adsorbent trap into the
GC/MS system according to the procedures described in Method 8240.

      7.4  Qualitative analysis

            7.4.1 The qualitative identification of compounds determined by this
      method is based  on  retention time,  and on  comparison of  the sample mass
      spectrum,  after  background  correction,  with  characteristic ions  in  a
      reference mass spectrum.  The reference  mass spectrum must be generated
      by the laboratory using the conditions of this method.  The characteristic
      ions from the reference mass  spectrum are defined to  be the three ions of
      greatest relative  intensity,  or  any ions over 30% relative intensity if
      less  than  three  such ions occur in the reference  spectrum.   Compounds
      should be identified as present when the criteria below are met.

                  7.4.1.1  The  intensities  of  the characteristic  ions  of  a
            compound maximize in the same  scan or within one scan of each other.
            Selection of a peak by  a data system target compound search routine,
            where the search is based on the presence of a target chromatographic
            peak containing ions specific  for the target compound at a compound-
            specific retention time, will  be accepted as meeting this criterion.

                  7.4.1.2  The RRT of the sample  component is within ± 0.06 RRT
            units of the RRT of the  standard component.

                  7.4.1.3  The relative intensities of the characteristic ions
            agree within  30% of the relative  intensities  of these ions in the
            reference spectrum.  (Example:  For an  ion with an abundance of 50%
            in the  reference spectrum, the corresponding abundance in a sample
            spectrum can range between 20% and 80%.)

                  7.4.1.4  Structural  isomers  that produce  very  similar mass
            spectra should be identified  as  individual  isomers  if  they have
            sufficiently different GC retention times.  Sufficient GC resolution
            is achieved if the height of the valley between two isomer peaks is
            less  than  25% of  the   sum  of the two peak  heights.   Otherwise,
            structural isomers are  identified as isomeric pairs.

                  7.4.1.5   Identification is  hampered when  sample components
            are  not  resolved  chromatographically and  produce  mass  spectra
            containing  ions  contributed by more  than  one analyte.   When gas
            chromatographic  peaks   obviously  represent more  than  one sample
            component  (i.e.,  a broadened peak with  shoulder(s)  or  a valley
            between two or more maxima), appropriate selection of analyte spectra

                                   5040A - 5                      Revision 1
                                                                  November 1990

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      and background spectra is important.  Examination of extracted ion
      current profiles  of  appropriate ions can aid  in  the selection of
      spectra,  and in  qualitative  identification  of compounds.   When
      analytes coelute (i.e.,  only one chromatographic peak is apparent),
      the identification criteria can be  met,  but each analyte spectrum
      will contain extraneous  ions contributed  by  the  coeluting compound.

      7.4.2 For  samples containing  components  not associated  with  the
calibration standards,  a library  search may be made  for  the purpose of
tentative  identification.     The  necessity to   perform  this  type  of
identification will be determined by the type of analyses being conducted.
Guidelines for making tentative identification are:

     (1)    Relative intensities of major ions in the reference spectrum
(ions >  10%  of the most abundant ion) should be  present  in the sample
spectrum.

     (2)    The relative intensities of the major ions should  agree within
+ 20%.   (Example:   For  an  ion with an  abundance  of 50% in the standard
spectrum, the corresponding sample ion abundance  must be  between 30 and
70%).

     (3)    Molecular ions  present  in the  reference  spectrum  should be
present in the sample spectrum.

     (4)    Ions present in the sample spectrum but not in the reference
spectrum  should  be  reviewed  for possible  background  contamination  or
presence of coeluting compounds.

     (5)    Ions present in the reference spectrum but not in the sample
spectrum  should  be reviewed  for  possible  subtraction  from the sample
spectrum  because  of background contamination or  coeluting peaks.   Data
system library reduction programs can sometimes create these discrepancies.

     Computer  generated   library  search   routines  should   not   use
normalization routines  that would misrepresent  the  library or unknown
spectra when compared to each  other.   Only after visual comparison of the
sample  with  the  nearest  library   searches  will  the  mass  spectral
interpretation specialist assign a tentative identification.

7.5  Quantitative analysis

      7.5.1  When   an   analyte   has   been  qualitatively  identified,
quantitation should be based on the integrated  abundance from the EICP of
the primary characteristic  ion chosen for  that analyte.   If the sample
produces an interference for the primary characteristic ion,  a secondary
characteristic ion should be used.

            7.5.1.1  Using the  internal  standard  calibration procedure,
      the amount  of analyte in the sample cartridge is calculated using
      the response factor (RF) determined in Section 7.2.5 and Equation 2.

      Amount of POHC  =  ASC|S/A|SRF                               (2)


                            5040A - 6                      Revision 1
                                                            November  1990

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            where:

            Ag   =Area of the characteristic ion for the analyte to be measured.

            A,s  = Area for the characteristic ion of the internal standard.

            C,8  = Amount (ng) of internal standard.

                  7.5.1.2  The choice of methods for evaluating data collected
            using VOST  for  incinerator trial  burns  is  a  regulatory decision.
            The procedures used extensively by one user are outlined below.

                  7.5.1.3  The total amount of the POHCs of interest collected
            on a pair of traps should be summed.

                  7.5.1.4  The observation of high  concentrations  of POHCs of
            interest   in  blank   cartridges   indicates   possible   residual
            contamination of the  sorbent cartridges prior to  shipment  to and
            use at the site.  Data that fall  in this category (especially data
            indicating high concentrations of POHCs in blank sorbent cartridges)
            should be qualified with regard to validity, and blank data should
            be reported separately.  The applicability of data of this type to
            the  determination of  ORE  is  a  regulatory  decision.    Continued
            observation  of  high   concentrations  of  POHCs   in  blank  sorbent
            cartridges  indicates  that  procedures   for  cleanup,  monitoring,
            shipment, and storage of sorbent cartridges by a particular user be
            investigated to eliminate this problem.

                  7.5.1.5  If any internal  standard  recoveries  fall outside the
            control  limits established  in  Section 8.4, data  for all  analytes
            determined  for  that  cartridge(s)  must be  qualified  with  the
            observation.
8.0  QUALITY CONTROL

      8.1  Refer to  Chapter One  for  specific quality control  procedures and
Method 0030 for sample preparation procedures.

      8.2  Before  performing  any analyses,  the  analyst must  demonstrate the
ability to generate  acceptable  precision  and accuracy  with this method.  This
ability is established as described in Section 7.2.

      8.3  The laboratory  must  spike all Tenax  and  Tenax/charcoal  cartridges
with the  internal  standard(s)  to monitor continuing  laboratory performance.
This procedure is described in Section 7.2.

      8.4  To  establish  the  ability  to generate  acceptable  accuracy  and
precision, the analyst must spike blank Tenax and  Tenax/charcoal cartridges with
the analytes of interest at two concentrations in the working range.

            8.4.1  The average  response factor (R) and the standard deviation
      (S) for each must be calculated.


                                   5040A - 7                       Revision 1
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            8.4.2  The average recovery and standard  deviation must fall within
      the expected range for determination of volatile  POHCs using this method.
      The expected range for recovery of volatile POHCs using this method is 50-
      150%.

      8.5  Each day,  the analyst must  demonstrate through analysis  of blank
Tenax  and  Tenax/charcoal   cartridges   and  organic-free  reagent  water  that
interferences from the analytical system are under control.

      8.6  The  daily GC/MS  performance tests  required  for  this method  are
described in Method 8240.
9.0  METHOD PERFORMANCE

      9.1  Refer to the determinative methods for performance data.


10.0 REFERENCES

1.   Protocol  for Collection  and  Analysis of  Volatile  POHC's  Using  VOST.
     EPA/600/8-84-007, March 1984.

2.   Validation of the Volatile Organic Sampling Train (VOST)  Protocol.  Volumes
     I and II.  EPA/600/4-86-014a, January 1986.
                                   5040A  - 8                       Revision 1
                                                                  November 1990

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                                       METHOD  5040A
ANALYSIS OF  SORBENT  CARTRIDGES FROM VOLATILE ORGANIC SAMPLING TRAIN  (VOST1
                  GAS CHROMATOGRAPHY/MASS  SPECTROMETRY TECHNIQUE
       Start
   7  1.1 Assemble
   purge and trap
     desorption
      device
    7  1.2 Connect
      thermal
    desorption
      device;
    calib. system
    7.2.1 Select
      internal
      standa rd
    7.2.3 Prep
     calibrati
   standards u
   flash evapo
      techniqu
ing
at.
    7.2.4 Direct
      gas flow
    through traps
              7 2.4 Expel
              contents of
            syringe through
             CC injection
                 port
             7.2.4 Analyze
             trap by P-T-D
                CC/MS
               procedure
             (Method 8240)
             725  Analyze
              each  ca1ib.
             standard for
            both cartridges
               (see 7.3)
7.2.S Tabulate
 area response
 and calculate
response factor
             7.2.6 Verify
               response
              factor each
                  day


7 3 Place
sample
cartridge in
desorp . appar . ;
desorb in P-T


7 . 3 Desorb
into CC/MS
system
(Method 8240)


74.1
Quantatively
identify
volatile POHCs
(Method 8240)


7.5.1 Use
primary
characteristic
ion for
quantification


7.5.1.1
Calculate
amount of
analyte in
sample





(
7 5 1 . 3 Sum
amount of POHCs
of interest for
eacK pair of
traps


7 5-1.4 Analyze
blanks for
signs of
residual
contamina ti on .


7 . 5 . 1 . 5 Compare
int. std.
recoveries to
section 8 . 4
control 1 imi ts


;"~~*x
Stop
_^"

                                         5040A  -  9
                                                                  Revision 1
                                                                  November 1990

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                                  METHOD  5050

                    BOMB COMBUSTION METHOD FOR SOLID WASTE
1.0   SCOPE AND APPLICATION

      1.1    This  method  describes the sample preparation  steps  necessary to
determine total  chlorine  in solid waste  and  virgin and used  oils,  fuels and
related materials,  including:  crankcase, hydraulic, diesel,  lubricating and fuel
oils,  and  kerosene  by bomb  oxidation and titration  or  ion  chromatography.
Depending on the analytical  finish chosen,  other halogens  (bromine and fluorine)
and other elements (sulfur  and nitrogen) may also be determined.

      1.2    The  applicable  range of  this method  varies  depending on  the
analytical  finish chosen.   In general, levels as low as  500 /zg/g chlorine in the
original oil  sample  can  be determined.   The  upper  range  can  be  extended to
percentage levels by dilution of the combustate.

      1.3    This  standard may  involve  hazardous materials,  operations,  and
equipment.   This standard  does not purport to address all  of the safety problems
associated with its use.  It is  the responsibility of the user  of this standard
to  establish  appropriate  safety  and health  practices  and  determine  the
applicability of regulatory limitations prior to use.  Specific safety statements
are given in Section 3.0.

2.0   SUMMARY OF METHOD

      2.1    The sample is oxidized  by combustion in a bomb containing oxygen
under  pressure.    The  liberated  halogen  compounds are  absorbed  in  a sodium
carbonate/sodium bicarbonate  solution.   Approximately 30  to   40  minutes  are
required to prepare a sample by  this  method.  Samples with a  high water content
(> 25%) may  not combust efficiently and may require the addition  of  a mineral oil
to facilitate combustion.   Complete combustion  is still not guaranteed for such
samples.

      2.2    The bomb combustate solution  can then be analyzed for the following
elements as their anion species by one or more of the following methods:
      Method          Title


      9252            Chloride (Titrimetric,  Mercuric Nitrate)
      9253            Chloride (Titrimetric,  Silver Nitrate)
      9056            Anion Chromatography Method (Chloride,  Sulfate, Nitrate,
                      Phosphate,  Fluoride,  Bromide)
                                   5050 - 1                       Revision 0
                                                                  November  1990

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NOTE:        Strict  adherence  to  all  of the provisions prescribed hereinafter
             ensures  against  explosive  rupture of  the  bomb,  or  a  blowout,
             provided the bomb is of proper design  and  construction and in good
             mechanical condition.  It is desirable, however, that the bomb be
             enclosed  in  a shield of steel  plate  at least  1/2  in.  (12.7 mm)
             thick,  or equivalent protection be provided against unforeseeable
             contingencies.

3.0   INTERFERENCES

      3.1    Samples  with very  high  water  content  (>  25%) may not  combust
efficiently  and may require  the addition  of a  mineral  oil   to  facilitate
combustion.

      3.2    To  determine total  nitrogen in samples,  the  bombs  must  first be
purged of ambient air.  Otherwise, nitrogen results will be biased high.

4.0   APPARATUS AND MATERIALS

      4.1    Bomb, having a  capacity  of not less  than  300 ml,  so constructed
that it will not leak during the test,   and  that quantitative  recovery of the
liquids from the bomb may  be readily achieved. The inner surface of the bomb may
be made of stainless  steel or any other material that will not be affected by the
combustion process or products.  Materials used  in the bomb assembly,  such as the
head gasket and  lead-wire insulation, shall  be  resistant to heat and  chemical
action and shall not  undergo  any reaction that will affect the chlorine content
of the sample in the bomb.

      4.2    Sample cup, platinum or stainless  steel, 24 mm in outside diameter
at the bottom, 27 mm  in outside diameter  at the top, 12 mm in height outside, and
weighing 10 to 11 g.

      4.3    Firing  wire,  platinum or stainless steel,  approximately  No.  26 B
& S gage.

      4.4    Ignition circuit, capable of supplying sufficient current to ignite
the nylon thread or cotton wicking without melting the  wire.

NOTE:        The  switch   in  the ignition  circuit  shall be  of the type  that
             remains open, except when held in closed position by the operator.

      4.5    Nylon sewing thread, or Cotton  Wicking, white.

      4.6    Funnel, to fit a  100-mL volumetric flask.

      4.7    Class A volumetric flasks,   100-mL, one per  sample.

      4.8    Syringe, 5-  or 10-mL disposable plastic.

      4.9    Apparatus for specific analysis methods are given in the  methods.

      4.10   Analytical balance:  capable of weighing to 0.0001 g.
                                   5050 - 2                       Revision 0
                                                                  November 1990

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5.0   REAGENTS

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

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

      5.3    Oxygen.   Free  of  combustible  material  and halogen  compounds,
available at a pressure of 40 atm.
WARNING:
Oxygen vigorously accelerates combustion (see Appendix Al.l)
      5.4    Sodium  bicarbonate/sodium  carbonate  solution.   Dissolve 2.5200 g
NaHC03 and 2.5440 g Na2C03 in reagent water and dilute to 1 L.

      5.5    White oil.  Refined.

      5.6    Reagents and materials for specific analysis methods are given in
the methods.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1    All samples must be collected using a  sampling plan that addresses
the considerations discussed in Chapter Nine.

      6.2    Ensure  that the portion of the sample used for the test is repre-
sentative of the sample.

      6.3    To  minimize  losses of volatile halogenated solvents  that  may be
present in the sample, keep the field and laboratory samples as  free of headspace
as possible.

      6.4    Because used oils may contain toxic and/or carcinogenic substances
appropriate field and laboratory safety procedures should be followed.
7.0   PROCEDURE
      7.1
 Sample Preparation
               7.1.1  Preparation of bomb and sample.  Cut a piece of firing wire
      approximately 100 mm in length and attach the free ends to the terminals.
      Arrange the wire  so  that it will be just  above and  not touching the sample
      cup.  Loop a cotton thread around the wire  so  that the ends will extend
      into the sampling cup.   Pipet  10 mL of the NaHCOj/NajCOj solution  into the
      bomb, wetting the sides.  Take an aliquot of the  oil  sample of approxi-
      mately 0.5 g using a 5- or 10-mL disposable plastic syringe, and place in
      the sample cup.   The actual sample weight is determined by the difference
                                   5050 - 3
                                                     Revision 0
                                                     November 1990

-------
      between the weight of the empty and  filled  syringe.  Do not use more than
      1 g of sample.

NOTE:         After repeated use of the bomb for  chlorine determination, a film
              may  be  noticed on the  inner surface.   This  dullness  should be
              removed by periodic polishing of the bomb.  A satisfactory method
              for  doing this is to rotate  the bomb in a lathe at about 300 rpm
              and  polish  the inside  surface  with Grit No. 2/0  or equivalent
              paper1 coated with  a light machine oil to  prevent cutting,  and
              then with  a paste of grit-free chromic oxide and water.   This
              procedure will remove all but very deep pits and put a high polish
              on the surface.  Before  using the bomb, it should be washed with
              soap and  water to remove  oil  or paste left  from  the  polishing
              operation.  Bombs with porous or pitted surfaces should never be
              used because  of  the tendency to retain chlorine  from  sample to
              sample.

NOTE:         If  the  sample  is  not  readily combustible,  other nonvolatile,
              chlorine-free  combustible  diluents such  as  white  oil  may  be
              employed.  However, the combined weight of sample and nonvolatile
              diluent shall not exceed 1 g.  Some  solid additives  are relatively
              insoluble but  may  be satisfactorily burned when  covered  with a
              layer of white oil.

NOTE:         The  practice of  alternately  running  samples high  and low  in
              chlorine  content should  be avoided whenever possible.    It  is
              difficult to rinse the last  traces of chlorine from the walls of
              the  bomb,  and  the tendency  for residual chlorine  to carry over
              from sample  to  sample  has  been  observed  in  a  number  of
              laboratories.  When a sample high in chlorine has preceded one low
              in chlorine content, the test on the low-chlorine sample should
              be  repeated,  and one  or both of  the  low values  thus  obtained
              should  be  considered  suspect  if they do  not agree within  the
              limits of repeatability  of  this method.

NOTE:         Do not use more  than 1  g total  of  sample  and  white oil  or other
              chlorine-free  combustible material.   Use  of excess amounts  of
              these materials could cause  a buildup of dangerously high pressure
              and  possible rupture of  the  bomb.

              7.1.2    Addition of oxygen.   Place the  sample  cup in  position
      and arrange the thread so that the end dips  into the sample.  Assemble the
      bomb  and  tighten  the  cover securely.   Admit oxygen  slowly (to  avoid
      blowing the oil  from the  cup) until  a pressure is reached as indicated in
      Table 1.

NOTE:         Do  not  add oxygen  or  ignite  the  sample if  the  bomb  has  been
              jarred, dropped, or tiled.
     1Emery Polishing Paper  grit No. 2/0 may be purchased from the Behr-Manning
Co., Troy, NY.

     2Chromic oxide may be purchased  from  J.T.  Baker  & Co.,  Phillipsburg,  NJ.

                                   5050 -  4                       Revision 0
                                                                  November 1990

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               7.1.3     Combustion.   Immerse the  bomb  in a  cold  water bath.
      Connect the terminals to the open electrical circuit.  Close the circuit
      to ignite the sample.  Remove the bomb from the bath after immersion for
      at least 10 minutes.  Release  the  pressure at  a slow,  uniform rate such
      that the operation requires at  least 1 min.  Open the bomb and examine the
      contents.  If traces of unburned oil or sooty deposits are found, discard
      the determination, and thoroughly clean the bomb before using it again.

               7.1.4     Collection of halogen solution.  Using reagent water and
      a funnel, thoroughly rinse the  interior of the bomb, the sample cup, the
      terminals,  and  the inner surface  of the  bomb  cover  into  a  100-mL
      volumetric flask.  Dilute  to the mark with reagent water.

               7.1.5     Cleaning procedure for bomb and  sample cup.  Remove any
      residual fuse wire from  the terminals and the cup.   Using hot water, rinse
      the interior of the bomb,  the  sample  cup, the  terminals,  and  the inner
      surface of the bomb cover.   (If any residue remains,  first scrub the bomb
      with Alconox solution).   Copiously rinse the bomb,  cover,  and  cup with
      reagent water.

      7.2      Sample  Analysis.   Analyze the combustate  for  chlorine  or other
halogens using the methods  listed in Step 2.2. It may be necessary to dilute the
samples so that the concentration will fall within the range of standards.

      7.3      Calculations.    Calculate the concentrations  of each  element
detected in the sample according to the following equation:

                             <=«. * Ve- X DF                    (1)

                     '  "   	5	

      where:

          C0      =  concentration of element in the sample,  /*g/g
          ^com     =  concentration of element in the combustate, ng/ml
          V       =  total volume of combustate, ml
          Dh      =  dilution factor
          W0      =  weight of sample combusted, g.

      Report  the  concentration  of  each  element  detected in  the sample  in
micrograms per gram.

      Example:  A 0.5-g oil sample was combusted, yielding  10 ml of combustate.
The combustate was diluted to 100 ml total  volume and  analyzed for  chloride,
which was measured to  be 5 /xg/mL.  The concentration of chlorine in the original
sample is then calculated as shown below:

                                5 ug  x  (10 ml) x (10)
                    C0  =      _mL	          (2)
                                         0.5 g


                    C0  =       1,000 MS                         (3)
                                       g

                                   5050 - 5                       Revision 0
                                                                  November 1990

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8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control procedures.

      8.2   One sample in ten should be bombed twice.  The results should agree
to within 10%, expressed as the relative percent difference of the results.

      8.3   Analyze matrix spike and matrix spike duplicates - spike samples with
the  elements  of  interest  at  a   level  commensurate  with  the  levels  being
determined.   The  spiked  compounds should be similar to  those  expected in the
sample.  Any  sample  suspected  of  containing  >  25% water should also be spiked
with organic chlorine.

      8.4   For   higher   levels   (e.g.,  percent  levels),  spiking   may  be
inappropriate.    For these  cases,  samples  of  known  composition  should  be
combusted.  The results should agree to within 10% of the expected result.

      8.5   Quality  control  for  the analytical  method(s) of choice should be
followed.

9.0   PERFORMANCE

      See analytical methods referenced in Step 2.2.

10.0 REFERENCES

1.    ASTM Method D  808-81,  Standard Test  Method  for Chlorine  in New and Used
Petroleum Products (Bomb Method).  1988 Annual  Book of ASTM Standards.  Volume
05.01 Petroleum Products and Lubricants.

2.    Gaskill, A.; Estes, E. D.; Hardison, D. L.; and Myers, L. E.  Validation
of Methods for Determining  Chlorine  in Used  Oils  and Oil Fuels.   Prepared for
U.S. Environmental Protection Agency, Office of Solid Waste.  EPA Contract No.
68-01-7075, WA 80.  July 1988.
                                   5050 - 6                       Revision 0
                                                                  November 1990

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                                   TABLE 1.
                                GAGE PRESSURES
Capacity of bomb, ml
                                 Minimum
                                 gage
                                 pressure , atm
                   Maximum
                   gage
                   pressure ,  atm
      300 to 350
      350 to 400
      400 to 450
      450 to 500
                                     38
                                     35
                                     30
                                     27
                       40
                       37
                       32
                       29
aThe minimum pressures are specified to provide sufficient oxygen for complete
combustion, and the maximum pressures  represent a safety requirement.  Refer to
manufacturers' specifications for appropriate gage pressure, which may be lower
than those listed here.
                                   APPENDIX
                         Al.   PRECAUTIONARY  STATEMENTS
Al.1  Oxygen
                          vigorously
      Warning—Oxygen
accelerates combustion.
      Keep oil and  grease  away.   Do
not use oil or grease on regulators,
gages, or control equipment.
      Use   only    with   equipment
conditioned  for   oxygen service  by
careful  cleaning   to   remove  oil,
grease, and other combustibles.
      Keep  combustibles  away  from
oxygen   and   eliminate   ignition
sources.
      Keep surfaces clean to prevent
ignition or  explosion, or  both,  on
contact with oxygen.
      Always    use    a    pressure
regulator.   Release  regulator tension
before opening cylinder valve.
      All  equipment and  containers
used must be suitable and recommended
for oxygen service.
      Never   attempt    to   transfer
oxygen from cylinder in which it is
received to any  other  cylinder.   Do
not mix gases in  cylinders.
      Do  not  drop  cylinder.    Make
sure  cylinder  is  secured  at  all
times.
      Keep cylinder valve closed when
not in use.
      Stand  away   from  outlet  when
opening cylinder valve.
      For technical use only.  Do not
use for inhalation purposes.
      Keep cylinder  out  of sun  and
away from heat.
      Keep cylinders  from  corrosive
environment.
      Do  not  use  cylinder  without
label.
      Do  not  use  dented or  damaged
cylinders.
      See Compressed Gas  Association
booklets G-4  and G4.1 for details of
safe practice in the use  of oxygen.
                                   5050 - 7
                                                                  Revision 0
                                                                  November 1990

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              METHOD 5050
BOMB COMBUSTION METHOD  FOR SOLID WASTE
       START

7.1.1 Prepare bomb
and sample







I
7.1.2 Slowly add
oxygen to sample
cup
1
7.1.3 Immerse bomb
in co 1 d wa ter ;
igni te sample ;
remove bomb from
water ; release
pressure; open bomb









1
7.1.4 Rinse bomb,
sample cup.
terminals, and bomb
cover with water



p4


715 Rinse bomb,
sample cup,
terminals, and bomb
cover with hot
water
1









7.2 Analyze
combustate

1

7 . 3 Calculate
concentration of
each element
detected




/^ ^\
/ \
I STOP

\^ J

                5050 -  8
Revision 0
November 1990

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                                  METHOD 5041

      Protocol for Analysis of Sorbent Cartridges from Volatile Organic
             Sampling Train; Wide-bore Capillary Column Technique
1.0  SCOPE AND APPLICATION

      1.1   This method describes  the analysis of  volatile  principal  organic
hazardous  constituents  (POHCs)  collected  from the  stack  gas effluents  of
hazardous waste incinerators using the VOST methodology (1).  For a comprehensive
description of  the  VOST sampling methodology see Method  0030.   The following
compounds may be determined by this method:
      Compound Name
CAS No.'
      Acetone
      Acrylonitrile
      Benzene
      Bromodi chloromethane
      Bromoform"
      Bromomethane0
      Carbon disulfide
      Carbon tetrachloride
      Chlorobenzene
      Chlorodi bromomethane
      Chloroethane0
      Chloroform
      Chloromethane0
      Dibromomethane
      1,1-Dichloroethane
      1,2-Dichloroethane
      1,1-Dichloroethene
      trans-1,2-Dichloroethene
      1,2-Di chloropropane
      cis-l,3-Dichloropropene
      trans-1,3-Dichloropropene
      Ethyl benzene"
      lodomethane
      Methylene chloride
      Styrene"
      1,1,2,2-Tetrachloroethane"
      Tetrachloroethene
      Toluene
      1,1,1-Tri chloroethane
      1,1,2-Tri chloroethane
      Trichloroethene
      Tri chlorof1uoromethane
      l,2,3-Trichloropropaneb
      Vinyl chloride6
      Xylenes"
   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
   79-01-6
   75-69-4
   96-18-4
   75-01-4
                                   5041 - 1
                 Revision 0
                 November 1990

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      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 132°C  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.

      When Method 5041  is used for survey analyses, values for compounds boiling
above 132°C may be reported and qualified since the quantity obtained represents
a minimum value for the compound.  These minimum values should not be used for
trial burn ORE  calculations or to prove insignificant risk.

      1.4  The VOST analytical methodology can  be used to  quantitate volatile
organic  compounds that  are   insoluble  or  slightly  soluble  in  water.    When
volatile,  water soluble compounds are  included in the VOST organic  compound
analyte list, quantitation limits can be expected  to  be  approximately ten times
higher than quantitation limits for water insoluble compounds (if the compounds
can be recovered at all) because the purging efficiency from water (and possibly
from Tenax-GC*) is poor.

      1.5   Overall  sensitivity of the  method is  dependent  upon the  level  of
interferences  encountered  in  the  sample  and  the  presence  of  detectable
concentrations of volatile POHCs in blanks.  The target  detection limit of this
method is 0.1 /*g/m3 (ng/L)  of flue gas,  to  permit  calculation of a ORE equal to
or greater than 99.99% for volatile  POHCs which  may be present in  the waste
stream at  100  ppm.  The upper end of the range  of applicability of this method
is limited by  the dynamic range of the analytical  instrumentation,  the overall
loading  of organic compounds  on  the exposed tubes,  and breakthrough  of the
volatile POHCs on  the sorbent traps used to  collect the sample.  Table 1 presents


                                   5041 -  2                       Revision 0
                                                                  November 1990

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retention  times  and characteristic ions  for volatile compounds which  can be
determined by this method.  Table 2 presents method detection limits for a range
of volatile compounds analyzed by the wide-bore VOST methodology.

      1.6  The wide-bore VOST  analytical  methodology  is  restricted  to use by,
or under the supervision of, analysts experienced in the use of sorbent media,
purge-and-trap systems, and  gas  chromatograph/mass  spectrometers,  and skilled
in the interpretation of mass spectra and their use as a quantitative tool.


2.0  SUMMARY OF METHOD

      2.1  The sorbent tubes are  thermally desorbed  by heating and purging with
organic-free helium.   The  gaseous effluent from  the  tubes  is  bubbled through
pre-purged organic-free reagent water and  trapped  on an analytical sorbent trap
in a purge-and-trap unit (Figure 2).  After desorption,  the analytical sorbent
trap is heated rapidly and  the  gas  flow  from  the analytical trap is directed to
the head of a wide-bore column under subambient conditions. The volatile organic
compounds  desorbed from  the  analytical  trap  are  separated  by  temperature
programmed high  resolution  gas  chromatography and detected by  continuously
scanning low resolution mass spectrometry (Figure 3).  Concentrations of volatile
organic compounds are  calculated from a multi-point calibration curve, using the
method of response factors.


3.0  INTERFERENCES

      3.1  Sorbent tubes which are to be analyzed for volatile organic compounds
can be  contaminated  by diffusion of volatile  organic compounds  (particularly
Freon* refrigerants and common  organic  solvents) through the external container
(even through a Teflon* lined screw cap  on a glass container) and the Swagelok®
sorbent tube caps  during shipment  and storage.  The sorbent tubes  can also be
contaminated if organic solvents  are present  in the  analytical laboratory.  The
use of  blanks  is  essential  to  assess the extent  of any  contamination.   Field
blanks must be prepared and taken to the field.  The end caps of the tubes are
removed for the period of time required to  exchange two  pairs  of traps on the
VOST sampling apparatus.  The tubes are recapped and  shipped  and handled exactly
as the actual  field samples  are shipped  and handled.   At least one pair of field
blanks is included with each six pairs of sample cartridges collected.

      3.2    At  least  one   pair   of  blank  cartridges  (one  Tenax-GC®,  one
Tenax-6C*/charcoal) shall  be included with shipment of cartridges to a hazardous
waste incinerator  site as trip blanks.   These trip blanks will  be treated like
field blanks except that the end  caps will not be  removed during storage at the
site.  This pair  of traps will be  analyzed  to  monitor potential  contamination
which may occur during storage and shipment.

      3.3    Analytical  system   blanks  are  required   to   demonstrate  that
contamination  of  the  purge-and-trap   unit  and  the  gas  chromatograph/mass
spectrometer has not occurred or that, in the event of analysis of sorbent tubes
with very  high  concentrations  of organic compounds, no  compound  carryover is
occurring.  Tenax® from the same  preparation  batch as the Tenax* used for field
sampling should be used in  the preparation  of  the method (laboratory) blanks.


                                   5041 - 3                       Revision 0
                                                                  November 1990

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A sufficient number  of  cleaned  Tenax® tubes from the same  batch  as  the field
samples should be reserved in the laboratory for use as blanks.

      3.4  Cross contamination can occur whenever low-concentration samples are
analyzed after high-concentration samples,  or  when  several  high-concentration
samples are  analyzed sequentially.   When an unusually  concentrated  sample is
analyzed, this analysis should be followed by a method blank to establish that
the  analytical  system  is free  of  contamination.    If analysis  of a  blank
demonstrates that the system  is  contaminated,  an  additional  bake  cycle  should
be used.  If the analytical system is still contaminated after additional baking,
routine system maintenance should be  performed: the  analytical  trap  should be
changed and  conditioned,  routine column  maintenance should be performed  (or
replacement of the column  and  conditioning of the new  column, if necessary), and
bakeout of the ion source  (or  cleaning of the ion source  and rods, if required).
After system maintenance has  been performed,  analysis of a blank is required to
demonstrate that the cleanliness of the system is  acceptable.

      3.5  Impurities in  the  purge  gas  and  from organic compounds out-gassing
in tubing account for the majority  of contamination  problems.   The analytical
system must be demonstrated to be free from contamination under the conditions
of the analysis by analyzing two  sets of clean, blank sorbent tubes with organic-
free reagent purge water as system blanks.  The analytical system is acceptably
clean when these two sets  of  blank tubes  show values  for the analytes which are
within one  standard deviation  of  the  normal  system blank.   Use of plastic
coatings,  non-Teflon*  thread   sealants,  or  flow  controllers  with  rubber
components should be avoided.

      3.6  VOST tubes are handled in the laboratory  to  spike  standards  and to
position the  tubes  within the desorption  apparatus.   When sorbent  media  are
handled in the  laboratory atmosphere, contamination  is possible  if  there  are
organic solvents in  use anywhere in the laboratory.   It is therefore necessary
to make daily use of system  blanks  to monitor  the cleanliness  of  the sorbents
and the absence of contamination from the  analytical system.   A single  set of
system blank  tubes  shall  be  exposed  to  normal  laboratory  handling procedures
and analyzed as a sample.   This  sample should be within one standard deviation
of normal VOST tube  blanks to demonstrate lack of contamination of the sorbent
media.

      3.7  If the  emission source has a high concentration of non-target organic
compounds (for example,  hydrocarbons at concentrations of hundreds of ppm), the
presence of  these non-target  compounds  will  interfere with  the performance of
the VOST analytical  methodology.  If one or more  of the compounds of interest
saturates  the  chromatographic   and  mass   spectrometric  instrumentation,  no
quantitative calculations  can be  made and the tubes which have been sampled under
the same conditions will yield no valid data for any of the saturated compounds.
In the presence of a  very high organic loading, even if the compounds of interest
are not saturated, the instrumentation is so saturated that the  linear range has
been surpassed. When instrument saturation occurs, it is possible that compounds
of  interest  cannot  even  be identified  correctly   because  a   saturated  mass
spectrometer  may  mis-assign  masses.    Even  if compounds  of   interest  can be
identified,  accurate quantitative   calculations  are  impossible   at  detector
saturation.  No determination can be made at detector saturation,  even  if the
target compound itself is  not  saturated.  At detector saturation, a negative bias


                                   5041  - 4                       Revision 0
                                                                  November  1990

-------
will be encountered In analytical measurements and no accurate calculation can
be made for the Destruction and Removal Efficiency if analytical values may be
biased negatively.

      3.8  The recoveries of  the  surrogate  compounds,  which are spiked on the
VOST tubes  immediately before analysis,  should  be monitored carefully  as an
overall indicator of the performance  of the methodology.   Since the matrix of
stack emissions is so variable, only a general guideline for recovery of 50-150%
can be used for surrogates.  The  analyst cannot use the surrogate recoveries as
a guide for correction  of compound recoveries.  The surrogates  are valuable only
as a general indicator of correct operation of the methodology.   If surrogates
are not observed or if recovery of one or more of  the surrogates is outside the
50-150% range, the VOST methodology  is not  operating  correctly.  The cause of
the failure in the methodology  is  not obvious.   The  matrix of stack emissions
contains large amounts  of  water,  may be  highly acidic,  and may contain large
amounts of target  and non-target organic  compounds.   Chemical  and  surface
interactions may be occurring on the tubes.  If recoveries of surrogate compounds
are extremely  low or  surrogate compounds  cannot even  be identified  in  the
analytical process, then failure  to observe  an analyte may or may not imply that
the compound of interest has been removed from the emissions with a high degree
of efficiency (that is, the  Destruction and  Removal Efficiency for that analyte
is high).


4.0  APPARATUS AND MATERIALS

      4.1  Tube desorption apparatus:  Acceptable performance of  the methodology
requires:    1)  temperature  regulation  to ensure  that  tube temperature during
desorption is regulated to  180°C ± 10°;  2)  good contact between tubes and the
heating apparatus  to  ensure that the  sorbent bed is  thoroughly and uniformly
heated  to  facilitate  desorption  of  organic  compounds;    and 3)  gas-tight
connections to the ends of  the  tubes  to ensure  flow  of desorption gas through
the tubes  without leakage  during the  heating/desorption  process.   A simple
clamshell  heater  which  will hold tubes which are 3/4"  in  outer diameter will
perform acceptably as a desorption apparatus.

      4.2  Purge-and-trap device:  The  purge-and-trap device consists of three
separate pieces of equipment:   a  sample purge vessel,  an analytical trap, and
a  desorber.   Complete  devices  are commercially  available from a  variety of
sources, or the  separate  components  may  be assembled.   The cartridge thermal
desorption apparatus  is  connected to the sample  purge  vessel by  1/8"  Teflon*
tubing  (unheated  transfer  line).   The  tubing  which  connects  the desorption
chamber to the sample purge vessel should be as short as is practical.

            4.2.1  The sample purge vessel is required  to hold 5 ml of organic-
      free reagent water, through which the  gaseous effluent from the VOST tubes
      is routed.  The  water column should be at  least 3 cm deep.   The gaseous
      headspace between the water column and the analytical  trap  must have a
      total volume of less than 15 ml.  The purge gas must pass  through the water
      column as finely divided bubbles with a diameter of less than 3 mm at the
      origin.  The  sample  purger shown  in  Figure 4  meets  these requirements.
      Alternate sample purging vessels may be used if equivalent performance is
      demonstrated.


                                   5041  - 5                      Revision 0
                                                                  November  1990

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      4.2.2   The analytical  trap  must be  at least  25  cm and  have an
internal diameter of at least 0.105 in.  The analytical trap must contain
the following components:

      2,6-diphenylene oxide polymer:    60/80  mesh,  chromatograph  grade
                                        (Tenax-GC*,  or equivalent)

      methyl silicone packing:          OV-1  (3%) on  Chromosorb-W  60/80
                                        mesh,  or  equivalent

      silica gel:                       35/60  mesh,  Davison grade  15 or
                                        equivalent

      coconut charcoal:                 prepare   from  Barneby   Cheney,
                                        CA-580-26,   or   equivalent,   by
                                        crushing  through  26 mesh  screen.

      The  proportions  are:   1/3  Tenax-GC*,  1/3  silica gel,   and  1/3
charcoal,  with  approximately  1.0  cm  of methyl  silicone packing.  The
analytical  trap  should  be conditioned for four  hours  at 180°C  with gas
flow (10 mL/min) prior  to use in sample analysis.   During conditioning,
the effluent of the  trap  should not  be  vented to the analytical  column.
The thermal desorption apparatus is connected to the injection system of
the mass spectrometer by  a transfer line which is heated to 100°C.

      4.2.3  The desorber must be capable of rapidly heating the analytical
trap to 180°C for desorption.   The  polymer section of the trap should not
exceed 180°C, and the remaining sections should not exceed 220°C, during
bake-out mode.

4.3  Gas chromatograph/mass spectrometer/data system:

      4.3.1   Gas chromatograph:    An  analytical  system  complete with  a
temperature  programmable  oven with sub-ambient  temperature capabilities
and all required  accessories,  including  syringes, analytical columns, and
gases.

      4.3.2  Chromatographic  column:  30 m x 0.53 mm ID  wide-bore  fused
silica capillary column,  3 2m film thickness,  DB-624 or equivalent.

      4.3.3  Mass spectrometer:  capable of scanning from  35-260 amu every
second or  less,  using 70 eV  (nominal)  electron energy  in  the  electron
ionization  mode  and  producing  a  mass  spectrum that  meets  all of the
criteria in Table 3 when  50 ng of 4-bromofluorobenzene (BFB)  is  injected
into the water in the purge vessel.

      4.3.4   Gas  chromatograph/mass  spectrometer  interface:   Any  gas
chromatograph  to  mass  spectrometer  interface  that  gives  acceptable
calibration points  at 50 ng or less per injection of each  of the analytes,
and achieves the performance  criteria for  4-bromofluorobenzene  shown in
Table 3,  may be used.  If  a glass jet separator is used with the wide-bore
column, a helium  make-up flow  of approximately 15 ml,  introduced after the
                             5041 - 6                       Revision 0
                                                            November 1990

-------
      end of  the column  and prior  to the  entrance  of  the  effluent  to  the
      separator, will be required for optimum performance.

            4.3.5  Data system:  A computer  system  that  allows the continuous
      acquisition and  storage  on machine  readable  media of all  mass spectra
      obtained throughout the duration of  the  chromatographic  program must be
      interfaced to  the mass  spectrometer.  The computer must have software that
      allows searching any gas chromatographic/mass  spectrometric data file for
      ions of a specified mass and plotting such ion abundances versus time or
      scan number.   This  type  of plot is defined as  an  Extracted Ion Current
      Profile  (EICP).     Software  must  also  be available  that  allows  the
      integration of the  ion abundances  in any EICP between  specified time or
      scan number limits.  The most recent version of the  EPA/NIST Mass Spectral
      Library should also be available.

      4.4  Wrenches:  9/16", 1/2", 7/16", and 5/16".

      4.5  Teflon* tubing:   1/8" diameter.

      4.6  Syringes: 25 /il_ syringes  (2), 10 /xL  syringes  (2).

      4.7  Fittings:   1/4" nuts, 1/8" nuts, 1/16" nuts, 1/4" to  1/8" union, 1/4"
to 1/4" union, 1/4"  to 1/16" union.

      4.8   Adjustable  stand  to raise the  level of  the desorption  unit,  if
required.

      4.9  Volumetric flasks:  5 ml,  class A with ground glass stopper.

      4.10  Injector port or equivalent, heated to  180°C for loading standards
onto VOST tubes prior to analysis.

      4.11  Vials:  2 ml, with Teflon* lined screw  caps or crimp tops.

      4.12  Syringe:  5 ml, gas-tight with shutoff valve.


5.0  REAGENTS

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

      5.2  Organic-free reagent water - All references to water in this method
refer to organic-free reagent water,  as defined in Chapter One.

            5.2.1  It is advisable to maintain the stock of organic-free reagent
      water generated for use in the  purge-and-trap  apparatus with a continuous
      stream of inert gas  bubbled through the water.  Continuous bubbling of the
                                   5041 - 7                       Revision 0
                                                                  November 1990

-------
      Inert gas maintains  a  positive  pressure  of Inert gas above the water as
      a safeguard against contamination.

      5.3   Methanol,  CH3OH.   Pesticide  quality or  equivalent.    To  avoid
contamination with  other laboratory  solvents,  it is  advisable  to  maintain a
separate stock of methanol  for the preparation of standards for VOST analysis
and to regulate the use of this methanol very carefully.

      5.4   Stock  standard  solutions  - Can  be  prepared  from  pure  standard
materials or  can  be purchased as  certified solutions.  Commercially prepared
stock standards can be used if they are verified against  EPA standards.  If EPA
standards are not available  for  verification,  then standards  certified by the
manufacturer  and  verified  against  a  standard  made  from pure material  is
acceptable.  Stock standard solutions  must  be prepared  in high purity methanol.
All  preparation  of  standards should  take place in  a hood,  both  to  avoid
contamination and to ensure  safety of the analyst preparing the standards.

            5.4.1  Place about 4 ml of high purity methanol  in  a 5 ml volumetric
      flask.  Allow the flask to  stand,  unstoppered,  for  about 10 min, or until
      all alcohol  wetted surfaces have dried.

                  5.4.1.1  Add appropriate volumes of  neat liquid chemicals or
            certified  solutions,  using a  syringe of  the  appropriate volume.
            Liquid which  is  added to  the volumetric flask must  fall  directly
            into the alcohol  without contacting the neck  of the flask.  Gaseous
            standards  can be  purchased as  methanol  solutions  from several
            commercial vendors.

                  5.4.1.2  Dilute to volume with high purity methanol, stopper,
            and then  mix  by  inverting  the  flask several times.   Calculate
            concentration  by  the dilution  of  certified  solutions  or  neat
            chemicals.

            5.4.2  Transfer  the stock  standard  solution  into  a  Teflon* sealed
      screw cap  bottle.   An  amber bottle may  be  used.  Store,  with minimal
      headspace,  at -10°C to -20°C,  and  protect  from  light.

            5.4.3  Prepare fresh  standards  every two months for gases. Reactive
      compounds such as  styrene may need to be prepared more  frequently.   All
      other standards must be replaced after six months, or  sooner if comparison
      with check standards indicates a problem.

      5.5   Secondary  dilution standards:   Using  stock  standard  solutions,
prepare, in high purity  methanol,  secondary dilution standards  containing the
compounds of  interest, either singly  or  mixed  together.   Secondary dilution
standards must be  stored  with minimal headspace and should be checked frequently
for  signs  of  degradation  or evaporation,  especially  just  prior  to preparing
calibration standards from them.

      5.6   Surrogate  standards:   The  recommended  surrogates are  toluene-d6,
4-bromofluorobenzene, and l,2-dichloroethane-d4.  Other  compounds may be used as
surrogate compounds, depending upon the requirements of the  analysis.  Surrogate
compounds are selected to span the elution range of the compounds of interest.


                                   5041 - 8                       Revision 0
                                                                  November 1990

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Isotopically labeled compounds are selected to preclude the observation of the
same compounds In the stack emissions.   More  than one surrogate is used so that
surrogate measurements can still be made even if analytical interferences with
one or more of the  surrogate compounds are encountered.   However,  at least three
surrogate compounds should  be used to monitor the performance of the methodology.
A stock surrogate compound solution in high purity methanol should be prepared
as described in  Section  5.4,  and  a surrogate standard  spiking solution should
be prepared from the  stock at a concentration of 250 /ig/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  /ul_ of  the surrogate spiking
solution prior to GC/MS analysis.

      5.7    Internal   standards:    The recommended  internal   standards  are
bromochloromethane, 1,4-difluorobenzene, and chlorobenzene-d5.  Other compounds
may be used as internal standards as long as they have retention times similar
to the  compounds being analyzed by GC/MS.   The internal  standards  should be
distributed through the chromatographic elution range.  Prepare internal standard
stock  and secondary  dilution  standards  in  high  purity  methanol   using  the
procedures described in Sections 5.2 and 5.3.  The secondary dilution standard
should be prepared  at a concentration of 25 mg/L of each  of the  internal standard
compounds.  Addition of  10 pi of this  internal  standard solution to each pair
of VOST tubes (or to each VOST tube, if the tubes are analyzed individually) is
the equivalent of 250 ng total.

      5.8  4-Bromofluorobenzene (BFB)  standard:  A standard  solution containing
25 ng//il_ of BFB  in  high purity methanol should be prepared  for use as a tuning
standard.

      5.9  Calibration standards:   Calibration  standards at a minimum of five
concentrations will be required from the secondary dilution of stock standards
(see Sections  5.2  and  5.3).   A range  of concentrations  for calibration can be
obtained  by  use  of different  volumes  of a  50  mg/L methanol solution  of the
calibration  standards.    One of  the  concentrations   used  should   be  at  a
concentration  near, but  above,  the method  detection  limit.    The  remaining
concentrations should correspond to the expected range of concentrations found
in field samples  but should not exceed  the linear range of the GC/MS analytical
system (a typical range for a  calibration would be 10,  50, 100, 350, and 500 ng,
for  example).    Each  calibration  standard  should  contain  each analyte  for
detection by this  method.  Store  calibration  standards  for one  week only in a
vial with no headspace.

      5.10  Great care must be taken to maintain the integrity of all standard
solutions.  All  standards  of  volatile  compounds  in  methanol must be stored at
-10° to -20°C  in  amber  bottles with Teflon* lined screw caps or crimp tops.  In
addition, careful attention must be paid to the use of syringes designated for
a specific purpose  or for  use with only a single standard solution since cross
contamination of volatile  organic standards can occurs very readily.

                            /
6.0  SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1  See Method 0030 for the VOST Sampling Methodology.
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                                                                  November 1990

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      6.2  VOST samples are  collected  on  paired  cartridges.   The first of the
pair of  sorbent cartridges  is  packed  with approximately  1.6 g  of  Tenax-GC®
resin.   The second cartridge  of  the pair is packed with Tenax-GC* and petroleum
based charcoal  (3:1  by  volume;  approximately  1 g of each).   In sampling, the
emissions gas stream passes through the Tenax-GC* layer first and then through
the charcoal  layer.   The Tenax-GC* is cleaned and reused; charcoal  is not reused
when tubes are prepared.  Sorbent is cleaned and the tubes are packed.  The tubes
are desorbed and subjected to a blank  check prior  to  being sent to the field.
When the tubes  are used for  sampling (see Figure 5 for a  schematic diagram of
the Volatile Organic Sampling Train  (VOST)), cooling water  is circulated to the
condensers and the temperature of the cooling water is  maintained near 0°C.  The
end caps of  the sorbent cartridges are placed in  a clean,  screw capped glass
container during sample collection.

      6.3     After  the  apparatus  is  leak   checked,  sample  collection  is
accomplished by opening the valve to the first condenser,  turning on the pump,
and sampling at a rate of 1 liter/min for  20 minutes.  The volume of sample for
any pair of traps  should not exceed 20 liters.   An alternative set of conditions
for sample collection requires sampling at a reduced flow rate, where the overall
volume of sample collected is 5 liters at a rate of 0.25 L/min for 20 minutes.
The 20 minute period is required for collecting an integrated sample.

      6.4  Following  collection  of 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.


7.0  PROCEDURE

      7.1     Recommended   operating  conditions   for   cartridge   desorber,
purge-and-trap unit,  and gas chromatograph/mass spectrometer using  the wide-bore
column are:

      Cartridge Desorption Oven
      Desorb Temperature                    180°C
      Desorb Time                           11  minutes
      Desorption Gas Flow                   40  mL/min
      Desorption/Carrier Gas                Helium, Grade  5.0
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                                                                  November 1990

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      Purqe-and-Trap Concentrator
      Analytical Trap Desorption Flow
      Purge Temperature
      Purge Time
      Analytical Trap Desorb Temperature
      Analytical Trap Desorb Time

      Gas Chromatoaraph
      Column
      Carrier Gas Flow
      Makeup Gas Flow
      Injector Temperature
      Transfer Oven Temperature
      Initial Temperature
      Initial Hold Time
      Program Rate
      Final Temperature
      Final Hold Time

      Mass Spectrometer
      Manifold Temperature
      Scan Rate
      Mass Range
      Electron Energy
      Source Temperature
2.5 mL/min helium
Ambient
11 minutes
180°C
5 minutes
DB-624, 0.53 mm ID x 30 m thick film
(3 Mm)  fused silica capillary,  or
equivalent
15 mL/min
15 mL/min
200°C
240°C
5°C
2 minutes
6°C/min
240°C
1 minute, or until elution  ceases
105°C
1 sec/cycle
35-260 amu
70 eV (nominal)
According    to
specifications
manufacturer's
      7.2   Each  GC/MS system must  be  hardware tuned to meet  the  criteria in
Table 3 for a  50 ng injection of 4-bromofluorobenzene (2 ML  injection of the
BFB standard solution into the water of the purge vessel).   No analyses may be
initiated until the criteria presented in Table 3 are met.

      7.3   Assemble a purge-and-trap device that meets  the  specifications in
Method 5030.   Condition the  analytical  trap overnight  at 180°C in  the purge
mode, with  an  inert gas flow of  at  least  20 mL/min.  Prior to  use  each day,
condition the trap  for 10 minutes by backflushing at 180°C,  with the column at
220°C.

      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.
unit.
      7.6   Connect the VOST  tube  desorption apparatus to  the purge-and-trap
      7.7  Calibrate the instrument using  the internal standard procedure, with
standards  and  calibration  compounds  spiked   onto  cleaned  VOST  tubes  for
calibration.
                                   5041  -  11
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            7.7.1  Compounds in methanolic solution are spiked onto VOST tubes
      using the flash evaporation technique.  To perform flash evaporation, the
      injector of a  gas  chromatograph or an equivalent piece  of equipment is
      required.

                  7.7.1.1   Prepare a syringe  with the appropriate  volume of
            methanolic standard solution (either surrogates, internal standards,
            or calibration compounds).

                  7.7.1.2  With the injector port heated to 180°C, and with an
            inert gas flow of 10 mL/min through the injector port, connect the
            paired VOST tubes  (connected as  in  Figure  1, with  gas flow in the
            same direction  as the  sampling  gas flow)  to  the  injector  port;
            tighten  with  a wrench  so that  there  is  no leakage of gas.   If
            separate  tubes  are  being  analyzed,   an   individual  Tenax®  or
            Tenax*/charcoal tube  is connected to the injector.

                  7.7.1.3  After directing  the  gas  flow through the VOST tubes,
            slowly  inject  the  first  standard  solution  over  a  period  of 25
            seconds.  Wait  for 5 sec before withdrawing the  syringe from the
            injector port.

                  7.7.1.4  Inject a second  standard  (if required) over a period
            of 25 seconds and wait for 5 sec before  withdrawing  the syringe from
            the injector port.

                  7.7.1.5  Repeat the sequence  above as  required until  all of
            the necessary compounds are spiked onto the VOST tubes.

                  7.7.1.6  Wait  for 30 seconds, with gas flow, after the last
            spike before disconnecting the  tubes.   The total time the tubes are
            connected to the injector port with gas flow should not exceed 2.5
            minutes.  Total gas flow through the tubes during the spiking process
            should  not  exceed  25 ml  to  prevent  break through of adsorbed
            compounds during  the  spiking  process.   To allow more  time  for
            connecting and disconnecting tubes, an on/off valve  may be installed
            in the  gas  line to the injector port  so  that  gas  is  not flowing
            through the tubes during the connection/disconnection process.

      7.8   Prepare  the  purge-and-trap unit with 5 ml  of organic-free reagent
water in the purge vessel.

      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.
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      7.11  Set the oven of the gas chromatograph to subambient temperatures by
cooling with liquid nitrogen.

      7.12  Prepare the GC/MS system for data acquisition.

      7.13  At  the conclusion of the tube/water purge time,  attach the analytical
trap to the gas  chromatograph, adjust  the purge-and-trap  device  to the desorb
mode,  and  Initiate  the  gas chromatograph1c  program   and  the  GC/MS  data
acquisition.   Concurrently,   Introduce  the  trapped   materials   to  the  gas
chromatographlc  column  by rapidly heating the  analytical  trap  to 180°C while
backflushing the trap with Inert gas  at  2.5 mL/min for  5 mln.   Initiate the
program for the  gas chromatograph and simultaneously Initiate data acquisition
on the GC/MS system.

      7.14    While  the  analytical  trap  1s   being   desorbed  Into  the  gas
chromatograph, empty the purging  vessel.  Wash the purging  vessel with a minimum
of two  5  ml flushes  of organic-free  reagent water (or  methanol  followed by
organic-free reagent  water)  to  avoid  carryover  of analytes into subsequent
analyses.

      7.15  After the sample has  been desorbed,  recondition the analytical trap
by employing a bake cycle on the purge-and-trap unit.  The analytical trap may
be  baked   at   temperatures  up  to  220°C.    However,  extensive   use  of  high
temperatures to recondition  the trap  will  shorten  the  useful  life  of the
analytical trap.  After  approximately  11  minutes,  terminate  the  trap bake and
cool the trap to ambient temperatures in preparation  for the next sample.  This
procedure is a convention for reasonable samples and should be adequate if the
concentration of contamination does  not saturate the  analytical system.  If the
organic compound concentration is so high that the analytical system is saturated
beyond the point where even extended system bakeout is not sufficient to clean
the system, a more extensive system maintenance must be performed.  To perform
extensive system maintenance, the analytical trap is replaced and the new trap
1s conditioned.  Maintenance is performed  on the GC column by removing at least
one  foot  from  the front  end  of  the column.   If the  chromatography  does not
recover after column maintenance, the chromatographic column must be replaced.
The  ion source should be baked  out and,  if the bakeout  1s  not  sufficient to
restore mass spectrometric  peak  shape  and sensitivity,  the  ion  source and the
quadrupole rods  must be cleaned.

      7.16  Initial calibration for  the analysis of VOST tubes: It is essential
that calibration be performed in the mode in which analysis will  be performed.
If tubes are being analyzed as pairs,  calibration standards should be prepared
on paired  tubes. If tubes are being analyzed Individually, a calibration should
be performed on  individual Tenax® only tubes and Tenax'/charcoal  tubes.

            7.16.1   Prepare the  calibration  standards by spiking  VOST tubes
      using the  procedure described in Section 7.7.1.  Spike each pair of VOST
      tubes  (or each  of the individual  tubes) immediately  before analysis.
      Perform the calibration analyses in order from low concentration to high
      to minimize the  compound carryover.   Add  5.0 ml of  organic-free reagent
      water to the purging vessel.  Initiate tube desorb/purge according to the
      procedure  described above.
                                   5041  -  13                       Revision 0
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      7.16.2   Tabulate  the area response of  the  characteristic primary
ions  (Table 1)  against concentration  for each  target  compound,  each
surrogate compound, and each internal standard.  The first criterion for
quantitative  analysis  is  correct  identification  of  compounds.    The
compounds must elute  within  + 0.06 retention  time  units  of the elution
time of the standard analyzed on the  same analytical system on the day of
the analysis.  The analytes should  be quantitated relative to the closest
eluting  internal  standard,  according  to  the  scheme  shown in  Table  4.
Calculate response factors  (RF)  for each compound relative  to the internal
standard  shown in  Table  4.    The  internal   standard  selected for  the
calculation  of RF is the  internal standard  that  has  a  retention  time
closest to the  compound  being measured.  The RF is calculated as follows:

              RF = (VCJ/(VCJ

      where:   A,,  =    area  of  the characteristic  ion  for  the compound
                        being measured.

               Als =     area  of  the characteristic  ion  for  the specific
                        internal  standard.

               C,s =     concentration of the specific internal standard.

               Cx  *    concentration of the compound being measured.

      7.16.3 The average RF must be calculated for each compound. A system
performance  check  should be  made before the  calibration  curve is  used.
Five compounds (the System  Performance  Check Compounds,  or  SPCCs)  are
checked  for a minimum  average  response  factor.    These compounds  are
chloromethane,  1,1-dichloroethane,  bromoform,  1,1,2,2-tetrachloroethane,
and chlorobenzene.  The  minimum  acceptable average RF for these compounds
should be 0.300 (0.250 for bromoform).  These compounds typically have RFs
of 0.4  -  0.6,  and are used  to  check compound  instability and check for
degradation  caused by contaminated lines or active  sites  in the system.
Examples of  these occurrences are:

             7.16.3.1  Chloromethane:   This compound is the most  likely
      compound to be lost if the purge flow is too fast.

             7.16.3.2  Bromoform:   This  compound is  one  of the compounds
      most likely to be  purged very poorly  if  the purge  flow is too slow.
      Cold spots  and/or  active sites in transfer lines may adversely affect
      response.   Response  of the primary quantitation  ion  (m/z 173)  is
      directly affected  by  the tuning for 4-bromofluorobenzene at the ions
      of masses 174 and 176. Increasing the ratio of ions 174 and 176 to
      mass 95  (the base peak of the mass spectrum of bromofluorobenzene)
      may improve bromoform  response.

             7.16.3.3  1,1,2,2-Tetrachloroethane and 1,1-dichloroethane:
      These  compounds  are degraded  by contaminated  transfer  lines  in
      purge-and-trap systems and/or active sites in trapping materials.
                             5041  -  14                       Revision 0
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      7.16.4   Using  the response factors from  the Initial  calibration,
calculate  the  percent  relative  standard  deviation  (%RSD)  for  the
Calibration Check Compounds (CCCs).

                       %RSD  =   (SD/X) x 100

      where:   %RSD =  percent relative standard deviation

               RF,   =  individual RF measurement

               RF  =   mean of 5 initial  RFs for a  compound  (the 5 points
                       over the  calibration range)

               SD    = standard  deviation of average RFs for a compound,
                       where SD  is calculated:
                  SD
                               - RF)5
The %RSD  for  each  individual  CCC should be less than  30  percent.   This
criterion must be met  in order for the individual calibration to be valid.
The CCCs are: 1,1-dichloroethene, chloroform, 1,2-dichloropropane, toluene,
ethylbenzene, and vinyl chloride.

7.17  Daily GC/MS Calibration

      7.17.1   Prior  to  the  analysis of  samples,  purge  50  ng of the
4-bromofluorobenzene  standard.  The  resultant  mass  spectrum for the BFB
must meet  all  of the  criteria given in Table 3 before  sample analysis
begins.   These  criteria must  be  demonstrated  every  twelve  hours  of
operation.

      7.17.2   The  initial  calibration  curve (Section  7.16)  for  each
compound of interest must be checked and  verified once every twelve hours
of  analysis time.    This verification  is  accomplished  by analyzing  a
calibration  standard  that   is  at  a  concentration near  the  midpoint
concentration for the working range of the GC/MS and  checking the SPCC
(Section 7.16.3) and CCC (Section 7.16.4).

      7.17.3   System  Performance Check  Compounds   (SPCCs):    A  system
performance check must be made each  twelve  hours of  analysis.  If the SPCC
criteria  are  met,   a  comparison  of  response  factors  is  made for all
compounds.  This is the same  check that is applied during  the initial
calibration.  If the minimum response factors are not achieved, the system
must be evaluated,  and corrective  action  must be taken before analysis is
allowed to begin. The minimum response factor for volatile  SPCCs is 0.300
(0.250 for bromoform).  If these minimum response factors are not achieved,
some  possible problems  may  be   degradation  of the standard  mixture,
contamination of the injector port,  contamination at the front end of the
analytical  column,  and active  sites in  the  column or  chromatographic
system.  If the problem is active sites at the  front  end of the analytical
                             5041  -  15                       Revision 0
                                                            November 1990

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column, column maintenance (removal of approximately 1 foot  from the front
end of the column) may remedy the problem.

      7.17.4  Calibration Check Compounds:  After the system performance
check has been met, CCCs  listed  in Section  7.16.4  are used to check the
validity of  the initial  calibration.  Calculate the  percent  difference
using the following equation:
                        (RF, -  RFC)  x 100
      % Difference = 	
                              RF,

      where:   RF,  =     average response factor from  initial calibration

               RFC =    response  factor from  current calibration  check
                        standard.

      If the percent difference for any compound is greater than 20, the
laboratory should  consider this  a warning limit.  Benzene,  toluene,  and
styrene will have problems with response factors if Tenax®  decomposition
occurs  (either  as  a  result   of   sampling   exposure   or  temperature
degradation), since these  compounds are decomposition products of Tenax9.
If the  percent difference  for each  CCC  is less  than 25%, the  initial
calibration is assumed to be valid. If the criterion of percent difference
less than 25% is  not met for any one CCC, corrective action MUST be taken.
Problems similar to those  listed  under SPCCs could  affect this criterion.
If a source  of the problem cannot be determined after corrective action
is taken,  a new  five-point calibration curve  MUST be  generated.   The
criteria for the  CCCs MUST  be met before quantitative analysis can begin.

      7.17.5  Internal standard responses and retention times in the check
calibration  standard must  be  evaluated  immediately after or during data
acquisition.  If the retention time for any internal standard changes by
more  than  30  seconds  from the  last check  calibration  (12  hr),  the
chromatographic system must be inspected for malfunctions and corrections
must be made,  as required.  A factor which may influence  the retention
times of the  internal standards  on sample tubes is the  level  of overall
organic compound loading on the  VOST  tubes.   If the VOST tubes  are very
highly  loaded  with either a single  compound  or  with multiple  organic
compounds, retention times  for standards  and  compounds  of  interest will
be affected.   If  the area for the primary ion of any  of  the  internal
standards changes  by a factor of two (-50% to  +100%) from the last daily
calibration check, the gas chromatograph and mass  spectrometer should be
inspected for malfunctions and corrections must be made,  as appropriate.
If the level of organic  loading of samples is high,  areas for the primary
ions  of both  compounds  of interest  and standards  will   be  adversely
affected.  Calibration check standards should not be subject  to variation,
since the concentrations of organic compounds on these samples are set to
be  within  the   linear  range  of the  instrumentation.     If  instrument
malfunction has occurred,  analyses of samples  performed under conditions
of malfunction may be invalidated.
                             5041  -  16                       Revision 0
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7.18   GC/MS Analysis of Samples

      7.18.1  Set up the cartridge desorption unit, purge-and-trap unit,
and GC/MS as described above.

      7.18.2   BFB  tuning criteria  and daily  GC/MS calibration  check
criteria must be met before analyzing samples.

      7.18.3 Adjust the helium purge gas flow rate (through the cartridges
and purge vessel) to approximately 40 mL/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.

      7.18.4  The first  analysis  performed  after  the tuning check and the
calibration or daily calibration check is a method blank.  The method blank
consists of clean VOST tubes (both Tenax* and Tenax*/charcoal)  which are
spiked with  surrogate compounds  and  internal  standards  according to the
procedure described in  Section 7.7.1.   The tubes which  are used for the
method blanks should  be  from the same batch of sorbent as the sorbent used
for the  field  samples.    After the tubes  are cleaned and  prepared for
shipment to the field, sufficient pairs of tubes should be retained from
the same  batch  in the  laboratory to  provide method blanks during the
analysis.

      7.18.5  The organic-free reagent water for  the purge vessel for the
analysis of  each of the VOST  samples  should be  supplied from the labor-
atory inventory which is  maintained with  constant bubbling of  inert gas
to avoid contamination.

      7.18.6  If the analysis of  a pair of  VOST tubes has a concentration
of analytes that exceeds the initial  calibration range,  no reanalysis of
desorbed VOST tubes is possible.   An additional  calibration point can be
added to bracket the  higher  concentration  encountered  in  the samples so
that  the   calibration   database  encompasses   six  or   more  points.
Alternatively, the  data may be  flagged in the  report  as  "extrapolated
beyond the upper range of  the calibration."  The use of the secondary ions
shown in Table 1  is permissible only  in the  case  of interference with the
primary quantitation  ion.   Use of secondary  ions  to  calculate compound
concentration in  the case of  saturation of  the  primary  ion  is  not an
acceptable procedure, since a negative bias  of an unpredictable magnitude
is  introduced  into the quantitative  data  when  saturation of  the  mass
spectrum of a compound  is encountered.  If high organic loadings, either
of a single  compound or of  multiple compounds, are encountered, it is vital
that a method blank  be  analyzed  prior to the analysis  of another sample
to demonstrate that no compound carryover is occurring.  If concentrations
of organic  compounds  are  sufficiently high  that  carryover problems are
profound, extensive bakeout of the purge-and-trap unit will be required.
Complete  replacement of   the  contaminated  analytical  trap,   with  the
associated requirement for conditioning the new trap, may also be required
for VOST samples which show excessive concentrations of organic compounds.
Other  measures  which  might  be  required  for   decontamination of  the


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analytical system Include bakeout  of  the  mass spectrometer,  replacement
of the filament of the mass  spectrometer,  cleaning  of the ion source of
the  mass  spectrometer,   and/or  (depending  on  the   nature   of  the
contamination) maintenance of  the  chromatographic column or replacement
of  the  chromatographic  column,  with  the  associated  requirement  for
conditioning the new chromatographic column.

7.19  Data Interpretation

      7.19.1  Qualitative analysis:

            7.19.1.1    The  qualitative   identification  of  compounds
      determined  by  this  method  is  based  on  retention  time,  and  on
      comparison of the sample mass spectrum, after background correction,
      with characteristic ions  in a reference mass spectrum. The reference
      mass  spectrum must  be  generated  by  the  laboratory  using  the
      conditions  of this  method.    The  characteristic  ions from  the
      reference mass spectrum are defined to be the three  ions of greatest
      relative intensity,  or any ions  over  30% relative intensity if less
      than three  such  ions  occur in  the reference  spectrum.   Compounds
      should be identified as present when the criteria below are met.

                  7.19.1.1.1  The intensities of the characteristic ions
            of a compound maximize in  the  same scan or within one scan of
            each  other.   Selection of  a  peak  by  a data  system target
            compound search  routine  where  the search  is based on  the
            presence of  a target  chromatographic  peak  containing ions
            specific for  the  target compound  at  a compound  specific
            retention time will be accepted as meeting this criterion.

                  7.19.1.1.2   The  RRT of  the sample component is within
            +0.06 RRT units of the RRT of the standard component.

                  7.19.1.1.3      The    relative  intensities   of   the
            characteristic   ions   agree  within 30%  of  the  relative
            intensities of these ions in the reference spectrum. (Example:
            For an ion with an  abundance of 50% in the reference spectrum,
            the corresponding  abundance  in a sample  spectrum can  range
            between 20% and 80%.)

                  7.19.1.1.4 Structural isomers that produce very similar
            mass spectra should be identified as individual isomers if they
            have  sufficiently  different GC retention times.   Sufficient
            GC resolution is achieved  if the height of the valley between
            two isomer peaks is less than 25% of the sum of the two peak
            heights.   Otherwise,  structural  isomers are  identified  as
            isomeric pairs.

                  7.19.1.1.5    Identification is hampered when  sample
            components are not resolved chromatographically  and produce
            mass  spectra  containing  ions  contributed  by more  than  one
            analyte.  When gas chromatographic peaks obviously represent
            more than one sample  component (i.e., a broadened peak with
            shoulder(s)  or  a  valley  between  two  or  more  maxima),

                             5041 - 18                      Revision 0
                                                            November 1990

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      appropriate selection of analyte spectra and background spectra
      is important.  Examination of extracted ion current profiles
      of appropriate ions can aid in the selection of spectra, and
      in qualitative  identification  of compounds.   When analytes
      coelute (i.e., only one chromatographic peak is apparent), the
      identification criteria can be  met, but each analyte spectrum
      will   contain  extraneous  ions  contributed by  the  coeluting
      compound.

      7.19.1.2   For  samples containing components  not associated
with the calibration  standards, a library search may  be made for
the purpose of tentative identification.  The necessity to perform
this  type  of  identification  will be  determined by  the type  of
analyses  being   conducted.     Guidelines   for  making  tentative
identification are:

      (1)   Relative  intensities  of major  ions in  the  reference
spectrum (ions > 10% of the  most abundant ion) should be present in
the sample spectrum.

      (2)  The relative intensities of the major ions should agree
within ± 20%.   (Example:   For an ion with an  abundance  of  50% in
the standard spectrum, the corresponding sample ion abundance must
be between 30 and 70%).

      (3)  Molecular ions present in the reference spectrum should
be present in the sample spectrum.

      (4)   Ions  present  in the  sample spectrum  but  not  in the
reference  spectrum should  be  reviewed  for possible  background
contamination or presence of coeluting compounds.

      (5)   Ions  present in  the reference spectrum  but  not  in the
sample spectrum  should be reviewed  for possible  subtraction from
the sample  spectrum because of background contamination or coeluting
peaks.  Data system library  reduction programs can sometimes create
these discrepancies.

      Computer  generated  library search  routines should not use
normalization routines that would misrepresent the library or unknown
spectra when compared to each other.  Only after visual comparison
of sample with the nearest library searches will the mass spectral
interpretation specialist assign a tentative identification.

7.19.2  Quantitative analysis:

      7.19.2.1  When a compound has been identified, the quantitative
analysis of that compound will  be based on the integrated abundance
from the extracted ion  current profile of the  primary characteristic
ion  for that  compound (Table  1).    In  the event  that  there  is
interference with the primary ion so  that quantitative measurements
cannot  be  made,  a  secondary  ion may  be  used.   Note:    Use  of a
secondary ion to perform quantitative calculations in the event of
the  saturation  of the primary  ion is not  an acceptable procedure

                       5041  -  19                      Revision 0
                                                      November 1990

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because of the  unpredictable  extent  of the negative bias which is
introduced.   Quantitative  calculations are  performed  using  the
internal standard technique.  The  internal  standard  used to perform
quantitative calculations shall be the internal  standard nearest the
retention time of a given analyte (see Table 4).

      7.19.2.2  Calculate the  amount of each identified  analyte from
the VOST tubes as follows:

         Amount  (ng)  =   (ASC|S)/(A(SRF)

         where:  As  =  area  of  the  characteristic  ion for  the
                        analyte to be measured.
                 Als =   area  of  the  characteristic   ion  of  the
                        internal standard.
                 Cls =   amount (ng) of the internal standard.

      7.19.2.3  The choice of  methods for evaluating data collected
using  the VOST methodology  for  incinerator  trial   burns  is  a
regulatory decision.  Various  procedures are used to decide whether
blank correction should be performed and how blank correction should
be performed.  Regulatory agencies to which VOST data are submitted
also vary in their preferences for data which are or which are not
blank corrected.

      7.19.2.4  The total  amount of the  POHCs of interest collected
on a pair of traps should be summed.

      7.19.2.5   The occurrence of high concentrations  of analytes
on method blank cartridges indicates possible residual contamination
of sorbent cartridges prior to  shipment  and use at the sampling site.
Data with high associated blank values must be qualified  with respect
to validity,  and all blank data should be reported separately.   No
blank corrections should  be made in this case.  Whether or not data
of this type  can be applied  to the determination of Destruction and
Removal Efficiency is  a regulatory decision.  Continued observation
of  high concentrations  of  analytes  on blank  sorbent cartridges
indicates that procedures for cleanup  and  quality  control  for the
sampling tubes are  inadequate.  Corrective action  MUST be applied
to tube  preparation and  monitoring procedures  to  maintain  method
blank concentrations below detection  limits for analytes.

      7.19.2.6  Where applicable,  an  estimate of concentration for
noncalibrated components  in the sample  may be  made.  The formulae
for quantitative calculations presented above  should  be  used with
the following modifications:  The  areas  A,, and Als should be from the
total   ion   chromatograms,  and  the   Response  Factor   for  the
noncalibrated compound  should be  assumed  to  be  1.   The  nearest
eluting internal standard free from interferences in the total  ion
chromatogram should be  used to determine  the  concentration.   The
concentration which is obtained  should  be reported indicating:  (1)
that the value is an estimate; and (2)  which internal   standard was
used.
                       5041  -  20                       Revision 0
                                                      November 1990

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                  7.19.2.7   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   Each  laboratory that uses  these methods is required to  operate  a
formal quality control  program.   The minimum Quality Control  requirements of
are specified in Chapter One.   In  addition,  this  program  should consist of an
initial demonstration of laboratory capability and an ongoing analysis of check
samples to  evaluate  and document data quality.    The  laboratory must maintain
records to  document  the quality of the data generated.  Ongoing  data quality
checks are  compared  with established performance  criteria  to determine if the
results of  analyses  meet the  performance characteristics of the method.   When
sample analyses indicate atypical  method performance, a quality control  check
standard (spiked method blank)  must be analyzed to  confirm that the measurements
were performed in an in-control mode of instrument operation.

      8.2 Before processing any samples, the analyst should demonstrate, through
the analysis of a method blank (laboratory  blank  sorbent  tubes, reagent water
purge) that interferences  from the  analytical system, glassware,  sorbent tube
preparation, and reagents are under control.  Each time a  new  batch of sorbent
tubes is analyzed,  a method blank should be processed as  a safeguard against
chronic laboratory contamination.  Blank tubes which have  been  carried through
all  the  stages of   sorbent  preparation  and handling  should  be  used  in  the
analysis.

      8.3   The experience  of the  analyst  performing the  6C/MS analyses  is
invaluable to the success of the analytical  methods.  Each day that the analysis
is  performed,  the  daily  calibration  check standard should  be evaluated  to
determine if  the chromatographic  and  tube  desorption  systems are  operating
properly.   Questions that  should be asked are:  Do the peaks look normal?  Is
the  system  response  obtained  comparable  to   the  response   from  previous
calibrations?   Careful  examination of  the chromatogram  of  the  calibration
standard can  indicate whether column  maintenance is required  or whether the
column is  still  usable, whether  there are leaks  in  the  system, whether the
injector septum requires replacing, etc.  If  changes are made to the system (such
as  change of a column),  a calibration check must be carried  out  and  a new
multipoint calibration must be generated.

      8.4   Required  instrument quality  control   is  found in  the  following
sections:

            8.4.1  The mass spectrometer must be tuned to meet the specifications
      for 4-bromofluorobenzene in Section 7.2 (Table 3).

            8.4.2        An    initial     calibration     of    the     tube
      desorption/purge-and-trap/GC/MS must be performed as specified in Section
      7.7.
                                   5041  - 21                       Revision  0
                                                                  November 1990

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            8.4.3  The  GC/MS system must meet the  SPCC  criteria specified in
      Section 7.16.3 and the CCC  criteria  in  Section 7.16.4 each twelve hours
      of instrument operation.

      8.5   To  establish  the   ability  to  generate  acceptable  accuracy  and
precision, the analyst must perform the following operations.

            8.5.1  A quality control (QC) check sample concentrate is required
      containing each  analyte  at  a concentration of  10 mg/L in  high  purity
      methanol.   The QC check  sample concentrate  may be  prepared  from pure
      standard materials or purchased as certified solutions.  If the QC check
      sample concentrate  is prepared by the  laboratory, the QC  check  sample
      concentrate must be prepared using  stock standards prepared independently
      from the stock standards used for calibration.

            8.5.2  Spike four pairs of cleaned,  prepared  VOST tubes with 10 /xL
      of the QC  check  sample concentrate and analyze  these spiked VOST tubes
      according to the method beginning in  Section 7.0.

            8.5.3  Calculate the  average recovery (X) in ng  and the standard
      deviation of the recovery  (s) in ng for each analyte using the results of
      the four analyses.

            8.5.4  The average recovery and  standard  deviation must fall  within
      the expected range for determination  of volatile organic compounds using
      the VOST  analytical  methodology.   The expected range for  recovery of
      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 8240,  direct transposition of Method 8240 criteria
      is questionable.  If the recovery and  standard  deviation for all analytes
      meet the acceptance criteria,  the system performance is acceptable and the
      analysis of field samples may begin.  If any individual standard deviation
      exceeds the precision limit or any individual  recovery falls outside the
      range for accuracy, then the  system performance  is  unacceptable for that
      analyte. NOTE:  The  large number of  analytes  listed in Table 1 presents
      a substantial probability that one or more will fail at least one of the
      acceptance criteria when all  analytes for this method are determined.

            8.5.5  When one  or more of the  analytes tested  fails at least one
      of the acceptance criteria,  the analyst must proceed according to one of
      the alternatives below.

                  8.5.5.1  Locate  and correct the source of any problem with the
            methodology and repeat the test  for all the analytes beginning with
            Section 8.5.2.

                  8.5.5.2   Beginning with  Section 8.5.2,  repeat  the test only
            for those  analytes  that have failed to  meet acceptance criteria.
            Repeated failure, however,  will confirm a general  problem either


                                   5041  - 22                      Revision 0
                                                                  November  1990

-------
            with  the  measurement  system  or  with  the  applicability  of  the
            methodology to the particular analyte  (especially if the analyte in
            question is not listed in Table 1).   If the problem is identified
            as originating  in  the  measurement system,  locate  and  correct  the
            source of  the problem and  repeat the  test for all compounds  of
            interest beginning with Section 8.5.2.

      8.6  To determine acceptable accuracy and precision limits for surrogate
standards, the following procedure should be performed.

            8.6.1  For each sample analyzed, calculate the percent recovery of
      each surrogate compound in the sample.

            8.6.2  Once a minimum of thirty samples has  been analyzed, calculate
      the average percent  recovery  (p) and the  standard deviation of the percent
      recovery (s) for each of the surrogate compounds.

            8.6.3   Calculate the  upper and  lower  control  limits  for  method
      performance for each  surrogate  standard.  This calculation  is performed
      as follows:
            Upper Control  Limit (UCL) = p + 3s
            Lower Control  Limit (LCL) = p - 3s

            For  reference,  the  comparable control limits for  recovery  of  the
      surrogate compounds from water and soil  in Method 8240 are:

      4-Bromofluorobenzene   Water:  86-115%     Soil:  74-121%

      l,2-Dichloroethane-d4  Water:   76-114%    Soil:   70-121%

      Toluene-d8             Water:   88-110%    Soil:   81-117%

            The control limits for  the VOST methodology would be expected to be
      similar, but exact data are not presently available. Individual laboratory
      control limits can be established by the analysis of replicate samples.

            8.6.4  If  surrogate recovery is not within the  limits established
      by the laboratory, the following procedures  are required: (1) Verify that
      there  are  no errors  in  calculations, preparation of  surrogate  spiking
      solutions, and preparation of internal standard spiking solutions.  Also,
      verify that instrument performance criteria have been met. (2) Recalculate
      the data and/or analyze a replicate sample,  if replicates are available.
      (3)  If all  instrument  performance criteria  are met  and   recovery  of
      surrogates from spiked blank VOST tubes (analysis of  a method blank)  is
      acceptable, the problem  is due  to the matrix.   Emissions samples may be
      highly acidic and may be highly loaded with  target and non target organic
      compounds.  Both  of  these conditions  will affect the  ability to recover
      surrogate compounds which are spiked on  the  field samples.  The surrogate
      compound  recovery is thus a valuable indicator  of the  interactions  of
      sampled compounds with the matrix.  If surrogates spiked  immediately before
      analysis cannot be observed with acceptable recovery, the  implications for
      target  organic  analytes which  have been sampled  in  the field  must  be
      assessed very carefully.   If  chemical  or other  interactions are occurring
      on the exposed tubes, the failure to observe an analyte may not necessarily

                                   5041  - 23                      Revision 0
                                                                  November 1990

-------
      imply that  the Destruction and  Removal  Efficiency for that  analyte is
      high.

      8.7   It  is recommended  that  the  laboratory  adopt  additional  quality
assurance practices for use with this method.  The specific practices that are
most productive depend upon the  needs  of  the laboratory  and the nature of the
samples analyzed.  Field duplicates may be analyzed to assess the precision of
the environmental measurements.  When  doubt  exists  over  the identification of
a peak on the chromatogram, confirmatory techniques such  as gas chromatography
with a dissimilar column or a different  ionization mode using a mass spectrometer
may be  used,  if  replicate  samples showing  the  same compound  are  available.
Whenever possible, the laboratory  should  analyze  standard reference materials
and participate in relevant performance evaluation studies.


9.0  METHOD PERFORMANCE

      9.1  The method detection limit  (MDL) is defined in Chapter One.  The MDL
concentrations listed in Table 2 were obtained using cleaned blanked VOST tubes
and reagent water.  Similar results have been achieved with field samples.  The
MDL actually achieved in  a  given analysis will  vary depending upon instrument
sensitivity and the  effects  of the matrix.  Preliminary spiking studies indicate
that under these conditions, the method detection  limit for spiked compounds in
extremely complex matrices may be larger by a factor of 500-1000.


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.
                                   5041  -  24                      Revision 0
                                                                  November 1990

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                                      TABLE 1.
          RETENTION  TIMES  AND  CHARACTERISTIC  IONS  FOR VOLATILE  COMPOUNDS
                        WHICH CAN BE ANALYZED BY METHOD 5041
Retention
Compound Time (min)
Acetone
Acrylonitrile
Benzene
Bromochl oromethane
Bromodichloromethane
4-Bromof 1 uorobenzene
Bromoform
Bromomethane
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chi orodi bromomethane
Chloroethane
Chloroform
Chi oromethane
Di bromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans- 1,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans- 1,3-Dichloropropene
1 ,4-Di f 1 uorobenzene
Ethyl benzene
lodomethane
Methyl ene chloride
Styrene
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,1,1 -Tri chl oroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chl orof 1 uoromethane
1 , 2 , 3-Tri chl oropropane
Vinyl chloride
Xylenes*
7.1
8.6
13.3
12.0
16.0
23.4
22.5
4.1
7.1
12.6
20.5
19.3
4.2
12.2
3.0
15.4
10.0
13.3
6.4
8.6
15.2
17.0
18.2
14.2
21.1
7.0
8.1
22.3
24.0
18.6
17.4
12.4
18.4
14.5
5.1
24.0
3.2
22.2
Primary Ion
Mass
43
53
78
128
83
95
173
94
76
117
112
129
64
83
50
93
63
62
96
96
63
75
75
114
106
142
84
104
83
164
92
97
97
130
101
75
62
106
Secondary Ion(s)
Mass(es)
58
52, 51
52, 77
49, 130, 51
85, 129
174, 176
171, 175, 252
96, 79
78
119, 121
114, 77
208, 206
66, 49
85, 47
52, 49
174, 95
65, 83
64, 98
61, 98
61, 98
62, 41
77, 39
77, 39
63, 88
91
127, 141
49, 51, 86
78, 103
85, 131, 133
129, 131, 166
91, 65
99, 117
83, 85, 99
95, 97, 132
103, 66
110, 77, 61
64, 61
91
*  The retention  time given is for m-  and p-xylene, which coelute  on the Megabore
   column.  o-Xylene elutes approximately 50 seconds later.
                                      5041  -  25
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November 1990

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                                      TABLE 2.
               PRELIMINARY METHOD DETECTION LIMITS AND BOILING POINTS
                   FOR VOLATILE ORGANICS ANALYZED BY METHOD 5041*
Compound
Chloromethane
Bromomethane
Vinyl chloride
Chloroethane
Methyl ene chloride
Acetone
Carbon disulfide
1,1-Dichloroethene
1,1 -Di chloroethane
trans-l,2-Dichloroethene
Chloroform
1,2-Dichl oroethane
1,1,1-Trichloroethane
Carbon tetrachloride
Bromodi chloromethane
1,1,2 , 2-Tetrachl oroethane"
1 , 2 -Di chl oropropane
trans-l,3-Dichloropropene
Trichloroethene
Di bromochl oromethane
1 , 1 , 2-Tri chl oroethane
Benzene
cis-l,3-Djk:hloropropene
Bromoform"
Tetrachloroethene
Toluene
Chlorobenzene
Ethyl benzene"
Styrene"
Tr i chl orof 1 uoromethane
lodomethane
Acrylonitrile
Dibromomethane
1 , 2 , 3 -Tr i chl oropropane"
total Xylenes"
CAS Number
74-87-3
74-83-9
75-01-4
75-00-3
75-09-2
67-64-1
75-15-0
75-35-4
75-35-3
156-60-5
67-66-3
107-06-2
71-55-6
56-23-5
75-27-4
79-34-5
78-87-5
10061-02-6
79-01-6
124-48-1
79-00-5
71-43-2
10061-01-5
75-25-2
127-18-4
108-88-3
108-90-7
100-41-4
100-42-5
75-69-4
74-88-4
107-13-1
74-95-3
96-18-4

Detection
Limit, ng
58
26
14
21
9
35
11
14
12
11
11
13
8
8
11
23
12
17
11
21
26
26
27
26
11
15
15
21
46
17
9
13
14
37
22
Boiling
Point, °C
-24
4
-13
13
40
56
46
32
57
48
62
83
74
77
88
146
95
112
87
122
114
80
112
150
121
111
132
136
145
24
43
78
97
157
138-144
*  The method  detection limit  (MDL)  is defined as  the minimum concentration  of a
   substance that can be measured  and  reported  with  99% confidence that the analyte
   concentration is greater than zero and is determined from analysis of a sample in
   a given  matrix  containing the  analyte.   The  detection limits cited  above were
   determined according to Title 40 CFR,  Part 136, Appendix B, using standards spiked
   onto clean VOST tubes.   Since clean  VOST tubes were used,  the values cited above
   represent the best that the methodology can achieve.  The presence of an emissions
   matrix will  affect the ability of the methodology  to  perform at  its optimum level.
** Not appropriate for quantitative sampling by Method 0030.
                                      5041  -  26
Revision 0
November 1990

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                                   TABLE 3.
              KEY ION ABUNDANCE CRITERIA FOR 4-BROMOFLUOROBENZENE
Mass                           Ion Abundance Criteria
 50                            15 to 40% of mass 95
 75                            30 to 60% of mass 95
 95                            base peak, 100% relative abundance
 96                            5 to 9% of mass 95
173                            less than 2% of mass 174
174                            greater than 50% of mass 95
175                            5 to 9% of mass 174
176                            greater than 95%, but less than 101% of mass 174
177                            5 to 9% of mass 176
                                   5041  -  27                       Revision 0
                                                                  November 1990

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                                   TABLE 4.
           VOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
                           ASSIGNED FOR QUANTITATION
Bromochloromethane

Acetone
Acrylonitrile
Bromomethane
Carbon disulfide
Chloroethane
Chloroform
Chloromethane
1,1-Dichloroethane
1,2-Dichloroethane
l,2-Dichloroethane-d4 (surrogate)
1,1-Dichloroethene
Trichloroethene
trans-1,2-Dichloroethene
lodomethane
Methylene chloride
Tri chlorof1uoromethane
Vinyl chloride
1.4-Di f1uorobenzene

     Benzene
     Bromodichloromethane
     Bromoform
     Carbon tetrachloride
     Chlorodi bromomethane
     Dibromomethane
     1,2-Dichloropropane
     cis-l,3-Dichloropropene
     trans-1,3-Dichl oropropene
     1,1,1-Trichloroethane
     1,1,2-Tri chloroethane
                               Ch1orobenzene-d5
                               4-Bromofluorobenzene (surrogate)
                               Chlorobenzene
                               Ethyl benzene
                               Styrene
                               1,1,2,2-Tetrachloroethane
                               Tetrachloroethene
                               Toluene
                               Toluene-d8  (surrogate)
                               1,2,3-Tri chloropropane
                               Xylenes
                                   5041 - 28
                        Revision 0
                        November 1990

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Figure 1.  Cartridge Desbrptlon  Flow
              5041 - 29
Revision 0
November 1990

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                                     5041 - 32
Revision  0
November 1990

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                                    METHOD 5041
Protocol  for  Analysis  of  Sorbent Cartridges  from Volatile  Organic
         Sampling  Train;  Wide-bore Capillary Column Technique
            C   su
7 1  Conditions for
     Cartridge
 Desorption Oven.
  Purge & Trap
 Concentrator. CC.
     and MS
            7 2 Daily, tune
            the CC/MS with
            BFB and cheek
            calib curve
            See sect 7 17
               73 -76
             Assemble the
               sys tern.
          771 Calibrate the
         instrument system us-
         ing  the internal std
          procedure. Stds and
         calibration cmpds are
          spiked into cleaned
         UOST tubes using the
           flash evaporation
              technique.
             7.8 Prep the
             purge & trap
             unit Kith 5ml
             organic-free
            reagent Hater.
              7  9 Connect
              paired VOST
             tubes to the
             gas lines for
              desorption.
                           7 10 Initiate
                               tube
                            desorption/
                             purge and
                             heating
                                    7 11 Set  the CC
                                    oven to subam-
                                    bient tempera-
                                       ture with
                                    liquid nitrogen
    7  12 Prep the
    CC/MS system
      for data
    aquisition.
                          7 13 After  the
                         tube/water purge
                         time, attach the
                        analytical trap to
                           the CC/MS  for
                            desorption.
   7 .14  Hash purg-
   ing vessel with
   two Sml flushes
   of organic-free
   reagent water.
7.15 Recondition the
 analytical  trap by
  baking  it  out at
tamps up  to  220 C for
11 min. Trap replace-
ment may  be  necessary
  if the  analytical
  trap is saturated
   beyond cleanup.
     7  16.1 Prep
    calib  stds as
    in  7.7.1. Add
   *ater  to vessel
     and  desorb.
                             7 16 2
                          Tabulate the
                          area response
                          of all cmpds
                          of interest
                             7.16 3
                          Calculate the
                         average RF for
                          each compound
                          of interest
                                                  7.16  4 Calcu-
                                                  late  the XRSD
                                                  for the CCCs.
                                                  The XRSD must
                                                    be  <30V
                           7 18 CC/MS
                           analysis of
                            samples.
                                                 7 19 1  Qualita-
                                                  tive analysis
                                                   of data and
                                                  ident.  guide-
                                                 1ines of cmpds.
                                                 7 19 2  Quanti-
                                                 tative  analysis
                                                 of data for the
                                                  compounds of
                                                    interest.
                                     5041  - 34
                                             Revision  0
                                             November 1990

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                                 METHOD  5100

     DETERMINATION OF THE VOLATILE ORGANIC CONCENTRATION OF WASTE SAMPLES


1.0  SCOPE AND APPLICATION

      1.1  This method is applicable to the determination of the volatile organic
concentration of hazardous wastes.

      1.2  Performance  of this  method  should  not  be  attempted  by  persons
unfamiliar with the  operation  of a flame ionization detector  (FID)  or a Hall
electrolytic conductivity detector  (HECD), because  knowledge beyond  the scope
of this presentation is required.


2.0  SUMMARY OF METHOD

      2.1  A sample of waste is  collected from  a  source as close to  the point
of generation as practical.   The  sample is then  heated and purged with nitrogen
to separate the volatile organic  compounds.  Part  of the sample is analyzed for
carbon concentration, as methane, with an  FID, and part of the sample is analyzed
for chlorine concentration,  as chloride, with   an HECD.   The volatile organic
concentration is the sum of the measured carbon and chlorine concentrations of
the sample.


3.0  INTERFERENCES

      3.1  Refer to Methods 5030 and 8000.

      3.2  Samples  can  be  contaminated  by diffusion  of volatile  organics
(particularly chlorofluorocarbons  and methylene chloride)  through the sample
container  septum  during shipment  and storage.    A  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.


4.0  APPARATUS AND MATERIALS

      4.1  Sampling. The following equipment is required:

            4.1.1  Static Mixer. Installed in-line or as a by-pass loop, sized
      so that the drop size  of  the  dispersed phase is no greater than  1,000 urn.
      If the installation of the mixer is in a by-pass  loop,  then the entire
      waste stream must be diverted through the mixer.

            4.1.2  Tap. Installed no further than  two pipe diameters downstream
      of the static mixer outlet.

            4.1.3  Sampling Tube. Flexible Teflon, 0.25 in. ID.
                                   5100 - 1                      Revision 0
                                                                 November 1990

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       4.1.4  Sample Container. Borosilicate glass  or Teflon, 15 to 50 ml,
 and a Teflon lined screw cap capable of forming an air tight seal.

       4.1.5  Cooling Coil.  Fabricated from 0.25 in. ID 304 stainless steel
 tubing with a thermocouple at the coil  outlet.

4.2   Analysis. The following equipment is required:

       4.2.1  Purging Apparatus. For separating the volatile organics from
 the waste sample.  A schematic of  the  system  is shown  in  Figure 1.   The
 purging apparatus consists of the following major  components:

             4.2.1.1  Purging Chamber. A glass container to hold the sample
       while it is heated and purged with dry nitrogen.   Exact dimensions
       are shown in Figure 3.

             The cap of the purging chamber is equipped with three fittings:
       one for a mechanical  stirrer (fitted with the #11 Ace thread), one
       for a thermometer (top fitting),  and  one for the Teflon exit tubing
       (side fitting)  as shown in Figure 3.

             The base of the purging chamber is  a 50  mm inside diameter (ID)
       cylindrical glass tube.  One  end  of  the  tube is fitted with a 50 mm
       Ace-thread fitting, while the other  end  is sealed.  Near the sealed
       end in the side wall  is a fitting for a glass purging lance.

             4.2.1.2  Purging Lance. Glass  tube, 6  mm ID by 15.25 cm long,
       bent into an "L" shape.  The "L" end of the tube is sealed, and then
       pierced with fifteen holes, each 1 mm in diameter.

             4.2.1.3  Mechanical  Stirrer.    Stainless  steel  or  Teflon
       stirring rod driven by an electric motor.

             4.2.1.4  Coalescing Filter. Porous fritted disc incorporated
       into a container with  the  same dimensions as the purging chamber.
       The details of the design are shown in Figure 3.

             4.2.1.5  Constant Temperature  Bath.   Capable  of maintaining
       a temperature around  the purging chamber and coalescing  filter of
       75 ± 5°C.

             4.2.1.6  Three-way Valves.   Two, manually operated,  stainless
       steel.

             4.2.1.7  Flow Controller.   Capable of  maintaining a purge gas
       flow rate of 6 ± 0.006 L/min.

             4.2.1.8  Rotameters.   Two for  monitoring the air flow through
       the purging system (0-20 L/min).

             4.2.1.9  Sample Splitters.   Two heated flow restrictors.  At
       a purge rate of up to  6  L/min, one  will supply  a constant flow of
       70  to  100 mL/min  to the  analyzers.    The  second  will   split the
       analytical flow between the FID and  the  HECD.  The approximate flow

                              5100 - 2                     Revision  0
                                                           November  1990

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            to the FID will  be 40 mL/min  and  to the HECD will be 15 mL/nrin, but
            the exact flow must be adjusted to be  compatible with the Individual
            detector and to meet Its linearity requirement.

                  4.2.1.10   Adsorbent Tube.  To hold 10 g of activated charcoal.
            Excess purge gas Is vented through the adsorbent tube to prevent any
            potentially hazardous materials from entering the laboratory.

            4.2.2  Volatile Organic Measurement  System.   Consisting  of an FID
      to measure the carbon  concentration of  the  sample, and an HECD to measure
      the chlorine concentration (as chloride).

                  4.2.2.1  FID.  An FID meeting the following specifications Is
            required:

                        4.2.2.1.1  Linearity.  A linear response (+ 5 percent)
                  over the  operating  range as demonstrated by  the procedures
                  established in Section 8.1.1.

                        4.2.2.1.2  Range.  A full  scale range of 50 pg carbon/sec
                  to 50 jug  carbon/sec.   Signal  attenuators  shall  be available
                  to produce  a minimum  signal response of 10  percent  of full
                  scale.

                        4.2.2.1.3  Data Recording System.  Analog  strip chart
                  recorder or digital integration system compatible  with the FID
                  for permanently recording the output of the detector.

                  4.2.2.2  HECD.   An HECD meeting the following specifications
            is required:

                        4.2.2.2.1  Linearity. A  linear response (+ 10 percent)
                  over the response range as demonstrated by the procedures in
                  Section 8.1.2.

                        4.2.2.2.2  Range.  A full scale range of 5.0 pg/sec to
                  500 ng/sec  chloride.   Signal attenuators  shall  be available
                  to produce  a minimum  signal response of 10  percent  of full
                  scale.

                        4.2.2.2.3  Data Recording System.  Analog  strip chart
                  recorder  or digital  integration system compatible with the
                  output voltage range of HECD.


5.0  REAGENTS

      5.1  Reagent grade chemicals shall be used in all tests.  Unless otherwise
Indicated, it 1s 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 adversely impacting the accuracy of the determination.


                                   5100 - 3                     Revision 0
                                                                November 1990

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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  Sampling.

            5.3.1  Polyethylene glycol (PEG), 98  percent  pure with an average
      molecular weight of 400.  Remove any organic compounds that may be detected
      as volatile organics already present  in  the  polyethylene glycol before it
      is used,  by heating it to 250°C and purging it with nitrogen at a flow rate
      of 1  to  2 L/min  for  2  hours.   Waste  PEG  must be  disposed  of properly
      (consult local, State and Federal guidelines and regulations).

      5.4  Analysis.

            5.4.1  Sample Separation.  The following are required for the sample
      purging step:

                  5.4.1.1  Polyethylene glycol.   Same as Section 5.3.1.

                  5.4.1.2  Silicone, Mineral,  or Peanut Oil.  For use as the heat
            dispersing medium in the constant temperature bath.

                  5.4.1.3  Purging Gas.  Zero grade nitrogen (N2), containing
            less than 1 ppm carbon.

            5.4.2  Volatile Organics Measurement.   The  following are required
      for measuring the volatile organic concentrations:

                  5.4.2.1  Hydrogen (H2).   Zero grade H2, 99.999 percent pure.

                  5.4.2.2  Combustion Gas.  Zero grade air or oxygen, as required
            by the FID.

                  5.4.2.3  FID Calibration  Gases.

                        5.4.2.3.1  Low-level   Calibration  Gas.     Gas  mixture
                  standard with a nominal concentration of 35 ppm (v/v) propane
                  in N2.

                        5.4.2.3.2  Mid-level   Calibration  Gas.     Gas  mixture
                  standard with a nominal concentration of 175 ppm (v/v) propane
                  in N2.

                        5.4.2.3.3  High-level  Calibration  Gas.    Gas  mixture
                  standard with a nominal concentration of 350 ppm (v/v) propane
                  in N2.

                  5.4.2.4  HECD Calibration Gases.

                        5.4.2.4.1  Low-level   Calibration  Gas.     Gas  mixture
                  standard with a  nominal  concentration of 20  ppm (v/v)  1,1-
                  dichlproethene in N2.
                                   5100 - 4                      Revision  0
                                                                 November  1990

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                        5.4.2.4.2  Mid-level  Calibration  Gas.   Gas  mixture
                  standard with  a  nominal  concentration of 100 ppm (v/v) 1,1-
                  dichloroethene in N2.

                        5.4.2.4.3  High-level  Calibration  Gas.   Gas  mixture
                  standard with  a  nominal  concentration of 200 ppm (v/v) 1,1-
                  dichloroethene in N2.

                  5.4.2.5  n-Propanol, CH3CH2CH2OH.  ACS grade or better.

                  5.4.2.6  Electrolyte Solution.   For use in the conductivity
            detector.  Mix together 500 ml  of water and 500 ml of n-propanol and
            store in a glass container.

                  5.4.2.7  Charcoal.  Activated coconut,  12 to 30 mesh.


6.0  SAMPLE COLLECTION, PRESERVATION, AND  HANDLING

      6.1  See  Volume  One,   Section  B,   Chapter  Four,   "Organic  Analytes,"
Section 4.1.

      6.2  Sampling Plan Design  and  Development.   Use the procedures given in
Volume Two, Part III, Chapter Nine, "Sampling Plan."

      6.3  Waste in Enclosed Pipes.  Sample as close as practical to the point
of waste  generation  in  order to minimize  the loss  of organics.   Assemble the
sampling apparatus as  shown in Figure 4.  Install the static mixer in the process
line or  in a by-pass line.   Locate  the  tap within two  pipe  diameters of the
static mixer outlet.

      6.4  Prepare the sampling containers as follows:   Pour into the container
an amount of PEG equal to the total volume of the  sample container, less 10 mL.
PEG will  reduce, but not eliminate,  the  loss of volatile organic compounds during
sample collection.  Weigh the sample container with the screw cap, the PEG and
any labels to the nearest 0.01 g, and record  the weight  (mst).  Before sampling,
store the containers  in an ice bath until  the temperature of the PEG is less than
4°C.

      6.5  Begin sampling by purging the sample lines and cooling coil  with at
least four volumes of waste.  Collect the purged material in a separate container
and dispose of it properly.

      6.6  After purging, stop the sample  flow and direct the sampling tube to
a preweighed sample container, prepared as described in Section 6.4.  Keep the
tip of the tube below  the surface of the PEG during sampling to minimize contact
with the  atmosphere.   Sample at a flow rate  such that  the temperature of the
waste  is  less than 10°C.   Fill  the sample  container and  immediately  cap  it
(within 5 seconds) so that a minimum headspace exists in the container.  Store
immediately in a cooler and cover with ice.

      6.7  Alternative sampling techniques may be  used  upon the approval of the
Administrator.
                                   5100 - 5                      Revision  0
                                                                 November  1990

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7.0  PROCEDURE

      7.1  Sample Recovery.   Remove  the  sample container from the cooler, and
wipe the exterior of the container to remove any extraneous Ice, water, or other
debris.   Reweigh the sample  container and  sample to the  nearest  0.01  g, and
record the weight (msf).   Pour  the  contents of the  sample  container into the
purging flask.   Rinse the  sample  container  three times with PEG, transferring
the rinsings to the purging flask after each rinse.   The  total volume of PEG in
the purging  flask shall  be approximately 50 ml.   Add approximately  50  ml of
water.

      7.2  Apparatus Assembly. Assemble the purging apparatus as shown in Figure
2, leaving the purging chamber out of the constant temperature bath.  Adjust the
stirring rod so that it  nearly reaches  the bottom  of  the  chamber.  Position the
sparger so that it is within 1 cm of the bottom, but does  not interfere with the
stirring rod.  Lower the thermometer so that it extends  into the liquid.

      7.3  Sample Analysis. Turn on the constant temperature bath and allow the
temperature to equilibrate at  75 ± 5°C.   Turn the bypass valve so  that the purge
gas bypasses the  purging chamber.  Turn  on  the purge gas.  Allow both the FID
and the HECD to  warm up until a stable baseline is  achieved on each detector.
Pack the adsorbent tube  with 10 g  of  charcoal.   Replace the  charcoal after each
run and dispose of the spent charcoal properly.  Place the assembled chamber in
the constant temperature bath. When the temperature of the PEG reaches 75 ± 5°C,
turn the bypass valve so that the purge gas flows through the purging chamber.
Begin recording  the response  of the FID and the HECD.   Compare the readings
between the two rotameters in the system.   If the readings differ by more than
five percent, stop the purging and determine  the source of the discrepancy before
resuming.

      As purging continues, monitor the output of the FID to make certain that
the separation is proceeding correctly, and  that the  results  are  being properly
recorded.  Every 10 minutes, read  and record the purge flow  rate  and the liquid
temperature.  Continue purging for 30 minutes.

      7.4  Initial  Performance  Check of Purging  System.   Before  placing the
system in operation, after a shutdown of  greater than six months, and after any
major modification,  conduct the linearity checks described in Sections 7.4.1 and
7.4.2.  Install  all  calibration gases  at the three-way calibration gas valve.
See Figure 1.

            7.4.1  FID Linearity Check  and Calibration.  With the  purging system
      operating as in Section  7.3, allow the FID to establish a stable baseline.
      Set the  secondary pressure regulator  of the calibration gas  cylinder to
      the same pressure as the  purge gas cylinder,  and inject the calibration
      gas by turning the calibration gas valve to switch flow from the purge gas
      to  the  calibration  gas.    Continue  the  calibration  gas  flow  for
      approximately  two  minutes  before switching  to  the purge  gas.    Make
      triplicate injections of each  calibration gas (Section 5.4.2.3), and then
      calculate the average response  factor  for each concentration (R,), as well
      as the  overall mean of  the response  factor values,  R0.   The instrument
      linearity  is  acceptable if  each  R, is within 5 percent of R0 and if the
      relative standard deviation (Section  7.7.10) for each set of triplicate


                                   5100 - 6                      Revision  0
                                                                 November  1990

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      injections is less than 5 percent.  Record the overall mean value of the
      propane response factor values as the FID calibration response factor, R0.

            7.4.2  HECD Linearity Check and Calibration.  With the purging system
      operating as in Section 7.3, allow the HECD to establish a stable baseline.
      Set the secondary pressure regulator of the calibration  gas cylinder to
      the same pressure as  the  purge  gas  cylinder,  and  inject  the calibration
      gas by turning the calibration gas valve to switch  flow from  the purge gas
      to the calibration gas.  Continue the calibration gas flow for about two
      minutes before switching to the  purge gas.   Make triplicate  injections of
      each calibration gas  (Section  5.4.2.4), and then  calculate the average
      response factor for  each concentration,  R,h, as well  as the  overall mean of
      the response factors,  Roh.   The  instrument linearity is  acceptable if each
      R,h (Section 7.7.5) is  within 10 percent of Roh and if the relative standard
      deviation (Section 7.7.10) for each set of triplicate  injections is less
      than 10 percent.  Record the overall mean value of the chlorine response
      factors as the HECD response factor, Roh.

      7.5  Daily Calibrations.

            7.5.1  FID Daily Calibration.  Inject duplicate samples from the mid-
      level  FID  calibration gas (Section  5.4.2.3.2)  as  described  in Section
      7.4.1, and  calculate  the  average  daily response  factor  (DR,).   System
      operation is adequate if the DR,  is within 5 percent  of the  R0 calculated
      during the  initial  performance  test  (Section  7.4.1).   Use the DR, for
      calculation of carbon content in the samples.

            7.5.2  HECD Daily Calibration.   Inject duplicate samples from the
      mid-level HECD calibration gas (Section 5.4.2.4.2)  as described  in Section
      7.4.2, and calculate  the  average  daily response factor DR,h.  The system
      operation is adequate  if the DR,h is within 10 percent  of the Roh calculated
      during the  initial  performance test (Section  7.4.2).   Use  the DR,h for
      calculation of chlorine in the samples.

      7.6  Water Blank. Transfer about 60 ml of organic-free  reagent water into
the purging chamber.  Add  50 mL  of  PEG  to the purging chamber.  Treat the blank
as described in Sections 7.2 and 7.3.

      7.7  Calculations

            7.7.1  Nomenclature.

      A,, = Area under the water blank response curve, counts.

      A8 = Area under the sample response curve, counts.

      C =  Concentration of volatile organic  in the sample, ppm(w/w).

      Cc = Concentration of FID calibration gas, ppm(v/v).

      Ch = Concentration of HECD calibration gas,  ppm(v/v).

      DR,  = Average daily response factor of the FID,  ng  C/counts.


                                   5100 - 7                     Revision  0
                                                                November  1990

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DR,h =Average daily response factor of the HECD detector,  ng CV/counts.
mco =  Mass of carbon, as methane, in the FID  calibration  standard,  ng.
mch =  Mass of chloride  in the HECD calibration standard,  jug.
ms =   Mass of the waste sample, g.
msc =  Mass of carbon, as methane, in the sample,  jug.
msf = Mass of sample container and waste sample, g.
msh =  Mass of chloride  in the sample, ng.
mst = Mass of sample container prior to sampling,  g.
m,,,, =  Mass of volatile  organic  in the sample, ng.
Pa =   Ambient barometric pressure in the laboratory,  Torr.
Qc =   Flowrate of calibration gas, L/min.
tc =   Length of time standard gas is delivered to the analyzer,  min.
Ta =   Ambient temperature in the laboratory,  °K.
      7.7.2  Mass of Carbon, as Methane in  the FID Calibration Gas.
            mco =  k2 Cc tc Qc (PyiJ              Eq.  1
where k2 = 0.5773 /ig C-°K/ /zl -Torr
      7.7.3 Mass of Chloride  in  the  HECD  Detector Calibration Gas.
            mch -  k3 Ch tc  Qc (PyTJ               Eq.  2
where k3 = 1.1371 09 Cl -°K/Ml -Torr
      7.7.4 FID Response  Factor.
            R, = mco/A                            Eq.  3
      7.7.5 HECD Response Factor.
            Rth = mch/A                           Eq.  4
                              5100  -  8                      Revision 0
                                                           November 1990

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            7.7.6 Mass of Carbon  in the  Sample.

                  msc  = DR, (A.  - Ab)                    Eq.  5
            7.7.7 Mass of Chloride in  the  Sample.

                  msh  = DR,h  (A. - A,)                    Eq.  6

            7.7.8 Mass of Volatile Organic in  the  Sample.

                  m = msc +  msh                          Eq.  7
            7.7.9 Standard  Deviation.
                  SD = lOOx  [  z(x,-x)2/(n-l)]1/2         Eq.  8
            7.7.10 Relative Standard  Deviation.
                  RSD = SD/x                           Eq.  9
            7.7.11 Mass of Sample.

                  ms = msf -  mst                         Eq.  10
            7.7.12 Concentration  of Volatile  Organic in Waste.

                  C = m^/m.,                            Eq.  11
8.0  QUALITY CONTROL
      8.1  Refer to Chapter One for specific  Quality Control procedures.
      8.2  Maintain   a   record  of  performance  of   all   system  checks  and
calibrations.
      8.2  Calibrate  analytical balance  against  standard weights.
                                    5100  -  9                      Revision  0
                                                                 November  1990

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9.0  METHOD PERFORMANCE

9.1  Performance data are not currently available.


10.0 REFERENCES

1.   "Determination of the  Volatile  Organic Content of Waste  Samples"  Method
     25D; Proposed Amendment to 40 CFR Part 60, Appendix A,  January 1989.
                                   5100  -  10                     Revision 0
                                                                November 1990

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CALIBRATION GAS

VALVE     FLOW
          METER
  Ul
  i—•
  o
  o
                                                              FLOW
                                                   COALESCING METER
PURGING
CHAMBER

   X
                                                Vent
                                                                               FID
                                                                           SPLITTER
                                             HECD
                                                                                               «o
                                                                           
-------
                                FIGURE 2
     ROTAMETER
DATHIIOATCR/
CONlROLLER
                           STIRRING
                             MOTOR
                                                             DETECTORS
                                                             OIL 0 ATI I
                     PURGING CHAMBER
COALESCING FILTER
                              5100 - 12
            Revision 0
            November 1990

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                     FIGURE 3
                  Purging  Chamber
TRUBORE
STIRRER
                                #7ACETHRED
                                   #SOACETHRED
               BUNA-N
               0-RING
                                              u
                                              p
                                    o
                                    a
             #7ACETHRED
                     5100 -  13
Revision 0
November 1990

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                                      FIGURE 4
                 WASTE UNE
FROM SOURCE
                STATIC MIXER
                                           00
t
                                         VALVES
                 OPTIONAL PUMP
  REDUCER (1/4 " TUBE FITTING)
                                               TEFLON OR STAINLESS STEEL COIL


                                               ICED ATI!
               SAMPLE CONTAINER
                                     5100  -  14
                       Revision 0
                       November 1990

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                                  METHOD 5100
DETERMINATION  OF THE VOLATILE  ORGANIC CONCENTRATION  OF WASTE SAMPLES
           7.1  Pour sample
           contents in purgt
                flask
          7.1  Rinse sampe
          container 3 times
              with OOP
            7.1 Assemble
          purging apparatus
            as shown in
              Figure 1
            7.2 Equlibrat*
             the system
7.2 Oinct purgt
  gas through
purgt chombir
                                              7.2 Record
                                            response of HO
                                              and HECO
                             7.2 Stop
                          operations end
                             readjust
                                   5100  -  15
                           Revision 0
                           November 1990

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                                  METHOD  5110

        DETERMINATION OF ORGANIC PHASE VAPOR PRESSURE IN WASTE SAMPLES


1.0  SCOPE AND APPLICATION

      1.1  This  method  is applicable for determining the  organic phase vapor
pressure  of  waste  samples  from treatment,  storage,  and  disposal  facilities
(TSDF).

      1.2   Performance  of this  method  should  not be  attempted  by  persons
unfamiliar with the operation  of a Flame  lonization  Detector (FID) nor by those
who are unfamiliar with source sampling,  because knowledge beyond the scope of
this presentation is required.


2.0  SUMMARY OF METHOD

      2.1  A waste  sample  is  collected from  a  source  as  close to the point of
generation as  practical.   The headspace vapor of the sample  is analyzed for
carbon content by a headspace analyzer, which uses an FID.


3.0  INTERFERENCES

      3.1   Samples  can  be  contaminated  by diffusion  of volatile  organics
(particularly  chlorofluorocarbons  and methylene chloride) through  the sample
container septum  during  shipment and storage.   A field  sample blank prepared
from organic-free reagent water  and  carried through sampling  and subsequent
storage and handling can serve as a check on such contamination.

      3.2  Contamination  by carryover can occur  whenever a  low-concentration
sample is analyzed after a high-concentration sample.  To reduce  carryover, the
sample syringe must be rinsed  out between samples with  organic-free reagent
water.  Whenever  an unusually concentrated sample is encountered, it should be
followed by an analysis of organic-free reagent water.  It may be necessary to
wash out the syringe with  detergent,  rinse with distilled water, and dry in a
150°C oven between analyses.

      3.3  Before processing daily samples, the analyst should demonstrate that
the entire analytical  system  is free from interference by the analysis of an
organic-free reagent water or solvent blank.


4.0  APPARATUS AND MATERIALS

      4.1  Sampling.  The following equipment is required:

            4.1.1   Sample  Containers.  Vials,  glass,  with butyl rubber septa,
      Perkin-Elmer Corporation Part Numbers 0105-0129 (glass vials), 6001^0728
      (gray butyl rubber septa,  plug style),  0105-0131 (butyl rubber septa), or
      equivalent.   The  seal must be made from  butyl  rubber.   Silicone rubber
      seals are not acceptable.

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            4.1.2  Vial Sealer.   Perkin-Elmer Number 105-0106, or equivalent.

            4.1.3    Gas-Tight  Syringe.    Perkin-Elmer  Number  00230117,  or
      equivalent.

      4.2   The following  equipment  is  required if sampling  from  an enclosed
pipe:

            4.2.1  Static Mixer.  Installed in-line or  as  a by-pass loop, sized
      so that the drop size of the dispersed phase is not greater that 1,000 Aim.
      If the  installation  of the mixer is  in a  by-pass loop,  then the entire
      waste stream must be  diverted through the mixer.

            4.2.2  Tap.

            4.2.3  Tubing,  Teflon, 0.25 in. ID.

            4.2.4  Cooling  Coil.  Stainless steel  (304), 0.25 in. ID, equipped
      with a thermocouple at the coil outlet.

      4.3  Analysis.  The following equipment is required:

            4.3.1  Balanced Pressure  Headspace Sampler.  Perkin-Elmer HS-6, HS-
      100,  or equivalent,  equipped  with  a glass  bead  column  instead of  a
      chromatographic column.

            4.3.2   Flame  lonization Detector.   An FID meeting  the  following
      specifications is required:

                  4.3.2.1   Linearity.  A linear response (±5 percent) over the
            operating range, as  demonstrated by  the procedures  established in
            Sections 7.2.2  and 8.1.1.

                  4.3.2.2   Range.  A  full  scale  range  of 1 to 10,000 ppm  CH4.
            Signal attenuators should be available to produce a minimum signal
            response of 10  percent of full scale.

            4.3.3 Data Recording System. Analog strip chart recorder or digital
      integration system compatible with the FID for permanently recording the
      output of the detector.

            4.3.4  Thermometer.   Capable  of reading temperatures  in  the range
      of 30° to 60°C with an accuracy of ±0.1°C.


5.0  REAGENTS

      5.1  Analysis.   The following reagents are required for analysis:

            5.1.1  Hydrogen (H2).   Zero  grade.

            5.1.2 Carrier  Gas.  Zero grade nitrogen, containing less than 1 ppm
      carbon and less than  1 ppm carbon dioxide.


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            5.1.3  Combustion Gas.  Zero grade air or oxygen, as required by the
      FID.

      5.2  Calibration and Linearity Check.

            5.2.1   Stock Cylinder Gas  Standard.    100  percent propane.   The
      manufacturer shall  (a)  certify the gas  composition  to be accurate to ±3
      percent or better  (see  Section 5.2.1.1);   (b)  recommend a maximum shelf
      life over which the gas concentration does not change by greater than ±5
      percent from the certified value; and (c) affix the date of gas cylinder
      preparation,  certified propane  concentration,  and  recommended  maximum
      shelf life to the cylinder before shipment to the buyer.

                  5.2.1.1  Cylinder Standards Certification.   The manufacturer
            shall  certify the  concentration  of  the calibration  gas  in  the
            cylinder by (a)  directly  analyzing the cylinder and (b) calibrating
            his  analytical  procedure  on  the day  of cylinder analysis.   To
            calibrate his analytical  procedure, the manufacturer shall use, as
            a minimum, a three-point calibration curve.

                  5.2.1.2  Verification of Manufacturer's Calibration Standards.
            Before using, the manufacturer shall verify the concentration of each
            calibration  standard by  (a) comparing  it to gas mixtures prepared
            in accordance with the  procedure described in Section 7.1 of Method
            106 of 40 CFR Part 61,  Appendix B, or by  (b) calibrating it against
            Standard  Reference Materials  (SRMs),  prepared   by  the  National
            Institute of Science  and Technology,  if such  SRMs are available.
            The agreement between the initially determined concentration value
            and the verification concentration value must be within ±5 percent.
            The manufacturer must reverify all calibration standards on a time
            interval  that  is consistent with  the  shelf life  of  the cylinder
            standards sold.

      5.3  Blanks

            5.3.1 Organic-free reagent water.   All references  to water in this
      method refer to organic-free reagent water as defined in Chapter One.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the introductory material  to  this  Chapter, Organic Analytes,
Section 4.1.

      6.2  Sampling Plan  Design and  Development.   Use the procedures given in
Chapter Nine, "Sampling Plan."

      6.3  Collect samples according to the procedures in Chapter 9, or, if it
is necessary to sample from an enclosed pipe,  sample according  to the procedures
described below.

            6.3.1   The  apparatus  designed to sample from  an  enclosed pipe is
      shown in Figure 1.  The apparatus consists of an in-line static mixer, a
      tap,  a  cooling coil  immersed  in an ice bath,  a flexible  Teflon tube

                                   5110 -  3                       Revision 0
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      connected to the outlet of the cooling coil,  and sample container.  Locate
      the tap within two pipe diameters of the static mixer outlet.  Install the
      static mixer in the process line or in a by-pass  line.

            6.3.2   Begin  sample  collection  by purging  the  sample  lines  and
      cooling coil  with  at  least four volumes  of waste.  Collect  the purged
      material in a separate container.

            6.3.3  After purging, stop the sample flow  and  transfer the Teflon
      sampling tube to a  sample container.  Sample at a flow rate such that the
      temperature of the waste  is <10°C.  Fill the sample container halfway (±5
      percent) and cap immediately (within 5 seconds).

            6.3.4  Store the collected samples on ice or in a refrigerator until
      analysis.

            6.3.5  Alternative  sampling techniques may be  used upon the approval
      of the Administrator.
7.0  PROCEDURE

      7.1  Calibration

            7.1.1 Maintain a record of each item.

            7.1.2 Use the procedures in Section 7.1.3 to calibrate the headspace
      analyzer and FID, and to check  for  linearity  before  the  system is first
      placed in operation, after  any shutdown that is longer than 6 months, and
      after any modification of the system.

            7.1.3  Calibration and Linearity.   Use the  procedures  in Section
      6.2.1 of Method 18 of 40 CFR Part 60, Appendix  A,  to prepare the standards
      and calibrate the flowmeters,  using propane as  the standard gas.  Fill the
      calibration standard vials  halfway  (±5 percent) with organic-free reagent
      water.  Prepare a minimum  of three  concentrations  that will  bracket the
      applicable cutoff.   For a  cutoff of 5.2  kPa  (0.75  psi),  prepare nominal
      concentrations  of 30,000, 50,000, and 70,000 ppm as  propane.  For a cutoff
      of 27.6 kPa (4.0 psi), prepare nominal concentrations of 200,000, 300,000,
      and 400,000 ppm as propane.

                  7.1.3.1  Use the  procedures  in Section 7.2.3 to  measure the
            FID response  of each  standard.  Use a linear regression analysis to
            calculate the values  for the slope (k)  and the y-intercept  (b).  Use
            the procedures in Section 7.2  and  7.3 to  test  the  calibration and
            the linearity.

            7.1.4  Daily  FID Calibration  Check.  Check the  calibration at the
      beginning  and  at  the end  of  the  daily runs   by using the  following
      procedures.   Prepare two  calibration  standards at  the nominal  cutoff
      concentrations  using the procedures in  Section 7.1.3  Place  one at the
      beginning and end of the daily run.  Measure  the FID response of the daily
      calibration standard.  Use the values for k and b obtained from the most
      recent calibration  and use  Equation  4 to calculate the  concentration of

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the daily standard.  Use  an  equation  similar to Equation 2 to calculate
the percent difference between the daily standard and Cs.  If the percent
difference is within five,  then the previous values  for  k  and  b can be
used.  Otherwise, use the procedures in Section 7.1.3 to recalibrate the
FID.
7.2  Analysis.
      7.2.1  Allow one  hour for the headspace vials to equilibrate at the
temperature specified  in  the  regulation.   Allow the  FID to warm until a
stable baseline is achieved on the detector.
      7.2.2  Check the  calibration of  the  FID daily,  using the procedures
in Section 7.1.4.
      7.2.3   Follow the  manufacturer's recommended  procedures  for the
normal operation of the headspace  sampler and FID.
      7.2.4  Use the procedures in Sections  7.3.4 and 7.3.5 to calculate
the organic vapor pressure in the  samples.
      7.2.5  Monitor the  output of the detector to make certain that the
results are being properly recorded.
7.3  Calculations
      7.3.1  Nomenclature
A =    Measurement of the area under the response curve, counts.
b =    y-intercept of the linear  regression  line.
Ca =   Measured  vapor  phase  organic  concentration   of sample,  ppm as
       propane.
Cma =  Average measured vapor phase organic concentration of standard, ppm
       as propane.
Cm =   Measured  vapor  phase  organic  concentration  of  standard,  ppm as
       propane.
Cs =   Calculated standard concentration, ppm as propane.
k =    Slope of the linear regression  line.
Pbar =  Atmosphere pressure at  analysis  conditions, mm Hg  (in. Hg).
p* =   Organic vapor pressure  in  the sample,  kPa (psi).
B =    1.333 x 10"6 kPa/[(mm Hg)(ppm)],  4.91  x 10'7 psi/  [(in.Hg)(ppm)])
      7.3.2  Linearity.  Use Equation 1 to calculate the measured standard
concentration  for each  standard vial.
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                                                            January 1990

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            cm = k A + b                                    Eq. 1

                  7.3.2.1  Calculate the average measured standard concentration
            (Cma)  for each set of triplicate  standards,  and use Equation 2 to
            calculate the percent difference between Cma and Cs

                                    f  -  f
                                    Ls   ^ma
            Percent Difference =    	x 100           Eq. 2
                                       Cs

                  The  instrument  linearity  is  acceptable  if  the  percent
            difference is less than or equal to five for each standard.

            7.3.3   Relative  standard Deviation  (RSD).    Use  Equation  3  to
      calculate the RSD for each triplicate set of standards.
                        100
                 %RSD = 	
n  (Cm - Cma)2
Z  	               Eq.  3
'"1  (n - 1)
            The calibration is acceptable if the RSD is within five percent for
      each standard concentration.

            7.3.4  Concentration of Organics in the Headspace.  Use Equation 4
      to calculate the concentration of vapor phase organics in each sample.

             Ca = k A + b                                   Eq. 4

            7.3.5  Vapor  Pressure  of  Organics  in the Headspace.  Use Equation
      5 to calculate the vapor pressure of organics in the sample.

             P" - B Pbar Ca                                   Eq. 5


8.0   QUALITY CONTROL

      8.1  Refer to Chapter One for specific Quality Control procedures.

      8.'2    Maintain  a  record  of  performance  of  all  system  checks  and
calibrations.
9.0   METHOD PERFORMANCE

      9.1  No performance data are currently available.


10.0  REFERENCES

1.  "Determination  of Vapor Phase  Organic Concentrations  in  Waste Samples,"
    Method 25E; Proposed Amendment to 40 CFR Part  60, Appendix A, January 1989.
                                   5110 - 6                       Revision 0
                                                                  January 1990

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                                       FIGURE  1
                 WASTE LINE
FROM SOURCE
                STATIC MIXER
t
                                         VALVES
                 OPTIONAL PUMP
  REDUCER (1/4 " TUBE FITTING)
                                                TEFLON OR STAINLESS STEEL COIL  f ft " )


                                                ICEDATII
               SAMPLE CONTAINER
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                         Revision 0
                         January 1990

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                         METHOD 5110
DETERMINATION OF ORGANIC PHASE VAPOR PRESSURE IN WASTE SAMPLES
                Start
             7.2.1  Allow
              system  to
             equilibrate
             for  1  hour.
           7.2.2  Do  daily
           FID  calibration
            check using
           procedures  from
           section 7.1.4.
            7.2.3 Operate
             headspace
           sampler and FID
            according to
            manufacturer.
            7.2.4 Monitor
             detector
             output  to
            assure  proper
             recording.
7.3.2 Calculate
   linearity
 according to
   equations
    given.
7.3.3 Calculate
   relative
   standard
 deviation of
  standards.
7.3.4 Calculate
 concentration
of organics in
the headspace.
7.3.5 Calculate
   the vapor
pressure of the
organics in the
  headspace.
                                         Stop
                           5110 -  8
                     Revision 0
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                                 METHOD 801OB

                         HALOGENATED  VOLATILE ORGANICS

1.0  SCOPE AND APPLICATION

      1.1  Method 8010 is used to determine the concentration of various volatile
halogenated organic compounds.  The following compounds can be determined by this
method:
ADorooriate Techniaue
Compound Name
Allyl chloride
Benzyl Chloride
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl) ether
Bromoacetone
Bromobenzene
Bromod i chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chloroacetaldehyde
Chlorobenzene
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane
Chl oromethane
Chloromethyl methyl ether
Chloroprene
4-Chlorotoluene
Di bromochl oromethane
1 , 2-Di bromo-3-chl oropropane
Dibromomethane
1,2-Dichlorobenzene
1 , 3-Di chl orobenzene
1,4-Dichlorobenzene
l,4-Dichloro-2-butene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans- 1 , 2-Di chl oroethene
Di chl oromethane
1 , 2 -Di chl oropropane
1, 3-Di chl oro-2-propanol
cis-1, 3-Di chl oropropene
trans-l,3-Dichloropropene
CAS No.a
107-05-1
100-44-7
111-91-1
39638-32-9
598-31-2
108-86-1
75-27-4
75-25-2
74-83-9
56-23-5
107-20-0
108-90-7
75-00-3
107-07-03
110-75-8
67-66-3
544-10-5
74-87-3
107-30-2
126-99-8
106-43-4
124-48-1
96-12-8
74-95-3
95-50-1
541-73-1
106-46-7
764-41-0
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
75-09-2
78-87-5
96-23-1
10061-01-5
10061-02-6
Purge-and-Trap
b
PP
PP
b
PP
b
b
b
b
b
b
b
b
PP
b
b
pc
b
PP
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
PP
b
b
Direct
Injection
b
b
pc
b
b
b
b
b
b
b
b
b
b
b
b
b
pc
b
pc
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
                                   8010B  -  1
Revision 2
November 1990

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                                                     Appropriate Technique
                                                                      Direct
Compound Name                      CAS No.a         Purge-and-Trap     Injection
Epichlorhydrin
Ethyl ene di bromide
Methyl iodide
1,1,2, 2 -Tetrachl oroethane
1,1,1 , 2-Tetrachl oroethane
Tetrachl oroethene
1,1,1-Trichloroethane
1 , 1 , 2-Tri chl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
1 , 2 , 3 -Tri chl oropropane
Vinyl Chloride
106-89-8
106-93-4
74-88-4
79-34-5
630-20-6
127-18-4
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
75-01-4
PP
b
PP
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
a  Chemical Abstract Services Registry Number
b  Adequate response using this technique
pp Poor purging efficiency, resulting in high EQLs
pc Poor chromatographic performance.

      1.2  Table 1 indicates compounds that may be analyzed by this method and
lists the method detection limit for each compound in organic-free reagent water.
Table 2 lists the estimated quantitation limit for other matrices.


2.0  SUMMARY OF METHOD

      2.1  Method 8010 provides gas chromatographic conditions for the detection
of halogenated volatile organic compounds.  Samples can be introduced into the
GC using direct injection or purge-and-trap (Method 5030).  Ground water samples
must be analyzed using Method 5030.   A  temperature program  is used in the gas
chromatograph to separate  the  organic compounds.  Detection  is  achieved by a
electrolytic conductivity detector  (HECD).

      2.2  The method provides an optional gas chromatographic column that may
be helpful in  resolving the  analytes  from co-eluting non-target  compounds and
for analyte confirmation.


3.0  INTERFERENCES

      3.1  Refer to Methods 5030 and 8000.

      3.2  Samples  can be contaminated  by  diffusion of  volatile  organics
(particularly chlorofluorocarbons  and methylene chloride)  through the sample
container  septum  during shipment  and storage.   A  trip  blank  prepared from
organic-free reagent water and carried through sampling and subsequent storage
and handling can serve as a check on such contamination.


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4.0  APPARATUS AND MATERIALS

      4.1  Gas chromatograph

            4.1.1 Gas  chromatograph  -  analytical  system  complete  with  gas
     chromatograph suitable for  on-column  injections  or purge-and-trap sample
     introduction and all required accessories, including detector, analytical
     columns, recorder, gases, and syringes.  A data system for measuring peak
     heights and/or peak areas is recommended.

            4.1.2 Columns

                  4.1.2.1  Column 1 -  8  ft x 0.1 in.  ID stainless steel or glass
            column  packed  with  1%  SP-1000   on  Carbopack-B  60/80  mesh  or
            equivalent.

                  4.1.2.2  Column 2 -  6  ft x 0.1 in.  ID stainless steel or glass
            column packed with chemically bonded n-octane on Porasil-C 100/120
            mesh (Durapak) or equivalent.

            4.1.3 Detector - Electrolytic conductivity (HECD).

      4.2  Sample  introduction  apparatus,  refer  to  Method  5030  for  the
appropriate equipment for sample introduction purposes.

      4.3  Syringes, 5 ml Luerlok  glass hypodermic  and a 5 ml,  gas-tight with
shutoff valve.

      4.4  Volumetric flask,  Class A,  10, 50,  100,  500, and 1,000 ml  with a
ground glass stopper.

      4.5  Microsyringe, 10 and 25 /itL  with a 0.006 in.  ID needle (Hamilton 702N
or equivalent) and a 100 pi.

      4.6  Analytical balance - 0.0001 g.


5.0  REAGENTS

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

      5.2  Organic-free reagent water.  All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3  Methanol, CH3OH.   Pesticide quality or equivalent.   Store away from
other solvents.
                                   8010B  -  3                   Revision 2
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      5.4  Stock standards - Stock solutions may  be prepared from pure standard
materials or  purchased as  certified solutions.    Prepare stock  standards in
methanol using assayed  liquids or gases,  as appropriate.  Because of the toxicity
of some of  the organohalides,  primary dilutions of  these materials should be
prepared in a hood.

            5.4.1 Place about 9.8 ml of methanol  in a 10 ml tared ground glass
     stoppered volumetric  flask.   Allow the flask to  stand,  unstoppered,  for
     about 10 minutes until all alcohol-wetted surfaces have dried.  Weigh the
     flask to the nearest 0.0001 g.

            5.4.2 Add the assayed reference material, as described below.

                  5.4.2.1  Liquids.  Using a 100 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,
            dichlorodifluoromethane, trichlorofluoromethane,  vinyl  chloride),
            fill a 5 ml valved  gas-tight syringe  with the  reference standard to
            the  5.0  ml mark.   Lower the  needle to  5  mm above  the methanol
            meniscus.  Slowly introduce the reference standard above the surface
            of the liquid.   The heavy gas  rapidly dissolves  in the methanol.
            This may also be accomplished by using a lecture bottle equipped with
            a Hamilton Lecture  Bottle Septum (#86600).  Attach Teflon tubing to
            the side-arm relief valve and direct  a gentle stream of gas into the
            methanol meniscus.

            5.4.3 Reweigh, dilute to volume, stopper,  and  then mix by inverting
      the flask  several times.   Calculate  the  concentration in milligrams per
      liter (mg/L) from the net gain  in weight.  When  compound  purity is assayed
      to  be  96%  or  greater,  the weight  may  be  used  without correction to
      calculate the concentration of the stock standard.   Commercially prepared
      stock standards may be used at  any concentration if  they are certified by
      the manufacturer or by an independent source.

            5.4.4 Transfer the  stock standard solution  into a bottle  with  a
      Teflon lined screw-cap.  Store, with minimal  headspace,  at -10°C to -20°C
      and protect from light.

            5.4.5 Prepare  fresh  standards  every 2 months,  for gases  or  for
      reactive compounds such as 2-chloroethylvinyl ether. All other standards
      must  be replaced after  6  months,  or sooner  if comparison  with  check
      standards  indicates a problem.

      5.5  Secondary dilution standards. Using stock standard solutions, prepare
secondary dilution standards in  methanol,  as needed,  containing the compounds
of interest, either singly or mixed together.  The secondary dilution standards
should be prepared at concentrations  such that the aqueous  calibration standards
prepared in Section 5.6 will  bracket  the working range of the analytical system.
Secondary  dilution  standards  should  be  stored with  minimal  headspace  for


                                   8010B -  4                   Revision  2
                                                               November  1990

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volatiles  and  should  be  checked  frequently  for  signs  of  degradation  or
evaporation, especially just  prior to preparing calibration standards from them.

      5.6  Calibration standards.  Prepare calibration standards in organic-free
reagent water from the secondary dilution of the stock standards, at a minimum
of five concentrations.  One  of the  concentrations  should  be at a concentration
near, but above, the method detection limit.  The remaining  concentrations should
correspond to the expected range of  the concentrations found in real samples or
should define the working  range of  the GC.   Each standard should contain each
analyte for detection by this method (e.g. some or all of the compounds listed
in Table  1 may be  included).  In order to prepare  accurate  aqueous  standard
solutions, the following precautions must be observed.

            5.6.1 Do  not  inject more  than  20  /uL  of  alcoholic  standards into
      100 ml of water.

            5.6.2 Use  a  25  p.i  Hamilton  702N  microsyringe  or  equivalent
      (variations in needle geometry will adversely  affect the ability to deliver
      reproducible volumes of methanolic standards into water).

            5.6.3 Rapidly  inject  the  alcoholic  standard  into  the  filled
      volumetric flask.  Remove the  needle as fast  as possible after injection.

            5.6.4 Mix aqueous standards by inverting the flask three times only.

            5.6.5 Fill the sample syringe from the standard solution contained
      in the expanded  area of  the flask (do not use  any solution contained in
      the neck of the flask).

            5.6.6 Never use  pipets  to  dilute  or transfer  samples or aqueous
      standards.

            5.6.7 Aqueous standards  are not stable and should be discarded after
      one hour, unless properly sealed and  stored.   The aqueous  standards can
      be stored up to 24 hours, if held in sealed vials with zero headspace.

      5.7  Internal  standards  (if internal  standard  calibration  is  used)  - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical  behavior  to  the  compounds  of  interest.   The analyst
must further demonstrate that  the measurement  of the internal  standard is not
affected by method or  matrix interferences.   Because of these  limitations, no
internal  standard can be  suggested  that is applicable  to all samples.   The
compounds recommended for use as surrogate spikes  (Section 5.8) have been used
successfully as internal  standards,  because  of  their generally unique retention
times.

            5.7.1 Prepare  calibration  standards   at   a  minimum   of   five
      concentrations for each analyte of interest as  described in Section 5.5.

            5.7.2 Prepare  a  spiking  solution containing  each of  the  internal
      standards using the procedures described in Sections 5.4 and 5.5.  It is
      recommended that  the  secondary dilution  standard  be  prepared  at  a
      concentration   of 15 ng//*L of  each  internal  standard  compound.    The


                                  8010B -  5              :    Revision 2
                                                              November 1990

-------
      addition  of 10 juL  of  this standard to 5.0 ml  of sample or  calibration
      standard  would be equivalent to 30 M9/L-

            5.7.3 Analyze  each  calibration standard according to Section  7.0,
      adding  10  p.1 of  internal standard spiking solution directly  to  the
      syringe.

      5.8  Surrogate standards - The  analyst should monitor both the  performance
of the analytical  system and the effectiveness of the method in dealing with  each
sample matrix by  spiking  each sample, standard,  and organic-free reagent water
blank  with  surrogate  halocarbons.     A   combination   of  bromochloromethane,
bromochlorobenzene and bromofluorobenzene is recommended to encompass the range
of  temperature  program used  in this method.    From  stock standard  solutions
prepared as in  Section  5.4,  add a volume  to give 750  /ig of each surrogate to
45 mL of organic-free reagent water contained in a 50 ml volumetric  flask,  mix,
and  dilute  to  volume  for a concentration of  15 ng//iL.  Add 10  /il_ of  this
surrogate spiking solution directly into the 5 ml syringe with  every sample and
reference standard analyzed.   If the  internal  standard  calibration procedure is
used, the surrogate compounds  may be added directly  to the internal standard
spiking solution  (Section  5.7.2).


6.0  SAMPLE COLLECTION, PRESERVATION, AND  HANDLING

      6.1  See  the  introductory material  to  this  Chapter,  Organic Analytes,
Section 4.1.
7.0  PROCEDURE

      7.1  Volatile compounds are  introduced  into  the gas chromatograph using
either direct  injection  or purge-and-trap (Method 5030).   Method  5030 may be
used directly on ground  water  samples or low-concentration contaminated soils
and  sediments.    For medium-concentration   soils  or  sediments,  methanolic
extraction, as described  in Method  5030,  may  be necessary prior to purge-and-
trap analysis.

      7.2  Gas chromatographic conditions (Recommended)

            7.2.1  Column 1:
                  Helium flow rate = 40 mL/min
                  Temperature program:
                           Initial temperature = 45°C, hold for 3 minutes
                           Program = 45°C to  220°C at  8°C/min
                           Final temperature = 220°C,  hold for 15 minutes.
            7.2.2  Column 2:
                  Helium flow rate = 40 mL/min
                  Temperature program:
                           Initial temperature = 50°C,  hold for 3 minutes
                           Program = 50°C to 170°C at 6°C/min
                           Final temperature = 170°C,  hold for 4 minutes.
                                   8010B  -  6                    Revision  2
                                                               November  1990

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      7.3  Calibration.  The procedure for  internal or external calibration may
be used.  Refer to Method  8000  for  a description of  each of these procedures.
Use Table  1  and  Table 2  for guidance on  selecting  the lowest point  on the
calibration curve.

            7.3.1 Calibration must take place using the same sample introduction
      method that will be  used to analyze actual samples (see Section 7.4.1).

      7.4  Gas chromatographic analysis

            7.4.1 Introduce volatile compounds into the gas chromatograph using
      either Method 5030  (purge-and-trap)  or  the direct  injection method (see
      Section 7.4.1.1).  If the internal standard calibration technique is used,
      add 10 /iL of internal  standard  to the sample prior to purging.

                  7.4.1.1  In very  limited applications  (e.g.  aqueous  process
            wastes) direct injection  of  the  sample onto the GC  column  with a
            10 juL syringe may be appropriate.   The  detection limit is very high
            (approximately 10,000 /ig/L)  therefore, it is only permitted where
            concentrations in excess of 10,000 /xg/L are expected or for water-
            soluble compounds that do not purge.  The  system must be calibrated
            by direct  injection (bypassing the purge-and-trap device).

            7.4.2 Method 8000 provides instructions  on  the  analysis sequence,
      appropriate dilutions,  establishing  daily retention  time windows,  and
      identification criteria.  Include a mid-concentration standard after each
      group of 10 samples  in the analysis sequence.

            7.4.3 Table 1  summarizes  the estimated retention  times  on  the two
      columns for a number of organic compounds analyzable  using this  method.
      An example of the separation achieved by Column 1  is shown in Figure 1.

            7.4.4 Record the sample volume  purged or  injected and the resulting
      peak sizes  (in area  units or peak heights).

            7.4.5 Refer  to   Method   8000  for  guidance on   calculation  of
      concentration.

            7.4.6 If analytical  interferences  are suspected, or for the purpose
      of confirmation, analysis using the second GC column is recommended.

            7.4.7 If the response for a  peak  is off-scale,  prepare  a dilution
      of the  sample with  organic-free reagent  water.   The dilution must  be
      performed on a second aliquot of the sample which has been properly sealed
      and stored prior to  use.


8.0  QUALITY CONTROL

      8.1  Refer  to  Chapter One  for  specific quality control  procedures and
Method 8000 for gas chromatographic procedures.  Quality control to ensure the
proper operation of the purge-and-trap device is covered in  Method 5030.
                                   8010B -  7                   Revision 2
                                                              November 1990

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      8.2  Mandatory quality control to validate the GC system operation is found
in Method 8000.

            8.2.1 The quality  control  check sample concentrate  (Method 8000)
     should contain each analyte of  interest at a concentration  of 10 mg/L in
     methanol.

            8.2.2 Table 3 indicates the calibration  and QC acceptance criteria
      for this method.  Table 4 gives method accuracy and precision as functions
      of concentration for the analytes of interest.  The contents  of both Tables
      should be used to  evaluate a  laboratory's  ability to perform and generate
      acceptable data by this method.

      8.3  Calculate surrogate  standard  recovery on all  samples,  blanks,  and
spikes.  Determine if recovery is within limits (limits established by performing
QC procedure outlined in Method 8000).

            8.3.1 If recovery is not  within limits, the following are required:

                  8.3.1.1  Check to  be  sure that there  are no  errors  in  the
            calculations, surrogate solutions or internal  standards.  If errors
            are found,  recalculate the data accordingly.

                  8.3.1.2  Check  instrument performance.    If  an  instrument
            performance problem is identified, correct the problem  and re-analyze
            the extract.

                  8.3.1.3  If no problem is found, re-extract and  re-analyze the
            sample.

                  8.3.1.4  If, upon re-analysis, the recovery is again not within
            limits,  flag the data as "estimated concentration".


9.0  METHOD PERFORMANCE

      9.1  This method was  tested by  20 laboratories using organic-free reagent
water, drinking water, surface  water,  and three industrial  wastewaters  spiked
at six concentrations over the range 8.0-500 M9/L.  Single operator precision,
overall precision,  and method accuracy were found to be directly  related to the
concentration of the analyte, and essentially independent  of  the  sample matrix.
Linear equations to describe these relationships are presented in Table 4.

      9.2  The accuracy and precision obtained will be determined by the sample
matrix, sample introduction technique, and by the calibration procedure used.


10.0  REFERENCES

1.   Bellar, T.A.;  Lichtenberg, J.J.  «L. Amer.  Water  Works Assoc.  1974, 66(12),
     pp. 739-744.
                                   8010B  -  8                   Revision  2
                                                              November  1990

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2.   Bellar,  T.A.;  Lichtenberg,  J.J.,  Semi-Automated  Headspace Analysis  of
     Drinking  Waters  and  Industrial Waters  for  Purgeable Volatile  Organic
     Compounds, Measurement of Organic Pollutants in Water and Wastewater; Van
     Hall, Ed.; ASTM STP 686, pp 108-129,  1979.

3.   "Development and Application of Test  Procedures for Specific Organic Toxic
     Substances  in  Wastewaters: Category  11  -  Purgeables  and Category  12  -
     Acrolein,  Acrylonitrile,   and  Dichlorodifluoromethane";  report  for  EPA
     Contract 68-03-2635 (in preparation).

4.   U.S. EPA 40 CFR Part 136,  "Guidelines Establishing Test Procedures for the
     Analysis of Pollutants Under the Clean Water  Act:  Final  Rule and Interim
     Final Rule and Proposed Rule",  October 26, 1984.

5.   "EPA Method Validation Study 23, Method 601 (Purgeable Halocarbons)"; Report
     for EPA Contract 68-03-2856 (in preparation).

6.   Gebhart, J.E., S.V. Lucas,  S.J. Naber, A.M. Berry, T.H.  Danison and H.M.
     Burkholder, "Validation of SW-846 Methods 8010, 8015,  and 8020";  Report for
     EPA Contract 68-03-1760,  Work  Assignment  2-15;   US EPA,  EMSL-Cincinnati,
     1987.
                                   8010B  -  9                   Revision 2
                                                              November 1990

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                       TABLE  1.
CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION LIMITS
           FOR HALOGENATED VOLATILE ORGANICS
Compound
Ally chloride
Benzyl chloride*'0
Bis(2-chloroethoxy)methane"
Bis(2-chloroisopropyl) ether"
Bromobenzene
Bromodi chl oromethane
Bromoform*
Bromomethane*
Carbon tetrachloride*
Chl oroacetal dehyde*
Chlorobenzene"
Chl oroethane
Chloroform*
1-Chlorohexane
2-Chloroethyl^ vinyl ether*
Chl oromethane*
Chloromethyl methyl ether*
4-Chlorotoluene
Di bromochl oromethane
1 , 2-Di bromo-3-chl oropropane*
Dibromomethane*
1,2-Dichlorobenzene] ,
1,3-Dichlorobenzene] '
1,4-Dichlorobenzene*
l,4-Dichloro-2-butene
Di chl orodi f 1 uoromethane*'"
1,1-Dichloroethane"
1,2-Dichloroethane]
1,1-Dichloroethene*
trans-l,2-Dichlproethene*
Di chl oromethane*
1, 2-Di chl oropropane*
trans-l,3-Dichloropropene*
Ethyl ene di bromide
1,1,2, 2 -Tetrachl oroethane]
1,1,1 , 2-Tetrachl oroethane*
Tetrachl oroethene*
1,1,1 -Tri chl oroethane
1 , 1 , 2-Trichl oroethane"
Tri chl oroethene*
Tri chl orof 1 uoromethane]
1,2, 3 -Tri chl oropropane*
Vinyl Chloride*
CAS
Registry
Number
107-05-1
100-44-7
111-91-1
39638-32-9
108-86-1
75-27-4
75-25-2
74-83-9
56-23-5
107-20-0
108-90-7
75-00-3
67-66-3
544-10-5
110-75-8
74-87-3
107-30-2
106-43-4
124-48-1
96-12-8
74-95-3
95-50-1
541-73-1
106-46-7
764-41-0
75-71-8
75-34-3
107-06-2
75-35-4
156-60-5
75-09-2
78-87-5
10061-02-5
106-93-4
79-34-5
630-20-6
127-18-4
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
75-01-4
Retention Time
(minutes)
Column 1 Column 2
10.17
30.29
38.60
34.79
29.05
15.44
21.12
2.90
14.58
(b)
25.49
5.18
12.62
26.26
19.23
1.40
8.88
34.46
18.22
28.09
13.83
37.96
36.88
38.64
23.45
3.68
11.21
13.14
10.04
11.97
7.56
16.69
16.976
19.59
23.12
21.10
23.05
14.48
18.27
17.40
9.26
22.95
3.25
(b)
(b)
(b)
(b)
(b)
14.62
19.17
7.05
11.07
(b)
18.83
8.68
12.08
(b)
(b)
5.28
(b)
(b)
16.62
(b)
14.92
23.52
22.43
22.33
(b)
(b)
12.57
15.35
7.72
9.38
10.12
16.62
16.60
(b)
(b)
21.70
14.97
13.10
18.07
13.12
(b)
(b)
5.28
Method
Detection
Limit"
(M9/L)
(b)
(b)
(b)
(b)
(b)
0.002
0.020
0.030
0.003
(b)
0.001
0.008
0.002
(b)
0.130
0.010
(b)
(b)
(b)
0.030
(b)
(b)
(b)
(b)
(b)
(b)
0.002
0.002
0.003
0.002
(b)
(b)
0.340
(b)
0.010
(b)
0.001
0.003
0.007
0.001
(b)
(b)
0.006
                       8010B -  10
Revision 2
November 1990

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                                   TABLE 1.
                                   Continued
a = Using purge-and-trap method (Method 5030)
b = Not determined
* = Appendix VIII compounds
c = Demonstrated very erratic results when tested by purge-and-trap
d = See Section  4.10.2  of Method  5030  for guidance on  selection  of trapping
    material
e = Estimated retention time
                                   TABLE 2.
             DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQL)
                             FOR VARIOUS MATRICES8
               Matrix                              Factor"
               Ground water         ',                    10
               Low-concentration soil                    10
               Water miscible liquid waste             500
               High-concentration soil and sludge     1250
               Non-water miscible waste               1250
               Sample EQLs are highly matrix-dependent.  The EQLs listed herein
               are provided for guidance and may not always be achievable.

               EQL = [Method  detection  limit  (Table  1)]  X [Factor (Table 2)].
               For non-aqueous samples, the factor is on a wet-weight basis.
                                  8010B - 11                  Revision 2
                                                              November 1990

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                                TABLE 3.
                 CALIBRATION AND QC ACCEPTANCE CRITERIA8
Analyte
Bromod i chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethylvinyl ether
Chloroform
Chl oromethane
Di bromochl oromethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans- 1 , 2-Dichl oroethene
Dichl oromethane
1,2-Dichloropropane
ci s-1 ,3-Dichl oropropene
trans- 1,3-Di chl oropropene
1,1,2 , 2-Tetrachl oroethane
Tetrachl oroethene
1,1,1 -Tri chl oroethane
1 , 1 , 2-Tri chl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
Vinyl chloride
Range
for Q
(M9/L)
15.2-24.8
14.7-25.3
11.7-28.3
13.7-26.3
14.4-25.6
15.4-24.6
12.0-28.0
15.0-25.0
11.9-28.1
13.1-26.9
14.0-26.0
9.9-30.1
13.9-26.1
16.8-23.2
14.3-25.7
12.6-27.4
12.8-27.2
15.5-24.5
14.8-25.2
12.8-27.2
12.8-27.2
9.8-30.2
14.0-26.0
14.2-25.8
15.7-24.3
15.4-24.6
13.3-26.7
13.7-26.3
Limit
for S
(M9/U
4.3
4.7
7.6
5.6
5.0
4.4
8.3
4.5
7.4
6.3
5.5
9.1
5.5
3.2
5.2
6.6
6.4
4.0
5.2
7.3
7.3
9.2
5.4
4.9
3.9
4.2
6.0
5.7
Range
for x
(M9/L)
10.7-32.0
5.0-29.3
3.4-24.5
11.8-25.3
10.2-27.4
11.3-25.2
4.5-35.5
12.4-24.0
D-34.9
7.9-35.1
1.7-38.9
6.2-32.6
11.5-25.5
11.2-24.6
13.0-26.5
10.2-27.3
11.4-27.1
7.0-27.6
10.1-29.9
6.2-33.8
6.2-33.8
6.6-31.8
8.1-29.6
10.8-24.8
9.6-25.4
9.2-26.6
7.4-28.1
8.2-29.9
Range
P> PS
(%)
42-172
13-159
D-144
43-143
38-150
46-137
14-186
49-133
D-193
24-191
D-208
7-187
42-143
47-132
51-147
28-167
38-155
25-162
44-156
22-178
22-178
8-184
26-162
41-138
39-136
35-146
21-156
28-163
Q =     Concentration measured in QC check sample, in M9/L.

s =     Standard deviation of four recovery measurements, in M9/L-

X =     Average recovery for four recovery measurements, in Aig/L.

P, Ps = Percent recovery measured.

D =     Detected; result must be greater than zero.

a  Criteria from 40 CFR Part 136  for  Method 601 and were calculated assuming
   a QC check sample concentration of 20 M9/L-
                               8010B - 12
Revision 2
November 1990

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                                TABLE 4.
      METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION3
Analyte
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethyl vinyl ether"
Chloroform
Chloromethane
Di bromochl oromethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans- 1 , 2 -Di chl oroethene
Di chloromethane
l,2-Dichloropropaneb
cis-l,3-Dichloropropeneb
trans-l,3-Dichloropropeneb
1,1,2 , 2-Tetrachl oroethane
Tetrachl oroethene
1,1,1 -Trichl oroethane
1, 1, 2 -Tri chl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
Vinyl chloride
Accuracy, as
recovery, x'
(M9/L)
1.12C-1.02
0.96C-2.05
0.76C-1.27
0.98C-1.04
l.OOC-1.23
0.99C-1.53
l.OOC
0.93C-0.39
0.77C+0.18
0.94C+2.72
0.93C+1.70
0.95C+0.43
0.93C-0.09
0.95C-1.08
1.04C-1.06
0.98C-0.87
0.97C-0.16
0.91C-0.93
l.OOC
l.OOC
l.OOC
0.95C+0.19
0.94C+0.06
0.90C-0.16
0.86C+0.30
0.87C+0.48
0.89C-0.07
0.97C-0.36
Single analyst
precision, s/
(M9/L)
0.11X+0.04
0.12X+0.58
0.28X+0.27
0.15X+0.38
0.15X-0.02
0.14X-0.13
0.20X
0.13X+0.15
0.28X-0.31
0.11X+1.10
0.20X+0.97
0.14X+2.33
0.15X+0.29
0.08X+0.17
0.11X+0.70
0.21X-0.23
0.11X+1.46
0.11X+0.33
0.13X
0.18X
0.18X
0.14X+2.41
0.14X+0.38
0.15X+0.04
0.13X-0.14
0.13X-0.03
0.15X+0.67
0.13X+0.65
Overall
precision,
S' (M9/L)
0.20X+1.00
0.21X+2.41
0.36X+0.94
0.20X+0.39
0.18X+1.21
0.17X+0.63
0.35X
0.19X-0.02
0.52X+1.31
0.24X+1.68
0.13X+6.13
0.26X+2.34
0.20X+0.41
0.14X+0.94
0.15X+0.94
0.29X-0.04
0.17X+1.46
0.21X+1.43
0.23X
0.32X
0.32X
0.23X+2.79
0.18X+2.21
0.20X+0.37
0.19X+0.67
0.23X+0.30
0.26X+0.91
0.27X+0.40
x' =  Expected recovery for one or more measurements of a sample containing
s/ =
C
X
   a concentration of C, in M9/L.
   Expected single analyst standard deviation of measurements at an average
   concentration of x, in M9/L.
=  Expected  interlaboratory standard  deviation of  measurements  at  an
   average concentration found of x, in M9/L.
=  True value for the concentration, in p.g/1.
=  Average  recovery  found  for  measurements  of  samples  containing  a
   concentration of C, in jug/L.
a From 40 CFR Part 136 for Method 601.
b Estimates based upon the performance  in a single laboratory.
                               8010B - 13
                                                        Revision 2
                                                        November 1990

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                    FIGURE 1.
GAS CHROMATOGRAM OF HALOGENATED VOLATILE ORGANICS
                    8010B - 14
Revision 2
November 1990

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                    METHOD 8010B
         HALOGENATED VOLATILE ORGANICS
 7 3  Calibrate
   (refer to
 Method 8000)
7.4.1  Introduce
•ample into CC
   by  direct
 injection or
purge-and-trap.
 742  folio.
  Method 8000
 for analyiia
   sequence.
     ete.
                       744  Record
                       volume purged
                            or
                       injected,and
                        peak  liiet.
7.4.S Calculate
concentration*
   (refer to
 Method 8000)
   7  4  6 Are
 interference*
  •u*peeted?
 7 4.7  !• peak
 reaponte off
    icala?
746 Analyie
•ample uoing
  teeond CC
   eoluam.
747  Dilute
   second
 aliquot of
   •anple
                      8010B  -  15
                                    Revision  2
                                    November  1990

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                                 METHOD 8020B

               AROMATIC VOLATILE ORGANICS BY GAS CHROMATOGRAPHY
1.0  SCOPE AND APPLICATION

      1.1  Method 8020 is used to determine the concentration of various aromatic
volatile organic compounds.  The following compounds can be determined by this
method:
Compound Name
CAS No.'
Appropriate Technique
                   Direct
Purge-and-Trap  Injection
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Ethyl benzene
2-Picoline
Pyridine
Styrene
Toluene
Thiophenol (Benzenethiol)
o-Xylene
m-Xylene
p-Xylene
71-43-2
108-90-7
95-50-1
541-73-1
106-46-7
100-41-4
109-06-8
110-86-1
100-42-5
108-88-3
108-98-5
95-47-6
108-38-3
106-42-3
b
b
b
b
b
b
PP
pc
b
b
pc
b
b
b
b
b
b
b
b
b
b
pc
b
b
pc
b
b
b
a  Chemical Abstract Services Registry Number.
b  adequate response by this technique.
pp Poor purging efficiency, resulting in high EQLs
pc Poor chromatographic performance.

     1.2   Table 1 lists the method detection limit for each target analyte in
organic-free reagent water.  Table 2 lists the estimated quantitation limit (EQL)
for other matrices.
2.0  SUMMARY OF METHOD

      2.1  Method 8020 provides chromatographic  conditions for the detection of
aromatic volatile compounds.  Samples can be introduced into the GC using direct
injection  or purge-and-trap  (Method  5030).    Ground water  samples must  be
determined  using Method  5030.   A  temperature program  is  used  in the  gas
chromatograph to  separate  the  organic compounds.  Detection is  achieved  by a
photo-ionization detector (PID).
                                   8020B -1
                             Revision 2
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      2.2  If interferences are encountered, the method provides an optional gas
chromatographic column that may be  helpful  in  resolving the analytes from the
interferences and for analyte confirmation.


3.0  INTERFERENCES

      3.1  Refer to Method 5030 and 8000.

      3.2  Samples  can  be contaminated  by  diffusion  of volatile  organics
(particularly chlorofluorocarbons  and  methylene chloride)  through  the sample
container septum during shipment and storage. A field sample blank prepared from
organic-free reagent water and  carried through sampling and subsequent storage
and handling can serve as a check on such contamination.


4.0  APPARATUS AND MATERIALS

      4.1  Gas chromatograph

            4.1.1  Gas Chromatograph  -  Analytical  system  complete with  gas
      chromatograph suitable for on-column injections or purge-and-trap sample
      introduction and all  required accessories, including  detectors,  column
      supplies, recorder, gases, and syringes.  A data  system for measuring peak
      heights and/or peak areas is recommended.

            4.1.2 Columns

                  4.1.2.1  Column 1:  6 ft x 0.082 in. ID #304 stainless steel
            or  glass  column packed with 5% SP-1200  and 1.75% Bentone-34  on
            100/120 mesh Supelcoport,  or equivalent.

                  4.1.2.2  Column 2: 8 ft x 0.1 in.  ID stainless steel or glass
            column packed with 5% l,2,3-Tris(2-cyanoethoxy)propane on 60/80 mesh
            Chromosorb W-AW, or equivalent.

            4.1.3 Detector  -  Photoionization  (PID)  (h-Nu Systems,  Inc.  Model
      PI-51-02 or equivalent).

      4.2  Sample  introduction  apparatus   -  Refer  to  Method 5030  for  the
appropriate equipment for sample introduction purposes.

      4.3  Syringes - A 5 ml Luerlok glass hypodermic and a 5 ml, gas-tight with
shutoff valve.

      4.4  Volumetric flask, Class  A  -  10, 50, 100,  500, and  1,000 ml with a
ground glass stopper.

      4.5  Microsyringe - 10 and 25 /xL with a 0.006 in. ID needle (Hamilton 702N
or equivalent) and a 100 fj,i.

      4.6  Analytical balance - 0.0001 g.


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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  Stock standards - Stock solutions may  be prepared from pure standard
materials  or purchased as certified  solutions.   Prepare stock  standards  in
methanol  using  assayed  liquids.    Because  of  the  toxicity  of  benzene  and
1,4-dichlorobenzene, primary dilutions of these materials  should be prepared in
a hood.

             5.3.1  Place about 9.8 ml of methanol  in  a  10  ml tared ground glass
      stoppered volumetric flask.   Allow the  flask  to stand,  unstoppered, for
      about  10 min or until all alcohol wetted surfaces have dried.  Weigh the
      flask  to the nearest 0.0001 g.

             5.3.2  Using a 10 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.

             5.3.3  Reweigh, dilute to volume, stopper, and then mix  by inverting
      the flask several times.   Calculate the  concentration  in milligrams per
      liter  (mg/L) from the net gain in weight.  When  compound  purity is assayed
      to  be  96%  or  greater,  the   weight  may  be used  without correction  to
      calculate the concentration of the stock  standard.   Commercially prepared
      stock  standards may be used at any concentration  if  they are certified by
      the manufacturer or  by an independent source.

             5.3.4  Transfer  the  stock standard solution  into a Teflon-sealed
      screw-cap bottle.  Store, with minimal headspace,  at 4°C and protect from
      light.

             5.3.5  All standards must be replaced after 6 months,  or sooner if
      comparison with check standards indicates a problem.

      5.4  Secondary dilution standards:  Using stock standard solutions, prepare
in methanol secondary dilution standards,  as needed,  that  contain the compounds
of interest,  either singly or mixed  together.  The secondary dilution standards
should be prepared at concentrations such that the aqueous  calibration standards
prepared in Section 5.4 will bracket the working range of the analytical system.
Secondary  dilution  standards  should  be  stored  with  minimal  headspace  for
volatiles  and  should  be  checked  frequently  for   signs of  degradation  or
evaporation,  especially just  prior to preparing  calibration standards from them.

      5.5  Calibration standards:   Calibration standards  at a minimum of five
concentrations are prepared  in organic-free reagent water from the  secondary
dilution of  the  stock standards.   One of the  concentrations should be  at  a
concentration near,  but  above,  the  method  detection limit.   The  remaining
concentrations should correspond to the expected range of concentrations found


                                   8020B -3                       Revision 2
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in real samples  or  should define the working range of  the  GC.   Each standard
should contain each analyte for detection by this method (e.g., some or all of
the compounds listed in the target analyte list may be included).  In order to
prepare accurate aqueous standard solutions, the following precautions must be
observed.

            5.5.1  Do not  inject  more than 20 /il_  of  alcoholic standards into
      100 ml of organic-free reagent water.

            5.5.2  Use  a  25  /iL  Hamilton  702N   microsyringe  or  equivalent
      (variations in needle geometry will adversely  affect the ability to deliver
      reproducible volumes of methanolic standards into water).

            5.5.3  Rapidly  inject  the  alcoholic  standard  into  the  filled
      volumetric flask.  Remove the needle  as fast  as possible after injection.

            5.5.4  Mix aqueous standards by inverting the flask three times only.

            5.5.5  Fill the sample syringe  from the standard solution contained
      in the expanded area of  the flask (do not  use  any solution contained in
      the neck of the flask).

            5.5.6  Never  use  pipets  to dilute or  transfer  samples or aqueous
      standards.

            5.5.7  Aqueous standards are not stable  and should be discarded after
      1 hr, unless  properly  sealed and stored.   The  aqueous  standards  can be
      stored up to 24 hr,  if held in sealed vials with zero headspace.

      5.6  Internal  standards  (if internal  standard calibration  is used):   To
use this approach, the analyst must select one or more internal standards that
are similar in analytical  behavior  to  the  compounds of interest.   The analyst
must further demonstrate  that  the measurement of  the  internal  standard is not
affected by method or matrix  interferences.   Because  of these limitations, no
internal  standard  can  be  suggested  that is  applicable  to  all  samples.
Alpha,alpha,alpha-trifluorotoluene has  been used  successfully as  an  internal
standard.

            5.6.1  Prepare  calibration standards  at  a  minimum   of  five
      concentrations for each  parameter of interest as  described in  Section 5.5.

            5.6.2  Prepare a spiking  solution containing  each  of the internal
      standards using the  procedures described in Sections 5.3 and 5.4.  It is
      recommended  that  the   secondary  dilution  standard  be  prepared  at  a
      concentration of 15 mg/L  of  each internal  standard compound,  the addition
      of 10 jitL of this  standard  to  5.0 ml  of sample  or  calibration  standard
      would be equivalent  to 30 /xg/L.

            5.6.3  Analyze each calibration standard according to Section 7.0,
      adding  10  nl  of  internal  standard  spiking solution  directly to  the
      syringe.
                                   8020B -4                       Revision 2
                                                                  November  1990

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      5.7  Surrogate standards: The analyst should monitor both the performance
of the analytical  system and the effectiveness  of the method in dealing with each
sample matrix by spiking each sample, standard, and organic-free reagent water
blank with surrogate compounds (bromochlorobenzene, bromofluorobenzene, 1,1,1-
trifluorotoluene,  fluorobenzene,  and  difluorobenzene are  recommended)  which
encompass the range of the temperature program used in this  method.   From stock
standard solutions prepared as in Section  5.3, add a  volume to  give 750 jig of
each  surrogate  to 45 ml  of organic-free  reagent  water  contained in  a  50 ml
volumetric flask,  mix, and dilute to volume for a concentration  of 15 ng//uL.
Add 10 /nL of this  surrogate spiking solution directly into the 5 ml syringe with
every  sample and  reference  standard  analyzed.    If  the  internal  standard
calibration procedure is  used, the surrogate compounds may be  added directly to
the internal standard spiking solution  (Section 5.6.2).


6.0  SAMPLE COLLECTION, PRESERVATION, AND  HANDLING

      6.1  See  the introductory material  to  this  chapter,  Organic Analytes,
Section 4.1.
7.0  PROCEDURE

      7.1  Volatile compounds are introduced into the gas chromatograph either
by direct injection or  purge-and-trap  (Method  5030).   Method 5030 may be used
directly on  ground  water samples or low-concentration  contaminated soils and
sediments.  For medium-concentration soils  or sediments, methanolic extraction,
as described in Method 5030,  may be  necessary prior to purge-and-trap analysis.

      7.2  Gas chromatography conditions (Recommended):
            7.2.1  Column 1:
      Carrier gas (He) flow rate:
      For lower boiling compounds:
            Initial temperature:
            Temperature program:

      For higher boiling compounds:
            Initial temperature:
            Temperature program:
      36 mL/min

      50°C,  hold  for 2  min;
      50°C to 90°C at 6°C/nrin, hold until
      compounds have eluted.
all
      50°C,  hold  for 2  min;
      50°C to 110°C  at  3°C/min,  hold until
      all compounds have eluted.
           Column  1  provides  outstanding  separations  for  a wide  variety of
      aromatic hydrocarbons.  Column 1 should be  used  as the primary analytical
      column because of its unique ability to resolve para-, meta-, and ortho-
      aromatic isomers.
            7.2.2  Column 2:
      Carrier gas (He) flow rate:
      Initial temperature:
      Temperature program:
30 mL/min
40°C,  hold for 2  min;
40°C to  100°C  at 2°C/min,  hold  until  all
compounds have eluted.
                                   8020B -5
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           Column 2,  an  extremely high polarity  column,  has been  used  for a
      number of years to resolve aromatic hydrocarbons from alkanes in complex
      samples.  However,  because resolution between some of the aromatics is not
      as efficient as with Column 1, Column 2 should be used as a confirmatory
      column.

      7.3  Calibration:  Refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table  2  for  guidance on  selecting the lowest point
on the calibration curve.

            7.3.1  Calibration must take place using the same sample introduction
      method that will be used to analyze actual  samples (see Section 7.4.1).

            7.3.2  The procedure  for  internal  or  external  calibration  may be
      used.  Refer to  Method 8000 for a description of each of these procedures.

      7.4  Gas chromatographic analysis:

            7.4.1  Introduce volatile compounds into the gas chromatograph using
      either Method  5030  (purge-and-trap method) or the direct injection method.
      If the  internal standard  calibration  technique  is used,  add 10 ML of
      internal standard to the sample prior to purging.

                  7.4.1.1  Direct injection:  In very limited applications (e.g.,
            aqueous  process wastes), direct  injection of the sample  into the GC
            system with a 10 /xL syringe may be appropriate.  The detection limit
            is very  high (approximately 10,000 /ig/L);  therefore,   it  is  only
            permitted when concentrations  in  excess of 10,000 ng/L are expected
            or for water soluble compounds that do not purge.  The  system must
            be calibrated  by direct  injection (bypassing  the  purge-and-trap
            device).

            7.4.2 Method 8000 provides instructions on the analysis sequence,
      appropriate dilutions,  establishing daily  retention~time windows,  and
      identification criteria.  Include  a mid-concentration standard after each
      group of 10 samples in the analysis sequence.

            7.4.3 Table 1 summarizes the estimated retention times and detection
      limits for  a  number  of organic compounds analyzable  using this  method.
      An example of the  separation achieved  by Column  1  is  shown in Figure 1.
      Figure 2 shows an example  of the separation  achieved using Column 2.

            7.4.4 Record the sample volume purged  or injected and the resulting
      peak sizes (in area units  or peak heights).

            7.4.5 Calculation of concentration is covered in Method 8000.

            7.4.6  If analytical interferences are  suspected, or for the purpose
      of confirmation, analysis  using the second GC  column is recommended.

            7.4.7  If the response for a peak is off scale,  prepare a dilution
      of the  sample with organic-free  reagent water.    The dilution must be


                                   8020B -6                      Revision 2
                                                                 November  1990

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      performed on a second  aliquot of the sample which has been properly sealed
      and stored prior to use.


8.0  QUALITY CONTROL

      8.1  Refer  to  Chapter One  for  specific quality control  procedures and
Method 8000 for gas chromatographic procedures.  Quality control to ensure the
proper operation of the purge-and-trap device is covered in Method 5030.

      8.2  Mandatory quality control to validate the GC system operation is found
in Method 8000.

           8.2.1  The quality  control  check sample concentrate  (Method 8000)
     should contain each parameter of  interest  at a concentration  of 10 ng//uL
     in methanol.

            8.2.2  Table 3 indicates  the calibration and QC acceptance criteria
      for this method.  Table 4 gives method accuracy and precision as functions
      of concentration for the analytes of interest.  The contents of both Tables
      should be used to  evaluate a laboratory's  ability to perform and generate
      acceptable data by this method.

      8.3  Calculate surrogate  standard recovery on  all samples,  blanks, and
spikes.  Determine if recovery is within  limits (limits  established by performing
QC procedure outlined in Method 8000).

            8.3.1  If recovery is not within limits, the following is required.

                  8.3.1.1  Check  to  be sure that there  are no  errors  in the
            calculations, surrogate solutions or internal standards.  If errors
            are found,  recalculate the data accordingly.

                  8.3.1.2  Check  instrument performance.    If  an  instrument
            performance problem is identified, correct the problem and re-analyze
            the extract.

                  8.3.1.3  If  no problem is found, re-extract  and re-analyze
            the sample.

                  8.3.1.4  If, upon re-analysis, the recovery is again  not within
            limits, flag the data as "estimated concentration".


9.0  METHOD PERFORMANCE

      9.1  This method was tested by  20 laboratories using organic-free reagent
water, drinking water, surface  water,  and three industrial  wastewaters spiked
at six concentrations over the range 2.1 - 500 M9/L.  Single operator precision,
overall precision, and method accuracy were found to be directly  related to the
concentration of the parameter  and essentially independent of the  sample matrix.
Linear equations to describe these relationships are presented in Table 4.


                                   8020B  -7                       Revision 2
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      9.2  The accuracy and precision obtained will  be determined by the sample
matrix, sample introduction technique, and by the calibration procedure used.


10.0 REFERENCES

1.   Bellar, T.A., and J.J.  Lichtenberg,  J.  Amer.  Water Works Assoc., 66(12),
     pp. 739-744, 1974.

2.   Bellar, T.A., and J.J. Lichtenberg, "Semi-Automated Headspace Analysis of
     Drinking  Waters and  Industrial  Waters for  Purgeable  Volatile Organic
     Compounds", in Van Hall (ed.), Measurement of Organic Pollutants in Water
     and Wastewater, ASTM STP 686, pp. 108-129, 1979.

3.   Dowty, B.J., S.R.  Antoine,  and J.L. Laseter, "Quantitative and Qualitative
     Analysis of Purgeable Organics  by High  Resolution  Gas Chromatography and
     Flame  lonization  Detection", in  Van Hall,  ed.,  Measurement  of Organic
     Pollutants in Water and Wastewater.  ASTM STP 686,  pp. 24-35,  1979.

4.   Development and Application of Test Procedures for Specific Organic Toxic
     Substances  in Wastewaters.   Category 11  -  Purgeables and Category  12 -
     Acrolein,  Acrylonitrile,  and Dichlorodifluoromethane.    Report for  EPA
     Contract 68-03-2635 (in preparation).

5.   "EPA Method Validation Study 24, Method  602 (Purgeable Aromatics)", Report
     for EPA Contract 68-03-2856 (in  preparation).

6.   U.S. EPA 40 CFR  Part  136, "Guidelines Establishing Test Procedures for the
     Analysis of Pollutants Under  the  Clean  Water  Act;  Final  Rule  and Interim
     Final Rule and Proposed Rule", October 26, 1984.

7.   Gebhart, J.E., S.V. Lucas,  S.J. Naber,  A.M.  Berry,  T.H.  Danison and H.M.
     Burkholder, "Validation of SW-846 Methods 8010, 8015, and  8020"; Report for
     EPA Contract 68-03-1760, Work Assignment  2-15;   US EPA,  EMSL-Cincinnati,
     1987.
                                   8020B -8
Revision 2
November 1990

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                                  TABLE 1.
            CHROMATOGRAPHIC CONDITIONS  AND METHOD  DETECTION  LIMITS
                        FOR AROMATIC VOLATILE ORGANICS



Compound
Benzene
Chlorobenzene
1,4-Dichlorobenzene
1,3-Dichlorobenzene
1,2-Di chlorobenzene
Ethyl Benzene
Styrene
Toluene
o-Xylene
m-Xylene
p-Xylene
Retention
(min)

Col. 1
2.59
9.38
16.42
17.54
20.60
8.12
11.00
5.14
10.54
9.77
9.18
time


Col. 2
2.75
8.02
16.2
15.0
19.4
6.25
(b)
4.25
(b)
(b)
(b)
Method
detection
limit8
(M9/L)
0.06
0.13
0.11
0.4
0.12
0.01
0.12
0.01
0.03
0.13
0.08
a Using purge-and-trap method (Method 5030).
b Not determined.
                                  TABLE 2.
             DETERMINATION  OF  ESTIMATED  QUANTITATION  LIMITS  (EQLs)
                             FOR VARIOUS MATRICES8
      Matrix                                          Factor"
      Ground water                                      10
      Low-concentration soil                            10
      Water miscible liquid waste                      500
      High-concentration soil and sludge              1250
      Non-water miscible waste                        1250
   a  Sample EQLs  are highly matrix  dependent.   The  EQLs listed  herein  are
      provided for guidance and may not always be achievable.

   b  EQL =  [Method detection  limit  (Table  1)]  X  [Factor  (Table 2)].   For
      non-aqueous samples, the factor is on a wet-weight basis.


                                   8020B -9                       Revision  2
                                                                  November 1990

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                                 TABLE 3.
                          QC ACCEPTANCE CRITERIA8


Parameter
Benzene
Chl orobenzene
1 , 2-Di chl orobenzene
1,3-Dichlorobenzene
1 , 4-Di chl orobenzene
Ethyl benzene
Toluene
Range
for Q
(M9/L)
15.4-24.6
16.1-23.9
13.6-26.4
14.5-25.5
13.9-26.1
12.6-27.4
15.5-24.5
Limit
for s
(M9/L)
4.1
3.5
5.8
5.0
5.5
6.7
4.0
Range
for x
(M9/L)
10.0-27.9
12.7-25.4
10.6-27.6
12.8-25.5
11.6-25.5
10.0-28.2
11.2-27.7
Range
p p
r» rs

39-150
55-135
37-154
50-141
42-143
32-160
46-148
Q -    Concentration measured in QC check sample,  in M9/L.

s =    Standard deviation of four recovery measurements,  in M9/L-

x =    Average recovery for four recovery measurements,  in M9/L.

P, Ps =Percent recovery measured.

D =    Detected; result must be greater than zero.

a  Criteria from 40 CFR Part 136 for Method 602, and were calculated assuming
   as  check sample  concentration of  20  /ig/L.   These  criteria  are  based
   directly upon the method performance data in Table 4.  Where necessary, the
   limits for  recovery have been  broadened to assure applicability  of the
   limits to concentrations below those used to develop Table 1.
                                 8020B -10
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                              TABLE 4.
    METHOD  ACCURACY  AND  PRECISION  AS  FUNCTIONS OF  CONCENTRATION
Parameter
Benzene
Chlorobenzene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Ethyl benzene
Toluene
Accuracy, as
recovery, x'
0.92C+0.57
0.95C+0.02
0.93C+0.52
0.96C-0.04
0.93C-0.09
0.94C+0.31
0.94C+0.65
Single analyst
precision, s/
(M9/L)
0.09X+0.59
0.09X+0.23
0.17X-0.04
0.15X-0.10
O.lBx+0.28
0.17X+0.46
0.09X+0.48
Overall
precision,
S' (M9/L)
0.21X+0.56
0.17X+0.10
0.22X+0.53
0.19X+0.09
0.20X+0.41
0.26x+0.23
0.18x-0.71
x'


s/


S'
Expected  recovery  for one  or more measurements  of a  sample  containing
concentration C, in M9/L.

Expected  single analyst  standard deviation  of  measurements at  an average
concentration of x, in
Expected interlaboratory_ standard deviation of measurements at an average
concentration found of x, in /ig/L.

True value for the concentration, in M9/L-

Average  recovery   found  for  measurements  of   samples   containing  a
concentration of C, in M9/L-
                              8020B  -11
                                                                  Revision 2
                                                                  November 1990

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                          Figure 1
         I
                                        Column: S%SM200/1.7S%B«nloiw34
                                        Profram: 6QOC-2 IMftutM. 6°C/Min. 10 IW°C
                                        Ovtwtor: Phototonintion
                                        Samptt: 0.401«/1 Standard Mi«tur«
                   8       10      12       14

                    RETENTION TIME (MINUTES)
16
18
20      22
An example of  the separation achieved using  Column  1.

                         8020B  -12
        Revision 2
        November 1990

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                         Figure 2
                                                (2«Cy»no«ho«v)
        40»C-2 Minum
        *hetoioniation
••"pit: 2.0 MI/I Standard Mixture
                                                         to 100«C
An example of  the separation achieved using Column 2.

                        8020B -13
                              Revision 2
                              November 1990

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                       METHOD  8020B
AROMATIC  VOLATILE ORGANICS BY  GAS CHROMATOGRAPHY
         Start
      7.1 Introduce
   compound! into  gas
    chromatograph  by
   direct injection or
     purge-and-trap
      (Method 5030)
7 44  Record volume
purged or injected
  and  peak sizes
      7.2 Set gat
     chromatograph
       condition
      7.3 Calibrate
    (rafer to Method
         8000)
     74.1 Introduce
   volatile compound!
        into gas
    chromatograph by
    purge-and•trap or
    direct injection
   74.2  folio* Method
    8000  for analysis
     sequence, etc
  7.45 Calculate
   concentration
 (refer to Method
      8000)
     7.4.6 Ar
    analytical
   interferences
    suspected?
     74.7 Is
   response for
      a  peak
    off-scale?
7.4.6  Analyze using
 second CC column
7.4.7  Dilute second
 aliquot of sample
                      8020B -14
                               Revision 2
                               November 1990

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                                 METHOD 8021A

        HALOGENATED AND AROMATIC VOLATILES BY GAS CHROMATOGRAPHY USING
            ELECTROLYTIC  CONDUCTIVITY  AND  PHOTOIONIZATION  DETECTORS
                        IN SERIES; CAPILLARY TECHNIQUE
1.0   SCOPE AND APPLICATION

      1.1   Method 8021  is  used to determine volatile organic  compounds  in a
variety of solid waste matrices.  This  method  is applicable to nearly all types
of samples,  regardless of water content, including ground water, aqueous sludges,
caustic  liquors,  acid  liquors,  waste  solvents,  oily wastes,  mousses,  tars,
fibrous  wastes,  polymeric  emulsions,   filter  cakes,  spent  carbons,  spent
catalysts, soils, and sediments.  The following compounds can be determined by
this method:
Analyte
CAS No/
  Appropriate Technique
                  Direct
Purge-and-Trap    Injection
Benzene
Bromobenzene
Bromochl oromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chi orodi bromomethane
Chloroethane
Chloroform
Chi oromethane
2-Chlorotoluene
4-Chlorotoluene
1 , 2-Di bromo-3-chl oropropane
1,2-Dibromoethane
Di bromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-1, 2-Di chl oroethene
trans- 1, 2-Di chl oroethene
71-43-2
108-86-1
74-97-5
75-27-4
75-25-2
74-83-9
104-51-8
135-98-8
98-06-6
56-23-5
108-90-7
124-48-1
75-00-3
67-66-3
74-87-3
95-49-8
106-43-4
96-12-8
106-93-4
74-95-3
95-50-1
541-73-1
106-46-7
75-71-8
75-34-3
107-06-2
75-35-4
156-59-4
156-60-5
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
PP
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
                                   8021A  -  1
                              Revision 1
                              November 1990

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Analyte
CAS No.Ł
  Appropriate Technique
                  Direct
Purge-and-Trap    Injection
1,2-Dichloropropane
1 , 3 -Di chl oropropane
2 , 2 -Di chl oropropane
1,1-Dichloropropene
cis-l,3-dichloropropene
trans- 1,3-di chl oropropene
Ethyl benzene
Hexachl orobutad i ene
I sopropyl benzene
p-Isopropyl toluene
Methyl ene chloride
Naphthalene
n-Propyl benzene
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1,2, 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1 , 2 , 3-Tr i chl orobenzene
1,2,4-Trichlorobenzene
1,1,1-Trichloroethane
1,1,2-Tri chl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
1 , 2 , 3-Tri chl oropropane
1,2, 4-Trimethyl benzene
1 ,3 , 5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
78-87-5
142-28-9
590-20-7
563-58-6
10061-01-5
10061-02-6
100-41-4
87-68-3
98-82-8
99-87-6
75-09-2
91-20-3
103-65-1
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
87-61-6
120-82-1
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
95-63-6
108-67-8
75-01-4
95-47-6
108-38-3
106-42-3
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
b
a Chemical Abstract Services Registry Number.
b Adequate response by thi
pp Poor purging efficiency
i Inappropriate technique
s technique.
resulting in high EQLs.
for this analyte.






pc Poor chromatographic behavior.
      1.2   Method detection limits (MDLs) are compound dependent and  vary with
purging  efficiency and  concentration.    The MDLs  for selected  analytes  are
presented  in  Table 1.   The  applicable  concentration  range  of  this method is
compound  and  instrument dependent  but  is   approximately  0.1  to 200  /xg/L-
Analytes that  are inefficiently purged  from water will not  be detected when
present at low concentrations,  but they can be measured with acceptable accuracy
                                   8021A - 2
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and  precision  when  present  in  sufficient  amounts.    Determination of  some
structural isomers (i.e. xylenes) may be hampered by coelution.

      1.3   The  estimated  quantitation  limit  (EQL)  of  Method  8021  for  an
individual compound  is approximately 1  /xg/Kg (wet weight)  for soil/sediment
samples, 0.1 mg/Kg  (wet weight)  for wastes, and 1 p.g/1  for ground water (see
Table 3).  EQLs will be proportionately higher for sample extracts and samples
that require  dilution or reduced sample size to avoid saturation of the detector.

      1.4   This method is recommended for use only by analysts experienced in
the measurement of purgeable  organics at the low /xg/L level or by experienced
technicians under the close supervision of a qualified analyst.

      1.5   The toxicity  or carcinogenicity of  chemicals used  in  this  method
has not been  precisely defined.   Each chemical  should  be treated  as a potential
health  hazard,  and exposure  to these  chemicals should  be minimized.    Each
laboratory is responsible for maintaining awareness of OSHA regulations regarding
safe  handling  of chemicals  used  in  this  method.   Additional  references  to
laboratory safety are available for the information of the analyst (references
4 and 6).

      1.6   The following method analytes  have been  tentatively classified as
known or suspected human or mammalian carcinogens: benzene,  carbon tetrachloride,
1,4-dichlorobenzene,    1,2-dichloroethane,    hexachloro-butadiene,   1,1,2,2-
tetrachloroethane,   1,1,2-trichloroethane,   chloroform,   1,2-dibromoethane,
tetrachloroethene, trichloroethene, and vinyl chloride.  Pure standard materials
and  stock  standard  solutions  of these compounds should be  handled in  a hood.
A NIOSH/MESA approved  toxic  gas  respirator should be  worn when  the  analyst
handles high concentrations of these toxic compounds.


2.0   SUMMARY OF METHOD

      2.1   Method 8021 provides gas chromatographic conditions for the detection
of halogenated and aromatic  volatile organic compounds.  Samples can be analyzed
using direct injection  or purge-and-trap (Method 5030).   Ground water samples
must be  analyzed  using  Method 5030 (where  applicable).   A temperature program
is used in the gas chromatograph to separate the organic compounds.  Detection
is achieved by an electrolytic conductivity  detector (HECD) and  a photoionization
detector (PID) in series.

      2.2   Tentative identifications are obtained by  analyzing standards under
the same conditions  used for samples and comparing resultant  GC retention times.
Confirmatory information can  be gained by comparing the relative response from
the two detectors.  Concentrations  of the identified components are measured by
relating the response produced for that compound to the response produced by a
compound that is used as an internal standard.


3.0   INTERFERENCES

      3.1   Refer to Methods  5030  and 8000.
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      3.2   Samples  can be  contaminated  by  diffusion  of  volatile  organics
(particularly chlorofluorocarbons  and methylene chloride)  through  the sample
container  septum during shipment  and storage.   A  trip blank  prepared  from
organic-free reagent water and carried through sampling and subsequent storage
and handling can serve as a check on such contamination.


4.0  APPARATUS AND MATERIALS

      4.1   Sample  introduction apparatus  -  Refer to  Method  5030   for  the
appropriate equipment for sample introduction purposes.

      4.2   Gas  Chromatograph  - capable of temperature  programming;  equipped
with variable-constant differential flow controllers, subambient oven controller,
photoionization and electrolytic conductivity detectors connected with a short
piece of uncoated capillary tubing, 0.32-0.5 mm ID, and data system.

            4.2.1  Column - 60 m x 0.75 mm ID VOCOL wide-bore capillary column
      wi-th 1.5 fj.m film  thickness (Supelco  Inc., or equivalent).

            4.2.2  Photoionization  detector   (PID)   (Tracer  Model   703,   or
      equivalent).

            4.2.3  Electrolytic conductivity detector (HECD)  (Tracer Hall Model
      700-A, or equivalent).

      4.3   Syringes - 5 ml glass hypodermic with Luer-Lok tips.

      4.4   Syringe valves - 2-way with Luer ends (Teflon or Kel-F).

      4.5   Microsyringe - 25 /xL with  a 2  in. x 0.006  in.  ID,  22° bevel needle
(Hamilton #702N or equivalent).

      4.6   Microsyringes - 10, 100 juL.

      4.7   Syringes - 0.5, 1.0, and 5 ml, gas tight with shut-off valve.

      4.8   Bottles - 15 ml, Teflon lined with screw-cap or crimp top.

      4.9   Analytical balance  - 0.0001 g.

      4.10  Refrigerator.

      4.11  Volumetric flasks, Class A - 10 to 1000 ml.


5.0   REAGENTS

      5.1   Reagent grade inorganic chemicals shall be used in all tests.  Unless
otherwise  indicated, it  is  intended  that  all  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
                                   8021A - 4                      Revision 1
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used, provided it is first ascertained  that  the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.

      5.2   Organic-free reagent water.  All  references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3   Methanol, CH3OH - Pesticide quality or equivalent, demonstrated to
be free of analytes.  Store away from other solvents.

      5.4   Vinyl chloride, (99.9% pure), CH2=CHC1.  Vinyl chloride is available
from  Ideal  Gas  Products,  Inc.,   Edison,  New Jersey  and  from Matheson,  East
Rutherford, New Jersey, as well  as from other sources.   Certified mixtures of
vinyl chloride in nitrogen at 1.0 and 10.0 ppm (v/v) are available from several
sources.

      5.5   Stock standards - Stock solutions may either be prepared from pure
standard materials or purchased as  certified solutions. Prepare stock standards
in methanol  using assayed liquids or  gases,  as  appropriate.  Because  of the
toxicity of some of the organohalides, primary dilutions of these materials of
the toxicity should be prepared in a hood.

NOTE: If direct  injection  is  used, the solvent  system of  standards must match
      that of  the  sample.   It is  not  necessary to  prepare  high  concentration
      aqueous mixed standards when using direct injection.

            5.5.1  Place about 9.8 ml of methanol  in a 10 ml tared ground glass
      stoppered volumetric flask.  Allow the flask  to stand, unstoppered, for
      about 10 minutes until  all  alcohol-wetted surfaces have dried.  Weigh the
      flask to the nearest 0.1 mg.

            5.5.2  Add the assayed reference material, as described below.

                  5.5.2.1  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.

                  5.5.2.2  Gases:  To prepare standards for any compounds that
            boil  below 30°C  (e.g. bromomethane,  chloroethane,  chloromethane,
            dichlorodifluoromethane,  trichlorofluoromethane,  vinyl  chloride),
            fill a 5 ml valved gas-tight syringe with  the reference standard to
            the  5.0 ml mark.   Lower  the  needle  to  5  mm above  the methanol
            meniscus.  Slowly introduce the reference standard above the surface
            of the  liquid.   The heavy gas  rapidly  dissolves  in  the methanol.
            This may also  be accomplished by using a lecture bottle equipped with
            a Hamilton Lecture Bottle Septum (#86600). Attach Teflon tubing to
            the side-arm relief valve and direct a gentle stream of gas into the
            methanol meniscus.

            5.5.3  Reweigh, dilute to volume,  stopper, and then mix by inverting
      the flask  several times.   Calculate  the concentration  in milligrams per
      liter (mg/L) from the net gain  in weight. When compound  purity is assayed
      to  be  96%  or greater,  the weight  may be used  without correction to


                                   8021A -  5                      Revision 1
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      calculate the concentration of the stock standard.  Commercially prepared
      stock standards may be used at any concentration  if they are certified by
      the manufacturer or by an independent source.
            5.5.4  Transfer the  stock standard solution into a  bottle  with a
      Teflon lined screw-cap or  crimp top.   Store, with minimal  headspace, at
      -10°C to -20°C  and  protect  from light.

            5.5.5  Prepare  fresh  stock standards every  two  months  for gases.
      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.   Both gas and liquid standards must be monitored closely
      by comparison  to  the  initial  calibration curve  and by  comparison to QC
      reference samples.   It may be necessary to  replace the  standards more
      frequently if either check exceeds a 25% difference.

      5.6   Prepare secondary dilution standards, using stock standard solutions,
in methanol, as needed,  that contain the compounds of  interest,  either singly
or mixed  together.    The secondary   dilution  standards should be  prepared at
concentrations such that the aqueous calibration standards prepared in Section
5.7 will  bracket the  working range of the analytical  system.  Secondary dilution
standards should be  stored  with  minimal  headspace  for  volatiles  and  should be
checked frequently for signs of degradation or evaporation, especially just prior
to preparing calibration standards from them.

      5.7   Calibration  standards,  at a minimum of  five concentration  levels
are prepared in organic-free reagent water  from  the secondary  dilution  of the
stock standards.  One of the concentration levels should be at a concentration
near, but above, the  method detection limit.   The remaining concentration levels
should correspond to the expected  range  of the concentrations  found  in real
samples or should define the working range of the GC.  Standards (one or more)
should contain each  analyte for  detection by  this  method (e.g.  some  or all of
the target  analytes  may be included).   In  order to prepare  accurate aqueous
standard solutions,  the following precautions must be observed.

NOTE: Prepare calibration solutions  for  use with direct injection  analyses in
      water at the concentrations required.

            5.7.1  Do not inject  more than  20 jiL  of alcoholic  standards into
      100 ml of water.

            5.7.2  Use  a  25  p.1 Hamilton  702N  microsyringe  or  equivalent
      (variations in  needle geometry will  adversely affect the  ability to deliver
      reproducible volumes of methanolic standards into water).

            5.7.3  Rapidly  inject  the  alcoholic   standard  into  the  filled
      volumetric flask.   Remove the  needle as  fast as possible after injection.

            5.7.4  Mix aqueous standards by inverting the flask three times.

            5.7.5  Fill  the sample syringe from the  standard solution contained
      in the expanded area  of the flask  (do  not  use any solution contained in
      the neck of the flask).
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            5.7.6  Never use  pi pets  to dilute or transfer  samples or aqueous
      standards.

            5.7.7  Aqueous  standards  are not  stable  and should  be discarded
      after one hour, unless properly sealed and  stored.  The aqueous standards
      can be stored up to 12 hours, if held in sealed vials with zero headspace.

      5.8   Internal   standards   -   Prepare  a  spiking  solution  containing
fluorobenzene  and  2-bromo-l-chloropropane  in  methanol, using  the procedures
described in Sections 5.5 and 5.6.  It  is recommended that the secondary dilution
standard be  prepared at a  concentration  of 5 mg/L of  each internal  standard
compound.   The addition of 10  p.1 of  such  a standard to 5.0 ml  of sample or
calibration standard would be equivalent to  10 /xg/L.

      5.9   Surrogate standards  - The analyst should monitor both the performance
of the analytical system and the effectiveness of  the method in dealing with each
sample matrix  by spiking each sample,  standard,  and reagent blank with two or
more  surrogate compounds.    A  combination   of bromochloromethane, 2-bromo-l-
chloropropane,  1,4-dichlorobutane and bromochlorobenzene  is  recommended  to
encompass the range of the  temperature program used  in this  method.  From stock
standard solutions prepared as  in  Section 5.5, add  a  volume to  give 750 /ug of
each  surrogate to  45 ml of organic-free reagent water contained in  a  50 mL
volumetric flask,  mix,  and dilute to volume for a  concentration  of 15 ng//iL.
Add 10 juL of this surrogate spiking solution directly into the 5 ml  syringe with
every  sample  and  reference  standard  analyzed.    If  the  internal  standard
calibration procedure is used, the surrogate compounds may be added directly to
the internal standard spiking solution (Section 5.8).


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   See the  introductory material  to  this  chapter, Organic Analytes,
Section 4.1.
7.0   PROCEDURE

      7.1   Volatile compounds are introduced into  the gas chromatograph either
by direct injection or  purge-and-trap  (Method  5030).   Method 5030 may be used
directly on ground  water samples or low-concentration  contaminated soils and
sediments.  For medium-concentration soils  or sediments, methanolic extraction,
as described in Method 5030,  may be  necessary prior to purge-and-trap analysis.

      7.2   Gas chromatography conditions  (Recommended)

            7.2.1  Oven settings:

      Carrier gas (Helium) Flow rate:     6mL/min.
      Temperature program
            Initial  temperature:           10°C, hold  for 8 minutes at
            Program:                       10°C  to 180°C  at 4°C/nrin
            Final temperature:             180°C,   hold   until   all   expected
                                          compounds have eluted.


                                  8021A -  7                       Revision 1
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            7.2.2  The carrier gas flow  is  augmented  with  an additional  24 mL
      of helium flow before entering the photoionization detector.  This make-
      up gas is necessary to ensure optimal  response from both detectors.

            7.2.3  These halogen-specific systems eliminate misidentifications
      due to non-organohalides which are coextracted during the purge step.  A
      Tracer Hall Model 700-A detector was used to gather the single laboratory
      accuracy and precision data presented in Table 2.  The operating conditions
      used to collect these data are:
            Reactor tube:                       Nickel, 1/16 in OD
            Reactor temperature:                810°C
            Reactor base temperature:           250°C
            Electrolyte:                        100% n-Propyl alcohol
            Electrolyte flow rate:              0.8 mL/min
            Reaction gas:                       Hydrogen at 40 mL/min
            Carrier gas plus make-up gas:       Helium at 30 mL/min

            7.2.4  A sample chromatogram obtained with  this column is presented
      in Figure  5.   This  column was used  to develop the  method  performance
      statements in Section 9.0.   Estimated  retention  times  and MDLs that can
      be achieved under these conditions  are  given  in  Table  1.   Other columns
      or element specific detectors may be used if the requirements of Section
      8.0 are met.

      7.3   Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1 and  especially Table 2 for  guidance on  selecting the lowest point
on the calibration curve.

            7.3.1  Calibration must take place using the same sample introduction
      method that will  be used to analyze actual samples (see Section 7.4.1).

            7.3.2  The procedure for internal or external calibration  may be
      used.   Refer to Method 8000 for a description of each of these procedures.

      7.4   Gas chromatographic  analysis

            7.4.1  Introduce volatile compounds  into the gas chromatograph using
      either Method 5030 (purge-and-trap method) or the direct injection method
      (see Section 7.4.1.1).   If the internal  standard calibration technique is
      used,  add 10 /iL of internal  standard to the sample prior  to purging.

                  7.4.1.1  Direct injection -  In very limited  applications (e.g.
            aqueous process wastes) direct injection of the sample into the GC
            system with a 10 /iL  syringe may be appropriate.  The  detection limit
            is very  high  (approximately  10,000 M9/L), therefore,  it  is  only
            permitted where concentrations in excess of 10,000 /ug/L are expected
            or for water-soluble compounds that do not purge.  The system must
            be calibrated  by direct  injection (bypassing  the  purge-and-trap
            device).

            7.4.2  Follow Section  7.6 in Method 8000  for  instructions  on the
      analysis sequence,  appropriate dilutions, establishing  daily retention


                                   8021A - 8                      Revision 1
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      time windows, and identification criteria.   Include  a mid-concentration
      standard after each group of 10 samples in the analysis sequence.

            7.4.3  Table 1 summarizes the estimated retention times on the two
      detectors for a number of organic compounds analyzable using this method.

            7.4.4  Record the sample volume purged or injected and the resulting
      peak sizes (in area units or peak heights).

            7.4.5  Calculation of concentration is covered in Method 8000.

            7.4.6  If analytical  interferences are suspected, or for the purpose
      of confirmation, analysis using a second GC column is recommended.

            7.4.7  If the response for a peak is off-scale, prepare a dilution
      of  the  sample with organic-free  reagent water.   The dilution must  be
      performed on a second  aliquot of the sample which has  been properly sealed
      and stored prior to use.


8.0   QUALITY CONTROL

      8.1   Refer to Chapter  One  for  specific  quality control  procedures, and
to Method 8000 for  gas  chromatographic procedures.   Quality control  to ensure
the proper operation of the purge-and-trap device is covered in Method 5030.

      8.2   Mandatory quality control  to validate the GC  system  operation  is
found in Method 8000.

      8.3   Calculate surrogate standard recovery  on  all  samples,  blanks, and
spikes.  Determine if recovery is within limits (limits established by performing
QC procedure outlined in Method 8000).

            8.3.1  If recovery is  not within limits, the following are required.

                  8.3.1.1  Check  to  be  sure that  there  are no errors  in the
            calculations, surrogate solutions or internal standards.   If errors
            are found, recalculate the data accordingly.

                  8.3.1.2  Check  instrument performance.    If an  instrument
            performance problem is identified, correct  the problem and re-analyze
            the extract.

                  8.3.1.3   If no  problem  is found, re-extract and re-analyze the
            sample.

                  8.3.1.4   If, upon re-analysis, the recovery is again not within
            limits, flag the data as "estimated concentration".
                                   8021A -  9                      Revision 1
                                                                  November  1990

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9.0   METHOD PERFORMANCE

      9.1    Method detection  limits  for these analytes  have been calculated
from data collected by spiking  organic-free  reagent  water at 0.1 p.g/1.  These
data are presented in Table 1.

      9.2   This method  was  tested in a  single laboratory using organic-free
reagent water spiked at 10 jug/L.  Single  laboratory precision  and accuracy data
for each detector are presented for the method analytes in Table 2.


10.0  REFERENCES

1.   Volatile Organic Compounds in Water  by Purqe-and-Trap Capillary Column Gas
     Chromatoqraphv with  Photoionization and Electrolytic Conductivity Detectors
     in Series. Method 502.2; U.S.  Environmental Protection  Agency. Environmental
     Monitoring and Support Laboratory: Cincinnati, OH, September, 1986.

2.   The Determination of Haloqenated Chemicals in Water bv the Purge and Trap
     Method.  Method  502.1;   Environmental   Protection  Agency,  Environmental
     Monitoring and Support Laboratory: Cincinnati, Ohio 45268, September, 1986.

3.   Volatile Aromatic and Unsaturated Organic Compounds in Water by Purge and
     Trap Gas  Chromatoqraphv.  Method 503.1;  Environmental  Protection Agency,
     Environmental  Monitoring  and   Support  Laboratory:  Cincinnati,  Ohio,
     September, 1986.

4.   Glaser, J.A.; Forest, D.L.;  McKee,  G.D.;  Quave, S.A.; Budde, W.L. "Trace
     Analyses for Wastewaters"; Environ.  Sci. Technol.  1981,  15, 1426.

5.   Bellar, T.A.;  Lichtenberg,  J.J.  The Determination  of  Synthetic Organic
     Compounds in Water  by Purge  and  Sequential Trapping  Capillary Column Gas
     Chromatographv;  U.S.   Environmental   Protection   Agency,  Environmental
     Monitoring and Support Laboratory: Cincinnati, Ohio,  45268.
                                  8021A - 10                      Revision 1
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                               TABLE 1.

CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS  (MDL) FOR
  VOLATILE ORGANIC COMPOUNDS ON PHOTOIONIZATION DETECTION  (PID) AND
       HALL  ELECTROLYTIC CONDUCTIVITY  DETECTOR (HECD)  DETECTORS
Analyte
Di chl orodi f 1 uoromethane
Chloromethane
Vinyl Chloride
Bromomethane
Chloroethane
Tri chl orof 1 uoromethane
1,1-Dichloroethene
Methyl ene Chloride
trans- 1,2-Di chl oroethene
1,1-Dichloroethane
2 , 2-Di chl oropropane
cis- 1,2-Di chloroethane
Chloroform
Bromochl oromethane
1,1,1 -Tri chl oroethane
1,1-Dichloropropene
Carbon Tetrachloride
Benzene
1,2-Dichloroethane
Tri chl oroethene
1 , 2-Di chl oropropane
Bromodichl oromethane
Dibromomethane
Toluene
1 , 1 , 2-Tri chl oroethane
Tetrachl oroethene
1,3-Dichloropropane
Di bromochl oromethane
1,2-Dibromoethane
Chlorobenzene
Ethyl benzene
1,1,1 , 2-Tetrachl oroethane
m-Xylene
p-Xylene
o-Xylene
Styrene
Isopropyl benzene
Bromoform
1,1,2 , 2-Tetrachl oroethane
1, 2, 3-Tri chl oropropane
PID
Ret. Time8
minute
_b
-
9.88
-
_
-
16.14
-
19.30
-
-
23.11
-
-
-
25.21
-
26.10
-
27.99
-
-
-
31.95
-
33.88
-
-
-
36.56
36.72
-
36.98
36.98
38.39
38.57
39.58
-
-
-
HECD
Ret. Time
minute
8.47
9.47
9.93
11.95
12.37
13.49
16.18
18.39
19.33
20.99
22.88
23.14
23.64
24.16
24.77
25.24
25.47
-
26.27
28.02
28.66
29.43
29.59
-
33.21
33.90
34.00
34.73
35.34
36.59
-
36.80
-
-
-
-
-
39.75
40.35
40.81
PID
MDL
M9/L


0.02



NDC

0.05


0.02



0.02

0.009

0.02



0.01

0.05



0.003
0.005

0.01
0.01
0.02
0.01
0.05



HECD
MDL
M9/L
0.05
0.03
0.04
1.1
0.1
0.03
0.07
0.02
0.06
0.07
0.05
0.01
0.02
0.01
0.03
0.02
0.01

0.03
0.01
0.006
0.02
2.2

ND
0.04
0.03
0.03
0.8
0.01

0.005





1.6
0.01
0.4
                              8021A -  11
Revision 1
November 1990

-------
                                   TABLE 1.
                                  (Continued)
Analyte
   PID
Ret. Time8
  minute
  HECD
Ret. Time
 minute
PID
MDL
M9/L
                                                                        HECD
                                                                         MDL
n-Propylbenzene                   40.87
Bromobenzene                      40.99
1,3,5-Trimethylbenzene            41.41
2-Chlorotoluene                   41.41
4-Chlorotoluene                   41.60
tert-Butylbenzene                 42.92
1,2,4-Trimethylbenzene            42.71
sec-Butyl benzene                  43.31
p-Isopropyltoluene                43.81
1,3-Dichlorobenzene               44.08
1,4-Dichlorobenzene               44.43
n-Butylbenzene                    45.20
1,2-Dichlorobenzene               45.71
1,2-Di bromo-3-Chloropropane
1,2,4-Trichlorobenzene            51.43
Hexachlorobutadiene               51.92
Naphthalene                       52.38
1,2,3-Trichlorobenzene            53.34

Internal Standards
  Fluorobenzene                   26.84
  2-Bromo-1-chloropropane
                 41.03

                 41.45
                 41.63
                 44.11
                 44.47

                 45.74
                 48.57
                 51.46
                 51.96

                 53.37
                33.08
             0.004
             0.006
             0.004
             ND
             0.02
             0.06
             0.05
             0.02
             0.01
             0.02
             0.007
             0.02
             0.05

             0.02
             0.06
             0.06
             ND
          0.03

          0.01
          0.01
          0.02
          0.01
          0,
          3.
          0.
02
0
03
          0.02

          0.03
    Retention  times determined  on  60 m x  0.75 mm ID  VOCOL  capillary column.
    Program: Hold at 10°C for 8 minutes, then program  at 4°C/min to 180°C, and
    hold  until  all  expected  compounds have  eluted.

    Dash  (-) indicates  detector does  not respond.

    ND  =  Not determined.
                                  8021A - 12
                                Revision 1
                                November 1990

-------
                   TABLE 2.
SINGLE LABORATORY ACCURACY AND PRECISION DATA
   FOR VOLATILE ORGANIC COMPOUNDS  IN WATER"
Photoionization
Detector
Analyte
Benzene
Bromobenzene
Bromochloromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
1 , 2-Di bromo-3-chl oropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-1,2 Dichloroethene
trans - 1 , 2 -Di chl oroethene
1 , 2-Di chl oropropane
1,3-Di chl oropropane
2 , 2-Di chl oropropane
1,1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene .
I sopropyl benzene
p-Isopropyl toluene
Recovery,8
%
99
99
-
-
-
-
100
97
98
-
100
-
-
-
NDC
101
-
-
-
-
102
104
103
-
-
-
100
ND
93
-
-
-
103
101
99
98
98
Standard
Deviation
of Recovery
1.2
1.7
-
-
-
-
4.4
2.6
2.3
-
1.0
-
-
-
ND
1.0
-
-
-
-
2.1
1.7
2.2
-
-
-
2.4
ND
3.7
-
-
-
3.6
1.4
9.5
0.9
2.4
Hall Electrolytic
Conductivity Detector
Standard
Recovery,8 Deviation
% of Recovery
_b
97
96
97
106
97
-
-
-
92
103
96
98
96
97
97
86
102
97
109
100
106
98
89
100
100
103
105
99
103
100
105
103
-
98
-
-
.
2.7
3.0
2.9
5.5
3.7
-
-
-
3.3
3.7
3.8
2.5
8.9
2.6
3.1
9.9
3.3
2.7
7.4
1.5
4.3
2.3
5.9
5.7
3.8
2.9
3.5
3.7
3.8
3.4
3.6
3.4
-
8.3
-
-
                  8021A - 13
Revision 1
November 1990

-------
                                         TABLE 2.
                                        (Continued)
Analyte
                                  Photoionization
                                      Detector
                                  Recovery,
                                             Standard
                                             Deviation
                                             of  Recovery
Hall Electrolytic
Conductivity Detector
               Standard
Recovery,8     Deviation
 %             of  Recovery
Methyl ene chloride
Naphthalene
n-Propyl benzene
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1,2, 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1 -Tri chl oroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chl orof 1 uoromethane
1 , 2 , 3-Tri chl oropropane
1 , 2 , 4-Trimethyl benzene
1,3, 5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
-
102
103
104
-
-
101
99
106
104
-
-
100
-
-
99
101
109
99
100
99
.
6.3
2.0
1.4
-
-
1.8
0.8
1.9
2.2
-
-
0.78
-
-
1.2
1.4
5.4
0.8
1.4
0.9
97
-
-
-
99
99
97
-
98
102
104
109
96
96
99
-
-
95
-
-
~
2.8
-
-
-
2.3
6.8
2.4
-
3.1
2.1
3.4
6.2
3.5
3.4
2.3
-
-
5.6

-
~
    Recoveries and  standard  deviations were determined  from seven  samples  and spiked at
    10 /ig/L of each  analyte. Recoveries were determined by internal standard method.  Internal
    standards were:  Fluorobenzene for PID, 2-Bromo-l-chloropropane for HECD.

    Detector does not respond.

    ND = Not determined.
This method  was  tested  in  a  single  laboratory  using  water spiked  at  10
reference 8).
                                                                                       (see
                                        8021A  -  14
                                                                     Revision 1
                                                                     November 1990

-------
                      TABLE 3.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQL)
                FOR VARIOUS MATRICES8
  Matrix                              Factor"
  Ground water                             10
  Low-concentration soil                   10
  Water miscible liquid waste             500
  High-concentration soil and sludge     1250
  Non-water miscible waste               1250
  Sample EQLs are highly matrix dependent.  The EQLs listed herein
  are provided for guidance and may not always be achievable.

  EQL =  [Method  detection  limit (Table 1)]  X [Factor (Table 2)].
  For non-aqueous samples, the  factor  is on a wet-weight basis.
                     8021A - 15                      Revision 1
                                                     November 1990

-------
   FIGURE  1.
PURGING DEVICE
    3MWUMJT


    HVAT STftNGC VM.VI

    t? CM * GAUQC STWNGC NCIOU


    • MM 00 MU

    MUT (MM OO
                          00
 8021A - 16
Revision 1
November 1990

-------
                          FIGURE 2.
TRAP PACKINGS  AND CONSTRUCTION TO  INCLUDE  DESORB CAPABILITY
           PACKING OTTAJL
CONSTRUCTION OCT/ML
                         8021A -  17
                     Revision 1
                     November 1990

-------
                             FIGURE 3.
                 PURGE-AND-TRAP SYSTEM -  PURGE MODE
CAAMCftOAS
FLOW CONTROL
uouo
    r-COLUMN OVCN
IVQULATO*
                                                            COLUMN
                              OPTIONAL 4*OKT COLUMN
                              8CLECDON VALVf
                                       TfU^MLffT
AMOK GAS
FLOWCONTKX
1»MOLŁCULAM
8ICVC FH.TW
                                                ANALYTICAL COLUMN
ocvcc
                                              NOTt
                                              AU UNfS •CTWCCN
                                              AND OC SHOULD M HCA7IO
                                              towc
                            8021A - 18
                           Revision 1
                           November 1990

-------
                           FIGURE 4.
        SCHEMATIC OF  PURGE-AND-TRAP DEVICE - DESORB MODE
                                       COLUMN OVfN

                                                CONFWMATOOT COLUMN


                                               TOOCTfCTOA
PLOW CONTROL
iVMOLfCULAA
MVf RLTIft
                          8021A  -  19
Revision 1
November 1990

-------
                            FIGURE  5.
             GAS CHROMATOGRAM OF VOLATILE ORGANICS

-------
                           METHOD 8021A
VOLATILE ORGANIC COMPOUNDS IN WATER BY PURGE AND TRAP CAPILLARY
 COLUMN GAS CHRQMATOGRAPHY WITH PHOTO I ON I.Z AT I ON  AND ELECTROLYTIC
                 CONDUCTIVITY DETECTORS IN SERIES
          Start
          72 Set
      chromatographic
        condilions.
       7.3  Refer  to
       Method 8000
            for
       calibration
       techniques.
      7  4.1  Introduce
      sample into CC
      using direct
      injection or
      purge-and-trap.
       7.4.4  Record
       sample volume
        introduced
        into  CC  and
        peak  sizes.
 7.4.5 Refer
  to Method
  8000 for
calculations.
  7.4.6 Are
 analytical
interferences
 suspected?
7.4.7 Is peak
response off
   scale?
 Reanalyze
sample uing
 second CC
  column.
Dilute and
 reanalyze
  second
aliquot of
  sample.
                             8021A - 21
                                Revision  1
                                November 1990

-------
                                 METHOD 8031

                      ACRYLONITRILE  BY  GAS CHROMATOGRAPHY
1.0  SCOPE AND APPLICATION

      1.1  Method 8031 is used to determine the concentration of acrylonitrile
in water.  This method may also  be applicable to other matrices.  The following
compounds can be determined by this method:
     Compound Name                        CAS No.'
     Acrylonitrile                        107-13-1
     a  Chemical  Abstract Services  Registry  Number.


      1.2  The estimated quantitation limit of Method 8031 for determining the
concentration of acrylonitrile in water is approximately 10
      1.3  This method  is restricted  to  use by  or  under the  supervision  of
analysts  experienced in  the use  of  gas  chromatographs and  skilled  in  the
interpretation of gas chromatograms.   Each  analyst must demonstrate the ability
to generate acceptable results with this method.


2.0  SUMMARY OF METHOD

      2.1  A measured sample  volume  is micro-extracted  with  methyl  tert-butyl
ether.   The extract  is  separated  by  gas  chromatography and measured  with  a
Nitrogen/Phosphorus detector.


3.0  INTERFERENCES

      3.1  Method  interferences  may  be caused  by  contaminants  in  solvents,
reagents, glassware, and  other sample processing hardware that leads to discrete
artifacts and/or elevated baselines in gas chromatograms.  All  of these materials
must be routinely demonstrated to be free from interferences under the conditions
of the analysis by running laboratory reagent blanks.

      3.2  Samples can be contaminated by diffusion of volatile organics around
the septum  seal  into the sample during handling and storage.   A field blank
should  be prepared  from  organic-free reagent  water  and carried through  the
sampling and sample handling  protocol to serve as a check  on such contamination.
                                   8031 - 1                       Revision 0
                                                                  November 1990

-------
      3.3  Contamination by carryover can occur whenever high-concentration and
low-concentration samples are  sequentially  analyzed.  To  reduce carryover, the
sample syringe  must  be rinsed out  between  samples with  solvent.  Whenever an
unusually concentrated  sample is  encountered,  it should  be  followed  by the
analysis of solvent to check for cross contamination.


4.0  APPARATUS AND MATERIALS

      4.1  Gas chromatograph system

            4.1.1  Gas  chromatograph,  analytical  system complete  with  gas
      chromatograph  suitable  for   on-column   injections   and  all   required
      accessories, including detector, analytical columns, recorder, gases, and
      syringes.  A data system for measuring peak heights and/or peak areas is
      recommended.

            4.1.2  Column:   Porapak Q - 6  ft.,  80/10 Mesh, glass  column,  or
      equivalent.

            4.1.3  Nitrogen/Phosphorus detector.

      4.2  Materials

            4.2.1  Grab sample bottles - 40 ml VOA bottles.

            4.2.2  Mixing bottles - 90 ml bottle with a Teflon lined cap.

            4.2.3  Syringes - 10 /uL  and 50 /uL.

            4.2.4  Volumetric flask  (Class A) - 100 ml.

            4.2.5  Graduated cylinder - 50 ml.

            4.2.6  Pipet (Class A) - 5, 15,  and 50 ml.

            4.2.7  Vials - 10 ml.

      4.3  Preparation

            4.3.1  Prepare all materials to  be  used  as described in Chapter 4
      for volatile organics.


5.0  REAGENTS

      5.1  Reagent grade chemicals shall  be  used  in all tests. Unless otherwise
indicated, it is intended that all  reagents  shall conform to the specifications
of the Committee on Analytical  Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first
ascertained that the reagent  is  of sufficiently  high purity to permit its use
without lessening the accuracy of the determination.
                                   8031 - 2                       Revision 0
                                                                  November 1990

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      5.2  General

            5.2.1  Methanol, CH3OH -  Pesticide quality,  or equivalent.

            5.2.2  Organic-free reagent water.  All  references to water in this
      method refer to organic-free reagent water, as defined in Chapter One.

            5.2.3  Methyl tert-butyl ether,  CH3Ot-C4H9  -  Pesticide  quality,  or
      equivalent.

            5.2.4  Acrylonitrile, H2C:CHCN,  98%.

      5.3  Stock standard solution

            5.3.1  Stock standard solutions  - Can be prepared from pure standard
      materials  or can  be  purchased  as certified  solutions.    Commercially
      prepared stock  standards  can be  used  if they are  verified  against EPA
      standards.    If EPA standards  are not available  for verification,  then
      standards certified by the  manufacturer and  verified against a standard
      made from pure material is acceptable.

            5.3.2  The stock standard solution may be prepared by volume or by
      weight.  Stock  solutions  must  be replaced after  one year,  or sooner if
      comparison with the check standards indicates a problem.

CAUTION;   Acrylonitrile is toxic. Standard preparation  should be performed in
           a laboratory fume hood.

                  5.3.2.1   To  prepare  the stock standard  solution  by volume:
            inject 10 n\. of acrylonitrile (98%) into a 100 ml volumetric flask
            with a syringe.   Make up to volume with methanol.

                  5.3.2.2   To  prepare  the stock standard  solution  by weight:
            Place  about  9.8 ml  of organic-free  reagent  water  into a  10  ml
            volumetric flask before weighing  the  flask and stopper. Weigh the
            flask and record the weight to the nearest  0.0001 g.  Add two drops
            of pure acrylonitrile, using  a  50 pi syringe,  to the  flask.   The
            liquid must  fall directly  into  the water,  without  contacting the
            inside wall  of the  flask.   Stopper  the  flask  and  then reweigh.
            Dilute to  volume with organic-free reagent  water.   Calculate the
            concentration from the net gain in weight.

      5.4  Working standard solutions

            5.4.1  Prepare a minimum of 5  working standard  solutions that cover
      the range  of analyte concentrations  expected in the  samples.   Working
      standards of 20,  40, 60, 80, and 100 M9/L may be prepared by injecting 10,
      20, 30, 40, and 50 /xL of the stock standard solution prepared in Section
      5.3.2.1 into 5 separate 90 ml mixing bottles containing 40 ml of organic-
      free reagent water.
                                   8031 - 3                       Revision 0
                                                                  November 1990

-------
            5.4.2  Inject  15  ml of methyl  tert-butyl  ether  into  each mixing
      bottle, shake vigorously,  and let  stand  5 minutes,  or until  layers have
      separated.

            5.4.3  Remove 5 ml of top  layer by pipet, and place in a 10 ml vial.

            5.4.4  Keep all standard  solutions below 4°C until used.


6.0  SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1  See  the  introductory material to  this  chapter,  Organic  Analytes,
Section 4.1.


7.0  PROCEDURE

      7.1  Sample Extraction

            7.1.1  Pour 40 mL of the  sample into a 90 mL mixing bottle.  Pipet
      15 mL of Methyl tert-butyl ether into the mixing bottle.  Shake vigorously
      for about 2 min.  and let stand for  about  5 min.  Remove  about 5 mL of the
      top layer and store in a 10 mL  vial.

      7.2  Chromatographic Conditions  (Recommended)

Carrier Gas (He) flow rate: 35 mL/min.
Column Temperature:         180° C, Isothermal
Injection port temperature: 250° C
Detector temperature:       250° C
Detector Current (DC):       18 volts
Gases:  Hydrogen, 3 mL/min;  Air, 290  mL/min.

     7.3   Calibration of GC

            7.3.1  On a daily basis,  inject 3  pi of methyl  tert-butyl  ether
      directly  into the GC to flush  the  system.   Also purge the  system with
      methyl tert-butyl ether injections between injections  of  standards  and
      samples.

            7.3.2  Inject  3 juL of a  sample blank  (organic-free  reagent  water
      carried through the sample storage  procedures  and extracted  with methyl
      tert-butyl ether).

            7.3.3  Inject  3 pi of at  least five standard solutions:  one should
      be near the detection limit; one should  be near,  but below, the expected
      concentrations of the analyte; one should be near,  but above, the expected
      concentrations  of  the  analyte.    The   range   of  standard   solution
      concentrations used  should not exceed the working range of the GC system.

            7.3.4  Prepare  a  calibration curve  using  the  peak  areas of  the
      standards (retention time of acrylonitrile under the conditions of Section
      7.2 is  approximately  2.3 minutes).   If the calibration curve  deviates


                                   8031 - 4                        Revision  0
                                                                  November 1990

-------
      significantly from a straight line, prepare a new calibration curve with
      the existing standards, or,  prepare  new  standards  and a new calibration
      curve.   See  Method 8000,  Section  7.4.2,  for  additional  guidance  on
      calibration by the external standard method.

      7.4  Sample Analysis

            7.4.1  Inject  3  /iL   of   the   sample  extract,  using  the  same
      chromatographic conditions used  to prepare the standard curve.  Calculate
      the concentration of acrylonitrile in the extract,  using the area of the
      peak, against the calibration curve prepared in Section 7.3.4.


8.0  QUALITY CONTROL

      8.1  Refer to Chapter  One and Method 8000  for  specific  quality control
procedures.

      8.2  Prior  to  preparation  of   stock solutions,  methanol  and  methyl
tert-butyl ether reagents should be analyzed gas chromatographically under the
conditions described in Section  7.2,  to determine possible interferences with
the acrylonitrile peak.  If the solvent blanks show contamination, a different
batch of solvents should be used.
9.0  METHOD PERFORMANCE

      9.1  Method 8031 was tested in a single  laboratory over a period of days.
Duplicate samples and one spiked sample were run for each calculation.  The GC
was calibrated daily.  Results are presented in Table 1.


10.0  REFERENCES

1.   K.L. Anderson,  "The Determination of  Trace Amounts of  Acrylonitrile in
     Water by Specific Nitrogen  Detector  Gas  Chromatograph",  American Cynamid
     Report No. WI-88-13, 1988.
                                   8031 - 5                       Revision 0
                                                                  November 1990

-------
                        TABLE 1

         SINGLE LABORATORY METHOD  PERFORMANCE
                  CONCENTRATION
  SAMPLE          SPIKE  (jiig/L)         % RECOVERY
      A                  60                 100
      B                  60                 105
      C                  40                  86
      D                  40                 100
      E                  40                  88
      F                  60                  94

Average                                     96
                        8031  -  6                       Revision 0
                                                       November 1990

-------
               METHOD  8031
   ACRYLONITRILE  BY  GAS  CHRQMATQGRAPHY
     Start
 7.1.1 Extract
40ml of sample
  with methyl
 t-butyl ether
in 90ml bottle.
    72 Set
chroma tographic
  conditions
7.3.1 Flush CC
system with 3ul
methyl t-buty.l
    ether.
7.3.2 Analyze
3ul of sample
    blank
 7.3.3-7.3.4
  Establish
 calibration
curve with at
least S stds.
 7 .4 Sample
  Analysis
                               Stop
                 8031 - 7
                      Revision 0
                      November 1990

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                                  METHOD 8032

                       ACRYLAMIDE BY GAS CHROMATOGRAPHY
1.0  SCOPE AND APPLICATION

      1.1  Method 8032 is used to determine  trace amounts of acrylamide monomer
in aqueous matrices.   This method may  be applicable to other  matrices.   The
following compounds can be determined by this method:
     Compound Name                 CAS No.a


     Acrylamide                    79-06-01


     a  Chemical  Abstract Services Registry Number.


      1.2  The method detection limit (MDL) in clean water is 0.032 M9/L.

      1.3  This method  is  restricted  to use by, or  under  the supervision of,
analysts  experienced in  the use  of gas  chromatographs  and  skilled  in  the
interpretation of gas chromatograms.   Each  analyst must demonstrate the ability
to generate acceptable results with this method.


2.0  SUMMARY OF METHOD

      2.1  Method 8032  is  based on bromination  of  the acrylamide double bond.
The reaction product  (2,3-dibromopropionamide)  is  extracted  from the reaction
mixture with ethyl acetate, after  salting out with sodium sulfate.  The extract
is cleaned up using a Florisil column, and analyzed by gas chromatography with
electron capture detection (GC/ECD).

      2.2  Compound identification should be supported by at least  one additional
qualitative technique.   Analysis  using  a second gas  chromatographic column or
gas chromatography/mass spectrometry may be used for compound confirmation.


3.0  INTERFERENCES

      3.1  No interference is observed from sea water or in  the presence of 8.0%
of ammonium  ions derived  from  ammonium bromide.    Impurities from potassium
bromide are removed by the Florisil  clean up procedure.
                                    8032-1                        Revision 0
                                                                  November 1990

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4.0  APPARATUS AND MATERIALS
      4.1  Gas chromatographic System
            4.1.1  Gas chromatograph suitable for on-column injections with all
      required accessories,  including detector, analytical  columns,  recorder,
      gases, and syringes. A data system  for  measuring peak heights and/or peak
      areas is recommended.
            4.1.2  Column:   2 m  x 3  mm glass column,  5% FFAP (free fatty acid
      polyester) on 60-80 mesh acid washed Chromosorb W, or equivalent.
            4.1.3  Detector:  electron capture detector.
      4.2  Kuderna-Danish (K-D) apparatus.
            4.2.1  Concentrator tube -   10 ml graduated (Kontes K-570050-1025
      or equivalent).  A ground glass stopper is used to prevent evaporation of
      extracts.
            4.2.2  Evaporation  flask -   500 ml  (Kontes    K-570001-500   or
      equivalent).   Attach  to  concentrator tube  with  springs,  clamps,  or
      equivalent.
            4.2.3  Snyder column  -   Three ball  macro  (Kontes K-503000-0121 or
      equivalent).
            4.2.4  Snyder  column  -   Two  ball micro  (Kontes  K-569001-0219 or
      equivalent).
            4.2.5  Springs -  1/2 inch (Kontes K-662750 or equivalent).
      4.3  Separatory funnel - 150 ml.
      4.4  Volumetric flask (Class A) -  100 ml, with ground glass  stopper; 25 ml,
amber, with ground glass stopper.
      4.5  Syringe - 5 mL.
      4.6  Microsyringes - 5 /iL,  100 ML-
      4.7  Pipets (Class A).
      4.8  Glass column  (30  cm x 2 cm).
      4.9  Mechanical shaker.

5.0  REAGENTS
      5.1  Reagent grade chemicals shall  be used in all  tests.  Unless otherwise
indicated, it is intended that all reagents shall conform to the specifications
of the Committee on Analytical  Reagents of the American Chemical Society, where
                                    8032-2                        Revision 0
                                                                  November  1990

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such specifications  are available.  Other grades  may be used, provided  it  is
first ascertained that the reagent is of sufficiently high purity to permit its
use without lessening the accuracy of the determination.

      5.2  Organic-free reagent water.  All  references  to water  in  this  method
refer to organic-free reagent water, as defined  in Chapter One.

      5.3  Solvents

            5.3.1  Ethyl acetate, C2H5C02C2H5.  Pesticide quality,  or  equivalent.

            5.3.2  Diethyl ether,  C2H5OC2H5.   Pesticide  quality, or  equivalent.
      Must  be free  of  peroxides  as  indicated  by test  strips  (EM Quant,  or
      equivalent).   Procedures  for removal  of peroxides  are provided with the
      test strips.  After cleanup, 20 ml of  ethyl  alcohol  preservative must  be
      added to each liter of ether.

            5.3.3  Methanol, CH3OH.  Pesticide quality, or equivalent.

            5.3.4  Benzene, C6H6.   Pesticide  quality,  or equivalent.

            5.3.5  Acetone, CH3COCH3.  Pesticide  quality,  or  equivalent.

      5.4  Saturated  bromine  water.   Prepare  by shaking  organic-free reagent
water with bromine and  allowing to stand for 1 hour,  in the  dark,  at 4°C.   Use
the aqueous phase.

      5.5  Sodium sulfate  (anhydrous, granular), Na2S04.   Purify by  heating  at
400°C for 4 hours in a shallow tray, or by precleaning  the sodium sulfate with
methylene chloride.   If the sodium sulfate is  precleaned with methylene chloride,
a method blank must be analyzed,  demonstrating that  there is no interference from
the sodium sulfate.

      5.6  Sodium thiosulfate, Na2S203, 1 M aqueous  solution.

      5.7  Potassium bromide, KBr, prepared  for  infrared  analysis.

      5.8  Concentrated hydrobromic acid, HBr, specific gravity  1.48.

      5.9  Acrylamide  monomer,  H2C:CHCONH2,  electrophoresis  reagent   grade,
minimum 95% purity.

      5.10 Dimethyl phthalate, C6H4(COOCH3)2,  99.0% purity.

      5.11 Florisil (60/100 mesh):  Prepare Florisil by activating at 130°C for
at least 16 hours.  Alternatively, store Florisil  in  an oven at  130°C.   Before
use, cool the Florisil in a desiccator.   Pack 5 g of the Florisil, suspended  in
benzene, in a glass column (Section 4.8).

      5.12 Stock standard solutions

            5.12.1  Prepare a stock standard solution of  acrylamide monomer  as
      specified in Section 5.12.1.1.   When  compound purity is assayed to  be 96%
      or greater, the weight  can  be used without  correction to calculate the

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      concentration of the stock standard.  Commercially prepared standards can
      be used at any concentration  if they are certified by the manufacturer or
      by an independent source.

                  5.12.1.1   Dissolve  105.3   mg  of  acrylamide   monomer  in
            organic-free reagent water in a 100 ml volumetric flask, and dilute
            to the mark with organic-free reagent water. Dilute the solution of
            acrylamide monomer  so  as to obtain standard  solutions containing
            0.1 - 10 ng/ml of acrylamide monomer.

      5.13 Calibration standards

            5.13.1  Dilute  the  acrylamide  stock   solution  with  organic-free
      reagent water to produce  standard solutions containing 0.1-5  M9/roL of
      acrylamide.  Prior to injection the calibration standards are reacted and
      extracted in the same manner as environmental  samples  (Section 7).

      5.14 Internal standards

            5.14.1  The  suggested  internal  standard  is  dimethyl  phthalate.
      Prepare a  solution  containing  100 iig/ml of dimethyl  phthalate  in ethyl
      acetate.  The concentration of dimethyl phthalate in the sample extracts
      and calibration standards should be 4 M9/mL.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See  the  introductory material to this chapter,  Organic Analytes,
Section 4.1.
7.0  PROCEDURE

      7.1  Bromination

            7.1.1  Pipet 50 mL of  sample  into  a  100  mL glass stoppered flask.
      Dissolve 7.5 g of potassium bromide into the sample, with stirring.

            7.1.2  Adjust the pH of the solution with concentrated hydrobromic
      acid until the pH is between 1 and 3.

            7.1.3  Wrap the flask with aluminum foil  in order to exclude light.
      Add 2.5 mL of saturated bromine water, with stirring.  Store the flask and
      contents in the dark, at 0°C, for at least  1 hour.

            7.1.4  After reacting the solution for at least an hour, decompose
      the excess of bromine by adding 1 M sodium thiosulfate  solution, dropwise,
      until the color of the solution is discharged.

            7.1.5  Add 15 g of sodium sulfate, using a magnetic stirrer to effect
      vigorous stirring.
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      7.2  Extraction

            7.2.1  Transfer the solution  into a 150 ml separatory funnel.  Rinse
      the reaction flask three times  with 1 ml aliquots of organic-free reagent
      water.  Transfer the rinsings into the separatory funnel.

            7.2.2  Extract the aqueous solution with two 10 mL portions of ethyl
      acetate for 2 min each, using a mechanical shaker (240 strokes per min).
      Dry the organic phase with 1 g of sodium sulfate.

            7.2.3  Transfer  the  organic  phase  into  a 25 ml amber volumetric
      flask.   Rinse the  sodium  sulfate  with three  1.5  ml portions  of ethyl
      acetate and combine the rinsings with the organic phase.

            7.2.4  Add exactly  100 /xg  of dimethyl phthalate to the flask and
      make the solution up to the 25 ml  mark with  ethyl  acetate.   Inject 5 /xL
      portions of this solution into the gas chromatograph.

      7.3  Florisil cleanup:  Whenever interferences are observed, the samples
should be cleaned up as follows.

            7.3.1  Transfer the dried extract into a Kuderna-Danish evaporator
      with  15  ml  of  benzene.   Evaporate the  solvent at  70°C under  reduced
      pressure, and concentrate the solution to about 3 ml.

            7.3.2  Add 50 ml of benzene  and subject  the  solution to Florisil
      column chromatography at a flow rate of 3  mL/min.  Elute the column first
      with 50 ml of diethyl  ether/benzene (1:4)  at  a  flow  rate of  5 mL/min, and
      then with  25 ml of  acetone/benzene (2:1) at  a flow rate  of 2 mL/min.
      Discard all of the  first eluate and the initial  9 mL  portion  of the second
      eluate,  and use  the  remainder  for the  determination,  using  dimethyl
      phthalate (4 ng/ml) as  an  internal  standard.

Note: Benzene is toxic,  and  should be only be used  under a  ventilated laboratory
      hood.

      7.4  Gas chromatographic conditions:

           Nitrogen carrier gas flow rate:  40  mL/min
           Column temperature:              165°C.
           Injector temperature:            180°C
           Detector temperature:            185°C.
           Injection volume:                5  /xL

      7.5  Calibration:

            7.5.1  Inject 5  /nL of a sample blank  (organic-free  reagent water
      carried through all sample storage, handling, bromination and extraction
      procedures).

            7.5.2  Prepare  standard  solutions   of  acrylamide  as  described in
      Section 5.13.1.  Brominate  and extract each standard  solution as described
      in Sections 7.1 and 7.2.


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            7.5.2.1  Inject 5 p.1  of each of  a  minimum of five standard
      solutions: one should  be  near the detection  limit;  one should be
      near, but  below,  the expected concentrations  of the analyte; one
      should  be near,   but above,  the  expected  concentrations  of the
      analyte.

            7.5.2.2  Prepare a calibration curve using the peak areas of
      the standards.  If the calibration curve deviates  significantly from
      a straight line,  prepare a new calibration curve with the existing
      standards, or, prepare new  standards  and  a new calibration curve.
      See  Method  8000,  Section  7.4.3,  for  additional  guidance  on
      calibration by the internal standard method.

            7.5.2.3  Calculate  the response  factor  for  each  standard
      according to Equation 1.
                  (Ps)  (Mis)
             RF = 	                    Equation 1
                  (P,s)  (MA)
      RF = Response factor
      Ps = Peak height of acrylamide
      Mis = Amount of internal standard injected (ng)
      Pls = Peak height of internal standard
      MA = Amount of acrylamide injected (ng)

7.5.3 Calculate the mean response factor according to Equation 2,
                        n
                        2  RF
                       i=l

                 RF = 	                Equation 2
RF = Mean response factor
RF = Response factors from standard analyses  (calculated  in  Equation  1)
n =  Number of analyses

7.6  Gas chromatographic analysis:

      7.6.1  Inject  5  ^l  portions  of each  sample  (containing  4 ng/ml
internal  standard)  into  the  gas  chromatograph.    An  example GC/ECD
chromatogram is shown in Figure 1.

      7.6.2  The concentration of acrylamide monomer in the sample is given
by Equation 3.

                   (PA)  (Mis)
     [A] =  	—	                Equation  3
                       (V,) (V.)


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      [A] = Concentration of acryl amide monomer in sample (jug/mL)
      PA  = Peak height of acryl amide monomer
      Mls = Amount of internal standard injected (ng)
      Vs  = Total  volume of sample (ml)
      P^ = Peak height of internal standard
      RF = Mean response factor from Equation 2
      V,  =  Injection volume  (/iL)


8.0  QUALITY CONTROL

      8.1  Refer to Chapter  One  and Method 8000  for  specific quality control
procedures.


9.0  METHOD PERFORMANCE

      9.1  The  following  performance  data  have  been  generated  under  the
conditions described in this method:

            9.1.1  The calibration curve for Method 8032 is linear over the range
      0-5 /xg/L of acryl amide monomer.

            9.1.2  The limit of detection for an aqueous solution is 0.032 M9/L.

            9.1.3  The yields of the brominated compound are 85.2 + 3.3% and 83.3
      + 0.9%,  at fortification concentrations of 1.0 and 5.0 Mg/L, respectively.
      9.2  Table  1  provides the  recoveries  of acryl amide monomer  from river
water, sewage effluent, and sea water.

      9.3  The recovery of the bromi nation product as a function of the amount
of  potassium  bromide  and  hydrobromic acid  added to the  sample is  shown in
Figure 2.

      9.4  The effect  of the reaction  time on the recovery of the bromination
product  is shown  in Figure 3.   The yield  was constant  when  the reaction time
was more than 1 hour.

      9.5  Figure 4 shows the recovery of the bromination product as a function
of the initial pH from 1 to 7.35.   The  yield  was constant within this pH range.
The use of conventional buffer solutions,  such as sodium acetate - acetic acid
solution or phosphate  solution, caused a significant decrease in yield.


10.0  REFERENCES

1.  Hashimoto, A., "Improved Method for the Determination of Acrylamide Monomer
    in Water  by Means  of  Gas-Liquid Chromatography with  an Electron-capture
    Detector," Analyst, 101:932-938, 1976.
                                    8032-7                        Revision 0
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                                                   TABLE  1

                               RECOVERY OF ACRYLAMIDE  FROM WATER  SAMPLES  AS
                                          2,3-DIBROMOPROPIONAMIDE


Sampl e
Matrix
Standard


River Water
Sewage
Effluent
Sea Water

Acryl amide
Monomer
Spiked//Ltg
0.05
0.20
0.25
0.20
0.20
0.20

Amount of 2,

Calculated
0.162
0.649
0.812
0.649
0.649
0.649

3-DBPA7jug

Found"
0.138
0.535
0.677
0.531
0.542
0.524
Overall
Bromi nation
Recovery
%b
85.2
82.4
83.3
81.8
83.5
80.7

Recovery of
Acryl amide
Monomer, %b
...
—
—
99.4
101.3
98.8

Coefficient
of
Variation
3.3
1.0
0.9
2.5
3.0
3.5
a  2,3-Dibromopropionamide

b  Mean of five replicate determinations
                                                  8032 - 8
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                                   Figure 1
Typical gas  chromatograms of  the bromination  product obtained  from aqueous
acrylamide monomer solution:

   A.   Untreated
   B.   With  Florisil  cleanup
   BL.   Chromatogram of blank, concentrated five-fold before gas chromatographic
        analysis.

Peaks:

   1.   2,3-Dibromopropionamide
   2.   Dimethyl phthalate
   4-7. Impurities  from  potassium bromide

Sample size = 100 mL; acrylamide monomer = 0.1 M9
                                   8032 - 9
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                                   Figure 2
                 8
                 o
                 *»
                
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                                   Figure 3
                                                 24
Effect of reaction time on the bromination.  Reaction conditions:

   50 ml of sample;
   0.25 /ig of acrylamide monomer;
   7.5 g of potassium bromide;
   2.5 ml of saturated bromine water

Extraction conditions:

   15 g of sodium sulfate;
   extraction at pH 2;
   solvent = 10 ml of ethyl acetate (X2)
                                   8032  -  11
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                                   Figure 4
                 1  »
                         t    t     1
                     012345971

                                        PM
Effect of initial pH on the bromination.   Reaction and extraction conditions as
in Figure 3.  The pH was adjusted to below 3 with concentrated hydrobromic acid,
and to 4-5 with dilute hydrobromic  acid.   Reaction at pH  6 was  in distilled
water. pH  7.35 was  achieved  by careful  addition  of dilute  sodium hydroxide
solution.  The  broken line shows the result obtained by the use of sodium acetate
- acetic acid buffer solution.
                                   8032 -  12
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                                          METHOD 8032
                           ACRYLAMIDE  BY  GAS CHRQMATOGRAPHY
7.1  Sromination
7.1.1  Dissolve 7.5 gr. KBr into
      50  ml. sample in flask.
7.1.2 Adjust soln. pH with
     concentrated HBr to between
     1 and 3.
7.1.3 Wrap soln. flask w/aluminum.
     Add 2.5 ml. satd.  bromine
     water, stir, store at 0 C for
     1 hr.
7.1.4 Add 1  M sodium thiosulfate
     dropwise to flask to
     decompose excess bromine.
7.1.5  Add 15 gr. sodium sulfate,
      and stir.
7.2 Extraction
7.2.1 Transfer flask soln. to
     sep. funnel along with
     rinses.
7.2.2  Extract  soln.  twice w/ethyl
      acetate.  Dry organic  phase
      using sodium sulfate.
7.2.3 Transfer organic phase  and
     rinses into amber glass  flask.
7.2.4 Add 100 ug. dimethyl
     phthalate to flask, dilute to
     mark.   Inject 5 ul. into  GC.
7.3 Florisil Cleanup
                                                              7.3.1 Transfer dried extract to  K-D
                                                                   assembly w/benzene.
                                                                   Concentrate  to 3 ml. at 70 C
                                                                   under reduced pressure.
                                                              7.3.2 Add 50  ml. benzene  to
                                                                   solution. Pass soln.  through
                                                                   Florisil column.   Elute with
                                                                   diethyl ether/benzene, then
                                                                   acetone/benzene.  Collect
                                                                   the second elution  train  (less
                                                                   initial  9  ml.) for analysis.
                                           8032  -  13
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          METHOD  8032
            continued
7.4 GC Conditions
7.5 Calibration
7.5.1  Inject 5 ul. sample blank.
7.5.2  Brominqte and extract std.
      solns. similar to  the samples.
    .1 Inject  5  ul.  of each of the
       minimum 5 stds.
    .2 Plot peak area vs. f ].
    .3 Calculate response factor
       (RF) for each [ ].
7.5.3 Calculate mean RF from
     eqn. 2.
7.6  GC Analysis
7.6.1 Inject 5 ul. sample containing
     internal std. into GC.
7.6.2 Calculate acrylamide  monomer
     concentration in sample  using
     eqn. 3.
            8032  -  14
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                                  METHOD 8061

               PHTHALATE ESTERS BY CAPILLARY GAS CHROMATOGRAPHY
                   WITH ELECTRON CAPTURE DETECTION (GC/ECD)
1.0  SCOPE AND APPLICATION

      1.1  Method 8061  is  used  to  determine the identities and concentrations
of various phthalate esters in liquid, solid and sludge matrices.  The following
compounds can be determined by this method:
     Compound Name                                             CAS No.'
     Benzyl benzoate  (I.S.)                                  120-51-4
     Bis(2-n-butoxyethyl) phthalate (BBEP)                    117-83-9
     Bis(2-ethoxyethyl) phthalate (BEEP)                      605-54-9
     Bis(2-ethylhexyl) phthalate (DEHP)                       117-81-7
     Bis(2-methoxyethyl) phthalate (BMEP)                     117-82-8
     Bis(4-methyl-2-pentyl) phthalate  (BMPP)                  146-50-9
     Butyl benzyl phthalate (BBP)                              85-68-7
     Diamyl phthalate (DAP)                                   131-18-0
     Di-n-butyl phthalate (DBP)                                84-74-2
     Dicyclohexyl phthalate (DCP)                              84-61-7
     Diethyl phthalate (DEP)                                   84-66-2
     Dihexyl phthalate (DHP)                                   84-75-3
     Diisobutyl phthalate (DIBP)                               84-69-5
     Dimethyl phthalate (DMP)                                 131-11-3
     Dinonyl phthalate                                         84-76-4
     Di-n-octyl phthalate (OOP)                               117-84-0
     Hexyl 2-ethylhexyl phthalate (HEHP)                    75673-16-4


     a   Chemical  Abstract  Services  Registry Number.


      1.2  Table  1  lists the  method  detection  limits  (MDL)  for  the  target
analytes  in a water matrix.  The MDLs  for the components of a specific sample
may differ  from  those  listed  in Table 1  because MDLs  depend  on  the nature of
interferences in the sample matrix.   Table 2  lists  the estimated quantitation
limits (EQL) for other matrices.

      1.3  When this method  is used  to  analyze  for any or all  of  the target
analytes, compound identification should  be supported by at least one additional
qualitative technique.  This method describes conditions for  parallel column,
dual electron capture detector  analysis  which fulfills the  above requirement.
Retention time information obtained on two megabore fused-silica open tubular
columns is given in Table  1.  Alternatively, gas chromatography/mass spectrometry
could be used for compound confirmation.
                                   8061 - 1                       Revision 0
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      1.4  This method  is restricted to  use by  or  under the  supervision  of
analysts  experienced  in  the use  of gas  chromatographs and  skilled  in  the
interpretation of gas  chromatograms.   Each  analyst must demonstrate the ability
to generate acceptable results with this method.


2.0  SUMMARY OF METHOD

      2.1  A measured volume or weight of sample (approximately 1  liter  for
liquids,  10  to 30  grams  for solids  and  sludges) is  extracted by  using  the
appropriate sample  extraction  technique specified in Methods  3510,  3540,  and
3550.   Method  3520 is not  recommended  for the extraction of  aqueous samples
because the longer chain esters (dihexyl  phthalate, bis(2-ethylhexyl) phthalate,
di-n-octyl phthalate,  and  dinonyl phthalate) tend to adsorb to the glassware and
consequently, their extraction recoveries  are <40  percent.  Aqueous samples are
extracted at a  pH of  5  to 7, with methylene chloride,  in a  separatory funnel
(Method 3510).  Alternatively, particulate-free aqueous samples could be filtered
through membrane disks that  contain C18-bonded silica.  The phthalate esters are
retained by the silica and,  later eluted with acetonitrile.   Solid samples are
extracted with  hexane/acetone  (1:1)  or methylene chloride/acetone  (1:1)  in  a
Soxhlet extractor (Method 3540) or with an ultrasonic extractor (Method 3550).
After cleanup,  the extract  is  analyzed by  gas chromatography with  electron
capture detection (GC/ECD).

      2.2  The  sensitivity  of  Method  8061  usually  depends  on  the  level  of
interferences rather than  on  instrumental limitations.   If interferences prevent
detection of the analytes, cleanup  of the sample extracts  is necessary.  Either
Method 3610 or 3620 alone or  followed  by  Method 3660, Sulfur Cleanup, may be used
to eliminate  interferences in the analysis.  Method 3640,  Gel Permeation Cleanup,
is applicable for samples that contain high amounts of lipids and waxes.


3.0  INTERFERENCES

      3.1  Refer to Methods  3500, 3600,  and 8000.

      3.2  Interferences  coextracted  from  the  samples will  vary  considerably
from waste to waste. While general cleanup techniques  are referenced or provided
as part of this  method, unique samples may  require  additional cleanup approaches
to achieve desired sensitivities for the target analytes.

      3.3  Glassware must  be scrupulously clean.  All glassware require treatment
in  a muffle  furnace  at  400°C for  2 to 4 hrs,  or  thorough  rinsing  with
pesticide-grade solvent, prior to use.  Refer to Chapter 4,  Section 4.1.4,  for
further details regarding the cleaning of glassware. Volumetric glassware should
not be heated in a muffle furnace.

      If Soxhlet extractors  are baked in the  muffle furnace, care must be taken
to ensure  that  they are  dry (breakage may result if any water  is  left in the
side-arm). Thorough rinsing  with hot tap water,  followed by deionized water and
acetone  is not  an adequate  decontamination  procedure.    Even  after  a Soxhlet
extractor was refluxed with  acetone for  three days, with  daily solvent changes,
the concentrations  of bis(2-ethylhexyl) phthalate were  as high  as  500 ng  per
washing.  Storage of glassware in the  laboratory introduces contamination, even

                                   8061 -  2                       Revision 0
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if the glassware is wrapped in aluminum foil.  Therefore, any glassware used in
Method 8061 should be cleaned immediately prior to use.

      3.4  Florisil and alumina may be contaminated with phthalate esters and,
therefore,  use  of  these  materials  in  sample  cleanup  should  be  employed
cautiously.   If these materials are  used,  they must  be obtained packaged in
glass (plastic packaging will contribute to contamination with phthalate esters).
Washing of these  materials prior to use with the  solvent(s)  used for elution
during extract cleanup was  found helpful, however, heating at 3208C for Florisil
and 210"C for  alumina  is recommended.  Phthalate esters were  detected in Florisil
cartridge  method  blanks  at  concentrations  ranging  from  10  to  460  ng,  with
5 phthalate esters in the 105 to 460 ng range.  Complete removal of  the phthalate
esters from  Florisil  cartridges does  not  seem  possible,  and it  is  therefore
desirable to  keep the steps involved in sample preparation to a minimum.

      3.5  Paper thimbles and filter paper must  be exhaustively washed with the
solvent that will  be  used in the sample extraction.  Soxhlet extraction of paper
thimbles.and  filter paper for 12 hrs with fresh solvent should be repeated for
a minimum of  three times.  Method  blanks should be  obtained before any of the
precleaned thimbles or filter papers are used.  Storage of precleaned thimbles
and  filter paper  in  precleaned  glass  jars covered  with  aluminum  foil  is
recommended.

      3.6  Glass  wool  used  in  any  step  of  sample preparation  should  be  a
specially treated pyrex wool, pesticide grade,  and  must be baked  at  400°C for
4 hrs. immediately prior to use.

      3.7  Sodium sulfate must be obtained packaged in glass (plastic packaging
will contribute to contamination with  phthalate esters),  and  must be purified
by  heating  at  400°C  for  4  hrs.  in  a  shallow  tray,  or  by  precleaning  with
methylene chloride  (Section  5.3).    To avoid recontamination,  the precleaned
material   must be stored  in  glass-stoppered  glass  bottles, or glass  bottles
covered with precleaned aluminum foil.  The storage period should not exceed two
weeks.   To  minimize contamination,  extracts  should  be dried directly  in the
glassware in  which  they are  collected  by  adding small  amounts  of precleaned
sodium sulfate until an excess of free flowing material is noted.

      3.8  The presence of  elemental  sulfur will result in large peaks which
often mask the region of the compounds eluting  before dicyclohexyl  phthalate
(Compound No.  14) in  the gas  chromatograms  shown  in  Figure 1.   Method 3660 is
suggested for removal of sulfur.

      3.9  Waxes and  lipids  can be  removed by Gel  Permeation  Chromatography
(Method 3640).  Extracts containing high concentrations of lipids are viscous,
and may even  solidify at room temperature.


4.0  APPARATUS AND MATERIALS

      4.1  Gas chromatography

            4.1.1  Gas  chromatograph,   analytical  system   complete  with  gas
     chromatograph suitable  for  on-column  and  split/splitless  injections and
     all  required  accessories, including detector, analytical columns, recorder,

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     gases, and syringes.   A data  system  for measuring peak heights and/or peak
     areas is recommended.

                  4.1.1.1  Eight  inch  injection tee  (Supelco,   Inc.,  Catalog
            No. 2-3665, or equivalent)  or glass  Y splitter for megabore columns
            (J&W Scientific, "press-fit", Catalog No. 705-0733, or equivalent).

            4.1.2  Columns

                  4.1.2.1  Column  1, 30  m x  0.53  mm ID, 5%  phenyl/95% methyl
            silicone fused-silica  open  tubular column (DB-5, J&W Scientific, or
            equivalent), 1.5 jum film thickness.

                  4.1.2.2  Column  2, 30 m x 0.53 mm ID,  14% cyanopropyl phenyl
            silicone fused-silica  open  tubular column (DB-1701, J&W Scientific,
            or equivalent), 1.0 p,m  film  thickness.

            4.1.3  Detector - Dual electron capture detector  (ECD)

      4.2  Glassware, see Methods  3510, 3540,  3550, 3610,  3620,  3640, and 3660
for specifications.

      4.3  Kuderna-Danish (K-D) apparatus.

            4.3.1  Concentrator tube -  10 ml graduated (Kontes K-570050-1025 or
      equivalent).   A  ground glass stopper is  used to  prevent  evaporation of
      extracts.

            4.3.2  Evaporation  flask   -  500   ml  (Kontes   K-570001-500  or
      equivalent).   Attach  to concentrator  tube  with  springs,  clamps,  or
      equivalent.

            4.3.3  Snyder column  -  Three ball  macro (Kontes  K-503000-0121 or
      equivalent).

            4.3.4  Snyder column  - Two  ball  micro  (Kontes   K-569001-0219  or
      equivalent).

            4.3.5  Springs - 1/2 inch (Kontes K-662750  or  equivalent).

      4.4  Boiling chips,  approximately 10/40 mesh.  Heat  to  400°C for 30 min,
or Soxhlet-extract with methylene  chloride prior to use.

      4.5  Water bath, heated, with concentric ring cover, capable of temperature
control (± 2°C).

      4.6  Vacuum  system   for  eluting  disposable   solid-phase   extraction
cartridges.

            4.6.1  Vacuum manifold consisting of  individually adjustable, easily
      accessible  flow-control  valves  for up  to  24  cartridges, sample  rack,
      chemically resistant cover  and seals, heavy-duty  glass  basin,  removable
      stainless steel solvent guides, built-in  vacuum gauge and  valve.


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            4.6.2  Vacuum trap  made  of 500  ml side  arm  flask fitted  with  a
      one-hole stopper and glass tubing.

            4.6.3  6 mL,  1 g solid-phase extraction cartridges, LC-Florisil or
      equivalent, prepackaged, ready to use.

      4.7  Vials -  2  ml,  10 ml, glass  with  Teflon lined  screw-caps  or crimp
tops.

      4.8  Apparatus for  filtration of aqueous  samples through extraction disks
(optional).

            4.8.1  Vacuum apparatus: (Vac Elut SPS24, Analytichem International,
     or equivalent).

                  4.8.1.1  1 liter  suction flask.

                  4.8.1.2  Disk base.

                  4.8.1.3  Graduated  funnel.

                  4.8.1.4  Clamp.

                  4.8.1.5  Vacuum gauge.

                  4.8.1.6  Pinch clamp.

                  4.8.1.7  25 x 200  mm  test tube.

            4.8.2  47   mm   C1B-extraction   disks   (3M-Empore,   Analytichem
     International, Catalog No. 1214-5004, or equivalent).


5.0  REAGENTS

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

      5.2  Organic-free reagent water.   All references to water in this method
refer to organic-free reagent water,  as defined in Chapter One.

      5.3  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  Florisil - 60/80 mesh, activated at 400"C for 16 hrs, then deactivated
with water (3 percent by weight).


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      5.5  Alumina - Alumina Woelm N Super I,  activated/deactivated as described
for Florisil, or equivalent.

      5.6  Solvents:

            5.6.1  Hexane, C6H14 - Pesticide quality,  or equivalent.

            5.6.2  Methylene chloride, CH2C12  - Pesticide quality,  or equivalent.

            5.6.3  Acetone, CH3COCH3 - Pesticide quality, or equivalent.

            5.6.4  Acetonitrile, CH3CN -  HPLC grade.

            5.6.5  Methanol, CH3OH  - HPLC grade.

            5.6.6  Diethyl Ether, C2H5OC2H5 -  Pesticide quality, or equivalent.
     Must  be  free  of  peroxides, as  indicated  by test  strips  (EM  Quant,  or
     equivalent).   Procedures  for  removal of peroxides  are  provided with the
     test strips.   After  cleanup,  20 ml  of ethyl  alcohol preservative must be
     added to each liter of ether.

      5.7  Stock standard solutions:

            5.7.1  Prepare  stock standard  solutions  at  a  concentration  of
      1000 mg/L by dissolving 0.0100 g of assayed reference material in hexane,
      and diluting to volume in a 10 ml volumetric flask.  When compound purity
      is assayed to be 96 percent  or greater, the weight  can  be used without
      correction  to  calculate  the  concentration  of  the  stock  standard.
      Commercially  prepared  stock standard  solutions  can  be   used  at  any
      concentration  if  they  are  certified  by  the  manufacturer  or  by  an
      independent source.

            5.7.2  Transfer the stock standard solutions into glass vials with
      Teflon lined  screw-caps  or crimp  tops.   Store at 4eC and protect from
      light.  Stock standard solutions  should be checked  periodically  by gas
      chromatography for  signs  of  degradation or  evaporation,  especially just
      prior to preparation of calibration standards.

            5.7.3  Stock standard solutions must be replaced after  6 months, or
      sooner if comparison with check standards indicates a problem.

      5.8  Calibration standards: Calibration standards are prepared at a minimum
of five concentrations  for  each  parameter of interest through  dilution  of the
stock standard solutions with  hexane.  One of the  concentrations should be at
a concentration  near,  but above, the method detection limit.   The remaining
concentrations should correspond to the expected range of concentrations found
in real samples,  or should define the working  range of the GC.   Calibration
solutions must be  replaced  after 1 to 2  months, or  sooner  if  comparison with
calibration verification standards indicates a problem.

      5.9   Internal standards (if internal standard calibration is used):  To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to the compounds  of interest.  The analyst
must further demonstrate  that  the measurement of  the internal  standard  is not

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affected by method  or matrix interferences.  Benzyl  benzoate  has been tested
and found appropriate for Method 8061.

            5.9.1  Prepare a spiking  solution of  benzyl  benzoate in hexane at
      5000 mg/L.  Addition of 10 /iL of this solution to 1 ml of sample extract
      is recommended. The spiking concentration of the internal standard should
      be kept  constant  for  all  samples and calibration  standards.   Store the
      internal standard spiking  solution at 4eC in glass vials with Teflon lined
      screw-caps  or  crimp  tops.   Standard  solutions should be  replaced when
      ongoing QC  (Section 8) indicates a problem.

      5.10  Surrogate standards: The analyst should monitor the performance of
the extraction, cleanup  (when used),  analytical  system,  and the effectiveness
of  the  method  in dealing  with each  sample  matrix  by  spiking  each  sample,
standard, and blank  with surrogate  compounds.   Three surrogates are suggested
for  Method  8061: diphenyl  phthalate,  diphenyl   isophthalate,   and  dibenzyl
phthalate.

            5.10.1  Prepare  a surrogate standard spiking solution, in acetone,
      which contains  50  ng//ul_  of each compound.   Addition of 500 juL  of this
      solution to 1  L of water or 30 g  solid sample is equivalent to 25 /tg/L of
      water or  830  jug/kg of solid  sample.   The  spiking concentration  of the
      surrogate standards may be adjusted accordingly,  if  the  final  volume of
      extract is reduced below 2 ml for water samples or 10 ml for solid samples.
      Store the surrogate spiking  solution  at 4°C in glass vials with Teflon
      lined screw-caps  or  crimp tops.   The  solution must be  replaced  after
      6 months, or sooner if ongoing QC (Section 8) indicates  problems.


6.0  SAMPLE COLLECTION,  PRESERVATION,  AND HANDLING

      6.1  See  the  introductory material  to  this chapter, Organic  Analytes,
Section 4.1.
7.0  PROCEDURE

      7.1  Extraction:

            7.1.1  Refer to Chapter Two for guidance on choosing the appropriate
      extraction procedure.   In general,  water  samples are extracted at a pH of
      5 to 7  with methylene  chloride  in  a  separatory  funnel  (Method  3510).
      Method  3520  is not recommended  for the  extraction  of  aqueous  samples
      because  the  longer chain esters  (dihexyl   phthalate  bis(2-ethylhexyl)
      phthalate, di-n-octyl  phthalate,  and dinonyl  phthalate) tend to adsorb to
      the  glassware   and   consequently,  their   extraction   recoveries   are
      <40 percent.   Solid samples  are  extracted with hexane/acetone  (1:1)  or
      methylene chloride/acetone (1:1)  in a Soxhlet extractor (Method 3540)  or
      with  an  ultrasonic  extractor  (Method  3550).    Immediately  prior  to
      extraction,  spike 500 /xL  of the  surrogate  standard  spiking  solution
      (concentration = 50 ng//uL) into 1 L aqueous sample or 30 g solid sample.
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      7.1.2  Extraction  of   particulate-free  aqueous   samples   using
C16-extraction disks  (optional):

            7.1.2.1  Disk preconditioning:  Place the  C18-extraction disk
      into the filtration apparatus and  prewash the disk with 10 to 20 ml
      of acetonitrile.  Apply vacuum to pull  the solvent through the disk.
      Maintain vacuum to pull  air  through for 5  min.   Follow with 10 ml
      of methanol.  Apply vacuum and pull most of  the methanol through the
      disk.  Release vacuum before the disk gets  dry.   Follow with 10 mL
      organic-free reagent  water.  Apply vacuum and  pull most of the water
      through the disk.  Release the vacuum before  the disk gets dry.

            7.1.2.2  Sample preconcentration: Add 2.5 mL  of  methanol to
      the  500 ml  aqueous sample in  order  to get  reproducible  results.
      Pour the sample  into the filtration apparatus.   Adjust  vacuum so
      that it takes  approximately  20 min to  process 502.5 ml of sample.
      After all  of the sample has passed through  the membrane disk, pull
      air through the disk  for 5 to  10 min. to remove any residual  water.

            7.1.2.3  Sample elution: Break the vacuum and  place  the tip
      of the filter base into the test tube that  is contained inside the
      suction flask.   Add 10 ml of acetonitrile  to  the graduated funnel,
      making sure  to rinse the walls of the graduated funnel  with the
      solvent. Apply vacuum to pass the  acetonitrile through the membrane
      disk.

            7.1.2.4  Extract  concentration:   Concentrate  the extract to
      2 mL or less, using either the micro Snyder column technique (Section
      7.1.2.4.1)  or nitrogen blowdown technique  (Section  7.1.2.4.2).

                  7.1.2.4.1  Micro Snyder Column  Technique

                        7.1.2.4.1.1  Add one or  two clean  boiling chips
                  to the concentrator tube  and  attach a  two  ball  micro
                  Snyder column.  Prewet the column  by adding about 0.5 mL
                  of acetonitrile  to the top of the  column.  Place the K-D
                  apparatus in a hot water bath (15-20°C above the boiling
                  point of the solvent)  so that  the concentrator tube is
                  partially immersed in the hot water and the entire lower
                  rounded surface of the flask is bathed  with hot vapor.
                  Adjust the vertical position of  the  apparatus  and the
                  water  temperature,  as   required,  to   complete  the
                  concentration in 5-10 minutes.  At  the  proper rate of
                  distillation the balls of the  column   will  actively
                  chatter,  but the chambers will  not  flood.   When the
                  apparent volume  of liquid reaches  0.5 mL,  remove the K-D
                  apparatus from  the water bath and allow it to drain and
                  cool  for at least 10 minutes.   Remove the Snyder column
                  and rinse  the  flask and  its  lower  joints with  about
                  0.2 mL of  solvent and add to  the  concentrator  tube.
                  Adjust the final volume to 1.0-2.0 mL with solvent.
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                        7.1.2.4.2  Nitrogen Slowdown Technique

                              7.1.2.4.2.1  PI ace the concentrator tube i n a warm
                        water bath  (approximately 35°C) and evaporate the solvent
                        volume to  the required  level using  a  gentle  stream of
                        clean,  dry nitrogen  (filtered  through  a column  of
                        activated carbon).

CAUTION;   Do not use plasticized tubing between  the carbon trap and the sample.

                              7.1.2.4.2.2  The internal wall  of the  tube must
                        be rinsed  down  several  times with acetonitrile  during
                        the operation.   During  evaporation,  the solvent  level
                        in the  tube must be positioned to  prevent water from
                        condensing into the sample  (i.e.,  the  solvent  level
                        should be  below the level  of the water bath).   Under
                        normal operating conditions, the extract should  not be
                        allowed to become dry.

      7.2  Solvent Exchange:   Prior to  Florisil  cleanup  or gas chromatographic
analysis, the methylene chloride and methylene chloride/acetone  extracts obtained
in Section 7.1.1  must  be  exchanged to  hexane,  as described  in Sections  7.2.1
through 7.2.3.  Exchange is not  required for the acetonitrile extracts obtained
in Section 7.1.2.4.

            7.2.1  Add one or two  clean  boiling chips  to  the  flask and  attach
      a  three  ball Snyder column.   Concentrate the  extract  as  described in
      Section 7.1.2.4.1, using 1 ml of methylene chloride to prewet the column,
      and completing  the  concentration  in  10-20 minutes.   When  the apparent
      volume of liquid reaches 1-2 ml, remove the K-D apparatus from the  water
      bath and allow it to drain and cool for at least  10 minutes.

            7.2.2  Momentarily remove  the Snyder column,  add  50 ml of hexane,
      a new boiling chip,  and attach the macro Snyder column.   Concentrate the
      extract as described in Section  7.1.2.4.1, using  1 ml of  hexane to prewet
      the Snyder column, raising the temperature  of the water bath,  if necessary,
      to maintain proper distillation, and completing the concentration in 10-20
      minutes.  When the  apparent  volume of liquid  reaches  1-2 ml, remove the
      K-D apparatus and allow it to drain and cool  for at least 10 min.

            7.2.3  Remove  the Snyder column and rinse  the  flask and  its  lower
      joint into the concentrator  tube  with 1 to 2  ml  hexane.   A 5 ml syringe
      is recommended for this operation.  Adjust the extract volume to 2  ml for
      water samples,  using either  the micro Snyder column  technique (Section
      7.1.2.4.1) or nitrogen  blowdown  technique (Section  7.1.2.4.2),  or  10 ml
      for solid  samples.   Stopper the  concentrator tube  and  store  at 4°C if
      further processing will be performed immediately.  If the extract will be
      stored for two days  or  longer,  it should  be transferred to a glass vial
      with  a Teflon  lined  screw-cap  or  crimp top.   Proceed  with the  gas
      chromatographic analysis.
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7.3  Cleanup/Fractionation:

      7.3.1  Cleanup may not be necessary for extracts from a relatively
clean   sample   matrix.      If  polychlorinated  biphenyls   (PCBs)   and
organochlorine pesticides are known to be present in the sample, proceed
with the procedure outlined in Methods 3610 or 3620.  Collect Fraction 1
by eluting with 140  ml (Method 3610) or 100 ml (Method  3620) of 20-percent
diethyl  ether  in  hexane.    Note  that,  under these  conditions,  bis(2-
methoxyethyl)  phthalate,  bis(2-ethoxyethyl)  phthalate,  and  bis(2-n-
butoxyethyl) phthalate are not recovered  from the  Florisil  column.   The
elution patterns and compound recoveries are given in Table 3.

      7.3.2  As an  alternative to Method 3620, Florisil Cartridge Cleanup
may  be   used   be   used  for  extract  cleanup.     With  this  method,
bis(2-methoxyethyl)   phthalate,    bis(2-ethoxyethyl)   phthalate,   and
bis(2-n-butoxyethyl) phthalate are recovered quantitatively.

             7.3.2.1  If PCBs and  organochlorine pesticides are known to
      be  present  in the  sample,  and  if  Florisil  Cartridge  Cleanup is
      considered, then two fractions are collected: Fraction 1 is eluted
      with 5 ml of 20 percent methylene chloride  in hexane and Fraction 2
      is eluted with 5 ml  of  10-percent  acetone  in hexane.   The elution
      patterns and compound recoveries are given in Table 4.  Fraction 1
      contains  the  organochlorine  pesticides   and   PCBs,  and  can  be
      discarded.  Fraction  2 contains the phthalate esters and is analyzed
      by GC/ECD.

7.4  Gas chromatographic conditions (recommended):

      7.4.1  Column 1 and Column  2  (Section 4.1.2):
Carrier gas (He) =           6 mL/min.
Injector temperature =       250°C.
Detector temperature =       320°C.
Column temperature:
     Initial temperature =   150°C, hold for 0.5 min.
     Temperature program =   150"C  to 2208C at 5'C/min.,  followed by
                             220°C  to 275°C at 3°C/min.
     Final temperature =     275°C  hold for 13 min.

      7.4.2  Table  1  gives the  retention  times  and MDLs  that  can be
achieved by this method  for the 16 phthalate esters.   An example of the
separations achieved with the DB-5 and DB-1701 fused-silica open tubular
columns is shown in Figure 1.

7.5  Calibration:

      7.5.1  Refer to Method  8000 for proper calibration techniques.  Use
Tables  1  and  2  for guidance  on  selecting the  lowest  point on  the
calibration curve.

      7.5.2  The procedure for internal  or external  calibration  may be
used.    Refer  to  Method  8000  for  the  description  of each  of  these
procedures.
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      7.6  Gas chromatographic analysis:

            7.6.1  Refer to Method 8000.  If the internal standard calibration
      technique is used, add  10 juL of internal  standard solution at 5000 mg/L
      to the sample prior to injection.

            7.6.2  Follow Method 8000 for instructions on the analysis sequence,
      appropriate  dilutions,  establishing daily  retention  time  windows,  and
      identification criteria.

            7.6.3  Record the  sample  volume  injected  and the  resulting  peak
      areas.

            7.6.4  Using either   the   internal  or  the  external  calibration
      procedure (Method 8000), determine the identity and the quantity of each
      component  peak  in  the  sample   chromatogram  which corresponds to  the
      compounds used for calibration purposes.

            7.6.5  If the response of  a peak  exceeds  the working range of the
      system, dilute the extract and reanalyze.

            7.6.6  Identify compounds  in the sample by comparing the retention
      times of the peaks in the sample chromatogram with those of the peaks in
      standard chromatograms.  The retention time window used to make identifica-
      tions is based upon measurements of  actual retention time variations over
      the  course  of  10 consecutive  injections.    Three times  the  standard
      deviation of the  retention time can be used to calculate a suggested window
      size.
8.0  QUALITY CONTROL

      8.1  Refer to Chapter One for specific quality control  procedures.  Quality
control to  validate sample extraction  is covered in  Method 3500 and  in  the
extraction method  utilized.   If extract cleanup was performed,  follow  the QC
specified in Method 3600 and in the specific cleanup method.

      8.2  Mandatory quality  control  to evaluate  the  GC  system  operation is
found in Method 8000.

            8.2.1  The quality control  check  sample  concentrate  (Method 8000)
      should contain the test compounds at 5 to 10 ng//iL.

      8.3  Calculate the recoveries of the surrogate compounds for all samples,
method blanks,  and method spikes.  Determine if the  recoveries are within limits
established by performing QC procedures outlined in Method 8000.

            8.3.1  If the recoveries  are not  within  limits,  the  following  are
     required:

                  8.3.1.1     Make  sure  there are no  errors in  calculations,
            surrogate solutions and internal standards.  Also check instrument
            performance.


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                  8.3.1.2     Recalculate the data and/or reanalyze the extract
            if any of the above checks reveal a problem.

                  8.3.1.3     Reextract and reanalyze the sample  if none of the
            above are a problem,  or flag  the data  as "estimated concentration."

      8.4  An internal  standard peak area check must be performed on all samples.
The internal standard  must  be  evaluated  for  acceptance by determining whether
the measured area for the internal standard deviates by more than 30 percent from
the average area for the internal standard in the calibration standards.  When
the internal standard  peak  area  is outside that  limit,  all  samples  that fall
outside the QC criteria must be reanalyzed.

      8.5  GC/MS confirmation:  Any compounds confirmed by two columns may also
be confirmed by GC/MS if the concentration is  sufficient  for detection by GC/MS
as determined by the laboratory-generated detection limits.

            8.5.1  The GC/MS would normally require a minimum concentration of
      10 ng/jiL in the  final  extract for each  single-component compound.

            8.5.2  The sample extract and  associated  blank should  be analyzed
      by GC/MS as per Section 7.0 of Method 8270.   Normally, analysis of a blank
      is not required for confirmation analysis, however, analysis  for phthalates
      is a  special  case because  of the possibility  for sample  contamination
      through septum punctures, etc.

            8.5.3  A reference standard of the compound  must  also  be analyzed
      by GC/MS.   The  concentration of  the  reference standard  must be  at  a
      concentration that would  demonstrate the ability  to confirm the phthalate
      esters identified by GC/ECD.

      8.6  Include a mid-concentration calibration standard after each group of
20 samples  in   the   analysis   sequence.     The  response  factors   for  the
mid-concentration calibration must be within ± 15  percent of the average values
for the multiconcentration calibration.

      8.7  Demonstrate  through  the analyses  of  standards  that  the  Florisil
fractionation scheme  is reproducible.    When  using the  fractionation  schemes
given in Methods 3610 or 3620,  batch-to-batch variations in the composition of
the alumina or Florisil material  may cause variations in the recoveries of the
phthalate esters.


9.0  METHOD PERFORMANCE

      9.1  The MDL is  defined in  Chapter One.  The MDL concentrations listed in
Table 1 were  obtained  using organic-free  reagent water.   Details  on  how  to
determine MDLs are given in Chapter One.   The MDL actually achieved  in a given
analysis will vary,  as it  is  dependent  on instrument sensitivity and matrix
effects.

      9.2  This method  has been tested in a single  laboratory by using different
types of aqueous samples and solid  samples which  were fortified  with the test


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compounds at two concentrations.   Single-operator precision, overall precision,
and  method  accuracy  were found  to be  related  to  the  concentration  of the
compounds and  the type  of matrix.   Results of the  single-laboratory method
evaluation are presented  in Tables 5, 6, and 7.
      9.3  The  accuracy  and
matrix,  sample  preparation
procedures used.
precision obtained  is determined  by the  sample
technique,  cleanup  techniques,  and  calibration
10.0 REFERENCES

1.   Glazer, J.A.;  Foerst,  G.D.; McKee,  G.D.;  Quave, S.A.,  and  Budde,  W.L.,
     "Trace Analyses  for Wastewaters,"  Environ.  Sci. and  Technol.  15:  1426,
     1981.                      v

2.   Lopez-Avila, V.,  Baldin,  E., Benedicto, J., Milanes,  J., and Beckert, W.F.,
     "Application of Open-Tubular Columns to SW-846 GC Methods", EMSL-Las Vegas,
     1990.

3.   Beckert,  W.F. and Lopez-Avila,  V.,  "Evaluation  of SW-846 Method 8060 for
     Phthalate Esters", Proceedings of Fifth Annual Testing and Quality Assurance
     Symposium, USEPA, 1989.
                                  8061  -  13
                                     Revision 0
                                     November 1990

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                                        TABLE  1.
GAS CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS FOR THE  PHTHALATE  ESTERS3

Compound
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
IS
SU-1
SU-2
SU-3


Compound name
Dimethyl phthalate (DMP)
Diethyl phthalate (DEP)
Diisobutyl phthalate (DIBP)
Di-n-butyl phthalate (DBP)
Bis(4-methyl-2-pentyl) phthalate (BMPP)
Bis(2-methoxyethyl) phthalate (BMEP)
Diamyl phthalate (DAP)
Bis(2-ethoxyethyl) phthalate (BEEP)
Hexyl 2-ethylhexyl phtfralate (HEHP)
Dihexyl phthalate (DHP)
Butyl benzyl phthalate (BBP)
Bis(2-n-butoxyethyl) phthalate (BBEP)
Bis(2-ethylhexyl) phthalate (DEHP)
Dicyclohexyl phthalate (DCP)
Di-n-octyl phthalate (OOP)
Dinonyl phthalate
Benzyl benzoate
Diphenyl phthalate (DPP)
Diphenyl isophthalate (DPIP)
Di benzyl phthalate (DBZP)
Chemical
Abstract
Registry
No.
131-11-3
84-66-2
84-69-5
84-74-2
146-50-9
117-82-8
131-18-0
605-54-9
75673-16-4
84-75-3
85-68-7
117-83-9
117-81-7
84-61-7
117-84-0
84-76-4
120-51-4
84-62-8
744-45-6
523-31-9
Retention time
(min)

Column 1
7.06
9.30
14.44
16.26
18.77
17.02
20.25
19.43
21.07
24.57
24.86
27.56
29.23
28.88
33.33
38.80
12.71
29.46
32.99
34.40

Column 2
6.37
8.45
12.91
14.66
16.27
16.41
18.08
18.21
18.97
21.85
23.08
25.24
25.67
26.35
29.83
33.84
11.07
28.32
31.37
32.65
MDLb
Liquid
(ng/L)
640
250
120
330
370
510
110
270
130
68
42
84
270
22
49
22
c
c
c
c
                                        8061 - 14
Revision 0
November 1990

-------
                                     Table 1.  (continued)

Column 1 is a 30 m x 0.53 mm ID DB-5 fused-silica open tubular column (1.5 urn film thickness).
Column 2 is a 30 m 0.53 mm ID DB-1701 fused-silica open tubular column (1.0 /xm  film thickness).
Temperature program is 150°C (0.5 min hold) to 220'C at 5°C/min, then to 275°C  (13 min hold) at
3eC/min.  An 8-in Supelco injection tee or a J&W Scientific press fit glass inlet splitter is used
to connect the two columns to the injection port of a gas chromatograph.  Carrier gas helium at
6 mL/min; makeup gas nitrogen at 20 mL/min; injector temperature 250°C; detector temperature
320°C.

MDL is the method detection limit.  The MDL was determined from the analysis of seven replicate
aliquots of organic-free reagent water processed through the entire analytical method (extraction,
Florisil cartridge cleanup, and GC/ECD analysis using the single column approach:  DB-5 fused-
silica capillary column).  MDL = t(n.1-0_gg) x SD where t(rKli099)  is the  student's t value appropriate  for
a 99 percent confidence interval and' a standard deviation with n-1 degrees of freedom, and SD is
the standard deviation of the seven replicate measurements.  Values measured were not corrected
for method blanks.

Not applicable.
                                           8061 - 15                                      Revision  0
                                                                                          November 1990

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                             TABLE 2.
     ESTIMATED QUANTITATION LIMITS (EQL)  FOR VARIOUS MATRICES8


Matrix                                                Factor"
Groundwater                                                10
Low-concentration soil by ultrasonic extraction          670
  with GPC cleanup
High-concentration soil and sludges by ultrasonic      10,000
  extraction
Non-water miscible waste                              100,000
Sample EQLs are highly matrix dependent.  The EQLs listed herein are
provided for guidance and may not always be achievable.

EQL = [Method detection limit (Table 1)] X [Factor (Table 2)].  For
nonaqueous samples, the factor is on a wet weight basis.
                             8061  -  16                      Revision 0
                                                           November 1990

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                                   TABLE 3.
  AVERAGE RECOVERIES OF METHOD 8061 COMPOUNDS USING METHODS 3610, 3620, AND
            THE  ALUMINA AND  FLORISIL  DISPOSABLE  CARTRIDGE  PROCEDURE
Compound
Dimethyl phthalate
Diethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-pentyl) phthalate
Bis(2-methoxyethyl) phthalate
Diamyl phthalate
Bis(2-ethoxyethyl) phthalate
Hexyl 2-ethylhexyl phthalate
Dihexyl phthalate
Benzyl butyl phthalate
Bis(2-n-butoxyethyl) phthalate
Bis(2-ethylhexyl) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate
Method
3610
alumina8
64.5
62.5
77.0
76.5
89.5
70.5
75.0
67.0
90.5
73.0
87.0
62.5
91.0
84.5
108
71.0
Method
3620
Florisil*
40.0
57.0
80.0
85.0
84.5
0
81.5
0
105
74.5
90.0
0
82.0
83.5
115
72.5
Alumina
cartridge"
101
103
104
108
103
64. lc
103
111
101
108
103
108
97.6
97.5
112
97.3
Florisil
cartridge"
89.4
97.3
91.8
102
105
78. 3e
94.5
93.6
96.0
96.8
98.6
91.5
97.5
90.5
97.1
105
a 2 determinations; alumina and Florisil chromatography performed according
  to Methods 3610 and 3620, respectively.

b 2 determinations, using 1 g alumina cartridges; Fraction 1 was eluted with
  5 mL of 20-percent acetone in hexane.  40 /ug of each component was spiked
  per cartridge.

0 36.8 percent was recovered by elution with an additional 5 mL of
  20-percent acetone in hexane.

d 2 determinations, using 1 g Florisil cartridges; Fraction 1 was eluted
  with 5 mL of 10-percent acetone in hexane.  40 /ug of each component was
  spiked per cartridge.

e 14.4 percent was recovered by elution with an additional 5 mL of
  10-percent acetone in hexane.
                                   8061  -  17
Revision 0
November 1990

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                                TABLE 4.
     ELUTION AND AVERAGE RECOVERIES OF METHOD 8061 COMPOUNDS USING
                   THE FLORISIL DISPOSABLE CARTRIDGES
               Compound
    Percent recovery8

Fraction 1       Fraction  2
Dimethyl phthalate
Diethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-pentyl) phthalate
Bis(2-methoxyethyl) phthalate
Diamyl phthalate
Bis(2-ethoxyethyl) phthalate
Hexyl 2-ethylhexyl phthalate
Dihexyl phthalate
Benzyl butyl phthalate
Bis(2-n-butoxyethyl) phthalate
Bis (2-ethylhexyl) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate
0
0
0
12
0
0
3.3
0
0
0
0
0
0
0
0
0
130
88
118
121
123
32
94
82
126
62
98
135
110
106
123
102
(52)
(2.8)
(16)
(13)
(5.7)
(31)
(8.3)
(19)
(6.4)
(15)
(6.5)
(34)
(2.7)
(3.3)
(7.0)
(8.7)
The number of determinations was 3.  The values given in parentheses are
the percent relative standard deviations of the average recoveries.
                               8061  -  18
                     Revision 0
                     November 1990

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                                TABLE 5.
            ACCURACY  AND  PRECISION DATA FOR EXTRACTION USING
                   THE  3M-EMPORE DISKS AND METHOD 8061
HPLC-qrade water


Compound
Dimethyl phthalate
Diethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-pentyl) phthalate
Bis(2-methoxyethyl) phthalate
Dlamyl phthalate
Bis(2-ethoxyethyl) phthalate
Hexyl 2-ethylhexyl phthalate
Dlhexyl phthalate
Benzyl butyl phthalate
Bis(2-n-butoxyethyl) phthalate
Bis (2-ethylhexyl) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate
Average
recovery
(%)
88.6
92.3
87.6
90.3
87.2
107
93.6
108
93.9
98.4
97.3
94.8
91.3
106
84.9
96.9

Precision
(% RSD)
17.7
10.3
16.2
13.2
9.5
13.6
21.0
8.9
22.4
5.0
2.6
6.3
7.4
19.9
3.8
11.1
Groundwater
Average
recovery
i°/\
(A)
86.6
92.6
89.3
95.0
86.7
113
78.9
102
83.4
97.7
66.0
98.7
96.3
108
90.1
95.2

Precision
(% RSD)
14.3
7.2
1.6
1.5
4.9
2.8
5.8
4.0
8.8
14.8
39.3
6.0
7.9
13.3
6.1
12.7
The number of determinations was 4.
100 MgA per component.
The spiking concentration was
                               8061 - 19
                         Revision 0
                         November 1990

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                                                     TABLE 6.
                           ACCURACY AND  PRECISION DATA FOR METHOD 3510 AND METHOD 8061a
Spike Concentration
(20 ua/L)
Estuarine
Compound
Dimethyl phthalate
Di ethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-pentyl) phthalate
Bis(2-methoxyethyl) phthalate
Diamyl phthalate
Bis(2-ethoxyethyl) phthalate
Hexyl 2-ethylhexyl phthalate
Djhexyl phthalate
Benzyl butyl phthalate
Bis(2-n-butoxyethyl) phthalate
Bis (2-ethylhexyl) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate
Surrogates:
Diphenyl phthalate
Diphenyl isophthalate
Di benzyl phthalate
water
84.0
71.2
76.0
83.2
78.6
73.8
78.2
75.6
84.7
79.8
84.1
78.5
81.4
77.4
74.9
59.5

98.5
95.8
93.9
(4.1)
(3.8)
(6.5)
(6.5)
(2.6)
(1.0)
(7.3)
(3.3)
(5.3)
(7.2)
(6.4)
(3.5)
(4.1)
(6.5)
(4.9)
(6.1)

(2.6)
(1.9)
(4.4)
Leachate
98
82
95
97
87
87
92
90
91
102
105
92
93
88
87
77

113
112
112
.9 (19.6)
.8 (19.3)
.3 (16.9)
.5 (22.3)
.3 (18.2)
.2 (21.7)
.1 (21.5)
.8 (22.4)
.1 (27.5)
(21.5)
(20.5)
.3 (16.1)
.0 (15.0)
.2 (13.2)
.5 (18.7)
.3 (4.2)

(14.9)
(11.7)
(14.0)
Estuarine
Groundwater
87.1
88.5
92.7
91.0
92.6
82.4
88.8
86.4
81.4
90.9
89.6
89.3
90.5
91.7
87.2
67.2

110
109
106
(8.1)
(15.3)
(17.1)
(10.7)
(13.7)
(4.4)
(7.5)
(5.8)
(17.6)
(7.6)
(6.1)
(3.6)
(4.9)
(15.2)
(3.7)
(8.0)

(3.3)
(3.3)
(3.8)
Spike Concentration
(60 ua/U
water
87.1
71.0
99.1
87.0
97.4
82.5
89.2
88.7
107
90.1
92.7
86.1
86.5
87.7
85.1
97.2

110 (
104
111
(7.5)
(7.7)
(19.0)
(8.0)
(15.0)
(5.5)
(2.8)
(4.9)
(16.8)
(2.4)
(5.6)
(6.2)
(6.9)
(9.6)
(8.3)
(7.0)

12.4)
(5.9)
(5.9)
Leachate
112
88.5
100
106
107
99.0
112
109
117
109
117
107
108
102
105
108

95.1
97.1
93.3
(17.5)
(17.9)
(9.6)
(17.4)
(13.3)
(13.7)
(14.2)
(14.6)
(11.4)
(20.7)
(24.7)
(15.3)
(15.1)
(14.3)
(17.7)
(17.9)

(7.2)
(7.1)
(9.5)
Groundwater
90.9 (4.5)
75.3 (3.5)
83.2 (3.3)
87.7 (2.7)
87.6 (2.9)
76.9 (6.6)
92.5 (1.8)
84.8 (5.9)
80.1 (4.1)
88.9 (2.4)
93.0 (2.0)
92.4 (0.6)
91.1 (3.0)
71.9 (2.4)
90.4 (2.0)
90.1 (1.1)

107 (2.4)
106 (2.8)
105 (2.4)
The number of determinations was 3.
the average recoveries.
The values given in parentheses are the percent relative standard deviations of
                                                     8061  -  20
                                                                    Revision  0
                                                                    November 1990

-------
                                                          TABLE 7.
                                ACCURACY AND PRECISION DATA FOR METHOD 3550 AND METHOD 8061a
Spike Concentration
(1 mq/Ka)
Compound
Dimethyl phthalate
Di ethyl phthalate
Diisobutyl phthalate
Di-n-butyl phthalate
Bis(4-methyl-2-pentyl) phthalate
Bis(2-methoxyethyl) phthalate
Diamyl phthalate
Bis(2-ethoxyethyl) phthalate
Hexyl 2-ethylhexyl phthalate
Dihexyl phthalate
Benzyl butyl phthalate
Bis(2-n-butoxyethyl) phthalate
Bis(2-ethylhexyl) phthalate
Dicyclohexyl phthalate
Di-n-octyl phthalate
Dinonyl phthalate
Estuarine
sediment
77.9
68.4
103
121
108
26.6
95.0
c
c
103
113
114
c
36.6
c
c
(42.8)
(1.7)
(3.1)
(25.8)
(57.4)
(26.8)
(10.2)


(3.6)
(12.8)
(21.1)

(48.8)


Municipal
sludge
52.1
68.6
106
86.3
97.3
72.7
81.9
66.6
114
96.4
82.8
74.0
76.6
65.8
93.3
80.0
(35.5)
(9.1)
(5.3)
(17.7)
(7.4)
(8.3)
(7.1)
(4.9)
(10.5)
(10.7)
(7.8)
(15.6)
(10.6)
(15.7)
(14.6)
(41.1)
Sandy loam
soil
c
54.7
70.3
72.6
c
0
81.9
c
57.7
77.9
56.5
c
99.2
92.8
84.7
64.2

(6.2)
(3.7)
(3.7)


(15.9)

(2.8)
(2.4)
(5.1)

(25.3)
(35.9)
(9.3)
(17.2)
Spike Concentration
(3 U.Q/Q)
Estuarine
sediment
136
60.2
74.8
74.6
104
19.5
77.3
21.7
72.7
75.5
72.9
38.3
59.5
33.9
36.8
c
(9.6)
(12.5)
(6.0)
(3.9)
(1.5)
(14.8)
(4.0)
(22.8)
(11.3)
(6.8)
(3.4)
(25.1)
(18.3)
(66.1)
(16.4)

Municipal
sludge
64.8 (11.5)
72.8 (10.0)
84.0 (4.6)
113 (5.8)
150 (6.1)
59.9 (5.4)
116 (3.7)
57.5 (9.2)
26.6 (47.6)
80.3 (4.7)
76.8 (10.3)
98.0 (6.4)
85.8 (6.4)
68.5 (9.6)
88.4 (7.4)
156 (8.6)
Sandy loam
soil
70.2
67.0
79.2
70.9
83.9
0
82.1
84.7
28.4
79.5
67.3
62.0
65.4
62.2
115
115
(2.0)
(15.1)
(0.1)
(5.5)
(11.8)

(15.5)
(8.5)
(4.3)
(2.7)
(3.8)
(3.4)
(2.8)
(19.1)
(29.2)
(13.2)
a  The number of determinations was 3.  The values given in parentheses are the percent relative standard deviations of the
   average recoveries.  All samples were subjected to Florisil cartridge cleanup.

b  The estuarine sediment extract (Florisil, Fraction 1) was subjected to sulfur cleanup (Method 3660 with
   tetrabutylammonium sulfite reagent).

c  Not able to determine because of matrix interferant.
                                                          8061 - 21
Revision 0
November 1990

-------
                                             Figure 1
                                                  OB-S
                                                  30 m x 0.53 mm ID
                                                  1.5-p.m Film
                                  IS
                               11   12 SU-1 SU-2 SU-3
                  6    6

                     5
                                                             14
                                                                13
                                                                               16
             I-
             o
             L1J
1        IS
        I
                                                                SU-2 SU-3

                                                        12  SU-1 15  I  i 16
                                                        113
                                                   DB-1701
                                                   30 mx 0.53 mm ID
                                                   1.0-p.mFilm
                                                  10
                                                    11
                                                          14


V
u


u
u
JL
JL
MxJU^1
i i
                              10
                       20

                  TIME (min)
                                                                 30
                                                          40
GC/ECD chromatograms of a composite  phthalate esters standard  (concentration 10 ng//iL per
compound) analyzed on a DB-5 and a DB-1701 fused-silica open tubular column.  Temperature
program: 150°C (0.5  min hold) to 220°C at 5°C/min, then to  275°C  (13  min hold) at 3°C/nrin.
                                            8061  -  22
                                                     Revision  0
                                                     November  1990

-------
           ISTARf)
                         METHOD  8061
PHTHALATE ESTERS  BY  CAPILLARY  GAS CHRQMATQGRAPHY
     WITH  ELECTRON CAPTURE  DETECTION  (GC/ECD)
 7.1 Extraction
 7.1.1 Refer to Chapter 2  for
      guidance on choosing
      an extraction  procedure.
      Reccomendations given.
 7.1.2 Determine  spike sample
      recovery and detection limit
      for each new sample matrix
      and a given  extraction
      procedure.	
 7.1.3 Aqueous sample extraction
      with CIS disks:
     .1  Precondition disks using
        solvent train.
     .2  Concentrate sample
        analytes  on disk.
     .3  Elute sample analytes
        with acetonitrile.
     .4  Concentrate extract:
        .1 Micro-Snyder Column
          Technique
        .2 Nitrogen Slowdown
          Technique
          .1 Evaporate  solvent to
             desired level.
          .2 Rinse tube walls
             frequently  and  avoid
             evaporating to  dryness,
 7.2 Solvent Exchange  to Hexane
 7.2.1 Evaporate extract volume to
	1-2 ml. using  K-D assembly.
 7.2.2 Add hexane to K-D assembly
	and evaporate to 1-2 ml.
 7.2.3 Rinse K-D components and
      adjust volume to desired
      level.
                                                                             1
                                        7.3 Cleanup/Fractionation
                                        7.3.1 Cleanup may not be necessary
                                             for extracts w/clean sample
                                             matrices.  Fraction  collection
                                             and methods outlined for
                                             other compd. groups of
                                             interest.
                                        7.3.2 Florisil Cartridge Cleanup
                                            .1  Check each lot of  Florisil
                                               cartridge  for analyte
                                               recovery by eluting and
                                               analyzing a composite std.
                                            .2  Wash and adjust solvent
                                               flow through cartridges.
                                            .3  Place culture tubes or 5 ml.
                                               vol. flasks for eluate
                                               collection.
                                            .4  Transfer appropriate extract
                                               volume on cartridge.
                                            .5  Elute the cartridges and
                                               dilute to mark on  flask.
                                               Transfer eluate to  glass
                                               vials for concentration.
                                        7.3.3 Collect 2 fractions if PCBs
                                             and organochlorine pesticides
                                             are known to be present.
                                                              7.4 Gas Chromatograph
                                                            |  7.4.1 Set GC operating parameters.  |
                                                              7.4.2 Table  1 and Figure 1  shows
                                                                   MDLs and analyte retention
                                                                   times.
                                               8061  -  23
                                                                    Revision 0
                                                                    November 1990

-------
        METHOD 8061
             m  m
              A
7.5 Calibration
1
7.5.1
'
See Mefhod 8000 for
calibration technique.
1
7.5.2
F
Refer to Method 8000 for
internal/external std.
procedure.
1

7.6 GC Analysis
7.6.1  Refer to Method 8000.
1
7.6.2
F
Follow Section 7.6 in
Method 8000 for instructions
on analysis sequence,
dilutions, retention time
windows, and identification
criteria.
i
7.6.3

Record injection volume and
sample peak areas.
i
7.6.4
r
Identify and quantify each
component peak using the
internal or external std.
procedure.
\
7.6.5
r
Dilute extracts which show
analyte levels outside of the
calibration range.
i
7.6.6
r
Identify compounds in the
sample by comparing
retention times in the
sample and the standard
chromatograms.
i
i
        8061  -  24
Revision  0
November  1990

-------
                                 METHOD 8080B

            ORGANOCHLORINE PESTICIDES  AND  POLYCHLORINATED  BIPHENYLS
                             BY  GAS  CHROMATOGRAPHY
1.0  SCOPE AND APPLICATION

      1.1  Method  8080  is  used  to determine  the  concentration  of  various
organochlorine pesticides and polychlorinated biphenyls (PCBs).  The following
compounds can be determined by this method:
     Compound Name
CAS No.4
     Aldrin
     a-BHC
     /3-BHC
     6-BHC
     T-BHC  (Lindane)
     Chlordane (technical)
     4,4'-DDD
     4,4'-DDE
     4,4'-DDT
     Dieldrin
     Endosulfan I
     Endosulfan II
     Endosulfan sulfate
     Endrin
     Endrin aldehyde
     Heptachlor
     Heptachlor epoxide
     4,4'-Methoxychlor
     Toxaphene
     Aroclor-1016
     Aroclor-1221
     Aroclor-1232
     Aroclor-1242
     Aroclor-1248
     Aroclor-1254
     Aroclor-1260
  309-00-2
  319-84-6
  319-85-7
  319-86-8
   58-89-9
12789-03-6
   72-54-8
   72-55-9
   50-29-3
   60-57-1
  959-98-8
33212-65-9
 1031-07-8
   72-20-8
 7421-93-4
   76-44-8
 1024-57-3
   72-43-5
 8001-35-2
12674-11-2
 1104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
a  Chemical Abstract Services Registry Number.
      1.1  Table 1  lists the method detection limit for each compound in organic-
free reagent water.  Table  2  lists  the  estimated  quantitation  limit  (EQL)  for
other matrices.
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2.0  SUMMARY OF METHOD

      2.1  Method 8080 provides gas chromatographic conditions for the detection
of ppb concentrations of certain organochlorine pesticides and PCBs.  Prior to
the use of this method, appropriate sample extraction techniques must be used.
Both neat  and diluted  organic  liquids (Method  3580,  Waste  Dilution)  may be
analyzed by  direct injection.   A 2  to 5 nl sample  is  injected  into  a  gas
chromatograph (GC) using the  solvent  flush technique,  and compounds in the GC
effluent are detected by an electron capture detector (ECD) or an electrolytic
conductivity detector (HECD).

      2.2  The sensitivity of Method 8080 usually depends on the concentration
of  interferences  rather than on  instrumental limitations.   If interferences
prevent detection of the analytes,  Method 8080 may also be performed on samples
that have undergone cleanup.  Method  3620,  Florisil  Column Cleanup, by itself
or  followed  by  Method  3660,   Sulfur Cleanup,  may  be  used  to  eliminate
interferences in the analysis.


3.0  INTERFERENCES

      3.1  Refer to Methods 3500, 3600, and 8000.

      3.2  Interferences  by  phthalate esters  can  pose  a  major   problem  in
pesticide determinations  when  using   the  electron  capture  detector.   These
compounds generally  appear in the  chromatogram as large  late-eluting peaks,
especially in  the 15%  and  50%  fractions from  the  Florisil  cleanup.   Common
flexible plastics contain varying amounts of phthalates.   These phthalates are
easily extracted or leached  from such materials during laboratory  operations.
Cross contamination of clean glassware  routinely occurs when plastics are handled
during extraction  steps, especially when  solvent-wetted  surfaces are handled.
Interferences from phthalates can best  be minimized by  avoiding contact with any
plastic materials. Exhaustive cleanup  of reagents and  glassware  may be required
to  eliminate  background  phthalate  contamination.     The contamination  from
phthalate  esters  can  be  completely   eliminated  with  a microcoulometric  or
electrolytic conductivity detector.


4.0  APPARATUS AND MATERIALS

      4.1  Gas chromatograph

            4.1.1  Gas  Chromatograph:    Analytical  system  complete  with  gas
      chromatograph   suitable  for  on-column  injections  and   all  required
      accessories, including  detectors, column  supplies,  recorder,  gases,  and
      syringes.  A data system for measuring peak heights and/or peak areas is
      recommended.

            4.1.2  Columns

                  4.1.2.1  Column  1:   Supelcoport (100/120  mesh)  coated with
            1.5% SP-2250/1.95% SP-2401 packed in a 1.8 m  x 4  mm  ID glass column
            or equivalent.


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                  4.1.2.2  Column 2:   Supelcoport  (100/120 mesh) coated with 3%
            OV-1 in a 1.8 m x 4 mm ID glass column or equivalent.

            4.1.3  Detectors:     Electron  capture   (ECD)   or   electrolytic
      conductivity detector (HECD).

      4.2  Kuderna-Danish (K-D) apparatus:

            4.2.1  Concentrator tube:   10  ml,  graduated  (Kontes  K-570050-1025
      or equivalent).  A ground-glass stopper is used to prevent evaporation of
      extracts.

            4.2.2  Evaporation  flask:     500   mL   (Kontes  K-570001-500   or
      equivalent).   Attach  to  concentrator   tube  with   springs,  clamps,  or
      equivalent.

            4.2.3  Snyder column:   Three ball  macro  (Kontes K-503000-0121 or
      equivalent).

            4.2.4  Snyder  column:    Two ball   micro  (Kontes K-569001-0219 or
      equivalent).

            4.2.5  Springs -  1/2 inch  (Kontes  K-662750 or equivalent).

      4.3  Boiling chips:  Solvent  extracted, approximately 10/40 mesh (silicon
carbide or equivalent).

      4.4  Water  bath:    Heated,  with  concentric  ring  cover,  capable  of
temperature control  (±5°C).   The bath should be used  in a  hood.

      4.5  Volumetric flasks, Class A:  10,  50, and 100 ml, ground-glass stopper.

      4.6  Microsyringe:  10 nl.

      4.7  Syringe:  5 ml.

      4.8  Vials:  Glass, 2,  10, and 20 ml capacity with Teflon-lined screw caps
or crimp tops.

      4.9  Balances:  Analytical, 0.0001 g and  Top loading,  0.01  g.


5.0  REAGENTS

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

      5.2  Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.


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      5.3  Solvents

            5.3.1  Hexane, C6H14 - Pesticide quality or equivalent.

            5.3.2  Acetone,  CH3COCH3 - Pesticide quality or equivalent.

            5.3.3  Toluene, C6H5CH3 - Pesticide quality or equivalent.

            5.3.4  Isooctane, (CH3)3CCH2CH(CH3)2 - Pesticide quality or equivalent.

      5.4  Stock standard solutions:

            5.4.1  Prepare  stock  standard  solutions  at  a  concentration  of
      1000 mg/L by dissolving 0.0100 g of assayed reference material in isooctane
      and diluting to  volume  in  a 10 ml volumetric flask.  A  small  volume of
      toluene may  be necessary  to put some  pesticides  in solution.   Larger
      volumes can  be used at the  convenience of the analyst.   When compound
      purity is  assayed  to  be 96% or greater, the weight  can  be used without
      correction  to  calculate  the  concentration  of  the  stock  standard.
      Commercially prepared stock standards can  be  used at  any concentration if
      they are certified by the manufacturer or by an independent source.

            5.4.2  Transfer the stock standard solutions into vials with Teflon-
      lined screw  caps or crimp tops.   Store at  4°C and  protect  from light.
      Stock standards should be checked frequently for signs of degradation or
      evaporation, especially just  prior to preparing calibration  standards from
      them.

            5.4.3  Stock standard solutions must be replaced after one year, or
      sooner if comparison with check standards indicates a problem.

      5.5  Calibration standards:   Calibration  standards  at  a  minimum of five
concentrations for each parameter of interest are prepared through dilution of
the stock standards  with  isooctane.  One  of the concentrations should be at a
concentration near,  but  above,  the method detection limit.    The  remaining
concentrations should correspond to the expected range of concentrations found
in real  samples  or  should  define  the  working  range  of  the GC.   Calibration
solutions must be replaced after  six months, or sooner,  if comparison with check
standards indicates  a problem.

      5.6  Internal  standards  (if  internal  standard calibration  is  used):   To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior to  the compounds of interest.  The analyst
must further demonstrate  that  the  measurement of the  internal  standard is not
affected by method or  matrix  interferences.   Because  of  these  limitations, no
internal standard can be suggested that is applicable to all  samples.

            5.6.1  Prepare  calibration   standards  at  a  minimum   of  five
      concentrations for each analyte of interest as described in Section 5.5.

            5.6.2  To each calibration  standard,  add a  known constant amount of
      one or more internal standards, and dilute to volume with isooctane.

            5.6.3  Analyze each calibration standard according to Section 7.0.

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      5.7  Surrogate standards:  The analyst should monitor the performance of
the extraction, cleanup (when used), and analytical  system and the effectiveness
of  the  method  in  dealing  with  each  sample  matrix  by  spiking  each  sample,
standard,  and  organic-free  reagent water blank  with  pesticide  surrogates.
Because GC/ECD data are much more  subject to interference than GC/MS, a secondary
surrogate  is  to be  used when sample interference  is  apparent.   Two surrogate
standards (tetrachloro-m-xylene (TCMX)  and decachlorobiphenyl)  are added to each
sample;  however,  only  one need  be calculated  for  recovery.    Proceed  with
corrective action when both surrogates are out of limits for a sample (Section
8.3). Method  3500 indicates the proper  procedure for preparing these surrogates.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See  the  introductory  material  to  this  chapter, Organic  Analytes,
Section 4.1.   Extracts  must  be stored  under refrigeration and analyzed within
40 days of extraction.


7.0  PROCEDURE

      7.1  Extraction:

            7.1.1  Refer to Chapter Two for guidance on choosing the appropriate
      extraction  procedure.    In general,  water samples  are  extracted  at  a
      neutral,  or as  is,  pH  with methylene chloride,  using either Method 3510
      or 3520.  Solid samples are extracted using either Method 3540 or 3550.

            7.1.2  Prior to gas chromatographic analysis,  the extraction solvent
      must be exchanged to hexane.  The exchange  is  performed  during  the K-D
      procedures  listed in all  of the extraction  methods.  The  exchange is
      performed as follows.

                  7.1.2.1  Following K-D of the  methylene chloride extract to
            1 mL using the macro-Snyder column,  allow  the apparatus to cool and
            drain for at least 10 min.

                  7.1.2.2  Increase the  temperature of the hot  water  bath to
            about 90°C.   Momentarily remove the  Snyder  column,  add 50  mL of
            hexane, a  new  boiling  chip,  and reattach  the macro-Snyder column.
            Concentrate the extract using  1 mL  of hexane to prewet the Snyder
            column.   Place the  K-D apparatus  on  the water bath  so  that the
            concentrator tube  is  partially immersed in the hot water.   Adjust
            the vertical position  of  the  apparatus and the water temperature,
            as  required, to complete concentration  in 5-10 min.  At the proper
            rate of distillation  the balls  of the column  will actively chatter,
            but the chambers will  not flood.  When the  apparent volume of liquid
            reaches 1  mL,  remove the K-D apparatus and  allow it to drain and cool
            for at least 10 min.

                  7.1.2.3  Remove the Snyder column and rinse the flask and its
            lower joint into the concentrator tube with 1-2 mL of hexane.  A 5 mL
            syringe is recommended for this operation.  Adjust the  extract volume
            to  10.0 mL.   Stopper the  concentrator tube and store refrigerated

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            at 4°C,  if further processing will not be performed immediately.  If
            the  extract will be  stored longer  than two  days,  it  should be
            transferred to a vial with  a Teflon-lined screw cap or crimp top.
            Proceed with gas chromatographic analysis if further cleanup is not
            required.

      7.2  Gas chromatography conditions (Recommended):

            7.2.1  Column 1:
      Carrier gas (5% methane/95% argon) flow rate:   60 mL/min
      Column temperature:                             200°C isothermal

            When analyzing for the low molecular weight PCBs (PCB 1221-PCB 1248),
      it is advisable to set the oven temperature to 160°C.

            7.2.2  Column 2:
      Carrier gas (5% methane/95% argon) flow rate:   60 mL/min
      Column temperature:                             200°C isothermal

            When analyzing for the low molecular weight PCBs (PCB 1221-PCB 1248),
      it is advisable to set the oven temperature to 140°C.

            7.2.3  When analyzing  for most or all  of the analytes in this method,
      adjust the oven  temperature and column gas flow  so  that 4,4'-DDT has a
      retention time of approximately 12 min.

      7.3  Calibration:  Refer to Method 8000 for  proper  calibration techniques.
Use Table 1 and  especially Table  2  for  guidance  on selecting the  lowest point
on the calibration curve.

            7.3.1  The  procedure  for internal  or external  calibration  may be
      used.  Refer to Method 8000 for a description of each  of these procedures.

            7.3.2  Because  of  the  low  concentration  of  pesticide  standards
      injected on a GC/ECD,  column adsorption may be a problem when the GC has
      not been used  for a day.   Therefore, the  GC  column  should  be  primed or
      deactivated by injecting a PCB or pesticide  standard mixture approximately
      20 times more  concentrated  than the  mid-concentration standard.   Inject
      this prior to beginning initial or daily calibration.

      7.4  Gas chromatographic analysis:

            7.4.1  Refer to Method 8000.  If the internal standard calibration
      technique is used, add 10 /zL of internal standard to the sample prior to
      injection.

            7.4.2  Method 8000 provides  instructions on the analysis  sequence,
      appropriate dilutions,  establishing  daily  retention time windows,  and
      identification criteria.   Include  a mid-concentration  standard after each
      group of 10 samples in the analysis sequence.

Note: A 72 hour sequence is  not required with this method.
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           7.4.3  Examples of GC/ECD chromatograms for various pesticides and
     PCBs are shown in Figures 1 through 5.

           7.4.4  Prime the column as per Section 7.3.2.

           7.4.5  DDT and endrin are easily degraded in the injection port if
     the injection port or front of  the  column is dirty.   This is the result
     of  buildup of high  boiling  residue from sample  injection.   Check for
     degradation problems by injecting  a  mid-concentration standard containing
     only 4,4'-DDT and endrin.  Look for the degradation products of 4,4'-DDT
     (4,4'-DDE  and 4,4'-ODD)  and endrin  (endrin ketone and endrin aldehyde).
     If degradation of either  DDT or endrin exceeds 20%,  take corrective action
     before proceeding with calibration,  by following the GC system maintenance
     outlined in of Method 8000.  Calculate percent breakdown as follows:


% breakdown     Total DDT degradation peak area  (DDE + DDD)
for 4,4'-DDT =  	   x 100
                          peak areas (DDT + DDE + DDD)


                  Total endrin degradation peak area
% breakdown       (endrin aldehyde + endrin ketone)
for Endrin   =  	   x 100
                 peak areas (endrin + aldehyde + ketone)


           7.4.6  Record  the  sample volume  injected  and the  resulting  peak
     sizes (in  area units or peak heights).

           7.4.7  Using either the internal or external calibration procedure
     (Method 8000), determine the  identity and  quantity  of each component peak
     in the  sample  chromatogram which corresponds to the  compounds used for
     calibration purposes.

           7.4.8  If peak detection  and identification are  prevented  due to
     interferences, the hexane extract may need to undergo cleanup using Method
     3620.   The resultant extract(s) may  be  analyzed by GC  directly  or may
     undergo further cleanup to remove sulfur  using Method 3660.

     7.5  Cleanup:

           7.5.1  Proceed with Method 3620, followed by, if necessary,  Method
     3660, using the 10 ml hexane extracts obtained from Section 7.1.2.3.

           7.5.2  Following cleanup,  the extracts should be analyzed by GC, as
     described  in the previous sections  and in Method 8000.

     7.6  Quantitation of Multiple Component Analytes:

           7.6.1  Scope (excerpted from  U.S.  FDA, PAM):   Residues  which are
     mixtures of two or more components present problems in measurement.  When
     they  are  found   together,  e.g.,  toxaphene  and  DDT,   the  problem  of
     quantitation becomes even more difficult.   Suggestions are offered in the

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following sections for handing toxaphene, chlordane, PCB, DDT, and BHC.

      7.6.2  Toxaphene:  Quantitative calculation of toxaphene  or strobane
is difficult,  but reasonable  accuracy  can be  obtained.   To calculate
toxaphene on  GC/ECD:    (a)   adjust  the sample  size  so that  the major
toxaphene peaks are 10-70% of full-scale deflection (FSD);  (b)  inject a
toxaphene standard that  is estimated to  be  within  ±10 ng of the sample;
(c)  quantitate  using  the  five  major  peaks or  the  total  area  of  the
toxaphene pattern.

            7.6.2.1  To  measure  total  area, construct the baseline  of
      standard  toxaphene between  its  extremities;  and construct  the
      baseline under the sample,  using the distances of the peak troughs
      to baseline  on  the standard as a  guide.   This  procedure  is made
      difficult by the fact that the relative  heights and  widths of the
      peaks in the sample will  probably not  be identical to the standard.

            7.6.2.2  A series of toxaphene residues have been  calculated
      using the total peak area  for  comparison  to  the standard and also
      using the  area  of the  last  four  peaks  only,  in  both  sample  and
      standard.   The  agreement between  the results obtained  by  the  two
      methods justifies  the use  of  the  latter  method  for calculating
      toxaphene  in a  sample  where  the  early  eluting  portion   of  the
      toxaphene chromatogram  shows  interferences  from  other  substances
      such as DDT.

      7.6.3  Chlordane  is  a  technical   mixture  of  at  least 11  major
components and  30 or more minor components.   Trans-  and  cis-chlordane
(alpha and gamma),  respectively, are the two major components of technical
chlordane. However, the exact percentage  of each in  the technical material
is not completely defined,  and is not consistent from batch to batch.

            7.6.3,1  The GC  pattern  of  a  chlordane  residue  may differ
      considerably from that of the technical standard.  Depending on the
      sample substrate and  its  history,  residues  of chlordane can consist
      of  almost  any  combination  of:    constituents  from  the technical
      chlordane,  plant  and/or  animal   metabolites,   and  products  of
      degradation  caused by exposure to environmental  factors  such  as
      water and sunlight.

            7.6.3.2  When the chlordane residue does not resemble technical
      chlordane, but instead consists primarily of individual, identifiable
      peaks,  quantitate the peaks of alpha-chlordane, gamma-chlordane, and
      heptachlor separately against the appropriate reference materials,
      and report the individual residues.

            7.6.3.3  When the GC  pattern of the residue resembles that of
      technical chlordane,  the analyst may quantitate chlordane residues
      by comparing the total  area of  the  chlordane  chromatogram using the
      five major peaks or the total area.   If the heptachlor epoxide peak
      is relatively small,  include  it as  part of  the total chlordane area
      for calculation  of the residue.    If  heptachlor and/or  heptachlor
      epoxide are much out of proportion, calculate these separately and
      subtract  their areas  from the  total area  to  give a corrected

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      chlordane area.   (Note  that octachlor  epoxide,  a metabolite  of
      chlordane,  can  easily  be  mistaken  for heptachlor  epoxide on  a
      nonpolar GC column.)

            7.6.3.4  To  measure   the   total   area  of   the   chlordane
      chromatogram, proceed as in Section 7.6.2 on toxaphene.   Inject an
      amount  of  technical   chlordane   standard  which  will  produce  a
      chromatogram in which  the  major  peaks are  approximately  the same
      size as those in the sample chromatograms.

      7.6.4  Polychlorinated biphenyls  (PCBs):  Quantitation of residues
of PCB involves problems similar  to those encountered in the quantitation
of toxaphene, strobane, and chlordane.  In each case, the chemical is made
up of numerous compounds which generate multi-peak chromatograms.  Also,
in each case, the  chromatogram of  the  residue  may not  match that of the
standard.

            7.6.4.1  Mixtures of PCBs  of  various  chlorine contents were
      sold for many years  in  the  U.S. by the Monsanto Co. under the trade
      name Aroclor (1200  series  and  1016).  Although  these  Aroclors are
      no  longer marketed, the PCBs  remain in  the environment  and  are
      sometimes found as residues in foods, especially fish.

            7.6.4.2  Since standards are not generally available for all
      of  the  congeners  of  chlorinated  biphenyl,   PCB  residues  are
      quantitated by comparison to one  or more of the Aroclor materials,
      depending on the chromatographic  pattern of the residue.  A choice
      must be made as to which Aroclor or mixture of Aroclors will produce
      a chromatogram most similar to that of the residue.   This may also
      involve a judgement  about what  proportion of the different Aroclors
      to combine to produce the appropriate reference material.

            7.6.4.3  PCB  Quantitation   option #1-  Quantitate  the  PCB
      residues  by  comparing  the  total   area of the chlorinated biphenyl
      peaks to  the total  area of  peaks from  the  appropriate Aroclor(s)
      reference materials. Measure the total area  or height response from
      the common baseline  under all the peaks.  Use only those peaks from
      the sample that can be attributed to chlorobiphenyls.   These peaks
      must also be present in the chromatogram  of the reference materials.
      A mixture of Aroclors may be required to provide the best match of
      the GC patterns of the sample and reference.

            7.6.4.4  PCB  Quantitation   option #2-  Quantitate  the  PCB
      residues  by  comparing  the  responses  of  3 to 5  major peaks in each
      appropriate  Aroclor standard  with  the  peaks  obtained  from  the
      chlorinated biphenyls in the sample  extract.  The amount of Aroclor
      is calculated using  each of the major peaks,  and the results of the
      3 to 5 determinations are averaged. Major peaks are defined as those
      peaks in the Aroclor standards that are at least 30% of the height
      of  the largest  Aroclor peak.   Later  eluting  Aroclor  peaks  are
      generally the most stable in the environment.

      7.6.5  Hexachlorocyclohexane  (BHC,  from the former  name, benzene
hexachloride):  Technical  grade  BHC is a  cream-colored  amorphous solid

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      with a very characteristic  musty  odor;  it consists of a mixture  of six
      chemically distinct isomers and one  or  more  heptachlorocyclohexanes and
      octachlorocyclohexanes.   Commercial  BHC  preparations may  show  a  wide
      variance in the  percentage  of individual  isomers present.    Quantitate
      each  isomer  (a,  Ł, 7,  and  5)   separately  against  a  standard  of the
      respective pure isomer.


8.0  QUALITY CONTROL

      8.1  Refer to Chapter One for specific quality control procedures.  Quality
control to  validate  sample  extraction  is  covered in  Method  3500 and  in the
extraction method utilized.   If extract  cleanup was performed, follow the QC in
Method 3600 and in the specific cleanup method.

      8.2  Mandatory quality control  to evaluate  the  GC system  operation is
found in Method 8000.

            8.2.1  The quality control  check  sample  concentrate  (Method 8000)
      should contain  each single-component parameter of interest at the following
      concentrations  in  acetone:    4,4'-ODD,  10 mg/L;  4,4'-DDT,  10  mg/L;
      endosulfan II,  10 mg/L; endosulfan sulfate, 10 mg/L; endrin, 10 mg/L; and
      any other single-component pesticide, 2 mg/L.  If this method is only to
      be used to analyze for  PCBs, chlordane,  or toxaphene, the QC check sample
      concentrate  should  contain  the  most  representative  multi-component
      parameter at a concentration of 50 mg/L in acetone.

            8.2.2  Table 3 indicates the calibration and QC acceptance criteria
      for this method.  Table 4 gives method accuracy  and precision as functions
      of concentration  for the analytes of interest.  The contents of both Tables
      should be used to evaluate a laboratory's ability to perform and generate
      acceptable data by this method.

      8.3  Calculate surrogate standard recovery  on all  samples,  blanks, and
spikes.   Determine   if  the  recovery is  within  limits  (limits established by
performing QC procedures outlined in Method 8000).

            8.3.1 If recovery is  not within limits, the following are required.

                  8.3.1.1  Check  to  be  sure  that  there  are no errors  in the
            calculations, surrogate  solutions  or internal  standards.  If errors
            are found,  recalculate the data accordingly.

                  8.3.1.2  Check  instrument   performance.    If  an  instrument
            performance problem is identified,  correct the problem and re-analyze
            the extract.

                  8.3.1.3  If  no  problem is   found, re-extract  and  re-analyze
            the sample.

                  8.3.1.4  If, upon re-analysis, the recovery is again not within
            limits,   flag the data as "estimated concentration".
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      8.4  GC/MS confirmation:  Any compounds  confirmed  by two columns may also
be confirmed by GC/MS if the concentration  is  sufficient for detection by GC/MS
as determined by the laboratory generated detection limits.

            8.4.1  The GC/MS would normally require a minimum concentration of
      10 ng//iL  in the final  extract, for each single-component compound.

            8.4.2  The pesticide extract and associated blank should be analyzed
      by GC/MS as per Section 7.0 of Method 8270.

            8.4.3  The  confirmation  may  be   from  the  GC/MS  analysis  of  the
      base/neutral-acid extractables extracts (sample and blank).  However, if
      the compounds  are not detected in the base/neutral-acid  extract even though
      the concentration  is high enough,  a GC/MS analysis of the pesticide extract
      should be performed.

            8.4.4  A reference  standard of the  compound must also be analyzed
      by GC/MS.  The concentration of the  reference  standard  must  be at a level
      that  would  demonstrate  the  ability   to  confirm  the  pesticides/PCBs
      identified by GC/ECD.


9.0  METHOD PERFORMANCE

      9.1  The method was tested by 20 laboratories using organic-free reagent
water, drinking water,  surface  water,  and  three industrial  wastewaters spiked
at six  concentrations.   Concentrations used  in  the study ranged from 0.5 to
30 M9/L  for  single-component pesticides and  from  8.5 to 400 /xg/L  for multi-
component parameters.  Single operator  precision, overall precision, and method
accuracy were found  to be directly related to  the concentration of  the parameter
and essentially independent of the sample matrix.  Linear equations to describe
these relationships for a flame ionization detector are presented in Table 4.

      9.2  The accuracy and precision obtained will  be determined  by the sample
matrix,   sample-preparation   technique,   optional   cleanup   techniques,   and
calibration procedures used.


10.0  REFERENCES

1.   U.S.  EPA,  "Development and  Application  of Test Procedures  for Specific
     Organic Toxic Substances in Wastewaters,  Category 10: Pesticides and PCBs,"
     Report for EPA Contract 68-03-2605.

2.   U.S.  EPA,  "Interim  Methods  for  the  Sampling  and Analysis of Priority
     Pollutants  in  Sediments and  Fish  Tissue," Environmental  Monitoring  and
     Support Laboratory, Cincinnati, OH 45268, October 1980.

3.   Pressley,  T.A., and  J.E. Longbottom, "The  Determination  of Organohalide
     Pesticides and PCBs  in  Industrial and Municipal  Wastewater:  Method 617,"
     U.S. EPA/EMSL,  Cincinnati, OH, EPA-600/4-84-006, 1982.

4.   "Determination  of  Pesticides  and   PCB's   in  Industrial  and  Municipal


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     Wastewaters, U.S. Environmental Protection Agency," Environmental Monitoring
     and Support Laboratory, Cincinnati,  OH 45268,  EPA-600/4-82-023, June 1982.

5.   Goerlitz, D.F. and L.M. Law, Bulletin for Environmental Contamination and
     Toxicology, 6, 9, 1971.

6.   Burke,  J.A.,  "Gas  Chromatography for  Pesticide Residue  Analysis;  Some
     Practical  Aspects,"  Journal  of the  Association of  Official  Analytical
     Chemists, 48, 1037, 1965.

7.   Webb, R.G.  and A.C. McCall, "Quantitative PCB Standards for Electron Capture
     Gas Chromatography," Journal of Chromatographic Science, 11, 366, 1973.

8.   Millar,  J.D.,  R.E.  Thomas  and  H.J.  Schattenberg, "EPA  Method  Study 18,
     Method 608: Organochlorine  Pesticides and  PCBs," U.S. EPA/EMSL,  Research
     Triangle Park, NC, EPA-600/4-84-061,  1984.

9.   U.S. EPA 40 CFR Part 136,  "Guidelines  Establishing Test Procedures for the
     Analysis of Pollutants  Under  the  Clean Water  Act; Final  Rule and Interim
     Final Rule and Proposed Rule," October 26, 1984.

11.  U.S.  Food  and Drug Administration,  Pesticide Analytical  Manual,  Vol.  1,
     June 1979.

12.  Sawyer,  L.D., JAOAC, 56,  1015-1023  (1973),  61 272-281 (1978),  61 282-291
     (1978).
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                 TABLE 1.
GAS CHROMATOGRAPHY OF PESTICIDES AND  PCBs"
Retention time (min)

Analyte
Aldrin
a-BHC
0-BHC
6-BHC
7-BHC (Lindane)
Chlordane (technical)
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
Methoxychlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
•U.S. EPA. Method 617
Monitoring and Support

Col. 1
2.40
1.35
1.90
2.15
1.70
e
7.83
5.13
9.40
5.45
4.50
8.00
14.22
6.55
11.82
2.00
3.50
18.20
e
e
e
e
e
e
e
, e
Organochl

Col. 2
4.10
1.82
1.97
2.20
2.13
e
9.08
7.15
11.75
7.23
6.20
8.28
10.70
8.10
9.30
3.35
5.00
26.60
e
e
e
e
e
e
e
e
orine Pesticides
Laboratory, Cincinnati, Ohio
Method
Detection
limit (/ig/L)
0.004
0.003
0.006
0.009
0.004
0.014
0.011
0.004
0.012
0.002
0.014
0.004
0.066
0.006
0.023
0.003
0.083
0.176
0.24
nd
nd
nd
0.065
nd
nd
nd
and PCBs. Environmental
45268.
e = Multiple peak response.
nd = not determined.



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                                  TABLE 2.
DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQLs) FOR VARIOUS MATRICES8
        Matrix                                                Factor"
        Ground water                                               10
        Low-concentration soil by sonication with GPC cleanup     670
        High-concentration soil and sludges by sonication      10,000
        Non-water miscible waste                              100,000
           Sample EQLs are  highly matrix-dependent.   The  EQLs  listed herein
           are provided for guidance and may not always be achievable.

           EQL = [Method  detection limit (Table  1)] X  [Factor (Table 2)].  For
           non-aqueous samples, the factor is on a wet-weight basis.
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                                   TABLE 3.
                            QC ACCEPTANCE CRITERIA8
Analyte
Aldrin
o-BHC
0-BHC
5-BHC
T-BHC
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrin
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Test
cone.
(M9/L)
2.0
2.0
2.0
2.0
2.0
50
10
2.0
10
2.0
2.0
10
10
10
2.0
2.0
50
50
50
50
50
50
50
50
Limit
for s
(M9/L)
0.42
0.48
0.64
0.72
0.46
10.0
2.8
0.55
3.6
0.76
0.49
6.1
2.7
3.7
0.40
0.41
12.7
10.0
24.4
17.9
12.2
15.9
13.8
10.4
Range
for x
(M9/L)
1.08-2.24
0.98-2.44
0.78-2.60
1.01-2.37
0.86-2.32
27.6-54.3
4.8-12.6
1.08-2.60
4.6-13.7
1.15-2.49
1.14-2.82
2.2-17.1
3.8-13.2
5.1-12.6
0.86-2.00
1.13-2.63
27.8-55.6
30.5-51.5
22.1-75.2
14.0-98.5
24.8-69.6
29.0-70.2
22.2-57.9
18.7-54.9
Range
P. PS
(%)
42-122
37-134
17-147
19-140
32-127
45-119
31-141
30-145
25-160
36-146
45-153
D-202
26-144
30-147
34-111
37-142
41-126
50-114
15-178
10-215
39-150
38-158
29-131
8-127
s = Standard deviation of four recovery measurements, in

x = Average recovery for four recovery measurements, in M9/L.

P, Ps = Percent recovery measured.

D = Detected; result must be greater than zero.

"Criteria from  40 CFR Part 136 for Method 608.  These criteria are based directly
upon the method performance  data in  Table 4.   Where necessary, the limits for
recovery  have  been  broadened  to  assure  applicability   of  the  limits  to
concentrations below those used  to develop Table 4.
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                                   TABLE 4.
         METHOD ACCURACY AND PRECISION AS  FUNCTIONS OF CONCENTRATION8
Analyte
Aldrin
o-BHC
)3-BHC
6-BHC
7-BHC
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrin
Heptachlor
Heptachlor epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260
Accuracy, as
recovery, x'
(M9/L)
0.81C+0.04
0.84C+0.03
0.81C+0.07
0.81C+0.07
0.82C-0.05
0.82C-0.04
0.84C+0.30
0.85C+0.14
0.93C-0.13
0.90C+0.02
0.97C+0.04
0.93C+0.34
0.89C-0.37
0.89C-0.04
0.69C+0.04
0.89C+0.10
0.80C+1.74
0.81C+0.50
0.96C+0.65
0.91C+10.79
0.91C+10.79
0.91C+10.79
0.91C+10.79
0.91C+10.79
Single analyst
precision, s/
(M9/L)
0.16X-0.04
0.13x+0.04
0.22X+0.02
O.lSx+0.09
0.12x+0.06
0.13X+0.13
0.20X-0.18
O.lSx+0.06
0.17X+0.39
0.12X+0.19
O.lOx+0.07
0.41x-0.65
0.13X+0.33
0.20X+0.25
0.06X+0.13
O.lBx-0.11
0.09x+3.20
O.lSx+0.15
0.29x-0.76
0.21X-1.93
0.21X-1.93
0.21X-1.93
0.21X-1.93
0.21X-1.93
Overall
precision,
S' (M9/L)
0.20x-0.01
0.23X-0.00
0.33X-0.95
0.25X+0.03
0.22X+0.04
O.lSx+0.18
0.27X-0.14
0.28X-0.09
O.Slx-0.21
0.16X+0.16
O.lSx+0.08
0.47X-0.20
0.24X+0.35
0.24X+0.25
0.16x+0.08
0.25X-0.08
0.20x+0.22
O.lSx+0.45
0.35X-0.62
0.31X+3.50
O.Slx+3.50
O.Slx+3.50
0.31X+3.50
0.31x+3.50
x' =  Expected recovery  for  one or more  measurements of  a  sample containing
concentration C, in fj.g/1.

s/ =  Expected single  analyst standard deviation of measurements at an average
concentration of x, in /ug/L.

S' = Expected interlaboratory standard deviation of measurements at an average
concentration found of x, in
C = True value for the concentration, in M9/L-

x = Average recovery found for measurements of samples containing a concentration
of C, in
                                  8080B - 16
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              Figure 1
   Gas Chromatogram of Pesticides
Column :1.5% P 3250*
       1JS% SF-2401 en Suotieepen
TtmptrtTurc: XXPC
OttKter: Electron Cteturi
    4          I         12
       ftlTf NTION TIME (MINUTES)
             8080B  -  17
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             Figure 2
 Gas Chromatogram of Chlordane
Column: 1.5% SP-2250*
       1.MH SF 2401 en Swpcieeeoa
Ttmotrtturt 20C°C
DffUCtor: Electron C«oaurt
   4          I         12

  METENTION TIME (MINUTES)
16
           8080B  -  18
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           Figure 3
Gas Chromatogram of Toxaphene
                   Column: 1 J% SP-2250*
                          1JS% SP-2401 on Syptieooon
                   Ttmptrnurr 200°C
                   DetKtor: Iltetron Caoturi
          10       14       II

       RITINTION TIME (MINUTES)
22
26
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                      Figure 4
          Gas Chromatogram of Aroclor  1254
Column: 1.5% SP 2250*
       1JS% SP 2401 en Swpcieeeert
Ttmotntut: 200°C
Ocueter: Iltctron CiPTurt
         I         10          U
           MITINTION TIMC (MINUTIS)
It
22
                     8080B  - 20
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                        Figure  5
            Gas  Chromatogram of Aroclor  1260
          1Jf% S*-J401 on SuMlcooo*
             200°C
          Itetron Caeturt
lit
                 10       U       II
                HITINTION TIMf (MINUTIS)
M
                        8080B - 21
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                                  Figure  6
    J..L
Fig. e—Baseline construction for ram typical gas chromatosrapnlc peaks.
a, symmetrical separated flat baseline; b and c. overlapping flat bastllna;
d, saparaud (pan dots net rscum to baaalim bet wean peaks); a, separated
sloping baseline; f. separated (pan goes below'baseline between peaks):
g, «- andY-BHC sloping baseline; h. •-,Ł-, and 7-BHC sloping baseline;
1. chlordane flat baseline; J.  bepudUor and neptaddor epoxide super-
invosed on calordane; k,  cnalr-sbapad peaks, unsymmetrtcal peak; 1.
p,p'«OOT superimposed on to«sphane.
                                8080B  - 22
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                     Figure 7
Flf.7>-*Bu«llM construction for multlplt ruiduti with sundtrd
                     teuphtM.
                          far auiflpU mtdma »M>MK»-
                 008 Mtf «,pS Md P*'-OOT.
                   8080B  -  23
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                                Figure  8
Fit. ••—BaMllM construction (or multiple r»tldu»s:  standard toxaphtn*.
                         Mr multiple rasiduMt tie* bran with BHC,
                         DOT* aatf i
                             8080B  - 24
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                             Figure  9
          Fig. 0a—BaMlia* construction for multiple ratidiMi:  standard chlordan*.
Flf,
for mddpto rwtduMt rtc* bnn
MdOOT.
                             8080B  -  25
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                         METHOD 8080B
 ORGANOCHLORINE  PESTICIDES AND POLYCHLORINATED BIPHENYLS
                    BY GAS CHROMATOGRAPHY
     Start
 7.1.1 Choose
  appropriate
  extraction
  procedure.
     7.1.2
   Exchange
  extraction
  solvent  to
    hexane.
    7.2 Set
chromatographic
  conditions.
 7.3 Refer to
  Method 8000
  for proper
  calibration
  techniques.
7.3.2 Prime  or
deactivate the
CC column prior
   to daily
 calibration.
  7.4 Perform
 CC analysis .
     7.4.8
    Is peak
 detection and
identification
  prevented?
 7.5.1  Cleanup
 using  Method
 3620 and  3660
 if  necessary.
   7.6.1 Oo
 residues hav
  two or more
 7.6 Calculate
concentrations
  components?
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                                  METHOD 8081

     ORGANOCHLORINE  PESTICIDES  AND PCBs  AS  AROCLORS  BY  GAS  CHROMATOGRAPHY:
                          CAPILLARY COLUMN TECHNIQUE
1.0  SCOPE AND APPLICATION

      1.1  Method  8081  1s  used to  determine the  concentrations  of various
organochlorine pesticides, and polychlorinated biphenyls  (PCBs) as Aroclors, 1n
extracts from solid and liquid matrices.   A large number of compounds will give
a response in the electron capture detector (ECD) using this method; performance
data for the following compounds are provided as part of this method:
      Compound Name
CAS No.1
Aldrin
alpha-BHC
beta-BHC
delta-BHC
gamma- BHC (Lindane)
gamma- Chi ordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
4,4'-Methoxychlor
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
309-00-2
319-84-6
319-85-7
319-86-8
58-89-9
57-74-9
72-54-8
72-55-9
50-29-3
60-57-1
959-98-8
33212-65-9
1031-07-8
72-20-8
7421-93-4
76-44-8
1024-57-3
72-43-5
8001-35-2
12674-11-2
1104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
         Chemical  Abstract Services Registry Number.
      1.2  This capillary GC/ECD method allows the analyst the option of using
0.25-0.32 mm ID capillary columns (narrow  bore) or 0.53 mm ID capillary columns
(wide bore).  Performance data are provided for both options.
                                   8081 - 1
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      1.3  The  use  of narrow  bore columns are  recommended when  the analyst
requires greater chromatographlc resolution and 1s analyzing a relatively clean
sample or an  extract  that has  been prepared with one or  more  of the clean-up
options referenced in  the method.  Wider bore columns (0.53 mm) are suitable for
more complex environmental and waste matrices.   The 0.53  mm ID columns can be
mounted in 1/4 inch packed column injectors.

      1.4  Table  1  lists average retention times and method  detection limits
(MDLs) for each compound of interest,  in water and soil matrices, for the wide-
bore capillary column version of this method.  Table 2 lists average retention
times and method detection limits (MDLs) for each  compound  of interest, in water
and soil matrices, for the narrow-bore  capillary  column version of this method.
The MDLs for the  components  of  a specific  sample may differ from those listed
in Tables 1 and  2 because they  are dependent  upon  the nature of interferences
in the sample matrix.   Retention time  information given in Table 2 was obtained
on two wide-bore, open tubular columns connected to the injector port of a gas
chromatograph through an injection tee made of deactivated glass. Table 3 lists
the Estimated Quantitation Limits (EQLs) for other matrices.

      1.5  When this  method  is used to analyze  for any or all  of the target
compounds, compound identification  based  on single column  analysis should be
confirmed on  a second column,  or  should   be  supported  by at least one other
qualitative technique. This  method describes analytical  conditions  for a second
gas chromatographic column that can be used  to confirm the measurements made with
the primary column.

      1.6  This  method  is restricted  to  use by or under the  supervision of
analysts  experienced   in  the  use  of  a  gas  chromatograph  (GC)  and  in  the
interpretation of gas chromatograms.  Each  analyst must demonstrate  the ability
to generate acceptable results with this method.

      1.7  Extracts suitable for analysis  by  this  method  may also be analyzed
for organophosphorus pesticides (Method 8141) and triazine herbicides.


2.0  SUMMARY OF METHOD

      2.1  A measured volume or weight of sample (approximately 1  L for liquids,
2 g to  30 g  for  solids)  is  extracted  using the  appropriate sample extraction
technique specified in Methods  3510,  3520, 3540, 3541,  3550 and 3580.  Liquid
samples  are  extracted at  neutral  pH with methylene chloride using  either a
separatory funnel (Method 3510)  or a continuous liquid-liquid extractor (Method
3520).   Solid  samples  are  extracted  with hexane-acetone (1:1)  or methylene
chloride-acetone  (1:1) using either Soxhlet extraction (Method 3540), Automated
Soxhlet  (Method  3541),  or Ultrasonic Extraction (Method  3550).   A variety of
cleanup steps may be applied to the extract, depending on  (1) the nature of the
coextracted matrix  interferences and  (2)  the  target analytes.   After cleanup,
the extract is analyzed by injecting a 1 /iL sample into a gas chromatograph with
a  narrow- or  wide-bore  fused  silica capillary column  and  electron capture
detector  (GC/ECD).

      2.2  The  MDLs achievable in  routine analyses of complex  samples using
Method 8081 will  usually  be  dependent on the degree of interference associated


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with the presence of coelutlng compounds to which the ECD will respond, rather
than on  the Inherent limitations  in  detector performance or the Irreducible
noise  associated  with  Instrument electronics.    If  Interferences  prevent
Identification and  qualification  of the analytes within  quality control  (QC)
limits at relevant concentrations,  Method 8081 may also be performed on samples
that have undergone cleanup.  Method 3630, Silica Gel Column Cleanup, by itself,
or  followed  by  Method  3660,   Sulfur  Cleanup,  may  be  used  to  eliminate
Interferences  in  the   analysis.    Method  3640,  Gel-Permeation Cleanup,  is
applicable for samples  that contain high amounts of lipids, waxes  and other high
molecular weight co-extractables.


3.0  INTERFERENCES

      3.1  Refer to Methods 3550 (Section 3.5, in particular), 3600, and 8000.

      3.2  Sources  of  interference in this  method  can be grouped  into three
broad categories: contaminated solvents, reagents or sample processing hardware;
contaminated GC  carrier gas, parts, column  surfaces  or detector surfaces; and
the presence of coelutlng compounds in the sample matrix to which the ECD will
respond.  Knowledge of  good  laboratory practices  is assumed, including steps to
be  followed  in routine  testing  and cleanup of solvents, reagents  and sample
processing hardware, and Instrument maintenance.   The  discussion that follows
focuses on sources of interference associated with the sample matrix and compound
classes that represent  common sources of interference,  particularly phthalate
esters, organosulfur compounds,  lipids,  and waxes.   Interferences coextracted
from the  samples will   vary considerably from  waste to waste.   While general
cleanup techniques  are  referenced  or  provided as part of this method, unique
samples may require additional cleanup approaches to achieve desired degrees of
discrimination and quantitation.

      3.3  Interferences by phthalate esters  introduced during sample preparation
can pose a major problem in pesticide determinations.   These  materials may be
removed prior to  analysis using Gel  Permeation Cleanup -  pesticide  option (Method
3640) or  as Fraction III of the silica gel cleanup procedure (Method 3630).
Common flexible plastics contain varying amounts of phthalate esters which are
easily extracted or leached from such materials during laboratory operations.
Cross-contamination of  clean glassware routinely occurs when plastics  are handled
during extraction steps,  especially when solvent-wetted  surfaces are handled.
Interferences  from  phthalate esters can  best be minimized by  avoiding contact
with any plastic materials and checking all  solvents and reagents for phthalate
contamination.   Exhaustive cleanup of solvents,  reagents  and  glassware may be
required to eliminate background phthalate ester contamination.

      3.4  The presence of  elemental   sulfur will  result in  large  peaks  that
Interfere with the detection of later eluting organochlorine pesticides.  Method
3660 1s suggested for removal of sulfur.  Since  the recovery of endrin aldehyde
(using  the  TBA  procedure)  1s   drastically reduced,  this  compound must  be
determined prior to sulfur cleanup.

      3.5  Waxes, lipids other  high  molecular  weight  co-extractables  can  be
removed by Gel-Permeation Cleanup (Method 3640).
                                   8081 - 3                       Revision 0
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      3.6  Other pesticides may be interferences in  this method.  Table 4 lists
the names and retention times of organophosphorus pesticides which co-elute with
organochlorine  pesticides  on wide-bore  capillary columns.   Organophosphorus
pesticides  are eliminated  by  the Gel  Permeation  Chromatography cleanup  -
pesticide option (Method 3640).

      3.7  It  may  be  difficult  to quantitate Aroclor  patterns  and  single
component  pesticides  together.    Pesticides  can  be  removed  by  sulfuric
acid/permanganate cleanup (Method 3665)  and  silica fractionation (Method 3630).
Guidance on the identification of PCBs is given in Section 7.6.4.


4.0  APPARATUS AND MATERIALS

      4.1  Glassware (see Methods 3510,  3520,  3540,  3541, 3550, 3630, 3640, and
3660 for specifications).

      4.2  Kuderna-Danish (K-D) apparatus.

            4.2.1  Concentrator tube -  10 ml graduated  (Kontes K-570050-1025 or
      equivalent).  If extracts  are stored  in the concentrator tube,  a ground
      glass stopper is used to prevent evaporation of concentrates.

            4.2.2  Evaporation   flask   -   500 ml  (Kontes  K-570001-500   or
      equivalent).  Attach to concentrator with springs.

            4.2.3  Snyder column  -  Three ball  macro  (Kontes  K-503000-0121  or
      equivalent).

            4.2.4  Springs, clips and clamps - 1/2 inch  springs (Kontes K-662750
      or equivalent), or any other equivalent fastener, e.g., neck standard taper
      clips.  Clamp (Kontes 675300 or equivalent).

            4.2.5  Boiling chips - Approximately 10/40  mesh (silicon carbide or
     equivalent).  Prior to  use,  heat to 400°C  for 30 minutes or Soxhlet extract
     with methylene chloride.

      4.3  Gas chromatograph - Analytical system complete with gas chromatograph
suitable for on-column and split-splitless injection and all required accessories
including syringes, analytical columns,  gases,  electron capture detector,  and
recorder/integrator or data system.

            4.3.1  Narrow-bore columns

                  4.3.1.1  Column 1 -  30 m x 0.25 or 0.32  mm internal  diameter
            (ID) fused  silica capillary  column chemically bonded with  SE-54
            (DB 5 or equivalent), 1 /xm film thickness.

                  4.3.1.2  Column 2 -  30 m x 0.25 mm ID fused silica capillary
            column chemically bonded with 35 percent phenyl methylpolysiloxane
            (DB 608, SPB  608, or equivalent), 25 pm coating  thickness, 1 pm film
            thickness.
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                  4.3.1.3  Narrow   bore  columns   should  be   Installed  in
            split/splitless (Grob-type) injectors.

            4.3.2  Wide-bore columns

                  4.3.2.1  Column 1 - 30 m x 0.53 mm ID fused silica capillary
            column chemically bonded with 35 percent phenyl methylpolysiloxane
            (DB 608, SPB 608, RTx-35,  or  equivalent),  0.5 Aim or  0.83  Mm film
            thickness.

                  4.3.2.2  Column 2 - 30 m x 0.53 mm 10 fused silica capillary
            column chemically bonded with 50 percent phenyl methylpolysiloxane
            (OB 1701, or equivalent), 1.0 /xm film thickness.

                  4.3.2.3  Column 3 - 30 m x 0.53 mm ID fused silica capillary
            column  chemically  bonded  with   SE-54  (OB  5,   SPB 5,  RTx,  or
            equivalent), 1.5 urn film thickness.

                  4.3.2.4  Wide-bore columns  should be installed  in  1/4 inch
            injectors with deactivated liners designed specifically for use with
            these columns.

      4.4  GC  injector  ports can  be of  critical  concern, especially  in the
analysis of DDT and  Endrin.  Injectors that are  contaminated, chemically active,
or too hot can cause the degradation ("breakdown") of the  analytes.  Endrin and
DDT  breakdown to endrin  aldehyde,  endrin  ketone,  ODD,  or DDE.   When such
breakdown is observed, clean and deactivate the  injector port, break off at least
0.5 M of the  column  and remount  it.   Check the injector temperature and lower
it to 205°C, if required.  Endrin and DDT breakdown is  less  of  a problem when
ambient on-column injectors are used.


5.0  REAGENTS

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

      5.2  Organic-free reagent water.  All references to water in this method
refer to organic-free reagent water as defined in Chapter One.

      5.3  Solvents and reagents:  As appropriate for Method 3510, 3520, 3540,
3541, 3550, 3630, 3640, or 3660: n-hexane,  diethyl  ether, methylene chloride,
acetone, ethyl  acetate,  and  isooctane  (2,2,4-trimethylpentane).   All  solvents
should be pesticide  quality  or  equivalent,  and each lot  of  solvent should be
determined to be phthalate free.

      5.4  Silica gel (optional)  PR grade  (100/200 mesh) - Before use,  activate
at least  16 hours  at 130° to 140°C.   Deactivate with water (3.3  percent,  by
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weight) and equilibrate for 1  hour.  Disposable silica cartridges (LC-silica or
equivalent), 1 g each, may be used in place of the deactivated silica gel.

      5.5  Stock standard solutions:

            5.5.1  Prepare  stock standard  solutions  at  a  concentration  of
      1000 mg/L by dissolving 0.1000 ±  0.0010  g  of assayed reference material
      in isooctane or hexane and diluting to volume in a 100  ml volumetric flask.
      When compound  purity is assayed to be  96 percent or  greater,  the weight
      can be used without correction to calculate the concentration of the stock
      standard.   Commercially  prepared stock  standards can  be  used  at any
      concentration  if  they  are  certified  by  the  manufacturer  or  by  an
      independent source.

                  5.5.1.1  Beta-BHC and dieldrin are not adequately soluble in
            isooctane.  Acetone, or toluene should be used for the preparation
            of the stock standard solutions of these compounds.

            5.5.2  Transfer the stock  standard solutions  into bottles  with
      Teflon-lined screw-caps.   Store  at 4°C  and  protect  from light.   Stock
      standards  should be  checked  frequently  for  signs  of  degradation  or
      evaporation, especially  just prior to preparing calibration standards from
      them.

            5.5.3  Stock standard solutions must be replaced after six months,
      or sooner if comparison with check standards indicates a problem.

      5.6  Calibration standards;

            5.6.1  Calibration standards, at a minimum of three concentrations
      for each parameter of interest, are prepared through dilution of the stock
      standards  with isooctane.   One  of  the  concentrations  should  be  at  a
      concentration near, but  above,  the method detection limit.  The remaining
      concentrations should correspond to the expected range of concentrations
      found in real  samples or should define the working range of the GC.

            5.6.2  Calibration solutions must be replaced after two months, or
      sooner, if comparison with check  standards indicates a problem.

            5.6.3  Although all  single column analytes can  be resolved on a new
      35 percent phenyl  methylpolysiloxane column, some analytes co-elute on the
      other columns  or  on  older 35  percent  phenyl  methylpolysiloxane columns.
      Two  calibration mixtures  should  be prepared  for the  single  component
      analytes of this method to eliminate potential  resolution  and quantitation
      problems.  Recommended low point mixtures are given in Table 9.

      5.7  Internal  standards (if internal standard calibration is used):

            5.7.1  To use  this  approach, the analyst must select one  or more
      internal standards that are similar in analytical behavior to the compounds
      of interest.   The analyst must  further demonstrate that the measurement
      of the internal standard is not affected by method or matrix interferences.
      Pentachloronitrobenzene is suggested as an internal standard.


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            5.7.2  Prepare  calibration  standards  at   a   minimum  of  three
      concentrations for each analyte of interest as described in Section 5.6.

            5.7.3  To each calibration standard,  add a known constant amount of
      one or more internal standards.

            5.7.4  Analyze each calibration standard according to Section 7.0.

      5.8  Surrogate standards:  The analyst should monitor the performance of
the extraction,  cleanup (when used), and analytical system, and the effectiveness
of  the  method  in  dealing with  each sample matrix,  by spiking  each  sample,
standard,  and  organic-free  reagent  water blank  with   pesticide  surrogates.
Because GC/ECD  analyses  are more subject  to interference than GC/MS analyses,
a  secondary  surrogate is  to be used when  sample interference  is  apparent.
Decachlorobiphenyl  is the  primary  surrogate,   and  should  be used  whenever
possible.    However,  if  recovery  is   low,   or  compounds  interfere  with
decachlorobiphenyl, then  2,4,5,6-tetrachloro-m-xylene should  be  evaluated for
acceptance.   Proceed  with corrective action when both   surrogates are  out of
limits for a  sample (Section  8.3).   Method 3500, Section 5.3.2,  indicates the
proper procedure for preparing these surrogates.


6.0  SAMPLE COLLECTION, PRESERVATION AND HANDLING

      6.1  See  the  introductory material  to  this chapter,  Organic  Analytes,
Section 4.1.

      6.2  Extracts must  be stored  under  refrigeration  and analyzed within 40
days of extraction.


7.0  PROCEDURE

      7.1  Extraction;

            7.1.1  Refer to Chapter Two for guidance in choosing the appropriate
     extraction procedure. In general, water samples are extracted at a neutral
     pH with methylene chloride  as  a solvent using a separatory funnel  (Method
     3510) or a  continuous liquid-liquid extractor (Method 3520).   Extract solid
     samples with hexane-acetone (1:1) using either  of  the Soxhlet extraction
     (Method 3540 or 3541) or ultrasonic extraction (Method 3550) procedures.

NOTE: Hexane/acetone  (1:1)  may  be  a  more effective  extraction  solvent  for
      organochlorine pesticide and PCBs in some environmental and waste matrices.
      The  current solvent mixture  recommended  in Method  3550  is  methylene
      chloride/acetone (1:1).

            7.1.2  Spiked samples  are used to  verify  the applicability of the
      chosen extraction technique to each new sample type.   Each sample must be
      spiked with the  compounds  of interest to determine the percent recovery
      and the limit of detection for that sample.

                  7.1.2.1  Spiking of water samples should be performed by adding
            appropriate  amounts  of pesticide and  PCB compounds,  dissolved in

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      methanol, to the water sample immediately prior to extraction.  After
      addition of the spike,  mix the samples manually  for  1 to 2 minutes.
      Typical spiking concentrations for water  samples  are  1  to 10 jug/L
      for samples in which pesticides and PCBs were not detected and 2 to
      5 times the background concentration in those cases where pesticides
      and  PCBs  are  present  (use  of  mixtures  of  Aroclors  other than
      1016/1260  is not recommended with this method).

            7.1.2.2  Spiking of soil  samples should be  performed by adding
      appropriate  amounts of  pesticide and  PCB  compounds,  which  are
      dissolved in methanol, to the solid samples.  The  solid sample should
      be wet  prior to the  addition of the  spike (at least  20 percent
      moisture)  and should  be  mixed  thoroughly with  a  glass rod  to
      homogenize the material.   Allow  the  spike to  equilibrate with the
      solid for 1 hour at room temperature  prior to extraction.  Transfer
      the entire spiked portion with the test compounds to the extraction
      thimble  for Soxhlet extraction  (Method   3540),  Automated  Soxhlet
      (Method 3541),  or  proceed with  the  ultrasonic  extraction (Method
      3550).

7.2  Cleanup/Fractionation

      7.2.1  Cleanup  procedures  may not be  necessary for  a  relatively
clean sample matrix, but most extracts from environmental  and waste samples
will require additional preparation before analysis.  The specific cleanup
procedure used will depend on the nature of the  sample to be analyzed and
the data quality objectives  for  the measurements.   General  guidance for
sample extract cleanup is provided in this section.

      7.2.2  If  a  sample is  of  biological  origin,   or  contains high
molecular weight materials, the use of GPC cleanup/pesticide option (Method
3640) is recommended.

      7.2.3  If  only  PCBs are to be measured in  a  sample,  the sulfuric
acid/permanganate   cleanup   (Method  3665),   followed  by   silica  gel
fractionation (Method 3630) or Florisil cartridge cleanup (Method 3620),
is recommended.

      7.2.4  If both PCBs and  pesticides are to be measured in the sample,
isolation of the PCB  fraction  by silica gel  fractionation (Method 3630)
is recommended.

      7.2.5 If only pesticides are to be measured, cleanup by Method 3620
or Method 3630 is recommended.

      7.2.6  Elemental sulfur, which may appear in certain sediments and
industrial wastes, interferes with the electron capture gas chromatography
of certain pesticides.  Sulfur should be removed by the  technique described
in Method 3660,  Sulfur Cleanup.
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7.3  Gas chromatographv conditions  (Recommended):

      7.3.1  Narrow-bore columns:

            7.3.1.1  Column 1:
     Carrier gas  (He) = 16 psi
     Injector temperature = 225°C
     Detector temperature = 300°C
     Initial temeprature = 100°C, hold 2 minutes
     Temperature  program = 100°C to 160°C at 15°C/min,  followed  by;
                           160°C to 270°C at 5°C/nrin
     Final temperature = 270°C.

            7.3.1.2  Column 2:
     Carrier gas  (N2) =  20 psi
     Injector temperature = 225°C
     Detector temperature = 300°C
     Initial temeprature = 160°C, hold 2 minutes
     Temperature  program = 160°C to 290°C at 5°C/min
     Final temperature = 290°C, hold 1 minute.

            7.3.1.3  Table 1 gives  the retention times  and MDLs  that  can
      be  achieved by this method for  the organochlorine pesticides  and
      PCBs.   Examples  of the  separations  achieved  with the SE-54  fused
      silica capillary column  are shown  in  Figures 1 through 6.

      7.3.2  Wide-bore columns:

            7.3.2.1  Column 1  and Column  2:
      Carrier gas  (He) = 5-7 mL/minute
      Makeup gas  (argon/methane  (P-5 or  P-10) or N2)  = 30 mL/min
      Injector temperature = 250°C
      Detector temperature = 290°C
      Initial temeprature = 150°C, hold 0.5 minute
      Temperature  program = 150°C to 270°C at 5°C/min
      Final temperature = 270°C, hold 10 minutes.

            7.3.2.2  Column 3:
      Carrier gas  (He) = 6 mL/minute
      Makeup gas  (argon/methane  (P-5 or  P-10) or N2)  = 30 mL/min
      Injector temperature = 205°C
      Detector temperature = 290°C
      Initial temeprature = 140°C, hold 2 minutes
      Temperature  program = 140°C to 240°C at 10°C/min,
                            hold 5  minutes  at 240°C,
                            240°C to 265°C at 5°C,
      Final temperature = 265°C, hold 18 minutes.

      7.3.3  Additional columns - The columns listed  in this  section were
used to develop the method performance data; they are recommended for  use
in the  analysis of organochlorine pesticides and PCBs. Their specification
is  not  intended  to prevent  laboratories  from  using   columns  that  are
developed after promulgation of the method.  Laboratories may use  other
capillary  columns   if  they   document  method  performance  data  (e.g.

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      chromatographic  resolution,  analyte breakdown,  and MDL's)  equal  to or
      better than that provided with the method.

            7.3.4 Table 2 gives the retention times and MDLs that can be achieved
      by this method for  the organochlorine pesticides or PCBs.   Examples of the
      separations achieved  with  the 35 percent  phenyl  methylpolysiloxane, 50
      percent phenyl methyl polysiloxane and SE-54 fused-silica, wide-bore, open-
      tubular columns are shown in Figures 1 through 6.

      7.4  Calibration:

            7.4.1  Refer to Method 8000  for proper calibration techniques.  Use
      Tables  1   and  2  for guidance  on  selecting the  lowest  point  on  the
      calibration curve.

            7.4.2  The procedure  for  internal  or  external  calibration  may be
      used.  Refer to Method 8000 for a description of each of these procedures.

            7.4.3  Because several of the  pesticides may co-elute on any single
      column, two calibration mixtures are provided that  minimize the problem
      (Section 5.6.3).   These calibration mixtures are also listed in Table 9,
      along with  the low point  concentration of  each  analyte  in  the mixture.
      The concentrations provided should be detectable on a GC/ECD suitable for
      use with this method.  Mixtures of Aroclors other than 1016/1260 are not
      recommended for use with this method.

            7.4.4  Because  of the  low  concentration  of pesticide  standards
      injected on a GC/ECD, column adsorption may be a problem when the GC has
      not been used  for  a day.   Therefore,  the GC column should  be primed or
      deactivated by injecting a PCB or pesticide standard mixture approximately
      20 times more  concentrated  than the mid-concentration standard.   Inject
      this standard mixture prior to beginning initial  or daily calibration.

Caution: Several  analytes, including Aldrin, may  be observed  in the injection
         just following  this  system priming.   Always run an  acceptable  blank
         prior to running any standards or samples.

      7.5  Gas chromatographic analysis;

            7.5.1  Refer to Method 8000.   If the internal  standard calibration
      technique is used,  add  10 /xL  of  internal  standard  to  the sample extract
      prior to injection.

            7.5.2  Follow Method  8000  for  instruction on the analysis sequence,
      appropriate dilutions,  establishing daily  retention  time windows,  and
      identification criteria.  Analysis of a mid-concentration standard after
      each group of 20  samples is recommended (Section  8.3.4).

            7.5.3  Examples of GC/ECD  chromatograms generated  by  instruments
      with wide-  or narrow-bore  columns  are presented  in Figures 1 through 6.

            7.5.4  Record the sample  volume injected  and the  resulting  peak
      sizes (in area units or peak heights).


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      7.5.5  If  the  peak response Is  less  than 2.5 times  the baseline
noise level, the validity of the  quantitative result may be questionable.
The  analyst  should consult with  the  source of the  sample  to determine
whether further  concentration of the  sample is  warranted  by the context
in which the result is to be used.

      7.5.6  If the peak response exceeds the working range of the system,
dilute the extract and reanalyze.

      7.5.7  Identification of mixtures (i.e. PCBs and toxaphene) is based
on  the  characteristic  "fingerprint"   retention  time and  shape of  the
indicator  peak(s); and  quantitation   is  based  on  the  area   under  the
characteristic  peaks  as  compared to   the  area  under the  corresponding
calibration peak(s) of the same retention time and shape generated using
either internal or external calibration procedures (Section 7.6).

      7.5.8  Identify compounds in the sample by comparing the retention
times of the peaks in the sample chromatogram with those of the peaks in
standard  chromatograms.    The  retention  time  window  used  to  make
identifications  is based  upon  measurements  of  actual  retention  time
variations over  the course  of 7  to 10 consecutive injections.  (Tables 5
and  6).   A suggested window  size can be calculated by multiplying  the
standard deviation of a retention time window by three.

      7.5.9  Quantitation of the compound(s) of interest is premised on:
1)   a linear response of the  BCD to the  ranges  of concentrations  of the
compound(s)  of  interest encountered  in  the  sample  extract  and  the
corresponding calibration extract; and  2)   a  direct linear proportionality
between the  magnitude  of response of  the  ECD over the width(s)  of  the
retention window(s) (the  area under the  characteristic  or "fingerprint"
peak[s])  in  the sample  and  calibration  extracts.   Proper  quantitation
requires the appropriate selection of a baseline from which the area under
the characteristic peak(s) can be calculated.

      7.5.10  If compound  identification  or quantitation  are  precluded
due to interference (e.g., broad, rounded peaks or ill-defined baselines
are present) cleanup of the extract or  replacement of the capillary column
or detector  is warranted.   Rerun sample  on  alternate instrumentation to
determine if the problem is of  instrument  or sample origin.    Refer to
Section 7.2 for the procedures to be followed in sample  cleanup.

7.6  Quantitation of Multiple Component Analvtes:

      7.6.1  Scope (excerpted from U.S.  FDA,  RAM):  Residues  which  are
mixtures of two or more  components present problems  in measurement.  When
they  are  found  together,  e.g.,  toxaphene  and DDT,  the  problem  of
quantitation becomes even more difficult.  Suggestions are offered in the
following sections for handing toxaphene,  chlordane, PCB,  DDT,  and BHC.

      7.6.2  Toxaphene:   Quantitative calculation of toxaphene or strobane
is difficult,  but reasonable accuracy can be  obtained.    To  calculate
toxaphene on  GC/ECD:    (a)   adjust the  sample  size so  that  the  major
toxaphene peaks are 10-70% of full-scale  deflection (FSD);  (b)   inject a
toxaphene standard that  is estimated to be  within ±10 ng  of the sample;

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(c)  quantitate  using  the  five major  peaks or  the  total  area  of  the
toxaphene pattern.

            7.6.2.1  To measure  total  area, construct the  baseline  of
      standard  toxaphene   between  Its  extremities;  and  construct  the
      baseline under the sample,  using the distances of the peak troughs
      to baseline  on  the  standard as  a  guide.   This  procedure  Is made
      difficult by the fact that the relative heights and widths of the
      peaks in the sample will  probably not be identical to the standard.

            7.6.2.2  A series of toxaphene residues have been calculated
      using the total  peak area for comparison to  the standard and also
      using the  area  of the  last  four peaks only,  in both  sample  and
      standard.   The  agreement between the results obtained  by  the  two
      methods justifies  the use  of the  latter  method for  calculating
      toxaphene  in a  sample  where  the  early  eluting portion   of  the
      toxaphene chromatogram  shows  interferences from  other substances
      such as DDT.

      7.6.3  Chlordane  is  a  technical  mixture  of  at least 11  major
components and  30 or more minor  components.   Trans-  and cis-chlordane
(alpha and  gamma),  respectively, are the two major components of technical
chlordane.  However, the exact percentage of each in the technical material
is not completely defined,  and is not consistent  from batch to batch.

            7.6.3.1  The GC  pattern  of a chlordane residue  may differ
      considerably from that of the technical standard.  Depending on the
      sample substrate and  its  history, residues of chlordane can consist
      of almost  any combination  of:   constituents from  the technical
      chlordane,  plant  and/or  animal  metabolites,   and  products  of
      degradation  caused by exposure  to  environmental factors  such  as
      water and sunlight.

            7.6.3.2  When the chlordane residue does not resemble technical
      chlordane, but instead consists primarily of individual, identifiable
      peaks,  quantitate the peaks of alpha-chlordane, gamma-chlordane, and
      heptachlor separately against the appropriate reference materials,
      and report the individual residues.

            7.6.3.3  When the GC  pattern  of the residue resembles that of
      technical chlordane,  the analyst may quantitate chlordane residues
      by comparing the total  area of the chlordane chromatogram using the
      five major peaks or the total area.   If the heptachlor epoxide peak
      is relatively small,  include  it as part of the total  chlordane area
      for calculation  of the residue.   If heptachlor and/or heptachlor
      epoxide are much out of proportion, calculate these  separately and
      subtract  their   areas  from the  total  area  to  give  a corrected
      chlordane  area.   (Note  that octachlor epoxide,  a  metabolite  of
      chlordane,  can  easily  be  mistaken  for  heptachlor  epoxide on  a
      nonpolar GC column.)

            7.6.3.4  To  measure   the   total   area   of   the  chlordane
      chromatogram, proceed as in Section 7.6.2 on toxaphene.  Inject an
      amount  of  technical   chlordane  standard  which  will  produce  a

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      chromatogram in which  the major peaks are  approximately  the  same
      size as those in the sample chromatograms.

      7.6.4  Polychlorinated biphenyls (PCBs):   Quantitation of residues
of PCB involves problems  similar to those encountered in the quantitation
of toxaphene, strobane, and chlordane.  In each  case, the chemical is made
up of numerous compounds which generate multi-peak chromatograms.  Also,
in each case, the chromatogram  of the  residue  may not  match that of the
standard.

            7.6.4.1  Mixtures of PCBs  of  various  chlorine contents  were
      sold for many years in  the U.S.  by the Monsanto Co. under the trade
      name Aroclor (1200  series  and  1016).   Although  these Aroclors are
      no  longer  marketed, the  PCBs  remain  in  the environment  and are
      sometimes found as residues in foods, especially fish.

            7.6.4.2  Since standards are not generally available for all
      of  the  congeners  of  chlorinated  biphenyl,  PCB  residues   are
      quantitated by comparison to one or more of the Aroclor materials,
      depending on the chromatographic pattern of the residue.  A choice
      must be made as to which Aroclor or mixture of Aroclors will produce
      a chromatogram most similar to that of the residue.  This may also
      involve a judgement about  what  proportion of the different Aroclors
      to combine to produce the appropriate reference material.

            7.6.4.3  PCB  Quantitation  option  #1- Quantitate  the  PCB
      residues by  comparing  the total area of the chlorinated biphenyl
      peaks  to the  total  area of peaks  from the  appropriate Aroclor(s)
      reference materials. Measure the total area  or height response from
      the common baseline under all  the peaks.  Use only those peaks from
      the sample that can be attributed to chlorobiphenyls.  These peaks
      must also be present in the chromatogram of the reference materials.
      A mixture of Aroclors may be required to provide the best match of
      the GC patterns of the sample and reference.

            7.6.4.4  PCB  Quantitation  option  #2- Quantitate  the  PCB
      residues by comparing  the responses  of 3 to 5 major peaks in  each
      appropriate  Aroclor standard  with  the  peaks  obtained  from the
      chlorinated biphenyls in the  sample extract.  The amount of Aroclor
      is calculated using each of the major peaks,  and the results of the
      3 to 5  determinations are averaged. Major peaks are defined as those
      peaks  in the Aroclor standards that are at least 30% of the height
      of  the largest Aroclor peak.   Later eluting  Aroclor  peaks are
      generally the most stable in the environment.

            7.6.4.5  For samples where Aroclor  patterns are not apparent,
      but appear to contain weathered PCBs,  several diagnostic peaks have
      been identified in  Table 10.  Analysts should examine chromatographs
      containing these peaks  carefully, as these samples may contain PCBs.

      7.6.5  Hexachlorocyclohexane  (BHC,  from  the  former  name, benzene
hexachloride):   Technical  grade BHC is  a  cream-colored  amorphous solid
with  a  very  characteristic  musty odor; it consists of  a mixture of six
chemically distinct  isomers  and one  or more heptachlorocyclohexanes and

                             8081 -  13                      Revision 0
                                                            November 1990

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      octachlorocyclohexanes.   Commercial  BHC  preparations  may  show  a  wide
      variance in  the  percentage  of individual  isomers present.    Quantitate
      each  isomer  (a,  0,  7,  and  6)  separately against  a standard  of  the
      respective pure isomer.


8.0  QUALITY CONTROL

      8.1  Refer to Chapter  One for  specific  quality control (QC) procedures.
Quality control to validate sample extraction is covered in Method 3500 and in
the extraction method utilized.   If  the  extract  cleanup was performed, follow
the QC in Method 3600 and in the specific cleanup method.

      8.2  DDT and  endrin are easily degraded  in the  injection  port,  if  the
injection port  or  front  of  the column  is  contaminated with buildup  of  high
boiling  residue  from  sample injection.   Check  for degradation  problems  by
injecting a  mid-concentration standard  containing  only 4,4'-DDT  and  endrin.
Look for the degradation products of 4,4'-DDT (4,4'-DDE and 4,4'-ODD) and endrin
(endrin ketone and  endrin aldehyde).   If degradation  of either  DDT  or endrin
exceeds 20%, take corrective action before proceeding with calibration, (refer
to Method 8000 and  Section 4.4 of  Method  8081).  Calculate percent breakdown as
fol1ows:
 % breakdown    Total DDT degradation peak area (DDE + ODD)
 for 4,4'-DDT = 	   x 100
                        peak areas (DDT + DDE + ODD)


                   Total endrin degradation peak area
 % breakdown       (endrin aldehyde + endrin ketone)
 for Endrin   = 	   x 100
                  peak areas (endrin + aldehyde + ketone)


      8.3  Mandatory quality control to evaluate the GC system operation is
found in Method 8000.  The following  steps  are recommended as additional method
QC.

            8.3.1  The  quality  control   (QC)  reference  sample  concentrate
      (Method 8000)  should  contain  the organochlorine pesticides at  10  /xg/L.
      If this method is to be used  for  analysis of PCBs, chlordane or toxaphene
      only,  the  QC  reference  sample  concentrate  should  contain  the  most
      representative multi-component mixture at a concentration  of  50  mg/L in
      acetone.  The frequency of the  QC reference sample analysis is equivalent
      to a minimum of 1 per 20 samples or  1 per batch if less than 20 samples.
      If the recovery of any compound found in the QC reference sample is less
      than 80 percent or  greater than  120  percent  of the certified value, the
      laboratory performance is judged to be out of control, and the problem must
      be corrected.  A new set of calibration standards should be prepared and
      analyzed.
                                   8081  -  14                       Revision 0
                                                                  November 1990

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            8.3.2  Calculate surrogate standard recovery on all samples, blanks,
      and spikes.  Determine if the recovery is within limits (limits established
      by performing QC procedures outlined in Method 8000).

      If recovery is not within limits,  the following are required:

                  8.3.2.1  Check to  be sure there are no errors in calculations,
            surrogate solutions and  internal  standards.  Also, check instrument
            performance.

                  8.3.2.2  Recalculate the data  and/or reanalyze the extract if
            any of the above checks reveal a problem.

                  8.3.2.3  Reextract  and  reanalyze  the  sample if  none  of the
            above are a problem or flag the data as "estimated concentration."

            8.3.3  The breakdown  of DOT and endrin  should be  measured  before
      samples are analyzed.   Injector maintenance  and recalibration  should be
      completed  if  the  breakdown  is greater  than 15%  for either  compound
      (Section 8.2).

            8.3.4  Include a mid-concentration calibration standard after each
      group of 20 samples in the analysis  sequence as a calibration check.  The
      response factors for  the  mid-concentration calibration should  be  within
      30 percent of the average values for the multiconcentration calibration.
      When this continuing  calibration  is out of this  acceptance  window, the
      laboratory should stop  analyses,  clean  the injector, replace the  septum
      and recalibrate the system.

            8.3.5  Whenever  quantitation  is  accomplished using   an  internal
      standard,  internal  standards  must  be  evaluated  for  acceptance.   The
      measured area of  the  internal standard must   be no  more  than 50 percent
      different from the average area calculated during  calibration.   When the
      internal standard peak  area is  outside  the limit,  all  samples  that fall
      outside the QC criteria must be reanalyzed.

      8.4  GC/MS confirmation:  Any compounds confirmed  by two columns  should
also be confirmed by GC/MS if the concentration is  sufficient for detection by
GC/MS as determined by the laboratory generated detection limits.

            8.4.1  The GC/MS would normally require a minimum concentration of
      10 ng/juL in the final extract for each single-component compound.

            8.4.2  The pesticide extract and associated blank  should be analyzed
      by GC/MS as per Section 7.0 of Method 8270.

            8.4.3  The  confirmation may  be  from  the  GC/MS  analysis  of the
      base/neutral-acid extracts (sample and  blank).  However, if the compounds
      are  not detected  in  the  base/neutral-acid  extract  even  though  the
      concentrations are high enough,  a  GC/MS analysis of the pesticide extract
      should be performed.
                                   8081  -  15                       Revision 0
                                                                  November 1990

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            8.4.4  A QC reference sample of the compound must also be analyzed
      by GC/MS.  The concentration of the QC reference  standard must demonstrate
      the ability to confirm the pesticides/Aroclors identified by GC/ECD.

      8.5  Whenever  silica   gel   cleanup  is  used,   demonstrate   that  the
fractionation  scheme  is   reproducible.    Batch  to  batch  variation  in  the
composition of the silica  gel  material  may cause  a change in the distribution
patterns of the organochlorine pesticides and  PCBs  as Aroclors.  When compounds
are found  in more than  one fraction,  add  the concentrations of  the  various
fractions, making corrections for the final volume of the fractions.  It is up
to the analyst to decide whether the cut-off point should be 5 percent or less
of the concentration in the fraction where the compound is expected to elute.


9.0  METHOD PERFORMANCE

      9.1  The MDL is defined in Chapter One.   The  MDL concentrations listed in
Tables 1  and  2 were  obtained using organic-free reagent  water  and  sandy loam
soil.   Details for determining MDLs  are  given  in Chapter One.  The MDL actually
achievable  in a given  analysis will   vary  depending  on  detector  response
characteristics,  irreducible  noise from  instrument  electronics  and  matrix
effects.

      9.2  This  method has been tested  in a  single laboratory  by  using clean
hexane and  liquid and  solid waste extracts  that were spiked  with the test
compounds at three concentrations. Single-operator precision,  overall precision,
and method accuracy were found to be  related to the concentration of the compound
and the type of matrix.  Results of  the  single-laboratory method evaluation are
given  in Table 4.

      9.3  The accuracy and precision obtainable following this method will be
determined by the sample matrix, sample  preparation technique, optional  cleanup
techniques, and calibration procedures used.


10.0  REFERENCES

1.  Lopez-Avila, V.; Schoen,  S.; Milanes,  J.  "Single-Laboratory  Evaluation of
    Method 8080 - Organochlorine Pesticides  and PCBs"; final  report to the U.S.
    Environmental Protection Agency  on Contract 68-03-3226; Acurex Corporation,
    Environmental Systems Division:  Mountain  View, CA,  1986. EPA-600/4-87/022.

2.  Development  and Application of  Test Procedures for Specific  Organic Toxic
    Substances in Wastewaters.  Category 10 -  Pesticides and  PCB Report for the
    U.S.  Environmental  Protection Agency on Contract 68-03-2606.

3.  Goerlitz, D.F.; Law,  L.M.   "Removal  of Elemental Sulfur  Interferences from
    Sediment Extracts for  Pesticide Analysis"; Bull. Environ. Contam.  Toxicol.
    1971, 6, 9.

4.  Blumer, M.  "Removal of Elemental Sulfur from Hydrocarbon Fractions"; Anal.
    Chem. 1957, 29, 1039.
                                   8081  -  16                       Revision 0
                                                                  November 1990

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5.  Ahnoff, M.; Josefsson,  B.   "Cleanup Procedures for  PCB  Analysis on River
    Water Extracts"; Bull. Environ. Contain. Toxicol. 1975, 13, 159.

6.  Jensen, S.; Renberg,  L.;  Reutergardth, L.   "Residue Analysis of Sediment
    and Sewage Sludge for Organochlorines in the  Presence of Elemental Sulfur";
    Anal. Chem. 1977, 49, 316-318.

7.  Wise, R.H.; Bishop,  D.F.;  Williams, R.T.; Austern,  B.M.   "Gel Permeation
    Chromatography  in  the  GC/MS  Analysis   of  Organics  in  Sludges";  U.S.
    Environmental  Research Laboratory.  Cincinnati, OH  45268.

8.  Pionke, H.B.;  Chesters,  G.;  Armstrong,  D.E.   "Extraction  of Chlorinated
    Hydrocarbon Insecticides from Soil"; Agron. J. 1968, 60,  289.

9.  Burke, J.A.; Mills, P.A.; Bostwick, D.C.   "Experiments with Evaporation of
    Solutions of Chlorinated Pesticides"; J.  Assoc. Off. Anal. Chem. 1966, 49,
    999.

10. Glazer, J.A.,  et al.   "Trace  Analyses  for Wastewaters";  Environ. Sci. and
    Technol. 1981, 15, 1426.
                                  8081  -  17                       Revision 0
                                                                  November 1990

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                                TABLE 1

       GAS CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION
    LIMITS FOR THE ORGANOCHLORINE PESTICIDES AND  PCBs AS AROCLORS8
                   USING  WIDE-BORE CAPILLARY  COLUMNS
Retention Time (min) MDLb Water MDLb Soil
Compound
Aldrin
alpha-BHC
beta-BHC
delta-BHC
gamma-BHC (Lindane)
alpha-Chlordane
gamma-Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan Sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
4,4'-Methoxychlor
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Water = Organic-free
DB 608C
11.84
8.14
9.86
11.20
9.52
15.24
14.63
18.43
16.34
19.48
16.41
15.25
18.45
20.21
17.80
19.72
10.66
13.97
22.80
MR
MR
MR
MR
MR
MR
MR
MR
DB 1701C
12.50
9.46
13.58
14.39
10.84
16.48
16.20
19.56
16.76
20.10
17.32
15.96
19.72
22.36
18.06
21.18
11.56
15.03
22.34
MR
MR
MR
MR
MR
MR
MR
MR
(M9/L)
0.034
0.035
0.023
0.024
0.025
0.008
0.037
0.050
0.058
0.081
0.044
0.030
0.040
0.035
0.039
0.050
0.040
0.032
0.086
NA
0.054
NA
NA
NA
NA
NA
0.90
(M9/Kg)
2.2
1.9
3.3
1.1
2.0

1.5
4.2
2.5
3.6
NA
2.1
2.4
3.6
3.6
1.6
2.0
2.1
5.7
NA
57.0
NA
NA
NA
NA
NA
70.0
reagent water.
Soil = Sandy loam soil.
MR = Multiple peak
responses.



NA = Data not available.
U.S.  EPA  Method  8081.    Organochlorine  Pesticides  and  PCBs  as Aroclors.
Environmental  Protection  Agency.    Office  of  Research  and  Development,
Washington, DC  20460.
                               8081 - 18
Revision 0
November 1990

-------
                               TABLE 1
                              (Continued)

MDL is the  method  detection limit.  MDL was  determined  from the analysis of
seven replicate aliquots of each matrix processed through  the  entire analytical
method (extraction,  silica gel  cleanup,  and  GC/ECD  analysis).   MDL = t(n-l,
0.99) x SD,  where  t(n-l, 0.99)  is the  student's t  value  appropriate for a 99%
confidence  interval and  a  standard deviation  with  n-1 degrees of freedom, and
SD is the standard deviation of the seven replicate measurements.

Temperature program:  150°C (hold  1/2 minutes) to 270°C at 5°C/min, helium head
pressure at 10 psi.
                               8081 - 19                       Revision 0
                                                               November 1990

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                           TABLE 2

   GAS CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION
LIMITS FOR THE ORGANOCHLORINE PESTICIDES AND PCBs AS AROCLORS"
             USING NARROW-BORE  CAPILLARY  COLUMNS

Compound
Aldrin
alpha-BHC
beta-BHC
delta-BHC
gamma -BHC (Lindane)
alpha-Chlordane
gamma-Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
Heptachlor epoxide
4,4'-Methoxychlor
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Retention
Col. lc
14.51
11.43
12.59
13.69
12.46

17.34
21.67
19.09
23.13
19.67
18.27
22.17
24.45
21.37
23.78
13.41
16.62
28.65
MR
MR
MR
MR
MR
MR
MR
MR
Liquid = Organic-free reagent
Time (min)
Col. ld
14.70
10.94
11.51
12.20
11.71

17.02
20.11
18.30
21.84
18.74
17.62
20.11
21.84
19.73
20.85
13.59
16.05
24.43
MR
MR
MR
MR
MR
MR
MR
MR
water.
MDLb Liquid
(M9/L)
0.034
0.035
0.023
0.024
0.025

0.037
0.050
0.058
0.081
0.044
0.030
0.040
0.035
0.039
0.050
0.040
0.032
NA
0.086
NA
0.054
NA
NA
NA
NA
0.90

Solid
(Mg/Kg)
2.2
1.9
3.3
1.1
2.0

1.5
4.2
2.5
3.6
NA
2.1
2.4
3.6
3.6
1.6
2.0
2.1
NA
5.7
NA
57.0
NA
NA
NA
NA
70.0

Solid = Sandy loam soil .
MR = Multiple
NA = Data not
peak responses.
available.



                          8081  -  20
Revision 0
November 1990

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                                TABLE  2
                              (Continued)

U.S.  EPA Method  8081.    Organochlorine  Pesticides  and  PCBs  as  Aroclors.
Environmental  Protection  Agency.    Office  of  Research  and  Development,
Washington,  DC  20460.

MDL is the  method  detection limit.   MDL was determined  from  the  analysis of
seven replicate aliquots of each matrix processed through  the entire analytical
method (extraction, cleanup,  and  GC/ECD analysis).   MDL  = t(n-l,  0.99) x SD,
where t(n-l, 0.99)  is  the  student's t value appropriate  for a 99% confidence
interval  and a standard  deviation with n-1  degrees  of freedom,  and SD is the
standard deviation of the seven replicate measurements.

30  m  x  0.25  mm  ID  DB 608  fused  silica,  open-tubular column  (1  pm  film
thickness).

30 m x 0.25  mm  ID DB 5 fused silica,  open-tubular column (1 urn film thickness).
                               8081  -  21                       Revision 0
                                                              November  1990

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                              TABLE 3

     ESTIMATED QUANTITATION LIMITS (EQL) FOR VARIOUS MATRICES8



Matrix                                                   Factor"
Ground water                                                  10
Low-concentration soil by sonication with GPC cleanup        670
High-concentration soil and sludges by sonication         10,000
Non-water miscible waste                                 100,000
Sample EQLs are highly matrix-dependent.  The EQLs listed herein are
provided for guidance and may not always be achievable.

EQL = [Method detection limit for water (Table 1) or (Table 2) wide bore
or narrow bore options] x [Factor (Table 3)].  For nonaqueous samples,
the factor is on a wet-weight basis.
                             8081  -  22                      Revision 0
                                                            November 1990

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                                    TABLE  4

  RETENTION TIMES OF OTHER PESTICIDES DETECTED USING METHOD 8081


Analyte                             DB 608            DB 1701


Trifluralin                          5.16              8.58
Diallate (isomer 1)                  7.15              8.05
Diallate (isomer 2)                  7.42              8.58
PCNB                                 9.03              9.91
Dichlone                            10.80             decomp.
Isodrin                             13.47             13.93
Dichlorvos
Naled
Prometon
Propazlne
Atrazine
Terbuthylazine
Simazine
Dichlorofenthion
Methyl chlorphrophos
Ronnel
Captan                              16.83             17.32
Chiorobenzilate                     17.58             18.97
Prometryn
Ametryn
Metribuzin
Terbutryn
Chlorpyrophos
Trichlorinate
Chlorfenvinphos
Tetrachlorovinphos
Anilazine
Cynazine
Hexazinone
Captafol                            22.51             23.11
Mirex                               22.75             23.11
Leptophos
Coumaphos


Temperature program:  150°C (hold 1/2  minutes)  to 270°C at  5°C/min, helium
head pressure at 10 psi.
                                  8081  - 23                       Revision 0
                                                                  November 1990

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                              TABLE  5

     REPRODUCIBILITY OF RETENTION TIMES OF THE ORGANOCHLORINE
             PESTICIDES  FOR TEN  CONSECUTIVE  INJECTIONS
              USING THE  NARROW-BORE  CAPILLARY  COLUMNS
                           Retention Time Reproducibility
Compound                           SD (min)a
alpha- BHC
beta-BHC
gamma -BHC
delta-BHC
Heptachlor
Aldrin
Heptachlor epoxide
alpha-Chlordane
gamma-Chlordane
Endosulfan I
4,4'-DDE
Dieldrin
Endrin
Endosulfan II
4,4'-DDD
Endrin aldehyde
Endosulfan sulfate
4,4'-DDT
4,4'-Methoxychlor
Toxaphene
Aroclor-1016
Aroclor-1260
0.010
0.009
0.011
0.011
0.008
0.009
0.009

0.012
0.010
0.008
0.008
0.007
0.006
0.008
0.007
0.008
0.008
0.007
0.004-0.006"
0.042-0.104"
0.035-0.040"
SD = Standard deviation.

a  Number of determinations is 10.

b
   Value determined for 3 major peaks of each mixture.
                             8081 - 24                      Revision 0
                                                            November 1990

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                              TABLE  6

     REPRODUCIBILITY  OF  RETENTION  TIMES  OF  THE  ORGANOCHLORINE
          PESTICIDES  FOR TEN  CONSECUTIVE INJECTIONS  USING
                  THE WIDE-BORE  CAPILLARY COLUMNS
Compound
                        Retention Time Reproducibility
                                    SD (min)a
DB 5
DB 608
alpha-BHC
beta-BHC
gamma -BHC
delta-BHC
Heptachlor
Aldrin
Heptachlor epoxide
alpha-Chlordane
gamma-Chlordane
Endosulfan I
4,4'-DDE
Dieldrin
Endrin
Endosulfan II
4,4'-DDD
Endrin aldehyde
Endosulfan sulfate
4,4'-DDT
4,4'-Methoxychlor
SD = Standard deviation
0.006
0.007
0.007
0.005
0.007
0.007
0.007
0.007
0.007
0.008
0.007
0.008
0.013
0.013
0.010
0.007
0.007
0.007

0.007
0.008
0.008
0.006
0.008
0.008
0.008
0.009
0.009
0.007
0.009
0.007
0.010
0.010
0.010
0.010
0.007
0.007

a Number of determinations is 9.
                     pairs cannot be resolved on the DB 5 wide-bore open
      tubular column under the conditions listed in Section 7.3.
                             8081 - 25
                                    Revision 0
                                    November 1990

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                                             TABLE 7
                  ELUTION  PATTERNS  AND AVERAGE  RECOVERIES OF THE ORGANOCHLORINE
               PESTICIDES  AND  AROCLOR BY METHOD 8081  WITH SILICA GEL FRACTIONATION
                                   (LIQUID WASTE NO. 1 EXTRACT)
Compound
                                       Average  Recovery + SD (RSD)
                                                                  a,b
Fraction I
hexane (80 ml)
Fraction II
hexane (50 mL)
Fraction III
 methylene
 chloride
 (15 mL)
Total Recovery
alpha-BHC
beta-BHC
gamma -BHC
delta-BHC
Heptachlor
Aldrin
Heptachlor epoxide
alpha-Chlordane
gamma-Chlordane
Endosulfan I
4,4'-DDE
Dieldrin
Endrin
Endosulfan II
4,4'-DDD
Endrin aldehyde
Endosulfan sulfate
4,4'-DDT
4,4'-Methoxychlor
Aroclor-1016
Aroclor-1260
57 + 2.5(4.4)



90 + 11(12)
92 ± 9.2(10)


85 + 7.2(8.5) 10 + 9.2(92)

95 ± 16(17)



33 ± 4.0(15)


88 ± 18(21)

118 + 9.8(8.3)
100 ± 18(18)
22 + 9.2(42)
90 + 3.1(3.4)
90 + 4.0(4.4)
90 ± 11(12)


89 ± 4.1(4.6)


88 + 3.8(4.3)

82 + 4.3(5.3)
65 + 3.1(4.7)
79 + 7.1(9.0)
43 + 16(37)
C
83 ± 4.0(4.8)

75 ± 4.6(6.1)


79 + 10(13)
90 + 3.1(3.4)
90 + 4.0(4.4)
90 + 11(12)
90 + 11(12)
92 + 9.2(10)
89 ± 4.1(4.6)

95 + 8.0(8.4)
88 + 3.8(4.3)
95 + 16(17)
82 + 4.3(5.3)
65 + 3.1(4.7)
79 + 7.1(9.0)
76 + 16(21)
C
83 + 4.0(4.8)
88 + 18(21)
75 + 4.6(6.1)
118 + 9.8(8.3)
100 + 18(18)
                             8081  -  26
                                         Revision 0
                                         November  1990

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                              TABLE 7
                            (continued)
The values given represent the average percent recoveries from three
replicate determination + one standard deviation.  The numbers in
parentheses are the relative standard deviations.

The amounts spiked are 15,000 30,000, and 150,000 ng per 2 ml extract
per column for the organochlorine pesticides and Aroclor-1016/Aroclor-
1260, respectively.

Unable to determine recovery because of interference.
                             8081  -  27                      Revision 0
                                                            November 1990

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                                                   TABLE 8
                        ELUTION  PATTERNS  AND AVERAGE RECOVERIES OF THE ORGANOCHLORINE
                             PESTICIDES AND AROCLOR BY SILICA GEL CHROMATOGRAPHY
Compound
                                             Average  Recovery + SD (RSD)
                                                                        a,b
Fraction I
hexane (80 mL)
Fraction II
hexane (50 mL)
Fraction III
 methylene
 chloride
 (15 mL)
Total Recovery
alpha-BHC
beta-BHC
gamma -BHC
delta-BHC
Heptachlor
Aldrin
Heptachlor epoxide
alpha-Chlordane
gamma-Chlordane
Endosulfan I
4,4'-DDE
Dieldrin
Endrin
Endosulfan II
4,4'-DDD
Endrin aldehyde
Endosulfan sulfate
4,4'-DDT
4,4'-Methoxychlor
Aroclor-1016
Aroclor-1260
55 ± 6.1(11)



70 + 7.7(11)
65 ± 4.6(7.1)


71 ± 3.2(4.5) 10 ± 2.0(20)

76 ± 7.1(9.3)



36 ± 2.0(5.6)


61 ± 7.9(13)

104 + 2.5(2.4)
95 ± 7.5(7.9)
20 + 1.7(8.7)
94 + 3.0(3.2)
89 + 4.1(4.6)
92 ± 5.2(5.6)


91 ± 5.7(6.3)


88 + 5.1(5.8)

85 + 9.4(11)
87 + 6.4(7.3)
81 + 4.5(5.5)
49 + 1.2(2.4)
71 + 9.2(13)
86 ± 5.0(5.8)

99 ± 17(17)


75 + 6.0(8.0)
94 + 3.0(3.2)
89 + 4.1(4.6)
92 + 5.2(5.6)
70 + 7.7(11)
65 + 4.6(7.1)
91 ± 5.7(6.3)

81 + 4.9(6.1)
88 + 5.1(5.8)
76 + 7.1(9.3)
85 + 9.4(11)
87 + 6.4(7.3)
81 + 4.5(5.5)
85 + 3.1(3.6)
71 + 9.2(13)
86 + 5.0(5.8)
61 + 7.9(13)
99 + 17(17)
104 + 2.5(2.4)
95 + 7.5(7.9)
                                   8081  -  28
                                         Revision 0
                                         November 1990

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                              TABLE 8
                            (Continued)
The values given represent the average percent recoveries from three
replicate determinations ± one standard deviation.  The numbers in
parentheses are the relative standard deviations.

The amounts spiked are 3,000, 6,000, and 30,000 ng per 2 ml extract per
column for the organochlorine pesticides and Aroclor-1016/Aroclor-1260,
respectively.
                            8081  -  29                       Revision 0
                                                            November 1990

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                                    Table 9

         Individual  Standard Mixtures  For Single Component Pesticides.
Individual
Standard Mix A
Low Point
Concentration
( g/L)
Individual
Standard Mix B
Low Point
Concentration
( g/L)
a-BHC                       5.0
Heptachlor                  5.0
7-BHC                       5.0
Endosulfan I                5.0
Dieldrin                   10.0
Endrin                     10.0
p,p'-DDD                   10.0
p,p'-DDT                   10.0
Methoxychlor               50.0
Tetrachloro-m-xylene       20.0
Decachlorobiphenyl         20.0
                  0-BHC
                  6-BHC
                  Aldrin
                  Heptachlor epoxide
                  o-Chlordane
                  'Y-Chlordane
                  p,p'-DDE
                  Endosulfan sulfate
                  Endrin aldehyde
                  Endrin ketone
                  Endosulfan II
                  Tetrachloro-m-xylene
                  Decachlorobiphenyl
                             5.0
                             5.0
                             5.0
                             5.0
                             5.0
                             5.0
                            10.0
                            10.0
                            10.0
                            10.0
                            10.0
                            20.0
                            20.0
                                   8081 - 30
                                             Revision  0
                                             November 1990

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                                   TABLE 10
        PEAKS  DIAGNOSTIC  OF  PCBs  OBSERVED  IN  0.53 mm  ID COLUMN ANALYSIS
Peak    RT on      RT on                                      Pesticide
 No.   DB 608a    DB 1701a            Aroclor"            Retention Window
I       4.90       4.66     1221                      Before TCmX

II      7.15       6.96     1221, 1232, 1248          Before o-BHC

III     7.89       7.65     1061, 1221. 1232, 1242,   Before o-BHC

IV      9.38       9.00     1016, 1232, 1242, 1248,   just after o-BHC on
                                                      DB 1701;just before
                                                      7-BHC on DB 608

V      10.69      10.54     1016. 1232. 1242.         1248 o-BHC and
                                                      heptachlor on DB 1701;
                                                      just after heptachlor on
                                                      DB 608

VI     14.24      14.12     1248. 1254                T-BHC and heptachlor
                                                      epoxide on DB 1701;
                                                      heptachlor epoxide and
                                                      T-chlordane on DB 608

VII    14.81      14.77     1254                      Heptachlor epoxide and
                                                      T-chlordane on DB 1701;
                                                      a- and 7-chlordane on
                                                      DB 608

VIII   16.71      16.38     1254                      DDE and dieldrin on
                                                      DB 1701; dieldrin and
                                                      endrin on DB 608

IX     19.27      18.95     1254, 1260                Endosulfan II on
                                                      DB 1701; DDT on DB 608

X      21.22      21.23     1260                      Endrin aldehyde and
                                                      endosulfan sulfate on
                                                      DB 1701; endosulfan
                                                      sulfate and methoxychlor
                                                      on DB 608

XI     22.89      22.46     1260                      Just before endrin
                                                      ketone on DB 1701; after
                                                      endrin ketone on DB 608

5Using oven temperature program:  T,  = 150°C, hold 30 seconds; increase
                                    temperature at 5°C/minutes to 275°C.
b  Underlined Aroclor indicates the largest peak in the pattern.

                                   8081 -  31                      Revision 0
                                                                  November  1990

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                                        FIGURE 1.
          GAS CHROMATOGRAM  OF THE MIXED ORGANOCHLORINE  PESTICIDE  STANDARD

    Start Tim : 0.00 min      End Time   : 33.00 nrin       Lou Point : 20.00 mv      High Point : 420.00 mV
    Scale Factor;  0         Plot Offset: 20 mv         Plot Scale: 400 mV
                                   Response  [mV]
                                          NJ
                  I I  I
•^f      i^^r      tji      \^j     \^t



 I I I  I I I  I I  I ill I I  I I  I I I  I I
     o      cp      o
I I  I I I  I I  I I I  I I  I I I  I I
   o"
3D
fD
rT
3
,-*-
6' ->_
~*i  L?l
IT
   Ln
   O'
                  =-4.68
                    7.99
                                         9.93
                                                       -23.18
                          26.23
                        - -28.64
                                                                         -0.95
                                                                         -8.60
                                               -30.19
     Column:                30 m x 0.25  mm ID,   DB 5
     Temperature  program:  100°C  (hold  2  minutes)  to J60°C at 15°C/min,  then  at
                             5°C/min to 270°C;  carrier He  at 16 psi.
                                        8081  -  32
                                                     Revision 0
                                                     November 1990

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                                           FIGURE  2.

        GAS CHROMATOGRAM  OF INDIVIDUAL ORGANOCHLORINE PESTICIDE STANDARD  MIX A
Start Time :  0.00 min

Scale factor:   0
   LI—
IT)


it"
6  -»_
D  Ui
ro
End Time  : 33.00 min

Plot Offset: 20 mv
                                           Low Point : 20.00 mv

                                           Plot Scale: 250 mv
                                                              Hign Point : 270.00 mv
                                    Response  [mV]
                     (_n         a         01
                     o         o         o
               i  i  i   I  i  i  i  i   I  i  i   i  i  I  i   i  i  i  I  i   i  i  i  I  j  i
                                   o
                                   o
                                                                     ro
                                                                     u->
                                                                     o
                       •J.3
                   =-7.93
                      -14.27
                       -17.08
   20.22
     .77
                             22.68
                            -23.73
                              •28.52
                                                                           •s.es
                                                                           -8 . 54
                                                                                  TCMX

-12.33


                                                     -9.86   Alpha-BHC

                                                  10.98    Gamma-BHC
                                                13.58    Heptachlor
                                        -17.54     Endosulfan I

                                        —18.47  Dieldrin
                                            •19.78    ODD


                                            —      21.13    DDT
                                                        -19.24   Endrin
                                                                           -23.08    Methoxychlor
                                                                     -30.05
       Column:                 30 m x  0.25 mm  10,   DB  5
       Temperature  program:  100°C (hold 2 minutes) to  160°C at 15°C/min,  then  at
                               5°C/m1n to  270°C; carrier He at 16 ps1.
                                          8081 - 33
                                                      Revision  0
                                                      November 1990

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                                            FIGURE  3.

         GAS  CHROMATOGRAM OF  INDIVIDUAL ORGANOCHLORINE PESTICIDE STANDARD MIX B


    St»rt ''"» : 3.30 t : 2'O.^C «v
    Scale Factor:  3         'lot Ot'set: JO mv         Plot Sole: 250 mV
                                     Response  [mV]
   Li—
 0 ->.
 "3 C/l


 H
l™~1 NO
 3 °-
   KJ
   g-
                                     _»          _i          hO
                         en          a          -9
                                 --10.71   Beta-BHC

                                 	11<73    Delta-BHC
                       14.27
V15.24

  i f. n«;
                            Ml
   j^2"0.69

                           22.00

                         -14.84   Aldrin
                    -16.23   Heptachlor Epoxide

                       -17.08   Gamma-Chlordane
                                                                            •$.93
                                                                            -3.54    TCMX
                      -17.63  Alpha-Chlordane
                      —        18.31  DDE

                                   13. ;t    Endosulfan II
-20.19     Endrin • Aldehyde

     -21.03    Endosulfan Sulfate
                                                      --22.68   Eftdrin    Ketone
                                             -30.04
                                                         OCB
        Column:                 30 m x 0.25 mm  ID,  DB  5
        Temperature program:  100°C (hold 2 minutes) to  160°C at  l5°C/m1n,  then at
                                5°C/min to  270°C;  carrier He  at 16  ps1.
                                           8081 - 34
                                                          Revision 0
                                                          November 1990

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                                     FIGURE 4.
                   GAS  CHROMATOGRAM OF THE TOXAPHENE STANDARD
    Start Time  : 0.00 min
    Scale Factor:  0
     End Tim  : 33.00 min
     Plot Offset: 20 mv
Low Point : 20.00 mv
Plot Scale: 60 mv
                                                            High Point : 80.00 mv
                                   Response [rnV]
r\>
O
                          O        O        O        O        O
                      I I I I II I I I I I I I III I I I I I I I I II I I I I I I I I II I I I I I I I I II I I I I I I I I II
CD
                       I
                                                                         24.32
  Column:               30  m x 0.25 mm ID, DB 5
  Temperature  program: 100°C  (hold 2 minutes) to 160°C  at  15°C/min, then at
                         5°C/min to 270°C; carrier He at  16  psi.
                                     8081 -  35
                                                      Revision  0
                                                      November 1990

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                                  FIGURE  5.
               GAS CHROMATOGRAM OF THE AROCLOR-1016 STANDARD
    Start Time : 0.00 min
    Sole factor:  0
End Time  : 33.00 min
Plot Offset: 20 mV
Low Point : 20.00 mv
Plot Scale: 100 mV
High Point : 120.00 mV
                                   Response  [mV]
                 N>          •*»•         O)         DO          C


                  I I I I I I  I I I III I I I I I I I  I I I I I I I I I I I  I I I I I I I I I I  I
                                      O
                                      O
                                        I I I I I I I I I
   Ul—
D
3
                             -1.81
                                                    -12.95
                                                                         -1.03
Column:                30 m x  0.25 mm ID   DB 5 fused  silica capillary.
Temperature program:  100°C (hold 2 minutes)  to 160°C at 15°C/min,  then at
                       5°C/min to  270°C;  carrier He at 16 psi.
                                  8081  - 36
                                              Revision  0
                                              November 1990

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                                   FIGURE 6.
           GAS  CHROMATOGRAM OF THE TECHNICAL CHLORDANE STANDARD
   Start Time : 0.00 min
   Scale Factor:   0
                      End Tim  : 13.00 min
                      Plot Offset: 20 mv
low Point : 20.00 mV
Plot Scale: 200 mV
                                                           High Point : 220.00 mV
                                   Response  [mV]
                         Ol

                        1
                                                                  10
                                                                  o
                                                                 1
                           I	I
rt)

D

6' -'.J

H

3'
0)


5'
                                                                        -0.97
                                 .59
                                      -12.92
                                           13.60
                                                          -17.11
                                                          17.65
Column:                30 m x  0.25 mm ID   DB 5 fused  silica capillary.
Temperature program:  100°C (hold  2 minutes)  to 160°C at 15°C/min,  then at
                       5°C/min to  270°C;  carrier He at 16 psi.
                                  8081  - 37
                                                                     Revision  0
                                                                     November 1990

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                             METHOD 8081
ORGANOCHLORINE PESTICIDES AND  PCBs AS AROCLORS  BY  GAS  CHROMATOGRAPHY:
                      CAPILLARY COLUMN TECHNIQUE
          Start


711 Choose
appropriate
• x traction
technique (see
Chapter 2)


7.12 Add
specified
matrix spike
to sample.


7 2 Routine
cleanup/
fractio nation .


73 Set
chromatographic
condi tions .



7 4 Refer to
Method 8000
for proper
calibration
technique*


744 Prime or
deactivate CC
daily
cal ibra tion .

i
7 . 5 Perform
CC
analysis («ee
Method 8000)
1
Si . 5 ION.
./Any sample >. Ye*
>. f erences? /
No
/I 6 IN.
X^Do residues >. Ye»
C have >1 ) »
>. component ^r
No |
1
r .... ^



7.5.10
Additional
cleanup/
f ractionation .
(see Sect. 7.2)

7 . 6 Calculation
of toxaphene ,
chlordane ,
PCB« . DDT , and
BHC done here


                               8081  -  38
Revision 0
November 1990

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                                 METHOD 8120A

                CHLORINATED HYDROCARBONS BY GAS CHROMATOGRAPHY
1.0  SCOPE AND APPLICATION

      1.1  Method  8120  is  used  to  determine  the  concentration  of  certain
chlorinated  hydrocarbons.   The following compounds can  be  determined  by this
method:
                                            Appropriate Preparation Techniques

Compounds                        CAS No"      3510     3520  3540   3550  3580
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachl orobutad i ene
Hexachl orocycl ohexane
Hexachl orocycl opentadi ene
Hexachl oroethane
Pentachlorohexane
Tetrachl orobenzenes
1,2,4-Trichlorobenzene
91-58-7
95-50-1
541-73-1
106-46-7
118-74-1
87-68-3
608-73-1
77-47-4
67-72-1


120-82-1
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
   a  Chemical Abstract Services Registry Number.
   x  Greater than 70 percent recovery by this technique
   ND Not determined.
      1.2  Table 1 indicates compounds that may be determined by this method and
lists the method detection limit for each compound in organic-free reagent water.
Table 2 lists the estimated quantitation limit (EQL) for other matrices.


2.0  SUMMARY OF METHOD

      2.1  Method 8120 provides gas chromatographic conditions for the detection
of ppb concentrations of certain chlorinated hydrocarbons.  Prior to use of this
method, appropriate  sample  extraction techniques must  be used.  Both neat and
diluted organic liquids (Method 3580, Waste Dilution) may be  analyzed by direct
injection.   A  2 to 5  /zL  aliquot  of the  extract  is  injected  into a  gas
chromatograph (GC) using the  solvent flush technique,  and  compounds  in the GC
effluent are detected by an electron capture detector (ECD).
                                   8120A  -  1                       Revision 1
                                                                  November 1990

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      2.2  If interferences are encountered in the analysis, Method 8120 may also
be performed on extracts that have undergone cleanup using Method 3620.


3.0  INTERFERENCES

      3.1  Refer to Methods 3500, 3600, and 8000.

      3.2  Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms.  All  of these  materials must be  demonstrated to be free
from interferences, under  the conditions  of the analysis,  by analyzing method
blanks.    Specific  selection  of  reagents  and  purification  of  solvents  by
distillation in all glass systems may be required.

      3.3  Interferences coextracted from  samples  will  vary considerably from
source to  source,  depending  upon  the  waste being  sampled.   Although general
cleanup techniques  are recommended as  part  of this method,  unique samples may
require additional  cleanup.


4.0  APPARATUS AND MATERIALS

      4.1  Gas chromatograph

            4.1.1  Gas  chromatograph -  Analytical system  complete  with  gas
      chromatograph  suitable  for   on-column injections   and  all  required
      accessories,   including  detectors,  column supplies,  recorder, gases,  and
      syringes.  A data system for measuring peak areas and/or peak heights is
      recommended.

            4.1.2  Columns

                  4.1.2.1  Column 1 - 1.8 m x 2 mm ID glass column packed with
            1% SP-1000 on Supelcoport (100/120 mesh) or equivalent.

                  4.1.2.2  Column 2 - 1.8 m x 2 mm ID glass column packed with
            1.5% OV-1/2.4% OV-225 on Supelcoport  (80/100 mesh) or equivalent.

            4.1.3  Detector - Electron capture (ECD).

      4.2  Kuderna-Danish  (K-D)  apparatus

            4.2.1  Concentrator tube -  10  ml, graduated (Kontes K-570050-1025
      or equivalent).   A ground glass stopper  is used to prevent evaporation of
      extracts

            4.2.2  Evaporation   flask   -   500  ml  (Kontes   K-570001-500   or
      equivalent).     Attach  to  concentrator  tube with  springs,  clamps  or
      equivalent.

            4.2.3  Snyder  column  -  Three ball macro (Kontes  K-503000-0121  or
      equivalent).


                                   8120A -  2                      Revision 1
                                                                  November 1990

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            4.2.4  Snyder  column -  Two ball  micro (Kontes  K-569001-0219 or
      equivalent).

            4.2.5  Springs -  1/2 inch  (Kontes K-662750 or equivalent).

      4.3  Boiling chips - Solvent extracted,  approximately  10/40 mesh  (silicon
carbide or equivalent).

      4.4  Water  bath  -  Heated,  with  concentric ring   cover,  capable  of
temperature control (± 5°C).   The bath should be used in a hood.

      4.5  Volumetric flasks - 10, 50,  and 100 ml, with ground glass stoppers.

      4.6  Microsyringe - 10 /zL-

      4.7  Syringe - 5 ml.

      4.8  Vials  - Glass,  2,  10, and 20 ml capacity with  Teflon  lined screw-
caps or crimp tops.


5.0  REAGENTS

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

      5.2  Organic-free reagent water.  All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3  Solvents

            5.3.1  Hexane, C6H14.   Pesticide quality or equivalent.

            5.3.2  Acetone, CH3COCH3.  Pesticide quality or equivalent.

            5.3.3  Isooctane, C6H18.   Pesticide quality or equivalent.

      5.4  Stock standard solutions

            5.4.1  Prepare  stock standard solutions  at a concentration  of
      1.00x/ig//iL  by  dissolving   0.0100  g of  assayed  reference  material  in
      isooctane or hexane and diluting  to  volume  in a  10 ml volumetric flask.
      Larger volumes  can be used at the  convenience  of the analyst.   When
      compound purity is assayed  to  be  96% or  greater,  the  weight  can be used
      without correction to calculate the concentration of the stock standard.
      Commercially prepared stock standards can be used  at any concentration if
      they are certified by the manufacturer or by an independent  source.
                                  8120A  - 3                       Revision 1
                                                                  November 1990

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            5.4.2  Transfer the stock standard solutions  into vials with Teflon
      lined screw  caps or crimp  tops.   Store at 4°C and  protect  from light.
      Stock standards should be checked frequently for signs of degradation or
      evaporation, especially just prior to preparing calibration standards from
      them.

            5.4.3  Stock standard solutions must  be  replaced after one year, or
      sooner if comparison with check standards indicates a problem.

      5.5  Calibration standards  -  Calibration standards at  a  minimum of five
concentrations should be prepared through dilution of the stock standards with
isooctane or hexane.   One of the concentrations should  be  at  a concentration
near, but above, the method detection limit.  The remaining concentrations should
correspond to  the  expected range of concentrations found in  real  samples or
should define  the working  range of  the  GC.   Calibration solutions  must be
replaced after  six months, or sooner  if comparison with check standards indicates
a problem.

      5.6  Internal standards  (if internal  standard calibration  is  used)  - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior  to the  compounds of  interest.   The analyst
must further demonstrate  that  the measurement of the internal  standard is not
affected by method or  matrix  interferences.   Because of  these  limitations, no
internal  standard can be suggested that is applicable to all  samples.

            5.6.1  Prepare  calibration   standards   at   a  minimum   of  five
      concentrations for each analyte of interest as described  in Section 5.5.

            5.6.2  To each calibration standard,  add a known constant amount of
      one or more  internal  standards, and dilute to volume with  isooctane or
      hexane.

            5.6.3  Analyze each calibration standard according  to Section 7.0.

      5.7  Surrogate standards - The analyst should monitor the performance of
the extraction, cleanup (when used), and analytical system and the effectiveness
of  the  method in  dealing with  each  sample matrix  by  spiking each  sample,
standard, and  organic-free reagent water blank with  one or two surrogates (e.g.
chlorinated hydrocarbons that are not expected to be  in the sample)  recommended
to encompass the range of the temperature program used in this  method.  Method
3500  details   instructions  on  the  preparation  of base/neutral  surrogates.
Deuterated  analogs of  analytes  should  not  be  used  as  surrogates  for  gas
chromatographic analysis due to coelution problems.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See the  introductory material   to this  chapter, Organic  Analytes,
Section 4.1.

      6.2  Extracts must be stored  under  refrigeration and  analyzed  within 40
days of extraction.
                                   8120A  - 4                       Revision 1
                                                                  November 1990

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7.0  PROCEDURE

      7.1  Extraction

            7.1.1  Refer to Chapter Two for guidance on choosing the appropriate
      extraction  procedure.    In  general, water  samples  are  extracted at  a
      neutral, or as is, pH with  methylene chloride,  using either Method 3510
      or 3520.  Solid samples are extracted using either Method 3540 or 3550.

            7.1.2  Prior to gas chromatographic analysis, the extraction solvent
      must be exchanged  to hexane.   The exchange  is performed  during  the  K-D
      procedures  listed  in all of  the extraction  methods.   The  exchange  is
      performed as follows.

                  7.1.2.1  Following K-D of the methylene  chloride extract  to
            1 ml using  the  macro Snyder column, allow the apparatus to cool  and
            drain for at least 10 minutes.

                  7.1.2.2  Momentarily remove the  Snyder column,  add  50 ml  of
            hexane, a new  boiling chip,  and reattach  the macro Snyder column.
            Concentrate the extract using 1 mL of  hexane to  prewet the Snyder
            column.   Place the K-D  apparatus on  the water  bath  so  that  the
            concentrator tube is  partially immersed in  the hot water.   Adjust
            the vertical position of the  apparatus and  the water temperature,
            as  required, to complete concentration in  5-10  minutes.   At  the
            proper rate of distillation  the balls  of  the column will  actively
            chatter, but the chambers will not flood.  When the apparent volume
            of  liquid reaches  1 ml,  remove the K-D apparatus  and  allow it  to
            drain and cool  for at  least 10 minutes.   The  extract will be handled
            differently at  this point,  depending on whether  or not cleanup  is
            needed.  If  cleanup  is  not required,  proceed  to  Section 7.1.2.3.
            If cleanup is  needed,  proceed to Section 7.1.2.4.

                  7.1.2.3   If cleanup of the extract is not  required, remove the
            Snyder column  and  rinse the  flask and its lower joint  into  the
            concentrator tube  with  1-2 ml  of  hexane.    A  5  ml  syringe  is
            recommended  for this operation.    Adjust  the  extract volume  to
            10.0 ml.  Stopper the concentrator tube and store refrigerated  at
            4°C  if further  processing will not  be  performed  immediately.  If the
            extract will  be stored longer than  two days, it should be transferred
            to a vial with  a Teflon  lined screw cap or crimp top.  Proceed with
            gas chromatographic analysis.

                  7.1.2.4   If cleanup  of the  extract  is required,  remove  the
            Snyder column  and  rinse the  flask and its lower joint  into  the
            concentrator tube with a minimum amount of hexane.  A 5 mL syringe
            is recommended for this  operation. Add a clean boiling chip to the
            concentrator tube and  attach  a two ball  micro Snyder column.  Prewet
            the column by  adding about 0.5 ml of hexane to  the top.  Place the
            micro K-D apparatus on the water bath  (80°C) so that the concentrator
            tube  is partially immersed  in the hot  water.   Adjust the vertical
            position of the apparatus  and the water temperature,  as required,
            to  complete concentration  in  5-10 minutes.   At the proper rate  of
            distillation the balls of the column will actively chatter, but the

                                  8120A - 5                       Revision 1
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            chambers will not flood.  When the apparent volume of liquid reaches
            0.5 ml, remove the K-D apparatus  and  allow it to drain and cool for
            at least 10 minutes.

                  7.1.2.5  Remove the micro  Snyder column  and  rinse the flask
            and its lower joint into the concentrator tube with 0.2 ml of hexane.
            Adjust the extract volume to 2.0 ml and proceed with Method 3620.

      7.2  Gas chromatographic conditions (Recommended)

            7.2.1  Column 1
      Carrier gas (5% methane/95% argon) flow rate = 25 mL/min
      Column temperature = 65°C  isothermal,  unless otherwise  specified  (see
                           Table 1).

            7.2.2  Column 2
      Carrier gas (5% methane/95% argon) flow rate = 25 mL/min
      Column temperature = 75°C  isothermal,  unless otherwise  specified  (see
                           Table 1).

      7.3  Calibration - Refer to Method 8000 for  proper calibration techniques.
Use Table 1 and especially Table  2  for  guidance  on  selecting  the  lowest point
on the calibration curve.

            7.3.1  The procedure  for  internal  or external calibration  may  be
      used.   Refer to Method 8000 for a description of  each of these procedures.

            7.3.2  If cleanup  is  performed on  the samples,  the analyst should
      process a  series  of standards  through  the  cleanup  procedure and  then
      analyze the samples by  GC.  This  will  validate  elution  patterns  and the
      absence of interferents from the reagents.

      7.4  Gas chromatographic analysis

            7.4.1  Refer to Method 8000.  If the  internal  standard  calibration
      technique is used, add  10 /uL of internal  standard to the sample prior to
      injecting.

            7.4.2  Method 8000 provides instructions on the analysis sequence,
      appropriate dilutions,  establishing daily  retention  time windows,  and
      identification criteria.  Include  a mid-concentration standard after each
      group of 10 samples in  the analysis sequence.

            7.4.3  Examples  of GC/ECD  chromatograms  for certain  chlorinated
      hydrocarbons are shown  in Figures 1 and 2.

            7.4.4  Record the sample volume injected and the resulting peak sizes
      (in area units or peak  heights).

            7.4.5  Using either the internal  or external  calibration procedure
      (Method 8000),  determine the identity and quantity of each component peak
      in the sample  chromatogram  which  corresponds  to the compounds used for
      calibration purposes.   See Method 8000 for  calculation equations.


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            7.4.6  If peak  detection  and identification are  prevented  due to
      interferences, the hexane extract may  undergo cleanup using Method 3620.

      7.5  Cleanup: If required,  the samples may be cleaned  up  using the Methods
presented in Chapter 4.

            7.5.1  Proceed  with  Method  3620  using the  2  ml  hexane  extracts
      obtained from Section 7.1.2.5.

            7.5.2  Following cleanup,  the extracts should be analyzed by GC, as
      described in the previous paragraphs and in Method 8000.


8.0  QUALITY CONTROL

      8.1  Refer to Chapter One for specific quality control  procedures.  Quality
control to  validate  sample extraction  is covered in  Method  3500 and  in  the
extraction method utilized.   If extract cleanup was performed, follow the QC in
Method 3600 and in the specific cleanup method.

      8.2  Procedures to check the  GC system operation are found  in Method 8000.

            8.2.1  The quality control  check  sample  concentrate (Method 8000)
      should contain  each parameter of  interest  in  acetone  at  the  following
      concentrations:  hexachloro-substituted  hydrocarbon,  10 ng/ml't  and  any
      other chlorinated hydrocarbon, 100 jug/mL.

            8.2.2  Table 3 indicates the calibration and QC acceptance criteria
      for this method.  Table 4 gives method  accuracy and precision as functions
      of concentration for the analytes of interest.  The contents of both Tables
      should be used to evaluate  a  laboratory's ability to perform and generate
      acceptable data by this method.

      8.3  Calculate surrogate standard  recovery  on  all samples,  blanks,  and
spikes.   Determine if the  recovery is  within  limits (limits  established by
performing QC procedures outlined in Method  8000).

            8.3.1  If recovery is  not  within  limits,  the  following procedures
      are required.

                  8.3.1.1  Check to be sure that  there  are  no  errors  in  the
            calculations, surrogate solutions  or internal standards.  If errors
            are found, recalculate the data  accordingly.

                  8.3.1.2  Check  instrument performance.    If  an  instrument
            performance problem is identified, correct the problem and re-analyze
            the extract.

                  8.3.1.3  If no  problem  is found,  re-extract and  re-analyze the
            sample.

                  8.3.1.4  If, upon re-analysis, the recovery is again not within
            limits, flag the data as "estimated concentration".


                                   8120A  - 7                       Revision  1
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9.0  METHOD PERFORMANCE

      9.1  The method was tested by 20 laboratories using organic-free reagent
water, drinking water,  surface  water,  and three industrial  wastewaters spiked
at  six  concentrations  over  the range  1.0  to 356  /xg/L.    Single  operator
precision, overall  precision,  and method  accuracy were found  to  be directly
related to the concentration of the parameter and essentially independent of the
sample matrix.   Linear  equations to describe these  relationships  for a flame
ionization detector are presented in Table 4.

      9.2  The accuracy and precision  obtained will be determined by the sample
matrix, sample preparation technique,  and calibration procedures used.


10.0  REFERENCES

1.   "Development and Application of Test Procedures  for Specific Organic Toxic
     Substances in  Wastewaters.   Category  3 -  Chlorinated  Hydrocarbons,  and
     Category 8 -  Phenols," Report for EPA Contract  68-03-2625 (in preparation).

2.   Burke,  J.A.  "Gas  Chromatography  for   Pesticide  Residue  Analysis;  Some
     Practical  Aspects,"  Journal of  the Association  of Official  Analytical
     Chemists, 48, 1037, 1965.

3.   "EPA Method  Validation Study 22,  Method 612 (Chlorinated Hydrocarbons),"
     Report for EPA Contract 68-03-2625  (in preparation).

4.   "Method Performance for Hexachlorocyclopentadiene by Method 612," Memorandum
     from  R.  Slater,   U.S.   Environmental   Protection  Agency,  Environmental
     Monitoring and Support Laboratory, Cincinnati, Ohio 45268, December 7, 1983.

5.   U.S. EPA 40 CFR Part  136,  "Guidelines Establishing Test  Procedures for the
     Analysis of  Pollutants Under the  Clean  Water  Act;  Final Rule  and Interim
     Final Rule and Proposed Rule,"  October 26,  1984.

6.   "Determination of  Chlorinated  Hydrocarbons  in  Industrial and  Municipal
     Wastewaters," Report for EPA Contract 68-03-2625 (in  preparation).
                                  8120A  - 8                       Revision 1
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                                   TABLE 1.
                GAS CHROMATOGRAPHY OF CHLORINATED HYDROCARBONS
Compound
Retention time (min)

Col. 1       Col. 2
   ND = Not determined.

   a!50°C column temperature.

   b!65°C column temperature.

   °100°C column temperature.
  Method
 Detection
limit (M9/L)
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachl orobutadi ene
Hexachl orocycl ohexane
Hexachl orocycl opentad i ene
Hexachl oroethane
Pentachlorohexane
Tetrachl orobenzenes
1,2,4-Trichlorobenzene
2.7a
6.6
4.5
5.2
5.6a
7.7

ND
4.9


15.5
3.6b
9.3
6.8
7.6
10. lb
20.0

16.5°
8.3


22.3
0.94
1.14
1.19
1.34
0.05
0.34

0.40
0.03


0.05
                                  8120A  -  9
                                  Revision 1
                                  November 1990

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                                TABLE 2.
                 DETERMINATION OF  ESTIMATED QUANTITATION
                   LIMITS  (EQL) FOR VARIOUS MATRICES3
Matrix                                                             Factor"
Ground water                                                            10
Low-concentration soil by ultrasonic extraction with GPC cleanup       670
High-concentration soil and sludges by ultrasonic extraction        10,000
Non-water miscible waste                                           100,000
      Sample EQLs are highly matrix  dependent.   The EQLs listed herein are
      provided for guidance and may not always be achievable.

      EQL = [Method detection limit (Table 1)]  X [Factor (Table 2)].   For non-
      aqueous samples, the factor is on a wet weight basis.
                               8120A - 10                      Revision 1
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                                   TABLE 3.
                            QC ACCEPTANCE CRITERIA8


Parameter
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachloroethane
1,2,4-Trichlorobenzene
Test
cone.
(M9A)
100
100
100
100
10
10
10
10
100
Limit
for s
(M9/L)
37.3
28.3
26.4
20.8
2.4
2.2
2.5
3.3
31.6
Range
for x
(M9/L)
29.5-126.9
23.5-145.1
7.2-138.6
22.7-126.9
2.6-14.8
D-12.7
D-10.4
2.4-12.3
20.2-133.7
Range
P, Ps
(%)
9-148
9-160
D-150
13-137
15-159
D-139
D-lll
8-139
5-149
s   = Standard deviation of four recovery measurements, in M9/L-

x   = Average recovery for four recovery measurements, in M9/L.

P,PS= Percent recovery measured.

D   = Detected; result must be greater than zero.

a   Criteria from  40 CFR Part 136  for  Method 612.   These criteria  are based
    directly upon the method performance data  in  Table  4.  Where necessary, the
    limits  for  recovery have  been  broadened  to assure  applicability  of the
    limits to concentrations below those used to develop Table 4.
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                                   TABLE 4.
         METHOD ACCURACY AND PRECISION AS  FUNCTIONS OF CONCENTRATION8
Parameter
Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentad i enea
Hexachloroethane
1,2,4-Trichlorobenzene
Accuracy, as
recovery, x'
(M9/L)
0.75C+3.21
0.85C-0.70
0.72C+0.87
0.72C+2.80
0.87C-0.02
0.61C+0.03
0.47C
0.74C-0.02
0.76C+0.98
Single analyst
precision, s/
(M9/L)
0.28X-1.17
0.22X-2.95
0.21X-1.03
0.16X-0.48
0.14X+0.07
0.18X+0.08
0.24x
0.23X+0.07
0.23X-0.44
Overall
precision,
S' (M9A)
0.38X-1.39
0.41X-3.92
0.49X-3.98
0.35X-0.57
0.36X-0.19
0.53X-0.12
0.50x
0.36X-0.00
0.40X-1.37
x' ^Expected  recovery  for one or  more  measurements of a  sample  containing a
    concentration of C,  in p.g/1.

s/= Expected  single  analyst  standard deviation of  measurements at  an average
    concentration of x,  in /xg/L.

S' =Expected  interlaboratory  standard deviation of  measurements at  an average
    concentration found  of x, in M9/L-

C  =True value for the concentration, in M9/L.

x = Average   recovery   found  for   measurements   of  samples  containing   a
    concentration of C,  in p.g/1.

a   Estimates based upon  the  performance in a single laboratory.
                                  8120A - 12
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November 1990

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                             FIGURE  1
            Column: 1.5% OV-1+1.5% OV-226 on Gas Chrom Q
            Ttmptriturr 76°C
            Dtuctor: Eltetron Capture
                                           »•
              4         8       12       16
                RETENTION TIME (MINUTES)
20
Gaschromatogram of chlorinattd hydrocarbons (low moltcular wtight compounds).
                             8120A - 13
            Revision  1
            November 1990

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                                FIGURE  2
                          Column: 1.5% OV-1+1.5% OV-225 on GM Chrom Q
                          Ttmptrtturt: 160°C
                          Detector: Electron Capturt
                       4        8       12       16
                     RETENTION TIME (MINUTES)
Gas chromatogram of chlorinated hydrocarbons (high molecular weight compounds).
                               8120A - 14
Revision  1
November 1990

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                         METHOD  8120A
    CHLORINATED  HYDROCARBONS BY  GAS  CHROMATOGRAPHY
      Start
   71.1 Choose
    appropriate
    ex trac11on
  procedure (see
    Chapter 2|
  7.1.2 Exchange
axtraction solvent
 to  hexane during
  K-D procedures
    7 2 Set gas
  chr oma tography
    conditions
7  3  Refer to Method
  8000 for proper
    calibration
    techniques
                 Yes
  7  3.2 Process a
series of standards
  through cleanup
procedure: analyze
      by CC
                                 No
7 4  Perform CC
 analysis (see
'Method 8000)
                      7.5 1 Cleanup using
                         Method  3620
                           8120A  - 15
                                          Revision  1
                                          November 1990

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                                 METHOD 8121

                CHLORINATED  HYDROCARBONS BY GAS CHROMATOGRAPHY:
                          CAPILLARY COLUMN TECHNIQUE
1.0   SCOPE AND APPLICATION

      1.1  This method  provides  procedures for  the determination of  certain
chlorinated  hydrocarbons  in  water,  soil/sediment  and  waste  matrices.    The
following compounds can be determined by this  method:
      Compound Name                                   CAS No."


      Benzal chloride                                  98-87-3
      Benzotrichloride                                 98-07-7
      Benzyl chloride                                 100-44-7
      2-Chloronaphthalene                              91-58-7
      1,2-Dichlorobenzene                              95-50-1
      1,3-Dichlorobenzene                             541-73-1
      1,4-Dichlorobenzene                             106-46-1
      Hexachlorobenzene                               118-74-1
      Hexachlorobutadiene                              87-68-3
      alpha-Hexachlorocyclohexane (alpha-BHC)         319-84-6
      beta-Hexachlorocyclohexane (beta-BHC)           319-85-7
      gamma-Hexachlorocyclohexane (gamma-BHC)          58-89-9
      delta-Hexachlorocyclohexane (delta-BHC)         319-86-8
      Hexachlorocyclopentadiene                        77-47-4
      Hexachloroethane                                 67-72-1
      Pentachlorobenzene                              608-93-5
      1,2,3,4-Tetrachlorobenzene                      634-66-2
      1,2,4,5-Tetrachlorobenzene                       95-94-2
      1,2,3,5-Tetrachlorobenzene                      634-90-2
      1,2,4-Trichlorobenzene                          120-82-1
      1,2,3-Trichlorobenzene                           87-61-6
      1,3,5-Trichlorobenzene                          108-70-3


      a   Chemical  Abstract  Services  Registry  Number.


      1.2  Table 1 lists method detection limits (MDL) for each compound in an
organic-free reagent water  matrix.   The MDLs for the compounds of  a  specific
sample may differ from those listed in Table 1 because they are dependent upon
the nature of interferences in the sample matrix.   Table 2 lists the estimated
quantitation limits (EQL) for other matrices.

      1.3  This method  is  restricted to  use by or  under the  supervision  of
analysts experienced in  the  use of a gas  chromatograph  and in the interpretation
of gas chromatograms.
                                   8121 - 1                     Revision 0
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2.0   SUMMARY OF METHOD

      2.1  A measured volume or weight  of  sample  is  extracted by using one of
the appropriate sample  extraction  techniques  specified  in Methods 3510, 3520,
3540, or 3550, or diluted using Method 3580.  Aqueous samples are extracted at
neutral pH with methylene chloride by using either a separatory funnel  (Method
3510) or a continuous liquid-liquid extractor  (Method 3520).   Solid samples are
extracted with hexane/acetone (1:1) by using a Soxhlet extractor (Method 3540)
or with methylene chloride/acetone (1:1)  by  using an ultrasonic extractor  (Method
3550).   After  cleanup,  the  extract or  diluted  sample  is  analyzed  by  gas
chromatography with electron capture detection (GC/ECD).

      2.2  When this  method  is  used to analyze  for  any or  all  of  the target
compounds, compound identification should be supported by at least one additional
qualitative technique.  This method describes analytical  conditions for a second
gas chromatographic column that can be used  to confirm the measurements made with
the  primary  column.     Retention   time   information   obtained   on  two  gas
chromatographic   columns   is   given   in   Table  3.      Alternatively,   gas
chromatography/mass  spectrometry  could  be  used  for compound  confirmation  if
concentration permits.

      2.3  The  sensitivity  of Method  8121 usually  depends  on  the  level  of
interferences rather than  on instrumental limitations.  If interferences prevent
detection of the analytes, Method 8121 may also be performed on samples that have
undergone cleanup.   This  method  may be used  in  conjunction  with  Method 3620,
Florisil  Column  Cleanup,  Method  3660,  Sulfur Cleanup,  and Method 3640,  Gel
Permeation Chromatography, to aid in the elimination of interferences.


3.0   INTERFERENCES

      3.1  Refer to Methods 3500,  3600,  and 8000.

      3.2  Solvents,  reagents,  glassware,  and other  hardware used in  sample
processing  may  introduce artifacts  which  may result  in  elevated  baselines,
causing misinterpretation of gas chromatograms.  These materials must therefore
be  demonstrated  to  be  free from  interferants,  under  the conditions  of  the
analysis,  by analyzing method  blanks.    Specific selection of  reagents  and
purification of solvents by distillation in all-glass systems may be required.
Pesticide grade or distilled-in-glass solvents are suitable for trace  analysis
without further purification.  Each new batch of solvent should be checked for
possible interferants as follows:   concentrate the amount of solvent equivalent
to the total volume to be  used in the analysis to  1  ml.   Inject  1 to 2 /xL of the
concentrate into a gas chromatograph  equipped with an electron capture detector
(ECD) set at the lowest  attenuation.   If extraneous peaks are detected that are
greater  than  10  pg on-column,   the   solvent  must  be  purified  either  by
redistillation or  by  passing  it  through a column of highly  activated alumina
(acidic or basic alumina,  activated at 300°C  to 400°C) or  Florisil.

      3.3  Interferants  coextracted from the samples will  vary considerably from
waste to waste.  While general  cleanup techniques are provided as part of this
method, specific samples may require additional cleanup steps  to achieve desired
sensitivities.


                                   8121  - 2                      Revision  0
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      3.4  Glassware must be scrupulously clean.   Clean  all  glassware as soon
as possible after use by rinsing with the last solvent used,  followed by thorough
washing of  the  glassware  in hot, aqueous detergent  solution.   Rinse with tap
water, distilled water, acetone, and finally pesticide quality hexane.  Heavily
contaminated glassware may require treatment  in a muffle  furnace at 400°C for 2
to 4 hours.  Some  high boiling materials,  such as PCBs,  may not be eliminated
by this  treatment.   Volumetric glassware should not be  heated in  a  muffle
furnace.    Glassware   should  be  sealed  and   stored  in   a clean  environment
immediately after drying and cooling to prevent  any accumulation of dust or other
contaminants.  Store the glassware by inverting or capping with aluminum foil.

      3.5  Phthalate esters, if present  in a  sample, will  interfere  only with
the  BHC  isomers because  they  elute in  Fraction  2 of the Florisil  procedure
described  in  Method 3620.   The presence of  phthalate  esters  can usually be
minimized by avoiding  contact with any plastic materials.

      3.6  The presence of elemental sulfur will  result in  large peaks, and can
often mask the  region of compounds eluting  after  1,2,4,5-tetrachlorobenzene
(Compound  No.   18  in the  gas  chromatogram  shown  in  Figure   1).     The
tetrabutylammonium  (TBA)-sulfite procedure (Method  3660)  works well  for the
removal  of elemental sulfur.

      3.7  Waxes  and  lipids can  be removed  by  gel  permeation  chromatography
(Method 3640).   Extracts  containing high concentrations  of lipids  are viscous
and may even solidify  at room  temperature.


4.0   APPARATUS  AND MATERIALS

      4.1  Gas chromatograph

            4.1.1   Gas chromatograph,  analytical  system  complete  with  gas
      chromatograph  suitable   for   on-column   injections  and   all   required
      accessories,  including detector,  analytical  columns,  recorder, gases, and
      syringes.  A  data system  for measuring  peak heights and/or peak areas is
      recommended.

            4.1.2   Columns

                  4.1.2.1   Column  1  - 30 m x 0.53 mm ID fused-silica capillary
            column  chemically  bonded with trifluoropropyl  methyl silicone  (DB-
            210  or  equivalent).

                  4.1.2.2   Column  2 - 30 m x 0.53 mm ID fused-silica capillary
            column  chemically  bonded with   polyethylene  glycol  (DB-WAX  or
            equivalent).

            4.1.3   Detector  -  electron capture detector

      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.

                                    8121  - 3                      Revision 0
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            4.3.2   Evaporation   flask  -    500 mi  (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   Springs -  1/2 inch  (Kontes K-662750 or equivalent).

      4.4  Glassware: See Methods 3510,  3520,  3540,  3550, 3580, 3620, 3640, and
3660 for specifications.

      4.5  Boiling chips, approximately 10/40 mesh.  Heat to 400°C for 30 min,
or Soxhlet-extract with methylene chloride, prior to use.

      4.6  Vials - 10 ml, glass, with Teflon lined screw-caps or crimp tops.


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  Preservatives:

            5.3.1  Sodium  hydroxide, NaOH,  (ACS  certified),  10 N in distilled
      water.

            5.3.2  Sulfuric acid, H2S04,  (ACS  certified),  mix equal volumes of
      concentrated sulfuric acid and distilled water.

      5.4  Solvents:

            5.4.1  Acetone, CH3COCH3 - pesticide  quality or equivalent.

            5.4.2  Hexane, C6H14 - pesticide quality or equivalent.

            5.4.3   Diethyl ether,  C2H5OC2H5  -  pesticide  quality or equivalent.
      Must  be  free of  peroxides as  indicated by  test  strips (EM  Quant,  or
      equivalent).  Procedures for  removal  of peroxides  are  provided with the
      test strips.  After cleanup, 20 ml of ethyl alcohol preservative must be
      added to each liter of ether.

            5.4.4  Methylene chloride, CH2C12 -  pesticide quality or equivalent.

            5.4.5  Petroleum ether - pesticide quality or equivalent.


                                   8121 - 4                      Revision  0
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      5.5  Sodium sulfate (granular, anhydrous), Na2S04.   Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride.  If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed,  demonstrating that there is no interference from
the sodium sulfate.

      5.6  Stock standard solutions

            5.6.1  Prepare  stock  standard  solutions  at a  concentration  of
      1000 mg/L by dissolving 0.0100 g of assayed reference  material in hexane
      and diluting to volume  in  a  10 ml  volumetric  flask.   Larger volumes can
      be used at  the convenience of the  analyst.  When compound purity is assayed
      to  be  96%  or  greater, the  weight can  be used without  correction  to
      calculate the  concentration of the  stock standard.  Commercially prepared
      stock standards can be used at any  concentration  if they are certified by
      the manufacturer or by an independent source.

            5.6.2  Transfer the stock  standard solutions into glass vials with
      Teflon lined  screw-caps or crimp  tops.   Store  at  4°C and  protect from
      light.    Stock  standards  should  be  checked  frequently  for signs  of
      degradation or evaporation, especially just prior to preparing calibration
      standards from them.

            5.6.3  Stock  standard  solutions  must be replaced  after one year,
      or sooner if comparison with check standards indicates a problem.

      5.7  Calibration standards -  Calibration standards  at a  minimum  of five
concentrations  should be prepared through dilution of the stock standards with
hexane.   One  of the concentrations should be at a  concentration near, but above,
the method detection limit.   The remaining concentrations should correspond to
the expected range of  concentrations found in real samples or should define the
working range of the GC.  The suggested  concentrations are  listed in Table 4.
Calibration solutions  must be  replaced  after six  months, or sooner  if comparison
with check standards indicates a problem.

      5.8   Internal standards (if internal  standard calibration is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical behavior  to  the compounds  of interest.   The  analyst
must further demonstrate  that the  measurement of the internal  standard is not
affected by method or matrix interferences.

            5.8.1   The suggested internal standards are:  2,5-dibromotoluene,
      1,3,5-tribromobenzene, and a,a'-dibromo-m-xylene. The analyst can use any
      of  the three  compounds  provided  that they   are  resolved  from matrix
      interferences.

            5.8.2   Prepare an internal standard spiking solution which contains
      50 mg/L of any of the compounds listed above.   Addition  of 10 /iL  of this
      solution   to  1  mL  of  sample  extract is recommended.    The  spiking
      concentration  of the  internal  standard should be kept constant  for all
      samples and calibration standards.  Store  the  internal  standard  spiking
      solutions at 4°C in Teflon-sealed containers.   Standard  solutions should
      be replaced when ongoing QC (Section 8) indicates a problem.


                                   8121 - 5                      Revision 0
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      5.9   Surrogate standards - The analyst should  monitor the performance of
the extraction, cleanup  (when used), and analytical system, and the effectiveness
of  the  method  in  dealing with  each sample  matrix,  by  spiking  each sample,
standard, and  organic-free reagent water blank with the surrogate compounds.

            5.9.1   Recommended  surrogate  compounds:  a,2,6-trichlorotoluene,
      1,4-dichloronaphthalene, and 2,3,4,5,6-pentachlorotoluene.

            5.9.2    Prepare a surrogate standard spiking solution which contains
      1  mg/L   of  a,2,6-trichlorotoluene and  2,3,4,5,6-pentachlorotoluene and
      10 mg/L  of 1,4-dichloronaphthalene.  Addition of 1 ml  of this solution to
      1  L of a water sample or  10  g  of a solid  sample is  equivalent to 1 /xg/L
      or 100 M9/k9 of a,2,6-trichlorotoluene and 2,3,4,5,6-pentachlorotoluene
      and  10   jug/L or  1000  /xg/kg  of  1,4-dichloronaphthalene.   The spiking
      concentration of the surrogate standards may be adjusted accordingly, if
      the final  volume  of extract  is reduced below  10 ml.   Store the spiking
      solutions  at 4°C  in Teflon-sealed containers.   The   solutions  must be
      replaced  after  6  months,  or sooner if  ongoing  QC  (Section  8)  indicates
      problems.


6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See  the introductory material  to this chapter,  Organic Analytes,
Section 4.1.
7.0   PROCEDURE

      7.1  Extraction:

            7.1.1  Refer to Chapter Two for guidance on choosing the appropriate
      extraction procedure.  In general, water samples are extracted at a neutral
      pH with methylene chloride by using a separatory funnel (Method 3510) or
      a continuous liquid-liquid  extractor (Method 3520).   Solid samples are
      extracted  with  hexane/acetone  (1:1  v:v)  by  using a  Soxhlet  extractor
      (Method 3540) or  with methylene chloride/acetone  (1:1 v:v)  by  using an
      ultrasonic extractor  (Method 3550).   Non-aqueous  waste samples  may be
      diluted using Method 3580.

      7.2  Solvent exchange:  Prior to Florisil  cleanup or gas chromatographic
analysis, the extraction solvent must be exchanged to hexane.  Sample extracts
that will  be  subjected to  gel  permeation chromatography do not  need  solvent
exchange.  The exchange is performed during the K-D procedures listed in all of
the extraction methods.  The exchange is performed as follows:

            7.2.1  Add  one  or two  clean  boiling chips to the flask and attach
      a three ball  Snyder column.   Prewet the column by adding about 1.0 mL of
      methylene chloride to the top of the column.  Place the K-D apparatus in
      a hot water bath (15-20°C  above  the  boiling point of the solvent) so that
      the concentrator tube  is partially immersed in the hot water and the entire
      lower rounded surface of the flask is bathed with hot  vapor.  Adjust the
      vertical position of the apparatus and the water  temperature, as required,


                                   8121  - 6                     Revision  0
                                                                November  1990

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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.

      7.2.2  Momentarily remove  the  Snyder column,  add  50 ml of hexane,
a new boiling chip, and attach the macro Snyder column.   Concentrate the
extract as described in Section 7.2.1,  using 1  ml of hexane to prewet the
Snyder column, raising  the temperature of the water bath, if necessary,
to maintain proper distillation,  and completing the concentration  in 10-20
minutes.  When the  apparent volume  of  liquid reaches  1-2  ml,  remove the
K-D apparatus and allow it to drain and cool for at least 10 min.

      7.2.3  Remove the  Snyder column  and rinse the flask and its lower
joint into the concentrator tube  with 1 to 2 ml of hexane.  A 5 mL syringe
is recommended for  this  operation.   Adjust the extract  volume to 10 mL.
Stopper the concentrator tube and store at 4"C  if further processing will
be performed immediately.  If the extract will be stored for two days or
longer,  it  should be  transferred  to a glass  vial  with  a  Teflon lined
screw-cap or crimp top.  Proceed with the cleanup or gas chromatographic
analysis.

7.3  Cleanup/Fractionation:

      7.3.1  Cleanup  procedures  may not  be necessary  for  a  relatively
clean matrix.  If removal  of  interferences such as  chlorinated phenols,
phthalate esters, etc., is required, proceed with the procedure outlined
in Method 3620.   Collect Fraction 1 by eluting with 200 ml petroleum ether
and Fraction  2 by eluting  with  200 ml  of diethyl  ether/petroleum ether
(1:1).    Note   that,   under   these   conditions,   benzal   chloride  and
benzotrichloride are not recovered from the Florisil column.  The elution
patterns and compound recoveries are shown  in Table 5.

      7.3.2  Removal of waxes and lipids by gel permeation chromatography
(optional): Refer to Method 3640.

      7.3.3  Elemental Sul.fur  Removal  (optional):  refer to Method 3660,
Section 7.3.

7.4  Gas chromatographic conditions (recommended):
      7.4.1  Column  1:
Carrier gas (He) =
Column temperature:
     Initial temperature =
     Temperature program =
     Final temeprature =
Injector temperature =
Detector temperature =
10 mL/min

65°C
65°C  to  175°C at 4°C/nnn
175°C, hold  20  minutes.
220°C
250°C
                             8121 - 7
                             Revision  0
                             November  1990

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      7.4.2  Column 2:
Carrier gas (He) =            10 mL/min
Column temperature:
     Initial temperature =    60°C
     Temperature program =    60°C to 170°C  at 4°C/min
     Final temeprature =      170°C,  hold 30 minutes.
Injector temperature =        200°C
Detector temperature =        230°C

      7.4.3  Tables 1 and 3 give the MDLs and the retention times for 22
chlorinated hydrocarbons.  Examples of the separations achieved with the
trifluoropropyl  methyl   silicone  and  polyethylene  glycol  fused-silica
capillary columns are shown in Figures 1 and 2,  respectively.

7.5  Calibration:

      7.5.1  Refer to Method 8000 for proper calibration techniques.  Use
Table 4 for guidance.

      7.5.2  The procedure  for  internal  or  external  calibration  may be
used.  Refer to Method 8000 for a description of each of these procedures.

7.6  Gas chromatographic analysis:

      7.6.1  Refer to Method 8000.  If the internal  standard calibration
technique is used,  add 10 /iL of internal standard to the sample prior to
injection.

      7.6.2  Follow Method  8000 for instructions on  analysis  sequence,
appropriate dilutions, daily retention  time windows,  and  identification
criteria.

      7.6.3  Record the  sample  volume  injected  and  the  resulting  peak
areas.

      7.6.4  Using  either  internal  or  external   calibration  procedures
(Method 8000),  determine the  identity and quantity of each component peak
in the  sample  chromatogram  which corresponds to  the  compounds  used for
calibration purposes.

      7.6.5  If  the response of  a  peak  exceeds the  working  range of the
system, dilute the extract and reanalyze.

      7.6.6  Identify compounds in the sample by comparing the retention
times of the peaks in the sample chromatogram with those of the peaks in
standard  chromatograms  obtained  on   the   two   columns   specified  in
Section 7.4. The retention time window used to make identifications should
be based upon  measurements of actual  retention time variations  over the
course of 10 consecutive injections.   Three times the standard deviation
of a retention time window  can  be used to  calculate  a  suggested window
size.
                             8121 - 8                      Revision  0
                                                           November  1990

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8.0   QUALITY CONTROL

      8.1  Refer to Chapter One for specific quality control  procedures.  Quality
control  to  validate  sample  extraction  is  covered  in  Method 3500 and  in  the
individual extraction method protocols.   If extract  cleanup is required, follow
the QC presented in Method 3600 and in the specific cleanup method protocols.

      8.2  Mandatory quality control  to evaluate  the  GC  system  operation is
found in Method 8000.

            8.2.1  Analyze a quality control  check standard to demonstrate that
      the operation of the gas  chromatograph  is  in control.   The frequency of
      the check  standard  analysis is equivalent to 10 percent  of the samples
      analyzed.  If the recovery of any  compound  found  in the check standard is
      less than 80 percent of the certified  value, the laboratory performance
      is judged to be out of control,  and the  problem must  be corrected.  A new
      set of calibration standards must be prepared and analyzed.

      8.3  Calculate surrogate standard  recoveries for  all  samples, blanks, and
spikes.   Determine if  the  recovery  is  within  limits  (limits  established by
performing QC procedures outlined in Method 8000).

            8.3.1  If  the recoveries  are not  within limits,  the following are
      required:

                  8.3.1.1  Check  to  be sure that  there  are   no  errors  in
               calculations, surrogate solutions, and internal standards.  Also
               check instrument performance.

                  8.3.1.2  Recalculate the data or reanalyze  the extract if any
               of the  above  checks reveals a  problem.

                  8.3.1.3  Reextract  and reanalyze the sample  if none of the
               above   is  a  problem  or  designate  the  data  as  "estimated
               concentration."

      8.4  An internal  standard peak area check must be performed  on all samples.
The internal standard  must be  evaluated for  acceptance by determining whether
the measured area for the internal standard deviates  by more than  30 percent from
the average area for the internal standard in the calibration standards.  When
the internal standard  peak  area is outside that  limit,  all  samples  that  fall
outside the QC criteria must be analyzed.

      8.5  GC/MS confirmation:  Any compound confirmed  by two columns may also
be confirmed by GC/MS if the  concentration is  sufficient for detection by GC/MS
as determined by the laboratory-generated detection limits.

            8.5.1  The GC/MS would normally require a minimum concentration of
              in the final extract for each compound.
            8.5.2  The  sample  extract  should  be  analyzed  by  GC/MS as  per
      Section 7.0 of Method 8270.
                                   8121 - 9                      Revision 0
                                                                 November 1990

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            8.5.3  A reference  standard  of  the  compound must also be analyzed
      by  GC/MS.   The  concentration of  the reference  standard  must be  at a
      concentration that would demonstrate the ability to confirm the compounds
      identified by GC/ECD.

      8.6  Include a mid-concentration  calibration  standard after each group of
20  samples  in  the  analysis  sequence.   The response  factors  for the  mid-
concentration calibration must be within ±15 percent of the average values for
the multiconcentration calibration.
9.0   METHOD PERFORMANCE

      9.1  The MDL is defined in Chapter One.  The MDLs listed in Table 1 were
obtained by using organic-free reagent water.  Details on how to determine MDLs
are given in Chapter One.  The MDLs actually achieved in a given analysis will
vary since they depend on instrument sensitivity and matrix effects.

      9.2  This method has been tested in a single laboratory by using organic-
free reagent water, sandy loam samples and extracts which were spiked with the
test compounds  at one  concentration.   Single-operator precision  and  method
accuracy were found to be related  to the concentration of compound and the type
of matrix.   Results of  the  single-laboratory  method evaluation are  given in
Tables 6 and 7.

      9.3  The accuracy and precision  obtained will be determined by the sample
matrix,  sample  preparation   technique,  optional   cleanup  techniques,   and
calibration procedures used.


10.0   REFERENCES

1.  Lopez-Avila,  V.,  N.S.  Dodhiwala,   and  J.  Milanes,  "Single  Laboratory
    Evaluation of  Method 8120, Chlorinated  Hydrocarbons",  1988,  EPA Contract
    Numbers 68-03-3226 and 68-03-3511.

2.  Glazer, J.A.,  G.D. Foerst,  G.D. McKee, S.A.  Quave,  and W.L.  Budde,  "Trace
    Analyses for Wastewaters," Environ. Sci.  and Technol. 15:1426-1431,  1981.

3.  Lopez-Avila, V., Baldin, E., Benedicto, J., Milanes, J., and Beckert, W.F.,
    "Application of Open-Tubular Columns  to SW-846 GC Methods", EMSL-Las Vegas,
    1990.
                                   8121  -  10                      Revision  0
                                                                 November  1990

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                                   Table 1.

             METHOD DETECTION LIMITS FOR CHLORINATED HYDROCARBONS
                             ON CAPILLARY COLUMNS
                                                                 MDLa
Compound name                                   CAS no.         (ng/L)


Benzal chloride                                  98-87-3            2-5b
Benzotrichloride                                 98-07-7            6.0
Benzyl chloride                                 100-44-7          180
2-Chloronaphthalene                              91-58-7        1,300
1,2-Dichlorobenzene                              95-50-1          270
1,3-Dichlorobenzene                             541-73-1          250
1,4-Dichlorobenzene                             106-46-1          890
Hexachlorobenzene                               118-74-1            5.6
Hexachlorobutadiene                              87-68-3            1.4
alpha-Hexachlorocyclohexane (alpha-BHC)         319-84-6           11
beta-Hexachlorocyclohexane (beta-BHC)           319-85-7           31
gamma-Hexachlorocyclohexane (gamma-BHC)          58-89-9           23
delta-Hexachlorocyclohexane (delta-BHC)         319-86-8           20
Hexachlorocyclopentadiene                        77-47-4          240
Hexachloroethane                                 67-72-1            1.6
Pentachlorobenzene                              608-93-5           38
1,2,3,4-Tetrachlorobenzene                      634-66-2           11
1,2,4,5-Tetrachlorobenzene                       95-94-2            9.5
1,2,3,5-Tetrachlorobenzene                      634-90-2            8.1
1,2,4-Trichlorobenzene                          120-82-1          130
1,2,3-Trichlorobenzene                           87-61-6           39
1,3,5-Trichlorobenzene                          108-70-3           12
    MDL is the method detection limit for organic-free reagent water.  MDL was
    determined from the analysis of eight replicate aliquots processed through
    the entire analytical  method  (extraction,  Florisil  cartridge cleanup, and
    GC/ECD analysis).

          MDL = t(n.1i0.99)xSD

    where  t(n.1099)  is  the  student's  t   value  appropriate  for  a  99  percent
    confidence interval and  a  standard  deviation  with n-1  degrees  of freedom,
    and SD is the  standard deviation of  the eight replicate measurements.

    Estimated from the instrument detection limit.
                                  8121  -  11                      Revision  0
                                                                 November  1990

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                                   Table 2.

       ESTIMATED QUANTITATION LIMIT  (EQL)  FACTORS FOR VARIOUS MATRICES8



      Matrix                                                Factor"


Ground water                                                     10

Low-concentration soil by ultrasonic extraction                 670
  with GPC cleanup

High-concentration soil and sludges by ultrasonic            10,000
  extraction

Waste not miscible with water                               100,000


a    Sample EQLs are highly matrix-dependent. The EQLs listed herein are provided
    for guidance  and  may  not always be  achievable.

b    EQL  =  [Method detection  limit  (Table 1)]  x  [Factor (Table  2)].    For
    nonaqueous samples, the  factor is on  a  wet-weight basis.
                                   8121  -  12                      Revision 0
                                                                 November 1990

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                                 Table 3
    GAS CHROMATOGRAPHIC RETENTION TIMES FOR CHLORINATED HYDROCARBONS
                          ON CAPILLARY COLUMNS
Compound
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22








Compound name
Benzal chloride
Benzotrichloride
Benzyl chloride
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadiene
alpha-BHC
beta-BHC
gamma-BHC
delta-BHC
Hexachl orocycl opentadi ene
Hexachloroethane
Pentachlorobenzene
1,2,3,4-Tetrachlorobenzene
1,2,4,5-Tetrachlorobenzene
1,2,3,5-Tetrachlorobenzene
1,2,4-Trichlorobenzene
1,2,3-Trichlorobenzene
1,3,5-Trichlorobenzene
Internal Standards
2,5-Dibromotoluene
1,3, 5-Tri bromobenzene
o,a'-Dibromo-meta-xylene
Surrogates
a,2,6-Trichlorotoluene
1,4-Dichloronaphthalene
2,3,4,5,6-Pentachlorotoluene
Retention
DB-210"
6.86
7.85
4.59
13.45
4.44
3.66
3.80
19.23
5.77
22.21
25.54
24.07
26.16
8.86
3.35
14.86
11.90
10.18
10.18
6.86
8.14
5.45

9.55
11.68
18.43

12.96
17.43
18.96
time (min)
OB-WAX"
15.91
15.44
10.37
23.75
9.58
7.73
8.49
29.16
9.98
41.62
33.84
54.30
33.79
c
8.13
23.75
21.17
17.81
17.50
13.74
16.00
10.37

18.55
22.60
35.94

22.53
26.83
27.91
GC operating conditions:   30 m x 0.53 mm  ID DB-210 fused-silica capillary
column; 1 /zm film thickness; carrier gas helium at  10 mL/min; makeup gas is
nitrogen  at  40  mL/min;  temperature  program from  65°C  to  175°C  (hold 20
minutes)  at  4°C/min;   injector  temperature 220°C;  detector  temperature
250°C.

GC operating conditions:   30 m x 0.53 mm  ID DB-WAX fused-silica capillary
column; 1 /im film thickness; carrier gas  helium  at  10 mL/min;  makeup gas is
nitrogen  at  40  mL/min;  temperature  program from  60°C  to  170°C  (hold 30
minutes) at 4°C/"nn;  injector temperature 200°C; detector temperature 230°C.
Compound decomposes on-column.
                                8121  -  13                      Revision 0
                                                              November 1990

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                               Table 4.

        SUGGESTED CONCENTRATIONS FOR THE CALIBRATION SOLUTIONS8
Concentration (ng//il)
Benzal chloride
Benzotrichloride
Benzyl chloride
2-Chl oronaphthal ene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadiene
alpha-BHC
beta-BHC
gamma- BHC
delta-BHC
Hexachl orocycl opentadi ene
Hexachloroethane
Pentachlorobenzene
1,2,3,4-Tetrachlorobenzene
1,2,4 , 5-Tetrachl orobenzene
1,2,3 , 5-Tetrachl orobenzene
1, 2, 4-Trichl orobenzene
1 , 2 , 3-Tri chl orobenzene
1, 3, 5-Trichl orobenzene
Surrogates
a,2,6-Trichlorotoluene
1,4-Di chl oronaphthal ene
2,3,4,5,6-Pentachlorotoluene
0.1
0.1
0.1
2.0
1.0
1.0
1.0
0.01
0.01
0.1
0.1
0.1
0.1
0.01
0.01
0.01
0.1
0.1
0.1
0.1
0.1
0.1

0.02
0.2
0.02
0.2
0.2
0.2
4.0
2.0
2.0
2.0
0.02
0.02
0.2
0.2
0.2
0.2
0.02
0.02
0.02
0.2
0.2
0.2
0.2
0.2
0.2

0.05
0.5
0.05
0.5
0.5
0.5
10
5.0
5.0
5.0
0.05
0.05
0.5
0.5
0.5
0.5
0.05
0.05
0.05
0.5
0.5
0.5
0.5
0.5
0.5

0.1
1.0
0.1
0.8
0.8
0.8
16
8.0
8.0
8.0
0.08
0.08
0.8
0.8
0.8
0.8
0.08
0.08
0.08
0.8
0.8
0.8
0.8
0.8
0.8

0.15
1.5
0.15
1.0
1.0
1.0
20
10
10
10
0.1
0.1
1.0
1.0
1.0
1.0
0.1
0.1
0.1
1.0
1.0
1.0
1.0
1.0
1.0

0.2
2.0
0.2
One or more  internal  standards should be  spiked  prior to GC/ECD analysis
into all  calibration  solutions.   The  spike  concentration of the internal
standards should be kept constant for all calibration solutions.
                               8121 - 14
Revision
November
0
1990

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                               Table  5.

             ELUTION PATTERNS OF CHLORINATED HYDROCARBONS
 FROM THE FLORISIL COLUMN BY ELUTION WITH PETROLEUM ETHER (FRACTION 1)
          AND  1:1  PETROLEUM  ETHER/DIETHYL  ETHER  (FRACTION 2)
                                            Recovery (percent)8
Compound
Benzal chloride"
Benzotrichloride
Benzyl chloride
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachl orobenzene
Hexachlorobutadiene
alpha-BHC
beta-BHC
gamma-BHC
delta-BHC
Hexachl orocycl opentadi ene
Hexachloroethane
Pentachlorobenzene
1,2,3 , 4-Tetrachl orobenzene
1,2,4 , 5-Tetrachl orobenzene6
1,2,3 , 5-Tetrachl orobenzene6
1 , 2 , 4-Tri chl orobenzene
1 , 2 , 3-Tr i chl orobenzene
1, 3, 5-Tri chl orobenzene
Amount

(/xg) Fraction 1"
10
10
100
200
100
100
100
1.0
1.0
10
10
10
10
1.0
1.0
1.0
10
10
10
10
10
10
0
0
82
115
102
103
104
116
101




93
100
129
104
102
102
59
96
102

Fraction 2C
0
0
16






95
108
105
71









Values given represent average values of duplicate experiments.

         1 was eluted with 200 mL petroleum ether.
Fraction 2 was eluted with 200 mL petroleum ether/diethyl ether (1:1).

This compound coelutes with 1,2,4-trichlorobenzene; separate experiments were
performed with benzal  chloride  to verify that this compound is not recovered
from the Florisil cleanup in either fraction.

This pair cannot be resolved on the DB-210 fused-silica capillary columns.
                               8121 - 15
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                                   Table 6.

          ACCURACY AND PRECISION DATA FOR METHOD 3510  AND METHOD 8121
Compounds
Benzal chloride0
Benzotrichloride
Benzyl chloride
2-Chl oronaphthal ene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachl orobenzene
Hexachlorobutadiene
alpha-BHC
beta-BHC
gamma-BHC
delta-BHC
Hexachl orocycl opentadi ene
Hexachl oroethane
Pentachl orobenzene
1,2,3 , 4-Tetrachl orobenzene
1,2,4 , 5-Tetrachl orobenzened
1,2,3 , 5-Tetrachl orobenzened
l,2,4-Trichlorobenzenec
1 , 2 , 3-Tri chl orobenzene
1 , 3 , 5-Tri chl orobenzene
Spike
concentration
(M9/L)
10
1.0
100
200
100
100
100
1.0
1.0
10
10
10
10
10
1.0
1.0
10
10
10
10
10
10
Average
recovery31"
(percent)
95
97
90
91
92
87
89
92
95
96
103
96
103
97
96
89
96
93
93
95
95
93
Precision
(percent RSD)
3.0
2.1
6.2
6.5
5.7
8.7
8.9
7.1
3.6
2.6
3.6
2.8
2.7
5.1
4.0
6.5
3.4
4.6
4.6
3.0
4.4
6.2
Surrogates

a,2,6-Trichlorotoluene
1,4-Dichloronaphthalene
2,3,4,5,6-Pentachlorotoluene
 1.0
10
 1.0
85
78
80
6.5
6.1
5.9
a  The number of determinations is 5.

b  Final volume of extract was  10 ml.  Florisil  cleanup was  not performed on any
   of the samples.

Cid  These pairs cannot be resolved on the DB-210 fused-silica capillary column.
                                   8121  -  16
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                                   Table 7.

          ACCURACY AND PRECISION DATA FOR METHOD 3550 AND METHOD 8121
   Compounds
    Spike
concentration
    (ng/L)
 Average
recovery
(percent)
                                                        ,a,b
  Precision
(percent RSD)
Benzal chloride0
Benzotrichloride
Benzyl chloride
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadiene
alpha-BHC
beta-BHC
gamma-BHC
delta-BHC
Hexachlorocyclopentadi ene
Hexachloroethane
Pentachlorobenzene
1,2,3,4-Tetrachlorobenzene
1,2,4,5-Tetrachlorobenzened
1,2,3,5-Tetrachlorobenzened
1,2,4-Trichlorobenzenec
1,2,3-Trichlorobenzene
1,3,5-Trichlorobenzene

Surrogates

a,2,6-Trichlorotoluene
1,4-Dichloronaphthalene
2,3,4,5,6-Pentachlorotoluene
     3,300
     3,300
    33,000
    66,000
    33,000
    33,000
    33,000
       330
       330
     3,300
       300
     3,300
     3,300
       330
       330
       330
     3,300
     3,300
     3,300
     3,300
     3,300
     3,300
       330
    3,300
       330
    89
    90
   121
   100
    84
    81
    89
    81
    83
   100
    92
    99
    97
    44
    83
    81
    88
    80
    80
    89
    79
    75
    86
    88
    98
        .5
        .9
 2.7
 2.9
 5.9
 6.4
 7.1
12.6
11.0
 3.2
 4.7
 2.9
 2.4
 4.1
 1
25.
 4.6
 3.5
 2.9
 4.4
 4.4
 2.7
 4.3
 5.3
      2.7
      4.5
     11.7
a  The number of determinations is 5.
b  Final volume of extract was  10 ml.  Florisil cleanup was  not performed on any
   of the samples.

Cid These pairs cannot be resolved on the DB-210 fused-silica capillary column.
                                   8121  -  17
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                        3   20 2 21
                                                         10  12 11 13
                                   19
                                  18
                                14
                                            16
10       15        20

     TIME (mln)
                                                              25
                                                     30
Figure 1.
GC/ECD chromatogram of Method 8121 composite standard analyzed
on a 30 m x 0.53 mm ID DB-210 fused-silica capillary column.
GC operating conditions are given in Section 7.4.  See Table
3 for compound identification.
                                   8121  -  18
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                             17
                                 4
                                 16
                                                        10
                                              11
                                              13
                                              JL
                                                            12
 0
10     15     20     25     30    35

                    TIME (min)
                                                     40
45
50
55
Figure 2.
     GC/ECD chromatogram of Method 8121 composite standard analyzed
     on a 30 m x 0.53 mm ID DB-WAX fused-silica capillary column.
     GC operating conditions are given  in Section 7.4.  See Table
     3 for compound identification.
                                   8121  -  19
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                                METHOD  8121
      CHLORINATED  HYDROCARBONS  BY  GAS  CHRQMATQGRAPHY.
                     CAPILLARY  COLUMN TECHNIQUE
                                    7.1.1 Choose appropriate
                                      extraction procedure
                                  7.1.2 Add appropriate spiking
                                  compounds to sample prior
                                    to extraction procedure
                                    7.2 Exchange extraction
                                    solvent to hexane during
                                       K-D procedures
                                 7.2.1 Following concentration of
                                  methylene chloride allow K-D
                                  apparatus to drain and cool
                                7.2.2 Increase temperature of hot
                                 water bath; add hexane;  attach
                                 Snyder column; place apparatus
                                   on water bath; concentrate;
                                  remove from  water bath; cool
                                7.2.3 Remove column; rinse flask
                                 and joints with hexane; adjust
                                        extract volume
  7.3 Choose approriate cleanup
    technique, if necessary;
fluorosil cleanup is  recommended.
   Refer to Method  3620 or to
         Section 7.3.2
                                      .2.3 Will furth
                                      processing be
                                     performed within
                                        two days?
7.2.3 Transfer extract to
Teflon sealed screw-cap
    vials; refrigerate
                              7.3.4 Elemental
                              sulfur removal
                                required?
  7.3.3 GPC
   cleanup
   required?
                             7.3.4 Refer to
                              Method 3660,
                               Section 7.3
7.3.3 Refer to
 Method 3640
                                8121  - 20
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         METHOD  8121
          (CONTINUED)
    7.2.3 Stopper concentrator
    and refrigerate
  7.4.1 Set column 1  conditions
  7.4.2 Set column 2 conditions
 7.5.1 Refer to Method 8000 for
 calibration techniques; select
 lowest point on calibration curve
  7.5.2 Choose and perform
  internal or external calibration
  (refer to Method 8000)
  7.6.1 Add internal standard if
  necessary
7.6.2 Establish daily retention time
windows, analysis sequence,
dilutions, and identification criteria
            8121   -  21
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      METHOD  8121
      (CONCLUDED)
  7.6.3 Record sample volume
  injected and resulting peak
  sizes
7.6.4 Determine identity and
quantity of each component peak
that corresponds to compound
used for calibration
                                     7.6.5 Dilute extract; reanalyze
 7.6.6 Compare standard and
 sample retention times; identify
 compounds
          8121  -  22
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                                 METHOD 8141A

               ORGANOPHOSPHORUS COMPOUNDS  BY  GAS  CHROMAT06RAPHY;
                          CAPILLARY COLUMN TECHNIQUE
1.0  SCOPE AND APPLICATION

      1.1  Method 8141  is  a  gas  chromatographic  (GC)  method used to determine
the concentration of various organophosphorus compounds.  The following compounds
can be determined by this method:
      Compound Name
CAS No.'
      Azinphos methyl
      Bolstar (Sulprofos)
      Chlorpyrifos
      Coumaphos
      Demeton, 0 and S
      Diazinon
      Dichlorvos
      Dimethoate
      Disulfoton
      EPN
      Ethoprop
      Fensulfothion
      Fenthion
      Malathion
      Merphos
      Mevinphos
      Monocrotophos
      Naled
      Parathion-ethyl
      Parathion-methyl
      Phorate
      Ronnel
      Sulfotep
      TEPP
      Stirophos (Tetrachlorovinphos)
      Tokuthion (Protothiofos)
      Trichloronate
    86-50-0
 35400-43-2
  2921-88-2
    56-72-4
  8065-48-3
   333-41-5
    62-73-7
    60-51-5
   298-04-4
  2104-64-5
 13194-48-4
   115-90-2
    55-38-9
   121-75-5
   150-50-5
  7786-34-7
  6923-22-4
   300-76-5
    56-38-2
   298-00-0
   298-02-2
   299-84-3
  3689-24-5
 21646-99-1
 22248-79-9
 34643-46-4
   327-98-0
         Chemical  Abstract Services Registry Number.
      1.2  Table 1 lists method detection  limits  (MDL)  for each compound in a
water and a soil matrix.  Table 2 lists the  estimated quantitation limits (EQLs)
for other matrices.
                                   8141A -  1
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      1.3  Analytical difficulties  encountered  with  specific organophosphorus
compounds may include (but are not limited to) the following:

            1.3.1 Tetraethyl  pyrophosphate  (TEPP)  is an  unstable diphosphate
      which  is  readily  hydrolyzed  in  water  and  is  thermally  labile  (TEPP
      decomposes  at  170°C).   Care  must  be taken  to minimize  loss  during  GC
      analysis and during  sample  preparation.   Identification of bad standard
      lots is difficult since the electron impact mass spectrum of TEPP is nearly
      identical  to its major breakdown product, triethyl phosphate.

            1.3.2 The water  solubility  of dichlorvos  is  10  g/L  at  20°C,  and
      recovery is poor from aqueous solution.

            1.3.3 Naled is converted to dichlorvos on column by debromination.
      This  reaction  may  also  occur during  sample  workup.    The  extent  of
      debromination will  depend  on the nature of the matrix being analyzed.  The
      analyst must consider the  potential  for  debromination when naled is to be
      determined.

            1.3.4 Trichlorofon  (not determined  by  this  method)  rearranges  and
      is dehydrochlorinated in acidic, neutral, or basic media to  form dichlorvos
      and hydrochloric acid.   If this method is to  be  used  for the determination
      of organophosphates  in  the  presence of  trichlorofon,  the  analyst should
      be aware  of the possibility  of  rearrangement  to dichlorvos to  prevent
      misidentification.

            1.3.5 Demeton    is    a    mixture    of    two     compounds;
      0,0-Diethyl 0-[2-(ethylthio)ethyl]    phosphorothioate   (Demeton-0)   and
      0,0-Diethyl S-[2-(ethylthio)ethyl]phosphorothioate(Demeton-S).  Standards
      for  the individual  isomers  are  no longer  available  through the  EPA
      repository, and two peaks will be observed in  all mixed Demeton standards.
      It is recommended that the early eluting compound  (Demeton-S) be used for
      quantitation.

            1.3.6 Tributyl phosphorotrithioite (Merphos) is a single  component
      compound that  is readily  oxidized  in the  environment and  during  storage
      to the  phosphorotrithioate.   The analyst may  observe two  peaks  in  the
      chromatograms of merphos standards.

      1.4  Recoveries for some additional organophosphorus compounds  have been
determined for water.  They include:

            Azinphos ethyl              HMPA
            Carbofenthion               Leptophos
            Chlorfenvinphos             Phosmet
            Dioxathion                  Phosphamidion
            Ethion                      Terbuphos
            Famphur                     TOCP

     As Method 8141 has not been fully validated for the determination of these
compounds,  the analyst must demonstrate  recoveries of greater than 70  percent
with precision of  no more than  15 percent RSD before Method  8141  is used  for
these or any additional analytes.

                                   8141A  -  2                       Revision  1
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      1.5  When Method  8141 is  used  to analyze unfamiliar  samples,  compound
identifications should be supported by a single confirmatory analysis.  Section
8.4 provides gas  chromatograph/mass  spectrometer  (GC/MS)  criteria appropriate
for the qualitative confirmation of compound identifications.

      1.6  This method  is restricted  to use by or  under the  supervision  of
analysts experienced in the use of gas chromatography and in the interpretation
of chromatograms.

      1.7  The use of Gel  Permeation  Cleanup (Method  3640)  for sample cleanup
has been demonstrated to yield recoveries of less than 85 percent for many method
analytes and is therefore not recommended for use with this method.


2.0  SUMMARY OF METHOD

      2.1  Method 8141  provides gas chromatographic conditions for the detection
of ppb concentrations of organophosphorus compounds.   Prior to the use of this
method, appropriate sample preparation techniques must be used.  Water samples
are extracted at  a neutral  pH  with methylene chloride  as  a solvent  by using a
separatory funnel  (Method 3510)  or a continuous liquid-liquid extractor (Method
3520).  Soxhlet extraction (Method 3540)  or ultrasonic extraction (Method 3550)
using methylene chloride/acetone  (1:1)  are  used  for  solid  samples.   Both neat
and diluted organic  liquids (Method 3580, Waste Dilution) may be analyzed  by
direct injection.  Spiked  samples  are used to verify  the  applicability of the
chosen extraction technique to each new  sample type.   A gas chromatograph with
a flame photometric or nitrogen-phosphorus detector is used  for this multiresidue
procedure.

      2.2  If interferences are encountered in the analysis, Method 8141 may also
be performed on extracts that have undergone cleanup using Method 3620 or Method
3660.
3.0  INTERFERENCES

      3.1  Refer to Methods 3500, 3600, and 8000.

      3.2  The use of Florisil cleanup materials (Method 3620) for some of the
compounds in  this  method has been demonstrated  to yield  recoveries  less than
85% and  is  therefore  not recommended for all compounds.   Refer  to Table 2 of
Method  3620 for  recoveries of  organophosphorus compounds  as  a function  of
Florisil fractions.  Use of phosphorus or halogen specific detectors, however,
often obviates the necessity for cleanup for relatively clean sample matrices.
If particular circumstances demand the use of an  alternative cleanup procedure,
the analyst must determine  the elution profile and demonstrate that the recovery
of each analyte is no less than 85%.

      3.3  Use  of  a flame  photometric detector in  the phosphorus  mode will
minimize interferences from materials  that do not contain phosphorus.  Elemental
sulfur, however, may interfere with the determination of certain organophosphorus
compounds by flame photometric gas chromatography.  Sulfur  cleanup using Method
3660 may alleviate this  interference.

                                   8141A  - 3                       Revision 1
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      3.4  A  halogen  specific  detector  (i.e.  electrolytic conductivity  or
microcoulometric) is  very  selective for the halogen  containing  compounds and
may be used for the determination of chlorpyrifos,  ronnel, coumaphos, tokuthion,
trichloronate, dichlorvos, EPN, naled, and stirophos only.

      3.5  Please note in Table 3 that a few analytes coelute on certain columns.
Therefore,  select a  second  column  for  confirmation  where coelution  of the
analytes of interest does not occur.

      3.6  Method  interferences  may  be  caused  by  contaminants  in  solvents,
reagents, glassware, and other sample processing  hardware that lead to discrete
artifacts or elevated baselines in gas chromatograms.   All these materials must
be routinely demonstrated to be free from  interferences under the conditions of
the analysis by analyzing reagent blanks (refer to Section 8.1).


4.0  APPARATUS AND MATERIALS

      4.1  Gas chromatograph

            4.1.1  Gas  chromatograph,  analytical   system   complete  with  gas
      chromatograph and all  required accessories  including syringes, analytical
      columns,  gases,  detector   and  data  system,   integrator  or  stripchart
      recorder.  A data system or integrator is recommended for measuring peak
      areas and/or peak heights.

            4.1.2  Columns

                  4.1.2.1 Column  1  - 15 m  x  0.53  mm wide-bore capillary column,
            1.0 urn film thickness,  coated with 50 percent trifluoropropyl, 50%
            methyl silicone (DB-210, SP-2401, QF1, UCON, HB-280X, Triton X-100),
            or equivalent.

                  4.1.2.2 Column  2-15mx0.53mm wide-bore capillary column,
            1.5   jum   film   thickness,   coated   with  35  percent   phenyl
            methylpolysiloxane (DB-608, SPB-608,  RTx-35), or equivalent.

                  4.1.2.3 Column  3  - 15 m  x  0.53  mm wide-bore capillary column,
            1.0 jum  film thickness,  coated  with  5 percent  phenyl,  95 percent
            methyl silicone (DB-5,  SE-54,  SPB-5,  RTx-5), or equivalent.

            4.1.3  Detector - These detectors have proven effective in analysis
      for all  analytes listed  in Table 1  and  Section 1.4 and  were  used to develop
      the accuracy and precision  statements in Section 9.0.

                  4.1.3.1  Nitrogen  Phosphorus Detector  (NPD)  operated in the
            phosphorus specific mode  is recommended.

                  4.1.3.2  Flame  Photometric  Detector  (FPD)  operated  in the
           phosphorus  specific mode is recommended.

                  4.1.3.3 Halogen specific detectors (electrolytic conductivity


                                   8141A -  4                      Revision 1
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           or  microcoulometric)  may  be used  if only  halogenated or  sulfur
           analytes are to be determined.

      4.2  Kuderna-Danish (K-D) apparatus (Kontes K-570025-0500):

            4.2.1  Concentrator tube - 10 ml graduated (Kontes K-570050-1025 or
      equivalent).  A  ground  glass stopper is used to  prevent  evaporation of
      extracts.

            4.2.2  Evaporation  flask   -  500  mL  (Kontes   K-570001-500  or
      equivalent).   Attach   to  concentrator  tube with   springs,  clamps  or
      equivalent.

            4.2.3  Snyder column  -  Three ball macro  (Kontes  K-503000-0121 or
      equivalent).

            4.2.4  Snyder column  -  Two ball   micro  (Kontes  K-569001-0219 or
      equivalent).

            4.2.5  Springs -  1/2 inch (Kontes K-662750 or equivalent).

      4.3  Vials - 10 ml, glass with Teflon lined screw-caps or crimp tops.

      4.4  Water bath - Heated with concentric ring cover, capable of temperature
control (± 2°C).   The  bath should  be used in  a hood.

      4.5  Balance - Analytical, capable of accurately weighing to the nearest
0.0001 g.

      4.6  Boiling  chips   -   Solvent   extracted  with   methylene  chloride,
approximately 10/40 mesh (silicon carbide or equivalent).


5.0  REAGENTS

      5.1  Reagent grade inorganic chemicals shall be used  in all  tests.  Unless
otherwise indicated, it  is  intended that all  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  Hexane, C6H14 - Pesticide quality or equivalent.

      5.3  Acetone, CH3COCH3 -  Pesticide  quality or equivalent.

      5.4  Isooctane,  C8H18 - Pesticide quality or equivalent.

      5.5  Surrogate standards - The analyst should monitor the performance of
the extraction, cleanup (when  used), and analytical  system  and the effectiveness
of  the method  in  dealing  with  each sample  matrix  by spiking  each sample,
standard, and blank with one or two  surrogates  (e.g. organophosphorus compounds
not expected to be present in  the  sample) recommended to encompass the range of

                                   8141A -  5                       Revision 1
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the temperature  program  used  in this method.   Deuterated  analogs  of analytes
should  not  be  used as  surrogates  for  gas chromatographic  analysis due  to
coelution problems.

      5.6  Stock  standard  solutions -  Can be  prepared  from pure  standard
materials or  can be purchased as  certified  solutions.   Commercially prepared
stock standards can be used if they are verified against EPA standards.  If EPA
standards are not  available for  verification,  then  standards  certified by the
manufacturer  and  verified against  a standard  made  from pure  material  is
acceptable.

            5.6.1  Prepare  stock  standard  solutions  by   accurately  weighing
      0.0100 g of  pure material.   Dissolve the material  in  hexane  or  other
      suitable solvent and dilute  to known volume in  a volumetric  flask.   If
      compound purity  is  certified at 96% or greater, the weight  can be used
      without correction to calculate the concentration of the stock standard.
      Commercially prepared stock standards can be used at any concentration if
      the are certified by the manufacturer or by an independent source.

            5.6.2  Transfer the stock standard solutions into bottles with Teflon
      lined screw-caps  or crimp tops.   Store  at 4°C and  protect  from light.
      Stock  standard  solutions  should  be  checked  frequently  for  signs  of
      degradation or evaporation, especially just prior to preparing calibration
      standards from them.

            5.6.3  Stock standard  solutions  must be  replaced  after six months
      or sooner  if comparison with check standards  indicates  a  problem.   All
      stock standards must be stored in a freezer at 4°C.

      5.7  Calibration standards  - A minimum of five  concentrations  for each
analyte of interest should be prepared through dilution of the stock standards
with hexane.  One of the concentrations should be at a concentration near, but
above, the MDL.  The remaining concentrations should  correspond to the expected
range of concentrations found  in real samples or should define the working range
of the GC.  Calibration standards must be replaced after one to two months, or
sooner if comparison with check standards indicates a problem.

      5.8  Internal standards  should only be used on well characterized samples.
To use this  approach, the analyst must select  one or more internal standards that
are similar in analytical  behavior to  the  compounds  of interest.   The analyst
must further  demonstrate that the  measurement  of  the internal  standard is not
affected by method  or  matrix  interferences.   Because of these limitations, no
internal standard can be suggested that is applicable to all samples.

            5.8.1  Prepare  calibration   standards   at  a  minimum   of   five
      concentrations for each analyte of interest as described in Section 5.7.

            5.8.2  To each calibration standard,  add  a known constant amount of
      one or more internal  standards, and dilute to volume with hexane or other
      suitable solvent.

            5.8.3  Analyze each calibration  standard according to Section 7.0.


                                   8141A  -  6                      Revision 1
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6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See  the  introductory material  to  this chapter,  Organic  Analytes,
Section 4.1.

      6.2  Extracts are to be  refrigerated  at 4°C and  analyzed within 40 days of
extraction.
7.0  PROCEDURE

      7.1  Extraction

            7.1.1  Refer to Chapter Two for guidance on choosing the appropriate
      extraction procedure.  In general,  water samples are extracted at a neutral
      pH with  methylene chloride, using  either Method  3510  or 3520.   Solid
      samples  are  extracted using either  Method  3540  or 3550  with methylene
      chloride/acetone  (1:1) as the extraction solvent.

            7.1.2  Prior to gas chromatographic analysis,  the extraction solvent
      may be  exchanged  to hexane.   The  exchange  is performed  during  the K-D
      procedures listed in all  of the  extraction  methods.   The  analyst must
      ensure quantitative transfer of the extract concentrate.  Single laboratory
      data indicates  that  samples  should  not be transferred with  100 percent
      hexane during  sample workup as the more  water  soluble  organophosphorus
      compounds  may   be lost.   This  transfer is  best  accomplished with  a
      hexane/acetone solvent mixture.  The exchange is performed as follows:

                  7.1.2.1  Following K-D concentration of the methylene chloride
            extract to  1 mL using the macro Snyder column, allow the apparatus
            to cool and drain for at least 10 minutes.

                  7.1.2.2  Momentarily remove the Snyder  column,  add  50  mL of
            hexane/acetone solvent mixture,  a  new glass  bead  or boiling  chip,
            and attach  the micro Snyder column.  Concentrate the extract  using
            1 mL of hexane to prewet the Snyder column.  Place the K-D apparatus
            on the  water bath so that  the concentrator tube is partially immersed
            in the  hot water.  Adjust the vertical  position of the apparatus and
            the water temperature,  as required, to complete  concentration in
            5-10 minutes.  At the proper rate of distillation the balls of the
            column will  actively chatter, but the chambers will not  flood.  When
            the apparent volume  of liquid reaches 1 mL, remove the K-D apparatus
            and allow it to drain and cool  for at least 10 minutes.

                  7.1.2.3  Remove the Snyder column  and rinse the flask and its
            lower joint  with 1-2 mL of hexane into the concentrator tube.  A 5 mL
            syringe is recommended for this  operation.  Adjust the extract volume
            to 10 mL.   Stopper the concentrator tube and store refrigerated at
            4°C if  further  processing will  not be performed immediately.  If the
            extract will be stored longer than two days,  it should be transferred
            to a vial with a Teflon lined screw-cap  or crimp top.  Proceed with
            gas chromatographic analysis if further cleanup is not required.


                                  8141A -  7                       Revision 1
                                                                  November  1990

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      7.2  Gas chromatography conditions (recommended):  Three megabore capillary
columns are included for analysis of organophosphates by this method.  Column 1
(DB-210 or equivalent) and Column 2  (SPB-608 or equivalent) are recommended if
a large  number of  organophosphorus analytes  are  to  be  determined.   If the
superior resolution offered by Column 1 and Column 2 is not required, Column 3
(DB-5 or equivalent) may be used.

            7.2.1  Columns 1 and 2
      Carrier gas (He) flow rate =   5 mL/min
      Initial temperature =        50°C,  hold for 1 minute
      Temperature program =        50°C to 140°C at  5°C/nrin, hold for 10 minutes,
                                   followed by 140°C to 240°C at  10°C/min, hold
                                   for 10 minutes (or a  sufficient amount of time
                                   for last compound to elute).

            7.2.2  Column 3
      Carrier gas (He) flow rate =   5 mL/min
      Initial temperature =        130°C,  hold for  3 minutes
      Temperature program =        130°C to 180°C at 5°C/min, hold for 10 minutes,
                                   followed by  180°C to 250°C at 2°C/min, hold
                                   for 15 minutes (or a  sufficient amount of time
                                   for last compound to elute).

            7.2.3  Retention times for  all analytes on each column are presented
      in Table 3.   The analyst  should note that  several method analytes coelute
      on column 3.

      7.3 Calibration, refer to Method 8000 for proper calibration techniques.
Use Table 1 and especially Table  2  for guidance on selecting the lowest point
on the calibration curve.

            7.3.1  The procedure  for internal  or  external  calibration  may be
      used.  Refer to  Method 8000 for a description  of each of these procedures.

            7.3.2  If cleanup  is  performed  on  the  samples,  the analyst should
      process  a  series of  standards through  the  cleanup procedure  and then
      analyze the samples  by  GC.   This will confirm elution  patterns  and the
      absence of interferences from  the reagents.

      7.4  Gas chromatographic analysis

            7.4.1  Refer to Method 8000.   If the internal  standard calibration
      technique is used, add 10 juL of internal standard to the sample prior to
      injection.

            7.4.2  Method 8000 provides instructions on the analysis sequence,
      appropriate dilutions,  establishing  daily  retention time windows,  and
      identification criteria.

            7.4.3  For megabore capillary columns,  automatic injections of 1 /iL
      are recommended.  Hand injections of no more  than 2  fj.1 may be used if the
      analyst  demonstrates  quantitation  precision of  <  10 percent relative


                                   8141A  - 8                      Revision 1
                                                                  November 1990

-------
      standard deviation.  The solvent flush technique may be used if the amount
      of solvent is kept at a minimum.

            7.4.4  Examples  of  chromatograms  for  various  organophosphorus
      compounds are shown in Figures 1  through 4.

            7.4.5  Record the sample volume  injected to the nearest 0.05 /xL and
      the resulting peak sizes (in area units or peak heights).

            7.4.6  Using either the internal or external  calibration procedure
      (Method 8000),  determine the identity  and quantity of each component peak
      in the  sample  chromatogram which corresponds to the compounds  used for
      calibration purposes.   See Method 8000 for calculation equations.

            7.4.7  If peak  detection and identification  is prevented  by the
      presence of interferences,  further cleanup  is required.  Before using any
      cleanup  procedure,  the  analyst  must  process   a  series of  calibration
      standards  through  the procedure  to establish  elution  patterns  and  to
      determine recovery of target compounds.  The absence of interference from
      reagents must  be  demonstrated by  routine  processing of reagent blanks
      through the chosen cleanup procedure.

            7.4.8  Naled has  been reported  to  be converted  to  DDVP  on  some
      columns by debromination.  If this process is demonstrated on the GC system
      that is used  for analysis, clean the injector and break off several inches
      of a megabore column  or change the  glass wool of a packed column prior to
      analyzing samples.  If subsequent  injections of naled  give  DDVP, report
      naled  as  DDVP,  but,   in  this instance, both naled  and  DDVP may  not  be
      reported in the same sample.

      7.5  Cleanup: If required,  the  samples may be cleaned up using the Methods
presented in Chapter 4,  Section 2.2.2.

            7.5.1  Proceed with Florisil  column Cleanup (Method 3620), followed
      by, if  necessary,  Sulfur  Cleanup (Method 3660), using the  10  ml hexane
      extracts obtained from Section 7.1.2.3.

NOTE: The use of  Gel  Permeation  (Method 3640)  for  sample  cleanup  has  been
      demonstrated to yield recoveries  of less than 85 percent for many method
      analytes and is therefore not recommended for use  with this  method.

            7.5.2  Following cleanup, the extracts  should  be analyzed by GC, as
      described in the previous Sections and in Method 8000.


8.0  QUALITY CONTROL

      8.1  Refer to Chapter One for specific quality control procedures.  Quality
control  to  validate  sample extraction  is covered in Method  3500 and  in the
extraction method utilized.   If extract cleanup was performed, follow the QC in
Method 3600 and in the specific cleanup method.
                                   8141A -  9                       Revision 1
                                                                  November 1990

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      8.2  Procedures to check the GC system operation are found in Method 8000.

      8.3  GC/MS confirmation

            8.3.1  GC/MS techniques should be judiciously  employed  to support
      qualitative  identifications  made with  this  method.    Follow the  GC/MS
      operating requirements specified in Method 8270.

            8.3.2  When  available,  chemical   ionization  mass  spectra may  be
      employed to aid in the qualitative identification process.

            8.3.3  To confirm an identification of a compound, the  background
      corrected mass spectrum of the compound must  be obtained from the sample
      extract  and  must  be  compared  with a  mass  spectrum  from  a  stock  or
      calibration standard analyzed under the same  chromatographic conditions.
      At least  25 ng  of material  should be injected  into  the  GC/MS.    The
      following criteria must be met for qualitative  confirmation:

            The  molecular  ion  and  all other  ions  present  above  20 percent
      relative abundance in the mass  spectrum of the standard must  be present
      in the mass spectrum of the sample  with agreement to ± 10  percent.   For
      example, if the  relative  abundance  of  an  ion  is 30  percent in  the  mass
      spectrum of the standard, the allowable limits for the relative abundances
      of that ion in  the mass spectrum for the sample  would  be  20 to 40 percent.

            The retention time of the  compound in the sample must be within six
      seconds  of the  retention  time   for  the  same  compound  in   the  standard
      solution.

            Compounds  that  have very  similar mass  spectra can  be  explicitly
      identified by GC/MS only on the basis of retention time data.

            8.3.4  Where available,  chemical  ionization mass spectra may  be
      employed to aid in the qualitative identification process because of the
      extensive  fragmentation  of organophosphorus  compounds during  electron
      impact MS processes.

            8.3.5  Should the MS procedure fail to provide satisfactory results,
      additional steps may  be taken  before reanalysis.  These steps may include
      the use of alternate packed or capillary GC columns  or additional sample
      cleanup.


9.0  METHOD PERFORMANCE

      9.1  Estimated MDLs and associated  chromatographic conditions for water
and clean soil (uncontaminated with synthetic organics) are listed in Table 1.
As detection limit will vary with the particular  matrix to be analyzed, guidance
for estimating EQLs is given in Table 2.

      9.2  Single operator accuracy and precision  studies  have been conducted
with spiked water and soil  samples.  The results of these studies are presented
in Tables 4-7.

                                  8141A - 10                      Revision 1
                                                                  November 1990

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10.0  REFERENCES

1.   Taylor, V.; Hickey, D.M.;  Marsden,  P.J.  "Single Laboratory Validation of
     EPA  Method 8140";  U.S.  Environmental  Protection Agency.  Environmental
     Monitoring Systems  Laboratory.  Office of  Research and  Development,  Las
     Vegas, NV, 1987; EPA-600/4-87-009.

2.   Pressley,  T.A;  Longbottom, J.E.  "The Determination  of Organophosphorus
     Pesticides  in  Industrial  and  Municipal  Wastewater:  Method  614";  U.S.
     Environmental  Protection  Agency.  Environmental  Monitoring  and  Support
     Laboratory. Cincinnati, OH, 1982; EPA-600/4-82-004.

3.   "Analysis  of  Volatile Hazardous  Substances  by GC/MS:  Pesticide  Methods
     Evaluation";  Letter  Reports  6,  12A, and  14  to the  U.S.Environmental
     Protection Agency on Contract 68-03-2697, 1982.

4.   "Method 622,  Organophosphorus  Pesticides";  U.S. Environmental Protection
     Agency. Environmental  Monitoring and Support  Laboratory.  Cincinnati,  OH
     45268.

5.   Chau,  A.S.Y.; Afghan, B.K.  Analysis  of Pesticides  in Water. Vol.  II;
     "Chlorine and Phosphorus-Containing Pesticides"; CRC:  Boca Raton, FL, 1982,
     pp 91-113, 238.

6.   Hild, J.;  Schulte, E; Thier, H.P. "Separation of Organophosphorus Pesticides
     and Their Metabolites on Glass-Capillary Columns"; Chromatooraphia. 1978,
     11-17.

7.   Luke,  M.A.;  Froberg,   J.E.;   Doose, G.M.;   Masumoto,  H.T.  "Improved
     Multiresidue  Gas   Chromatographic   Determination  of  Organophosphorus,
     Organonitrogen,  and  Organohalogen   Pesticides  in Produce,  Using  Flame
     Photometric and Electrolytic  Conductivity Detectors";  jh. Assoc. Off. Anal.
     Chem. 1981, 1187. 64.

8.   Sherma,  J.;   Berzoa,  M.  "Analysis  of Pesticide   Residues  in Human  and
     Environmental  Samples";  U.S.  Environmental  Protection  Agency.  Research
     Triangle Park, NC; EPA-600/8-80-038.

9.   Desmarchelier,  J.M.;  Wustner,  D.A.;  Fukuto,  T.R.   "Mass  Spectra  of
     Organophosphorus Esters  and Their Alteration  Products"; Residue Reviews.
     1974, pp 63,  77.
                                  8141A - 11                      Revision 1
                                                                  November  1990

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                             TABLE 1.
           METHOD DETECTION LIMITS IN A WATER AND A SOIL
             MATRIX USING A FLAME PHOTOMETRIC DETECTOR
Compound
                              Reagent
                              Water (3510)8
Soil (3540)b
(M9/Kg)
Azinphos methyl
Bolstar (Sulprofos)
Chlorpyrifos
Coumaphos
Demeton, 0, S
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfothion
Fenthion
Malathion
Merphos
Mevinphos
Naled
Parathion-ethyl
Parathion-methyl
Phorate
Ronnel
Sulfotep
TEPPC
Tetrachl orovi nphos
Tokuthion (Protothiofos)0
Trichloronate0
0.10
0.07
0.07
0.20
0.12
0.20
0.80
0.26
0.07
0.04
0.20
0.08
0.08
0.11
0.20
0.50
0.50
0.06
0.12
0.04
0.07
0.07
0.80
0.80
0.07
0.80
5.0
3.5
5.0
10.0
6.0
10.0
40.0
13.0
3.5
2.0
10.0
4.0
5.0
5.5
10.0
25.0
25.0
3.0
6.0
2.0
3.5
3.5
40.0
40.0
5.5
40.0
Sample  extracted  using Method  3510,  Separatory  Funnel  Liquid-Liquid
Extraction.

Sample extracted using Method 3540, Soxhlet Extraction.

Purity  of these  standards not  established by  the EPA  Pesticides and
Industrial  Chemicals Repository, RTP, NC.
                            8141A - 12
      Revision 1
      November 1990

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                                TABLE 2.
             DETERMINATION OF ESTIMATED QUANTITATION LIMITS
                       (EQL) FOR VARIOUS MATRICES8
Matrix                                                            Factor"
Ground water (Methods 3510 or 3520)                                 10
Low-concentration soil by Soxhlet and no cleanup                    10
Low-concentration soil by ultrasonic extraction with GPC cleanup     6.7
High-concentration soil and sludges by ultrasonic extraction       500
Non-water miscible waste (Method 3580)                            1000
 c

   c
1C
Sample EQLs are highly matrix dependent.  The EQLs  listed herein are provided
for guidance and may not always be achievable.

EQL =  [Method detection limit  (Table 1)]  X [Factor (Table  2)].  For non-
aqueous samples, the factor is on a wet-weight basis.

Multiply this factor times the soil MDL.
                               8141A - 13                      Revision 1
                                                               November 1990

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                TABLE 3.
RETENTION TIMES FOR METHOD 8141 ANALYTES
Compound
TEPP
Dichlorvos
Mevinphos
Demeton, 0 and S
Ethoprop
Naled
Phorate
Monocrotophos
Sul f otep
Dimethoate
Disulfoton
Diazinon
Merphos
Ronnel
Chlorpyrifos
Malathion
Parathion, methyl
Parathion, ethyl
Trichloronate
Tetrachlorovinphos
Tokuthion (Protothiofos)
Fensulfothion
Bolstar^ (Sulprofos)
Famphur*
EPN
Azinphos methyl
Fenthion
Coumaphos
"Method 8141 has not been fully val
Initial temperature
Initial time
Program 1 rate
Program 1 final temperature
Program 1 hold
Program 2 rate
Program 2 final temperature
Program 2 hold
Caoill
DBS
6.44
9.63
14.178
18.31
18.618
19.01
19.94
20.04
20.11
20.636
23.71
24.27
26.82
29.23
31.17
31.72
31.84
31.85
32.19
34.65
34.67
35.85
36.34
36.40
37.80
38.342
38.83
39.83
arv Column
SPB608
5.12
7.91
12.88
15.90
16.48
17.40
17.52
20.11
18.02
20.18
19.96
20.02
21.73
22.98
26.88
28.78
23.71
27.62
28.41
32.99
24.58
35.20
35.08
36.93
36.71
38.04
29.45
38.87

DB210
10.66
12.79
18.44
17.24
18.67
19.35
18.19
31.42
19.58
27.96
20.66
19.68
32.44
23.19
25.18
32.58
32.17
33.39
29.95
33.68
39.913
36.80
37.55
37.86
36.74
37.24
28.86
39.47
i dated for Famphur.
130°C
3 minutes
5°C/min
180°C
10 minutes
2°C/min
250°C
15 minutes
50°C
1 minute
5°C/min
140°C
10 minutes
10°C/min
240°C
10 minutes
50°C
1 minute
5°C/min
140°C
10 minutes
10°C/nrin
240°C
10 minutes
               8141A - 14
Revision 1
November 1990

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                               TABLE 4.
   RECOVERY OF  27  ORGANOPHOSPHATES  BY  SEPARATORY FUNNEL EXTRACTION
Compound
Azinphos methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfonthion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotep
TEPP
Tetrachlorvinphos
Tokuthion
Trichloroate
Low
126
134
7
103
33
136
80
NR
48
113
82
84
NR
127
NR
NR
NR
NR
101
NR
94
67
87
96
79
NR
NR
Medium
143 + 8
141 + 8
89 + 6
90 + 6
67 + 11
121 + 9.5
79 + 11
47 + 3
92 + 7
125 + 9
90 + 6
82 + 12
48 + 10
92 + 6
79
NR
18 + 4
NR
94 + 5
46 + 4
77 + 6
97 + 5
85 + 4
55 + 72
90 + 7
45 + 3
35
High
101
101
86
96
74
82
72
101
84
97
80
96
89
86
81
55
NR
NR
86
44
73
87
83
63
80
90
94
NR = Not recovered.
                            8141A - 15
Revision 1
November 1990

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                               TABLE 5.
    RECOVERY  OF  27  ORGANOPHOSPHATES BY  CONTINUOUS LIQUID EXTRACTION
Compound
Azinphos methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Dlazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Famphur
Fensulfonthion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotep
TEPP
Tetrachlorvinphos
Tokuthion
Trichloroate
Low
NR
NR
13
94
38
NR
81
NR
94
NR
39
--
90
8
105
NR
NR
NR
NR
106
NR
84
82
40
39
56
132
NR
Medium
129
126
82 + 4
79 + 1
23 + 3
128 + 37
32 + 1
10 + 8
69 + 5
104 + 18
76 + 2
63 + 15
67 + 26
32 + 2
87 + 4
80
87
30
NR
81 + 1
50 + 30
63 + 3
83 + 7
77 + 1
18 + 7
70 + 14
32 + 14
NR
High
122
128
88
89
41
118
74
102
81
119
83
--
90
86
86
79
49
1
74
87
43
74
89
85
70
83
90
21
NR = Not recovered.
                            8141A - 16
Revision 1
November 1990

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                               TABLE 6.
         RECOVERY OF 27 ORGANOPHOSPHATES BY SOXHLET EXTRACTION
Compound
Azinphos methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dlmethoate
Disulfoton
EPN
Ethoprop
Fensulfonthion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotep
TEPP
Tetrachlorvinphos
Tokuthion
Trichloroate
Low
156
102
NR
93
169
87
84
NR
78
114
65
72
NR
100
62
NR
NR
NR
75
NR
75
NR
67
36
50
NR
56
Medium
110 + 6
103 + 15
66 + 17
89 + 11
64 + 6
96 + 3
39 + 21
48 + 7
78 + 6
93 + 8
70 + 7
81 + 18
43 + 7
81+8
53
71
NR
48
80 + 8
41+3
77 + 6
83 + 12
72 + 8
34 + 33
81 + 7
40 + 6
53
High
87
79
79
90
75
75
71
98
76
82
75
111
89
81
60
63
NR
NR
80
28
78
79
78
63
83
89
53
NR = Not recovered.
                            8141A  -  17
Revision 1
November 1990

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                               TABLE 7.
       RECOVERY OF 27 ORGANOPHOSPHATES  BY ULTRASONIC EXTRACTION
Compound
Azinphos methyl
Bolstar
Chlorpyrifos
Coumaphos
Demeton
Diazinon
Dichlorvos
Dimethoate
Disulfoton
EPN
Ethoprop
Fensulfonthion
Fenthion
Malathion
Merphos
Mevinphos
Monocrotophos
Naled
Parathion, ethyl
Parathion, methyl
Phorate
Ronnel
Sulfotep
TEPP
Tetrachlorvinphos
Tokuthlon
Trichloroate
Low
NR
NR
NR
NR
NR
NR
41
NR
30
14
19
NR
NR
55
NR
NR
NR
82
NR
63
NR
70
NR
43
NR
NR
NR
Medium
27 + 10
103 + 15
79 + 7
60
NR
90 + 14
13 + 9
67
44 + 22
86 + 38
34 + 26
37
35
67
71
NR
NR
40
74 + 13
NR
51 + 9
84 + 8
68 + 10
7
47 + 24
NR
NR
High
21
114
77
15
16
78
27
NR
69
105
35
2
84
31
155
23
NR
33
75
17
64
81
76
3
69
82
31
NR = Not recovered.
                            8141A - 18
Revision 1
November 1990

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                                      FIGURE  1.
      CHARACTERISTIC  RESPONSE OF ORGANOPHOSPHATES ON DB210  WITH FPD DETECTOR
300.00
250.00
200.00
150.00
100.00
 50.00
  0.00
                          I
                          Q
ll


1
at g c
* 9- 1
c o
faraipinr
Tetrachlorovi
FensuM
' V... Jl




            I (...) I .. | I > I | I I I | I I I | I I •) I I I ) I I I | I I I f , I I | , I ,, I <. | I . I ( !,,,...,,.,,, I I ,,,,,,.., I , I ,..!,

            3   5  7   9  11  13  15  17  19  21  23  25  27  29 31  33 35  37 39  41  43  45
                                   8141A - 19
Revision  1
November 1990

-------
                                         FIGURE 2.
         CHARACTERISTIC  RESPONSE OF ORGANOPHOSPHATES ON DB210 WITH NPD DETECTOR
300.00
250.00
200.00-
150.00-
100.00-
 50.00-
                  »^  - i
  0.00 -1
         1   3   5  7   9  11  13  15  17  19 21  23 25 27  29 31  33 35  37  39 41  43  45
                                      8141A - 20
Revision  1
November 1990

-------
                                         FIGURE 3.
             CHROMATOGRAM OF ORGANOPHOSPHATES ON DB210 WITH  FPD DETECTOR
300.00
250.00
200.00
150.00
100.00
 50.00
  0.00
                                      V
                                                                        Q.
                                                                        UJ
                                                                             o

                                                                             0.
                                                                               •• i
            , I , I ,,,..,, ,, , •. I,...,,,. I I. , ,11 ,, I .. I ...,..., , . I I ,, . I, , .,   ,, ,, . ,,, I,..,,,,,,, ,.,,,.,

             3  5   7   9  11  13  15  17  19 21  23 25  27  29 31  33  35  37  39  41 43  45
                                      8141A - 21
Revision 1
November 1990

-------
                                     FIGURE 4.
           CHROMATOGRAM OF ORGANOPHOSPHATES ON DB210 WITH  NPD DETECTOR
300.00 -,
250.00-
200.00-
150.00-
100.00-
 50.00 -I
              DL
         1   3   5  7  9  11  13  15 17  19  21  23 25  27 29 31  33  35 37 39  41  43 45
                                   8141A -  22
Revision 1
November  1990

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        METHOD 8141A
ORGANOPHOSPHORUS COMPOUNDS
I Start 1
1
7.1.1 Refer to
Chapter Two for
guidance on
choosing the
appropr late
ex t ract ion
pr ocedur e



7.1.2 Perform
s o 1 vent exchange
during K-D
procedures in all
extraction methods


1
7.2 Select CC
condi tions
1
7.3 Refer to Method
8000 for
ca 1 ibration
techniques
I


7.3.1 In ternal or
ex ternal
calibration may be
used





























-J
-*





























7.4.1 Add internal
standard to sampl e
if necessary



7.4.2 Refer to
Method 8000. Step
7.6 for
ins t ructions on
analysis sequence,
di lutions ,
retention times ,
and identification
criteria
I

7.4.3 Inject sample
1
7.4.5 Record sample
volume injected and
resulting peak
sizes
I
7.4.6 Determine
identity and
quantity of each
component peak:
refer to Method — '
8000, Step 7.8 for
calculation
equations
                                 Yes
                                       7.5.1 Perform
                                     appropriate cleanup
                        No
                                     7.5.2 Reanalyze by
                                           CC
                                           Stc
       8141A -  23
Revision 1
November 1990

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                                 METHOD 8150B

                 CHLORINATED HERBICIDES BY GAS CHROMATOGRAPHY
1.0  SCOPE AND APPLICATION

      1.1  Method 8150  is a gas  chromatographic  (GC) method  for determining
certain chlorinated acid herbicides.  The following compounds can be determined
by this method:
      Compound Name                       CAS No."


      2,4-D                                  94-75-7
      2,4-DB                                 94-82-6
      2,4,5-TP (Silvex)                      93-72-1
      2,4,5-T                                93-76-5
      Dalapon                                75-99-0
      Dicamba                              1918-00-9
      Dichlorprop                           120-36-5
      Dinoseb                                88-85-7
      MCPA                                   94-74-6
      MCPP                                   93-65-2


      a   Chemical  Abstract Services  Registry  Number.


      1.2  Table 1 lists the method detection  limit for each compound in organic-
free reagent water.  Table 2  lists  the estimated quantitation limit  (EQL) for
other matrices.

      1.3  When Method  8150  is used  to analyze unfamiliar  samples,  compound
identifications should  be supported  by at  least  one  additional  qualitative
technique.   This  method describes  analytical  conditions for  a second  gas
chromatographic column that can be  used to confirm  measurements  made with the
primary column. Section 8.4 provides gas chromatograph/mass spectrometer (GC/MS)
criteria   appropriate   for    the  qualitative   confirmation   of   compound
identifications.

      1.4  Only experienced analysts should be allowed to work with diazomethane
due to the potential  hazards  associated with  its  use  (the compound is explosive
and carcinogenic).


2.0  SUMMARY OF METHOD

      2.1  Method   8150   provides    extraction,   esterification,   and   gas
chromatographic conditions  for the analysis  of chlorinated  acid herbicides.
Spiked samples  are used  to verify the  applicability  of the  chosen  extraction
technique to each  new  sample  type.   The esters  are  hydrolyzed with  potassium

                                  8150B - 1                       Revision 2
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hydroxide, and extraneous organic material  is  removed by a solvent wash.  After
acidification, the acids  are extracted with  solvent and converted to their methyl
esters using diazomethane as  the  derivatizing  agent.   After excess reagent is
removed, the esters are determined by gas chromatography employing an electron
capture  detector,    microcoulometric detector,  or electrolytic  conductivity
detector  (Goerlitz  and Lamar,  1967).   The results  are  reported as  the acid
equivalents.

      2.2  The  sensitivity  of  Method 8150 usually  depends  on the  level  of
interferences rather than on instrumental limitations.
3.0  INTERFERENCES

      3.1  Refer to Method 8000.

      3.2  Organic acids, especially chlorinated  acids,  cause  the most direct
interference with the determination.  Phenols,  including chlorophenols, may also
interfere with this procedure.

      3.3  Alkaline hydrolysis and subsequent extraction of the basic solution
remove many chlorinated hydrocarbons and phthalate esters that might otherwise
interfere with the electron capture analysis.

      3.4  The  herbicides,  being  strong  organic acids,  react  readily  with
alkaline substances and may be lost during analysis.   Therefore, glassware and
glass wool  must be  acid rinsed,  and  sodium sulfate must be  acidified  with
sulfuric acid prior to use to avoid this possibility.


4.0  APPARATUS AND MATERIALS

      4.1  Gas chromatograph

            4.1.1  Gas  chromatograph,   analytical system  complete  with  gas
      chromatograph  suitable   for  on-column   injections   and  all   required
      accessories, including detectors, analytical columns,  recorder, gases, and
      syringes.  A data system for measuring peak heights and/or peak areas is
      recommended.

           4.1.2  Columns

                  4.1.2.1  Column la and  Ib - 1.8 m x  4 mm ID glass, packed with
            1.5%  SP-2250/1.95%  SP-2401  on  Supelcoport  (100/120  mesh)  or
            equivalent.

                  4.1.2.2  Column 2 -  1.8 m x 4  mm ID glass, packed with 5% 0V-
            210 on Gas Chrom Q  (100/120 mesh)  or equivalent.

                  4.1.2.3  Column 3 - 1.98 m x 2 mm ID glass,  packed with 0.1%
            SP-1000 on 80/100 mesh Carbopack C or equivalent.

            4.1.3  Detector - Electron capture  (ECD).


                                   8150B  -  2                      Revision 2
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      4.2  Erlenmeyer flasks  -  250 and 500 mL Pyrex, with  24/40 ground glass
joint.

      4.3  Beaker - 500 ml.

      4.4  Diazomethane generator  - Refer to  Section 7.4  to  determine which
method of diazomethane generation should be used for a particular application.

            4.4.1  Diazald kit - recommended  for  the generation of diazomethane
      using the procedure  given  in Section 7.4.2 (Aldrich Chemical Co., Cat. No.
      210,025-2 or equivalent).

            4.4.2  Assemble from two 20 x 150 mm test tubes,  two Neoprene rubber
      stoppers, and a  source of nitrogen.   Use  Neoprene rubber  stoppers with
      holes drilled in them to accommodate  glass  delivery tubes.  The exit tube
      must be drawn to a point to bubble diazomethane through  the sample extract.
      The generator assembly is  shown in Figure 1.  The procedure for use of this
      type of generator is given in Section 7.4.3.

      4.5  Vials - 10 to 15 ml, amber glass, with Teflon lined screw  cap or crimp
top.

      4.6  Separatory funnel - 2000 mL, 125 ml, and 60 ml.

      4.7  Drying column  - 400 mm x 20 mm ID Pyrex chromatographic column with
Pyrex glass wool at bottom and a Teflon stopcock.

NOTE: Fritted  glass  discs   are  difficult   to   decontaminate  after  highly
      contaminated extracts have been passed through.   Columns without frits may
      be purchased.  Use a small pad of  Pyrex glass wool to retain the adsorbent.
      Prewash the glass wool pad with 50  ml  of acetone  followed  by  50 ml of
      elution solvent prior to packing the column with adsorbent.

      4.8  Kuderna-Danish (K-D)  apparatus

            4.8.1  Concentrator  tube - 10  ml,  graduated (Kontes  K-570050-1025
      or equivalent).   A ground glass stopper  is  used  to  prevent evaporation of
      extracts

            4.8.2  Evaporation   flask   -   500  ml  (Kontes  K-570001-500  or
      equivalent).   Attach  to concentrator  tube with springs,  clamps  or
      equivalent.

            4.8.3  Snyder column -  Three ball macro  (Kontes K-503000-0121 or
      equivalent).

            4.8.4  Snyder  column -  Two  ball  micro   (Kontes K-569001-0219 or
      equivalent).

            4.8.5  Springs -  1/2 inch (Kontes K-662750 or equivalent).

      4.9  Boiling chips - Solvent  extracted,  approximately  10/40 mesh (silicon
carbide or equivalent).


                                   8150B  -  3                       Revision 2
                                                                  November  1990

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      4.10  Water  bath  -   Heated,  with  concentric  ring  cover,   capable  of
temperature control (± 5°C).  The bath should be used in a hood.

      4.11  Microsyringe -  10 ^l.

      4.12  Wrist shaker -  Burrell Model 75 or equivalent.

      4.13  Glass wool - Pyrex, acid washed.

      4.14  Balance - Analytical, capable of accurately weighing to  the nearest
0.0001 g.

      4.15  Syringe - 5 ml.

      4.16  Glass rod.


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  Sulfuric acid solution

            5.3.1  ((1:1) (v/v)) - Slowly add  50 ml H2S04 (sp. gr. 1.84) to 50 ml
      of organic-free reagent water.

            5.3.2  ((1:3) (v/v)) - Slowly add  25 ml H2S04 (sp. gr. 1.84) to 75 ml
      of organic-free reagent water.

      5.4  Hydrochloric acid ((1:9)  (v/v)),  HC1.  Add one volume  of concentrated
HC1 to 9 volumes of organic-free reagent water.

      5.5  Potassium  hydroxide  solution  (KOH)  -  37% aqueous  solution (w/v).
Dissolve 37  g  potassium hydroxide pellets  in organic-free reagent water, and
dilute to 100 ml.

      5.6  Carbitol  (Diethylene  glycol  monoethyl  ether),  C2H5OCH2CH2OCH2CH2OH.
Available from Aldrich Chemical Co.

      5.7  Solvents

            5.7.1  Acetone,  CH3COCH3 -  Pesticide quality or equivalent.

            5.7.2  Methanol,  CH3OH - Pesticide quality or equivalent.
                                   8150B - 4                       Revision  2
                                                                   November 1990

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            5.7.3  Isooctane, (CH3)3CCH2CH(CH3)2 - Pesticide quality or equivalent.

            5.7.4  Hexane, C6H14 - Pesticide quality or equivalent.

            5.7.5  Diethyl Ether,  C2H5OC2H5.   Pesticide  quality or equivalent.
      Must  be  free of  peroxides as  indicated  by  test  strips  (EM  Quant,  or
      equivalent).  Procedures  for  removal  of peroxides are provided with the
      test strips.  After cleanup, 20 ml of ethyl alcohol  preservative must be
      added to each liter of ether.

      5.8  Sodium  sulfate  (granular,  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.

      5.9  N-Methyl-N-nitroso-p-toluenesulfonamide (Diazald), CH3C6H4S02N(CH3)NO.
 Available from Aldrich Chemical Co.

      5.10  Silicic acid.  Chromatographic  grade,  nominal  100 mesh.   Store at
130°C.

      5.11  Stock standard solutions - Stock standard  solutions can be prepared
from pure standard materials or purchased as  certified solutions.

            5.11.1 Prepare stock standard solutions by accurately  weighing about
      0.0100 g of pure acids.  Dissolve the acids in pesticide quality acetone
      and dissolve the esters in 10% acetone/isooctane  (v/v) and dilute to volume
      in a 10 ml volumetric flask.  Larger volumes can be used at the convenience
      of the analyst.   If  compound  purity  is  certified at  96% or greater, the
      weight can  be used without  correction to  calculate  the  concentration of
      the stock standard.   Commercially prepared stock standards  can  be used at
      any  concentration  if they  are  certified by  the manufacturer or  by an
      independent source.

           5.11.2 Transfer the stock standard solutions into vials with Teflon
     lined screw caps  or crimp tops.  Store at  4°C and protect from light.  Stock
     standard solutions should  be  checked  frequently  for  signs of degradation
     or evaporation,  especially  just  prior to preparing calibration standards
     from them.

           5.11.3 Stock standard  solutions  must be replaced  after 1 year, or
     sooner if comparison with check standards  indicates a problem.

     5.12  Calibration standards - A minimum of  five calibration  standards  for
each parameter  of interest should  be  prepared  through dilution  of  the stock
standards  with  diethyl  ether.    One  of  the  concentrations   should  be  at  a
concentration  near,  but  above,  the  method  detection  limit.    The  remaining
concentrations should correspond to the expected range of concentrations found
in real  samples  or should define the working  range  of the  GC.   Calibration
solutions must be replaced after six months, or  sooner  if comparison with check
standards indicates a problem.
                                   8150B -  5                      Revision 2
                                                                  November 1990

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     5.13  Internal standards  (if  internal  standard  calibration  is used) - To
use this approach, the analyst must select one or more internal standards that
are similar in analytical  behavior to  the compounds  of interest.   The analyst
must further demonstrate that  the  measurement  of the internal  standard is not
affected by method or matrix  interferences.   Because of these limitations, no
internal standard can be suggested that is applicable to all samples.

           5.13.1  Prepare  calibration   standards   at  a  minimum   of  five
     concentrations for each parameter  of  interest as  described  in Section 5.12.

           5.13.2  To each calibration standard,  add  a  known constant amount of
     one or more internal standards, and dilute to volume with hexane.

           5.13.3  Analyze each calibration standard according to Section 7.0.

     5.14  Surrogate standards - The analyst should monitor the performance of
the extraction,  cleanup  (when used), and analytical system and the effectiveness
of  the  method  in  dealing  with  each  sample  matrix  by  spiking each  sample,
standard,  and  organic-free  reagent water blank  with one  or two  herbicide
surrogates (e.g. herbicides that are not  expected to  be present in the sample).
The surrogates selected should elute over the range of the temperature program
used in this method.  2,4-Dichlorophenylacetic acid  (DCAA) is recommended as a
surrogate  compound.   Deuterated  analogs  of  analytes should  not  be  used as
surrogates for gas chromatographic analysis due to coelution problems.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See the  introductory material  to  this Chapter, Organic  Analytes,
Section 4.1.  Extracts must be stored  under refrigeration and analyzed within
40 days of extraction.


7.0  PROCEDURE

      7.1  Preparation of waste samples

            7.1.1 Extraction

                  7.1.1.1  Follow  Method  3580  except use  diethyl  ether as the
            dilution solvent,  acidified anhydrous sodium sulfate, and acidified
            glass wool.

                  7.1.1.2  Transfer 1.0 mL  (a  lesser volume or a dilution may
            be required if herbicide concentrations are high) to a 250 mL ground
            glass-stoppered  Erlenmeyer   flask.    Proceed  to  Section  7.2.2
            hydrolysis.

      7.2  Preparation of soil, sediment, and other  solid samples

            7.2.1 Extraction

                  7.2.1.1  To a 500 mL, wide mouth Erlenmeyer flask add 50 g (dry
            weight) of the well mixed, moist solid sample.  Adjust the pH to 2

                                   8150B  - 6                      Revision 2
                                                                  November 1990

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with  concentrated HC1  and monitor  the  pH for  15 minutes  with
occasional stirring.   If necessary, add  additional HC1 until the pH
remains at 2.

      7.2.1.2  Add 20 ml acetone to the flask and mix the contents
with the wrist shaker for  20 minutes.   Add  80  ml diethyl ether to
the same flask and shake again for 20 minutes.   Decant the extract
and measure the volume of solvent recovered.

      7.2.1.3  Extract the sample twice  more using 20 ml of acetone
followed by 80 ml  of diethyl ether. After addition of each solvent,
the mixture should be shaken with the  wrist shaker for 10 minutes
and the acetone-ether extract decanted.

      7.2.1.4  After the  third  extraction,   the  volume  of extract
recovered  should  be  at  least  75% of the  volume  of added solvent.
If this is  not the case,  additional  extractions  may be necessary.
Combine the extracts in a 2 liter separatory funnel containing 250 ml
of 5% acidified sodium  sulfate.   If  an  emulsion  forms,  slowly add
5 g of acidified  sodium  sulfate  (anhydrous)  until the solvent-water
mixture separates. A quantity of acidified  sodium sulfate equal to
the weight of the sample may be added,  if necessary.

      7.2.1.5  Check the pH of the extract.  If it is not  at or below
pH 2, add more concentrated HC1  until stabilized  at the desired pH.
Gently mix  the contents  of the  separatory funnel for 1 minute and
allow the layers  to separate.  Collect the aqueous phase  in a clean
beaker and the extract phase (top layer)  in  a 500 ml ground glass-
stoppered Erlenmeyer flask.  Place the aqueous phase back into the
separatory funnel  and re-extract using 25 ml  of diethyl  ether.  Allow
the layers to separate and discard the aqueous layer.  Combine the
ether extracts in the 500 ml Erlenmeyer flask.

7.2.2 Hydrolysis

      7.2.2.1  Add 30 ml of organic-free reagent  water,  5 ml of 37%
KOH, and one or two clean boiling chips to the flask.  Place a three
ball Snyder column on the  flask,  evaporate  the diethyl  ether on a
water bath, and continue to heat for a total of 90 minutes.

      7.2.2.2  Remove the  flask from the water  bath  and allow to
cool.  Transfer the water solution to a 125 mL separatory  funnel and
extract the basic  solutions once with  40  mL and then twice with 20 ml
of diethyl ether.  Allow sufficient time for the  layers to separate
and discard the ether layer each time.   The  phenoxy-acid herbicides
remain soluble in the aqueous phase as potassium salts.

7.2.3 Solvent cleanup

      7.2.3.1  Adjust the pH to  2 by adding  5 mL cold (4°C) sulfuric
acid (1:3) to the  separatory funnel.  Be  sure to check the pH at this
point.  Extract the herbicides  once with 40  mL  and twice with 20 mL
of diethyl ether.  Discard the aqueous phase.
                       8150B -  7                      Revision 2
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                  7.2.3.2  Combine ether extracts in a 125 ml Erlenmeyer flask
            containing 5-7 g  of acidified anhydrous sodium sulfate.  Stopper and
            allow the extract  to  remain in contact with  the acidified sodium
            sulfate.  If concentration and esterification are not to be performed
            immediately,  store the sample overnight in the refrigerator.

NOTE: The drying step is very critical to ensuring complete esterification.  Any
      moisture remaining in the ether will  result in low herbicide recoveries.
      The amount of  sodium  sulfate is adequate if some  free flowing crystals are
      visible when swirling the flask.   If  all the sodium  sulfate solidifies in
      a cake, add a few additional grams of acidified sodium sulfate and again
      test by  swirling.   The  2  hour drying time  is  a minimum,  however,  the
      extracts may be held overnight in contact with the sodium sulfate.

                  7.2.3.3  Transfer  the ether extract, through a funnel plugged
            with acid washed glass wool, into a 500 ml K-D flask equipped with
            a 10 ml concentrator tube.   Use a glass  rod  to  crush caked sodium
            sulfate during the transfer.  Rinse the Erlenmeyer flask and column
            with 20-30 ml of diethyl  ether to complete the quantitative transfer.

                  7.2.3.4  Add one or two clean boiling chips to the flask and
            attach  a  three ball  Snyder  column.   Prewet  the Snyder  column  by
            adding about  1  ml of diethyl  ether to the top.  Place the apparatus
            on  a  hot water  bath  (60°-65°C) so  that  the  concentrator  tube  is
            partially immersed  in the  hot  water and the  entire lower rounded
            surface  of  the  flask  is bathed  in  vapor.   Adjust the  vertical
            position of the  apparatus  and  the water  temperature,  as required,
            to complete  the concentration in 15-20 minutes.  At the proper rate
            of distillation the balls of the column will  actively chatter,  but
            the chambers will  not flood.  When the apparent volume  of liquid
            reaches 1 ml,  remove the  K-D apparatus from the water bath and allow
            it to drain  and cool for at least 10 minutes.

                  7.2.3.5  Remove  the Snyder column and rinse the flask and its
            lower joints into the concentrator tube with 1-2 ml of diethyl ether.
            A 5  ml  syringe  is  recommended for this  operation.   Add  a fresh
            boiling chip,  attach a micro Snyder column  to the concentrator tube,
            and prewet the column by adding 0.5  ml of  ethyl  ether  to the top.
            Place the micro  K-D  apparatus  on  the  water  bath  so  that  the
            concentrator tube is partially immersed in the  hot  water.   Adjust
            the vertical  position  of the  apparatus and the water temperature as
            required  to  complete concentration  in  5-10 minutes.   When  the
            apparent volume of the liquid reaches 0.5 ml, remove the micro K-D
            from the  bath  and  allow it to  drain and cool.   Remove  the Snyder
            column  and  add  0.1  ml of  methanol.   Rinse  the  walls   of  the
            concentrator tube while  adjusting the extract  volume to 1.0 ml with
            diethyl  ether.   Proceed  to Section 7.4 for esterification.

      7.3  Preparation of aqueous  samples

            7.3.1 Extraction

                  7.3.1.1  Using a 1 liter  graduated cylinder,  measure 1 liter
            (nominal) of sample, record the sample volume to the nearest 5 mL,

                                  8150B  -  8                       Revision 2
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and transfer  it  to the separatory funnel.  If  high concentrations
are anticipated,  a smaller volume  may be used and then diluted with
organic-free reagent water to 1 liter.   Adjust the pH to less than
2 with sulfuric acid (1:1).

      7.3.1.2  Add 150 ml  of diethyl  ether to  the sample bottle,
seal, and shake  for  30 seconds to rinse the walls.   Transfer the
solvent wash  to  the separatory funnel  and extract  the  sample by
shaking the funnel for 2  minutes  with  periodic venting to release
excess pressure.   Allow the organic layer to separate  from the water
layer for a minimum of 10 minutes.  If the emulsion interface between
layers is more than  one  third the size of  the  solvent layer, the
analyst must  employ mechanical techniques  to complete  the  phase
separation.   The optimum technique depends upon the sample and may
include stirring,  filtration of the emulsion  through  glass  wool,
centrifugation, or other  physical  methods.   Drain the aqueous phase
into a 1 liter Erlenmeyer flask.  Collect the solvent extract in a
250 mL ground  glass  Erlenmeyer flask containing 2 ml  of 37% KOH.
Approximately 80 ml  of the diethyl  ether  will  remain dissolved in
the aqueous phase.

      7.3.1.3  Repeat the extraction two more times using 50 mL of
diethyl ether  each  time.   Combine the extracts  in the Erlenmeyer
flask.   (Rinse the 1 liter  flask with each additional  aliquot of
extracting solvent.)

7.3.2 Hydrolysis

      7.3.2.1  Add one  or two  clean  boiling  chips  and 15  mL of
organic-free reagent water to  the 250  mL  flask and attach a three
ball Snyder column.  Prewet the Snyder column by adding about 1 mL
of diethyl ether to the top of the column.  Place the apparatus on
a hot water  bath  (60°-65°C)  so that the bottom of the flask is bathed
with hot water vapor.  Although the diethyl  ether will evaporate in
about  15  minutes,  continue  heating for  a  total  of  60  minutes,
beginning from  the time  the flask  is  placed  in  the  water  bath.
Remove the apparatus and  let  stand at room temperature for at least
10 minutes.

      7.3.2.2  Transfer the  solution to a  60 mL separatory funnel
using 5-10 mL of organic-free reagent water.  Wash the  basic solution
twice by shaking  for 1  minute with 20 mL portions of diethyl ether.
Discard the organic  phase.   The herbicides  remain in  the aqueous
phase.

7.3.3 Solvent cleanup

      7.3.3.1  Acidify the contents of the separatory funnel to pH 2
by  adding 2 mL of cold  (4°C)  sulfuric acid (1:3).  Test  with pH
indicator paper.   Add 20 mL diethyl  ether and shake vigorously for
2 minutes.  Drain the aqueous layer  into a 250 mL Erlenmeyer flask,
and pour the organic  layer into a 125 mL Erlenmeyer  flask containing
about 5-7 g of acidified sodium  sulfate.  Repeat the  extraction twice
more with 10 mL aliquots  of diethyl ether, combining  all solvent in

                       8150B  -  9                      Revision 2
                                                      November 1990

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            the 125 ml flask.  Allow the extract to remain in contact with the
            sodium sulfate for approximately 2 hours.

NOTE: The drying step is very critical to ensuring  complete esterification.  Any
      moisture remaining in the ether will result in low herbicide recoveries.
      The amount of sodium  sulfate is adequate if some free flowing crystals are
      visible when swirling the flask.   If all the sodium sulfate solidifies in
      a cake, add a few additional  grams of acidified sodium sulfate and again
      test by  swirling.    The  2  hour drying  time  is a minimum,  however,  the
      extracts may be held overnight in contact with the sodium sulfate.

                  7.3.3.2  Transfer the ether extract, through a funnel plugged
            with acid washed glass wool, into a 500 mL K-D flask equipped with
            a 10 ml concentrator tube.   Use  a glass  rod to  crush  caked sodium
            sulfate during the transfer.   Rinse the Erlenmeyer flask and column
            with 20-30 ml of diethyl  ether to complete the quantitative transfer.

                  7.3.3.3  Add one or two clean boiling chips to the flask and
            attach a  three ball  Snyder  column.   Prewet the Snyder  column by
            adding about 1  ml of diethyl  ether to the top.  Place the apparatus
            on  a  hot water bath  (60°-65°C)   so  that  the concentrator  tube is
            partially immersed  in the  hot water and the entire  lower rounded
            surface  of  the flask  is bathed  in  vapor.   Adjust  the  vertical
            position of the apparatus  and the water  temperature,  as required,
            to complete the concentration in  15-20 minutes.  At the proper rate
            of distillation the balls of the column will actively chatter, but
            the chambers will  not  flood.  When the  apparent volume  of liquid
            reaches 1 ml,  remove  the  K-D apparatus from the water bath and allow
            it to drain and cool for at least 10 minutes.

                  7.3.3.4  Remove the Snyder  column  and  rinse the flask and its
            lower joints into the concentrator tube with  1-2 ml of diethyl ether.
            A 5  mL syringe is  recommended  for this  operation.   Add  a fresh
            boiling chip,  attach  a micro Snyder column to the concentrator tube,
            and prewet the column by adding  0.5 ml  of  ethyl  ether to the top.
            Place  the micro  K-D apparatus  on  the water  bath  so that  the
            concentrator tube  is partially immersed  in  the  hot  water.   Adjust
            the vertical position of the  apparatus and the water temperature as
            required  to complete concentration  in  5-10 minutes.   When  the
            apparent volume of the liquid reaches 0.5 mL, remove the micro K-D
            from the  bath  and  allow it to drain and cool.   Remove the Snyder
            column  and  add  0.1  mL of  methanol.   Rinse  the walls   of  the
            concentrator tube while  adjusting the extract volume to 1.0 mL with
            diethyl ether.

      7.4  Esterification

            7.4.1  Two methods may be used for the generation of diazomethane:
      the bubbler method (set up shown  in Figure 1) and  the Diazald kit method.
      The bubbler  method   is suggested  when  small  batches  (10-15)  of samples
      require esterification.  The bubbler method works well with samples that
      have low concentrations of herbicides  (e.g. aqueous samples) and is safer
      to use than the Diazald kit procedure.  The Diazald kit method  is good for
      large quantities of samples needing esterification. The Diazald kit method

                                  8150B - 10                      Revision 2
                                                                  November  1990

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      is more effective than the  bubbler  method  for  soils or samples that may
      contain high concentrations  of herbicides (e.g.  samples such as soils that
      may result  in  yellow extracts  following hydrolysis may  be  difficult to
      handle by the bubbler method).  The diazomethane derivatization (U.S. EPA,
      1971) procedures, described  below, will  react efficiently with all of the
      chlorinated  herbicides described  in  this method  and should  be used only
      by experienced analysts,  due to  the  potential hazards associated with its
      use.  The following precautions should be taken:

CAUTION:   Diazomethane  is  a  carcinogen  and   can  explode   under  certain
           conditions.

           Use a safety screen.
           Use mechanical pipetting aides.
           Do not  heat above 90°C  --  EXPLOSION may result.
           Avoid grinding surfaces, ground glass joints, sleeve bearings, glass
           stirrers --    EXPLOSION may result.
           Store away from alkali  metals -- EXPLOSION may result.
           Solutions of diazomethane decompose rapidly  in  the presence of solid
           materials such as copper powder, calcium chloride,  and boiling chips.

            7.4.2  Diazald kit method  -  Instructions  for preparing diazomethane
      are provided with the generator kit.

                   7.4.2.1  Add 2 mL of diazomethane solution and let sample stand
            for 10 minutes with occasional swirling.

                   7.4.2.2  Rinse  inside wall of ampule with several  hundred pi
            of diethyl ether.   Allow solvent to evaporate  spontaneously at room
            temperature to about  2 mL.

                   7.4.2.3  Dissolve the residue in 5 mL of hexane.   Analyze by
            gas chromatography.

            7.4.3  Bubbler method -  Assemble the  diazomethane bubbler  (see
     Figure 1).

                   7.4.3.1  Add  5  mL of  diethyl  ether to  the first  test tube.
            Add 1 mL of diethyl ether, 1 mL of carbitol, 1.5 mL of 37% KOH, and
            0.1-0.2 g Diazald  to  the  second test  tube.   Immediately place the
            exit tube into the  concentrator tube containing the  sample extract.

                  Apply nitrogen flow  (10 mL/min) to bubble diazomethane through
            the extract for 10  minutes or until the yellow  color of diazomethane
            persists.     The   amount   of  Diazald   used   is  sufficient  for
            esterification of approximately three sample extracts. An additional
            0.1-0.2 g  of Diazald   may be  added  (after the  initial  Diazald is
            consumed) to extend the generation  of the  diazomethane.   There is
            sufficient KOH present in the original solution to perform a maximum
            of approximately 20 minutes of total esterification.
                                  8150B - 11                      Revision 2
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                  7.4.3.2  Remove  the  concentrator  tube  and  seal  it  with  a
            Neoprene or Teflon stopper.  Store at room temperature in a hood for
            20 minutes.

                  7.4.3.3  Destroy any unreacted diazomethane by adding 0.1-0.2 g
            silicic acid  to  the concentrator tube.  Allow to  stand  until  the
            evolution of nitrogen gas has  stopped.  Adjust the  sample volume to
            10.0  mL  with  hexane.    Stopper  the concentrator  tube and store
            refrigerated if further processing will not be performed immediately.
            It  is  recommended  that  the  methylated  extracts  be  analyzed
            immediately to minimize the trans-esterification and other potential
            reactions that may occur.  Analyze by gas chromatography.
      7.5  Gas chromatographic conditions (Recommended)
            7.5.1 Column la
      Carrier gas (5% methane/95% argon) flow rate:
      Temperature program: 185°C,  isothermal.
                        70 mL/min
           7.5.2  Column Ib
      Carrier gas (5% methane/95% argon) flow rate:   70 mL/min
      Initial temperature: 140°C,  hold for 6 minutes
      Temperature program: 140°C to 200°C  at  10°C/min, hold until last compound
                           has eluted.
           7.5.3  Column 2
      Carrier gas (5% methane/95% argon) flow rate:
      Temperature program: 185°C,  isothermal.
                        70 mL/min
           7.5.4  Column 3
      Carrier gas (ultra-high purity N2)  flow rate:    25 mL/min
      Initial temperature: 100°C,  no hold
      Temperature program: 100°C to 150°C  at  10°C/min, hold until last compound
                           has eluted.

      7.6  Calibration - Refer to Method 8000 for proper calibration techniques.
Use Table 1  and especially Table  2 for guidance on  selecting the lowest point
on the calibration curve.

            7.6.1  The  procedure  for internal or external  calibration  may be
      used.   Refer to  Method 8000 for a description of each of these procedures.

            7.6.2  The following gas  chromatographic columns are recommended for
      the compounds indicated:
            Analvte

            Dicamba
            2,4-D
            2,4,5-TP
            2,4,5-T
            2,4-DB
Column

 la,2
 la,2
 la,2
 la,2
 la
Analvte

Dalapon
MCPP
MCPA
Dichloroprop
Dinoseb
Column

   3
   Ib
   Ib
   Ib
   Ib
                                  8150B - 12
                                    Revision 2
                                    November 1990

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      7.7  Gas chromatographic analysis

            7.7.1  Refer to Method 8000.  If the internal  standard calibration
      technique is used, add 10 p.1 of internal standard to the sample prior to
      injection.

            7.7.2  Method 8000 provides instructions on the analysis sequence,
      appropriate dilutions,  establishing daily  retention time  windows,  and
      identification criteria.  Include a mid-concentration check standard after
      each group of 10 samples in the analysis sequence.

            7.7.3  Examples of chromatograms for various chlorophenoxy herbicides
      are shown in Figures 2 through 4.

            7.7.4  Record the  sample volume  injected  and the resulting  peak
      sizes (in area units or peak heights).

            7.7.5  Using either the internal  or external calibration procedure
      (Method 8000), determine the identity and quantity of each component peak
      in the  sample  chromatogram which corresponds to the compounds  used for
      calibration purposes.

            7.7.6  If calibration standards have been analyzed in the same manner
      as the samples (e.g. have undergone hydrolysis and esterification),  then
      the calculation  of concentration given  in  Method 8000  should  be  used.
      However,  if calibration  is done using standards made  from  methyl  ester
      compounds (compounds not esterified by application of this  method),  then
      the  calculation of  concentration  must include  a  correction  for  the
      molecular weight of the methyl ester versus the acid herbicide.

            7.7.7  If peak  detection  and identification  are  prevented  due to
      interferences,  further  cleanup is  required.   Before  using  any cleanup
      procedure, the  analyst  must process a  series of standards  through the
      procedure to validate elution  patterns  and  the  absence of  interferences
      from reagents.


8.0  QUALITY CONTROL

      8.1  Refer to  Chapter One for specific quality control procedures.  Quality
control  to  validate sample extraction  is covered  in  Method 3500 and  in the
extraction method utilized.   If extract  cleanup was  performed, follow the QC in
Method 3600 and in the specific cleanup method.

      8.2  Procedures to check the GC system operation are  found in Method 8000.

            8.2.1  Select a representative spike concentration for each compound
      (acid or ester) to be  measured.  Using stock standards, prepare a quality
      control check sample concentrate in  acetone 1,000 times more concentrated
      than the selected concentrations.
                                  8150B - 13                      Revision 2
                                                                  November 1990

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            8.2.2  Table 3 indicates Single Operator Accuracy and Precision for
      this method.   Compare  the  results obtained with  the results  given  in
      Table 3 to determine if the data quality is acceptable.

      8.3  Calculate surrogate  standard  recovery on all  samples,  blanks,  and
spikes.   Determine if  the  recovery is  within  limits (limits  established  by
performing QC procedures outlined in Method 8000).

            8.3.1  If recovery  is not within  limits,  the following procedures
      are required.

                  8.3.1.1  Check to  be  sure  that there  are no errors  in  the
           calculations, surrogate solutions  or internal  standards.  If errors
           are found,  recalculate the data accordingly.

                  8.3.1.2  Check  instrument  performance.   If an  instrument
           performance problem is identified,  correct the  problem and re-analyze
           the extract.

                  8.3.1.3  If no problem  is found, re-extract and re-analyze the
           sample.

                  8.3.1.4  If, upon re-analysis, the recovery is again not within
           limits, flag the data as "estimated concentration".

      8.4  GC/MS confirmation

            8.4.1  GC/MS techniques should be judiciously employed to support
      qualitative identifications made with this method.   Refer to Method 8270
      for the appropriate GC/MS operating conditions and analysis procedures.

            8.4.2  When  available,  chemical   ionization  mass  spectra may  be
      employed to aid the qualitative identification process.

            8.4.3  Should  these MS  procedures  fail  to   provide  satisfactory
      results, additional steps may be taken before reanalysis.   These steps may
      include the use  of alternate packed or capillary GC columns or additional
      cleanup.


9.0  METHOD PERFORMANCE

      9.1  In a single laboratory,  using organic-free reagent water and effluents
from publicly owned treatment works  (POTW), the average recoveries presented in
Table 3 were  obtained.   The standard deviations of the  percent recoveries  of
these measurements are also included in Table 3.
10.0  REFERENCES

1.   U.S. EPA,  National Pollutant Discharge Elimination System, Appendix A, Fed.
     Reg., 38, No. 75, Pt.  II,  Method  for Chlorinated Phenoxy Acid Herbicides
     in Industrial Effluents, Cincinnati, Ohio, 1971.


                                  8150B - 14                      Revision 2
                                                                  November 1990

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2.   Goerlitz, D.G., and W.L. Lamar, "Determination of Phenoxy Acid Herbicides
     in Water by Electron Capture and Microcoulometric Gas Chromatography," U.S.
     Geol.  Survey Water Supply Paper, 1817-C, 1967.

3.   Burke,  J.A.,  "Gas Chromatography  for  Pesticide Residue Analysis;   Some
     Practical Aspects,"   Journal  of  the Association of  Official  Analytical
     Chemists, 48, 1037, 1965.

4.   U.S. EPA, "Extraction and Cleanup Procedure for the Determination of Phenoxy
     Acid Herbicides  in  Sediment," EPA Toxicant and  Analysis  Center,  Bay St.
     Louis, Mississippi, 1972.

5.   "Pesticide Methods Evaluation," Letter Report  #33 for  EPA Contract No. 68-
     03-2697. Available from U.S. Environmental Protection Agency, Environmental
     Monitoring and Support Laboratory, Cincinnati, Ohio 45268.

6.   Eichelberger, J.W.,  L.E.  Harris,  and W.L.  Budde,  "Reference  Compound to
     Calibrate   Ion   Abundance   Measurement   in    Gas   Chromatography-Mass
     Spectrometry," Analytical Chemistry, 47, 995,  1975.

7.   Glaser, J.A. et.al., "Trace Analysis for Wastewaters," Environmental Science
     & Technology, 15, 1426, 1981.

8.   U.S.  EPA,  "Method  615.  The  Determination  of Chlorinated  Herbicides  in
     Industrial and Municipal  Wastewater," Environmental  Monitoring  and Support
     Laboratory, Cincinnati, Ohio, 45268, June 1982.
                                  8150B - 15                      Revision 2
                                                                  November  1990

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                                   TABLE 1.
                CHROMATOGRAPHIC CONDITIONS  AND DETECTION LIMITS
                           FOR CHLORINATED  HERBICIDES
Compound
     Retention time (min)a

Col.la   Col.lb  Col.2   Col.3
                                   TABLE 2.
                    DETERMINATION OF  ESTIMATED QUANTITATION
                       LIMITS  (EQL) FOR VARIOUS MATRICES3
  Method
 detection
limit (M9/L)
2,4-D
2,4-DB
2,4,5-T
2,4,5-TP (Silvex)
Dalapon
Dicamba
Dichloroprop
Dinoseb
MCPA
MCPP
2.0
4.1
3.4
2.7
-
1.2
-
-
-
-
.
-
-
-
-
-
4.8
11.2
4.1
3.4
1.6
-
2.4
2.0
5.0
1.0
-
-
-
- -
1.2
0.91
0.20
0.17
5.8
0.27
0.65
0.07
249
192
    Matrix
                                Factor15
Ground water (based on one liter sample size)
Soil/sediment and other solids
Waste samples
                                   10
                                  200
                              100,000
"Sample EQLs are highly matrix dependent.  The EQLs listed herein are provided for
guidance and may not always be achievable.

bEQL = [Method detection limit (Table 1)]  X  [Factor  (Table 2)]. For non-aqueous
samples, the factor is  on a wet weight basis.
                                  8150B  -  16
                                    Revision 2
                                    November 1990

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                                   TABLE 3.
                    SINGLE OPERATOR ACCURACY AND PRECISION8
Compound
2,4-D


Dalapon


2,4-DB


Dicamba


Dichlorprop


Dinoseb

MCPA


MCPP


2,4,5-T


2,4,5-TP


Sample
Type
DW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
DW
MW
MW
Spike
(M9/L)
10.9
10.1
200
23.4
23.4
468
10.3
10.4
208
1.2
1.1
22.2
10.7
10.7
213
0.5
102
2020
2020
21400
2080
2100
20440
1.1
1.3
25.5
1.0
1.3
25.0
Mean
Recovery
(%)
75
77
65
66
96
81
93
93
77
79
86
82
97
72
100
86
81
98
73
97
94
97
95
85
83
78
88
88
72
Standard
deviation
(%)
4
4
5
8
13
9
3
3
6
7
9
6
2
3
2
4
3
4
3
2
4
3
2
6
4
5
5
4
5
"All  results  based upon seven replicate analyses. Esterification performed using
the bubbler method. Data obtained from reference 9.

DW = ASTM Type II
MW = Municipal water
                                  8150B  -  17
Revision 2
November 1990

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                                 FIGURE 1.
                           DIAZOMETHANE GENERATOR
                                                                  glass tubing
    nitrogen
rubber  stopper
                     lube 1
tube 2
                                 8150B - 18
                     Revision  2
                     November 1990

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                         FIGURE 2.
       GAS  CHROMATOGRAM  OF CHLORINATED HERBICIDES
Column: 1.5% SP-2250/1.95* SP-2401 en Suptlcoport (100/120
Ttmpcriturt: Isothermal at 18S°C
Oflttetor: Electron Capture
          0     12346
            RETENTION TIME (MINUTES)
                         8150B  -  19
Revision  2
November 1990

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                  FIGURE  3.
GAS CHROMATOGRAM OF CHLORINATED HERBICIDES
 Column: 1.5% SP-2250/1.95% SP-2401 on Suptlcoport (100/120 Mttfi)
 Program: 140°C for 6 Min. 10°C/Minut§ to 200°C
 Octtctor: ElKtron Capturt
        4           68
        RETENTION TIME (MINUTES)
10
12
                  8150B  -  20
            Revision 2
            November 1990

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               FIGURE 4.
GAS CHROMATOGRAM OF DALAPON,  COLUMN 3

                Column: 0.1% SP-1000 on 80/100 Mtsh Cartaopak C
                Program: 100°C, 10°C/Min to 160°C
                Ofttetor: Electron Coptura
         0246
      RETENTION TIME (MINUTES)
               8150B - 21
Revision  2
November 1990

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                                    METHOD  8150B
                              CHLORINATED  HERBICIDES
    7.2.1.1
 Adjust sample
 pH with HC1.
               Liquid
               sample
7.2.1.2 Extract
 sample three
  times with
  acetone and
diethyl ether.
    7.2.1.4
    Combine
   extracts.
 7.2.1.5 Check
pH of extract ,
   adjust if
  necessary,
Separate layers
   7.2.1.5
 Re-extract
 and discard
   aqueous
   phase.
  7.1.1.1 Follow
  Method 3580  for
 extraction, using
  diethyl ether,
acidified anhydrous
sodium sulfate and
  acidified glass
       wool .
7.2.2 Proceed
    with
 hydrolysis.
    7.1.1.2  Use
     1.0 mL  of
    sample for
    hydrolysis .
7.2.3 Proceed
with solvent
  cleanup.
                            7.3.1 Extract
                             three times
                            with diethyl
                               ether.
   7.3.1.3
   Combine
  extracts.
7.3.2  Proceed
    with
 hydrolysis .
                             7.3.3 Proceed
                             with solvent
                              cleanup.
                                     8150B -  22
                                                    Revision 2
                                                    November 1990

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                                    METHOD 8150B
                                     (Continued)
7.4.3 Assembe
diazomethane
  bubbler;
  generate
diazomethane
7.42 Prepare
diazomethane
according  to
     kit
instructions .
                            7.5 Set
                        chromatographic
                          condi t i ons.
                          7.6 Claibrate
                          according to
                          Method 8000.
                          7.6.2 Choose
                          appropriate
                          CC column.
 7.7 Analyze
by CC (refer
  to MEthod
   8000) .
  7.7.7 Do
interferences
prevent peak
 detection?
 7.7.7  Process
   series  of
   standards
through system
   cleanup.
                                      8150B  - 23
                         Revision 2
                         November  1990

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                                  METHOD  8151

   CHLORINATED HERBICIDES BY GC USING METHYLATION OR PENTAFLUOROBENZYLATION
                  DERIVATIZATION; CAPILLARY COLUMN TECHNIQUE
1.0  SCOPE AND APPLICATION

      1.1  Method  8151  Is  a capillary  gas chromatographic  (GC) method  for
determining  certain  chlorinated acid  herbicides in  aqueous,  soil  and  waste
matrices.   Specifically,  Method 8151 may  be used to determine  the  following
compounds:
     Compound Name                  CAS No."


     Acifluorfen                    50594-66-6
     Bentazon                       25057-89-0
     Chloramben                       133-90-4
     2,4-D                             94-75-7
     Dalapon                           75-99-0
     2,4-DB                            94-82-6
     DCPA diacid"                    2136-79-0
     Dicamba                         1918-00-9
     3,5-Dichlorobenzoic acid          51-36-5
     Dichlorprop                      120-36-5
     Dinoseb                           88-85-7
     5-Hydroxydicamba                7600-50-2
     MCPA                              94-74-6
     MCPP                              93-65-2
     4-Nitrophenol                    100-02-1
     Pentachlorophenol                 87-86-5
     Picloram                        1918-02-1
     2,4,5-TP (Silvex)                 93-72-1
     2,4,5-T                           93-76-5


     a  Chemical Abstract Services Registry Number.

     b  DCPA monoacid  and diacid  metabolites  included in method  scope;  DCPA
        diacid metabolite used for validation studies.  DCPA is a dimethyl ester.

     Because these compounds are  produced and used in various  forms  (i.e., acid,
salt,  ester,  etc.),  Method 8151  includes  a hydrolysis  step to  convert  the
herbicide to the acid form prior to analysis.

      1.2  When  Method  8151 is  used  to analyze  unfamiliar  samples,  compound
identifications  should  be  supported  by at  least one  additional  qualitative
technique.   Section 8.4 provides  gas  chromatograph/mass  spectrometer (GC/MS)
criteria   appropriate   for   the  qualitative    confirmation   of   compound
identifications.
                                   8151 - 1                      Revision 0
                                                                 November 1990

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      1.3  The estimated detection limits for each of the compounds in aqueous
and soil matrices are  listed  in  Table  1.   The detection limits for a specific
waste sample  may differ from those  listed,  depending upon the  nature  of the
interferences and the sample matrix.

      1.4  This method  is  restricted  to  use by  or  under the  supervision  of
analysts  experienced  in the  use  of  gas  chromatographs and  skilled  in  the
interpretation of gas  chromatograms.  Each  analyst must demonstrate the ability
to generate acceptable results with this method.

      1.5  Only experienced analysts should be allowed to work with diazomethane
due to the potential hazards associated with  its use (explosive, carcinogenic).
2.0  SUMMARY OF METHOD

      2.1  Method 8151 provides hydrolysis, extraction,  derivatization and gas
chromatographic conditions for the  analysis  of  chlorinated  acid herbicides in
water, soil and waste samples.

            2.1.1  Water samples  are hydrolyzed  in situ, extracted with diethyl
      ether and then  esterified  with either  diazomethane  or pentafluorobenzyl
      bromide.  The  derivatives  are determined by gas  chromatography with an
      electron capture  detector  (GC/ECD).   The results are reported  as acid
      equivalents.

            2.1.2  Soil   and  waste  samples  are extracted,  then  hydrolyzed,
      reextracted and esterified with either diazomethane  or pentafluorobenzyl
      bromide.  The  derivatives  are determined by gas  chromatography with an
      electron capture  detector  (GC/ECD).   The results are reported  as acid
      equivalents.

      2.2  The sensitivity of Method 8151  depends on the level of interferences
in addition to instrumental  limitations.   Table 1 lists the GC/ECD  and GC/MS
limits of detection  that  can be  obtained in aqueous and soil  matrices in the
absence of interferences.  Detection  limits  for a  typical waste sample should
be higher.


3.0  INTERFERENCES

      3.1  Refer  to Method 8000.

      3.2  Method  interferences  may  be  caused  by  contaminants  in  solvents,
reagents, glassware,  and other sample processing hardware that lead to discrete
artifacts or elevated baselines in gas chromatograms.  All  these materials must
be routinely demonstrated to  be free from  interferences under the conditions of
the analysis, by analyzing reagent blanks.

            3.2.1  Glassware  must be scrupulously cleaned.  Clean each piece of
      glassware as soon  as possible after use  by  rinsing it with  the last solvent
      used in it.  This should be followed by detergent washing with  hot water
      and rinses with  tap water, then with organic-free reagent water.  Glassware

                                   8151 - 2                      Revision 0
                                                                 November 1990

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      should be solvent-rinsed with acetone and pesticide-quality hexane.  After
      rinsing  and  drying,  glassware  should  be sealed  and  stored in  a  clean
      environment to  prevent  any accumulation of dust  or  other contaminants.
      Store glassware inverted or capped with  aluminum foil.  Immediately prior
      to use, glassware should be rinsed with the next solvent to be used.

            3.2.2  The use of high purity reagents and solvents helps to minimize
      interference problems.  Purification of solvents by distillation in all-
      glass systems may be required.

      3.3  Matrix  interferences  may  be  caused  by  contaminants  that  are
coextracted  from  the sample.   The extent of matrix interferences  will  vary
considerably from waste  to  waste, depending upon the nature and  diversity of
the waste being sampled.

      3.4  Organic acids, especially  chlorinated acids,  cause  the most direct
interference  with  the  determination by  methyl ation.    Phenols,  including
chlorophenols, may also interfere with this procedure.  The determination using
pentafluorobenzylation is more sensitive,  and more prone to interferences from
the presence of organic acids or phenols than by methylation.

      3.5  Alkaline hydrolysis and subsequent extraction of the basic solution
removes many chlorinated hydrocarbons  and phthalate esters that might otherwise
interfere with the electron capture analysis.

      3.6  The  herbicides,  being  strong  organic  acids,  react  readily  with
alkaline substances and may  be  lost  during analysis.  Therefore, glassware must
be acid-rinsed and then rinsed to constant pH with organic-free reagent water.


4.0  APPARATUS AND MATERIALS

      4.1  Gas chromatograph

            4.1.1  Gas  chromatograph  - Analytical  system  complete with  gas
      chromatograph suitable for  Grob-type  injection  using  capillary columns,
      and  all  required  accessories  including detector, capillary  analytical
      columns, recorder, gases, and syringes. A data system for measuring peak
      heights and/or peak areas is recommended.

            4.1.2  Columns

                  4.1.2.1 Narrow Bore Columns

                        4.1.2.1.1  Primary  Column  1  -   30  m  x  0.25  mm,  5%
                  phenyl/95%  methyl   silicone  (DB-5,   J&W  Scientific,   or
                  equivalent), 0.25 urn film thickness.

                        4.1.2.1.2  Primary Column  la  (GC/MS)  -  30 m x 0.32 mm,
                  5%  phenyl/95% methyl  silicone,  (DB-5,  J&W  Scientific,  or
                  equivalent), 1 jum film thickness.
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                        4.1.2.1.3  Column  2   -  30  m x  0.25  mm  DB-608  (J&W
                  Scientific or equivalent) with a 25 ;um film  thickness.

                        4.1.2.1.4  Confirmation Column - 30 m x  0.25 mm, 14%
                  cyanopropyl  phenyl  silicone,  (DB-1701,  J&W  Scientific, or
                  equivalent), 0.25 pm  film thickness.

                  4.1.2.2  Megabore Columns

                        4.1.2.2.1  Primary Column - 30 m x  0.53 mm DB-608  (J&W
                  Scientific or equivalent) with 0.83 /xm film  thickness.

                        4.1.2.2.2  Confirmation Column - 30 m x  0.53 mm, 14%
                  cyanopropyl  phenyl  silicone,  (DB-1701,  J&W  Scientific, or
                  equivalent), 1.0 /*m film thickness.

            4.1.3  Detector - Electron Capture Detector (BCD)

      4.2  Kuderna-Danish (K-D) apparatus

            4.2.1  Concentrator tube -  10 ml graduated (Kontes K-570050-1025 or
      equivalent).   A ground glass stopper is used  to  prevent evaporation of
      extracts.

            4.2.2  Evaporation  flask   -  500  ml   (Kontes   K-570001-500  or
      equivalent).    Attach  to  concentrator   tube  with springs, clamps,  or
      equivalent.

            4.2.3  Snyder column  -  Three ball macro  (Kontes K-503000-0121 or
      equivalent).

            4.2.4  Snyder column  - Two ball   micro  (Kontes K-569001-0219 or
      equivalent).

            4.2.5  Springs - 1/2 inch (Kontes  K-662750 or equivalent).

      4.3  Diazomethane Generator:   Refer to  Section  7.5  to  determine which
method of diazomethane generation should be used for a particular generation.

            4.3.1  Diazald Kit -  Recommended for the generation of diazomethane
      (Aldrich Chemical Co., Cat No. 210,025-0, or equivalent).

            4.3.2  Assemble from two 20 mm x  150 mm test  tubes,  two Neoprene
      rubber stoppers, and a source of nitrogen.   Use Neoprene rubber stoppers
      with holes drilled in them to accommodate glass delivery tubes.  The exit
      tube must be drawn  to  a  point  to  bubble diazomethane through the sample
      extract.  The generator assembly  is shown in Figure 1.  The procedure for
      use of this type of generator is given in Section 7.5.1.1.

      4.4  Other Glassware

            4.4.1  Beaker - 400 ml, thick walled.
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            4.4.2  Funnel  -  75 mm diameter.
            4.4.3  Separatory funnel  -  500 ml,  with  Teflon  stopcock.
            4.4.4  Centrifuge bottle  -  500 ml (Pyrex 1260 or  equivalent).
            4.4.5  Centrifuge bottle  -  24/40 500 ml
            4.4.6  Continuous Extractor  (Hershberg-Wolfe type,  Lab Glass  No.
      LG-6915, or equivalent)
            4.4.7  Pipet - Pasteur, glass, disposable (140  mm x  5  mm  ID).
            4.4.8  Vials -  10 ml, glass, with  Teflon lined screw-caps.
            4.4.9  Volumetric flasks,  Class  A - 10 ml to 1000 ml.
      4.5  Filter paper -  15 cm diameter (Whatman No. 1  or  equivalent).
      4.6  Glass Wool - Pyrex, acid washed.
      4.7  Boiling    chips    -    Solvent     extracted     with    methylene
chloride,approximately 10/40 mesh (silicon carbide or equivalent).
      4.8  Water  bath  -  Heated, with   concentric  ring  cover,   capable  of
temperature control  (± 2°C).   The bath  should be used in a  hood.
      4.9  Balance - Analytical,  capable of accurately weighing  to the nearest
0.0001 g.
      4.10  Centrifuge.
      4.11  Ultrasonic preparation - A horn-type device equipped with a titanium
tip, or a device that will give equivalent performance,  shall be used.
            4.11.1  Ultrasonic Disrupter  -  The disrupter  must have  a minimum
      power wattage  of 300 watts, with  pulsing capability.   A device designed
      to reduce the cavitation sound  is recommended.  Follow  the manufacturers
      instructions for preparing the  disrupter for extraction of samples.   Use
      a 3/4" horn for most samples.
      4.12  Sonabox - Recommended with above disrupters for decreasing cavitation
sound (Heat Systems  - Ultrasonics, Inc., Model  432B or equivalent).
      4.13  Filter paper - Whatman #1,  or equivalent.
      4.14  pH paper.

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
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such specifications are available. Other grades may be used, provided it is  first
ascertained that the  reagent  is  of  sufficiently high purity to permit  its  use
without lessening the  accuracy of the determination.

      5.2  Organic-free reagent water.  All references to water in this method
refer to organic-free  water, as defined in Chapter One.

      5.3  Sodium  hydroxide solution  (0.1  N),  NaOH.   Dissolve  4 g  NaOH  in
organic-free reagent water  and dilute to 1.0 L.

      5.4  Potassium  hydroxide  solution  (37%  aqueous  solution  (w/v)),  KOH.
Dissolve 37  g potassium  hydroxide  pellets in  organic-free  reagent  water  and
dilute to 100 ml.

      5.5  Phosphate buffer pH = 2.5  (0.1  M).   Dissolve 12 g sodium phosphate
(NaH2P04) in  organic-free reagent water and  dilute to 1.0  L.   Add phosphoric
acid to adjust the pH  to  2.5.

      5.6  Carbitol (diethylene glycol monoethyl ether), C2H5OCH2CH2OCH2CH2OH.

      5.7  N-methyl-N-nitroso-p-toluenesulfonamide     (Diazald).        High
purity,available from  Aldrich Chemical Co. or equivalent.

      5.8  Silicic acid,  H2Si05.  100 mesh powder,  store at  130°C.

      5.9  Potassium carbonate, K2C03.

      5.10  2,3,4,5,6-Pentafluorobenzyl bromide (PFBBr),  C6F5CH2Br.   Pesticide
quality or equivalent.

      5.11  Sodium sulfate  (granular,  acidified, anhydrous),  Na2S04.  Purify  by
heating at 400°C for  4 hours  in  a shallow tray,  or  by precleaning the sodium
sulfate with  methylene chloride.   If the  sodium sulfate  is  precleaned with
methylene chloride, a  method  blank  must  be analyzed, demonstrating that  there
is no interference from the sodium sulfate.  Acidify by slurrying 100 g sodium
sulfate with enough diethyl ether to  just  cover the solid; then add 0.1  mL  of
concentrated sulfuric  acid  and mix thoroughly.   Remove the ether under  vacuum.
Mix  1  g of the  resulting solid with  5  ml of  organic-free  reagent  water  and
measure the pH of the  mixture.  It must be below  a pH of 4.   Store the remaining
solid at 130°C.

      5.12  Solvents

            5.12.1  Methylene chloride, CH2C12.   Pesticide quality or equivalent.

            5.12.2  Acetone, CH3COCH3.  Pesticide quality or equivalent.

            5.12.3  Methanol, CH3OH.   Pesticide quality or equivalent.

            5.12.4  Toluene, C6H5CH3.   Pesticide quality or equivalent.

            5.12.5  Diethyl Ether, C2H5OC2H5.   Pesticide quality or equivalent.
      Must  be free of peroxides as  indicated  by  test strips  (EM  Quant,  or
      equivalent).  Procedures  for  removal  of peroxides are provided with  the

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      test strips.  After cleanup, 20 mL of ethyl alcohol preservative must be
      added to each liter of ether.

            5.12.6  Isooctane,  (CH3)3CH2CH(CH3)2.  Pesticide quality or equivalent.

            5.12.7  Hexane,  C6H14.   Pesticide quality or equivalent.

      5.13  Stock standard  solutions  (1000 mg/L) - Can  be  prepared  from pure
standard materials  or  can be purchased as  certified  solutions.   Commercially
prepared stock standards can be used if they are verified against  EPA standards.
If EPA standards  are not available for verification,  then standards certified
by the manufacturer and  verified against a standard made from pure material is
acceptable.

            5.13.1  Prepare  stock  standard  solutions  by accurately  weighing
      about 0.010 g of  pure acid.   Dissolve the material in pesticide quality
      acetone and dilute to  volume  in a 10 ml volumetric flask.  Stocks prepared
      from pure  methyl   esters are dissolved in  10%  acetone/isooctane (v/v).
      Larger volumes may be  used at the convenience of the analyst.  If compound
      purity  is  certified at 96%  or  greater,  the weight may  be used without
      correction to calculate the  concentration of the stock standard.

            5.13.2  Transfer the stock standard solutions to vials with Teflon
      lined screw-caps.   Store at 4°C, protected from  light.   Stock standard
      solutions  should   be  checked  frequently  for  signs  of degradation  or
      evaporation,  especially  immediately  prior  to  preparing  calibration
      standards from them.

            5.13.3  Stock standard solutions of the derivatized  acids must be
      replaced  after  1   year,  or   sooner,  if  comparison with  check  standards
      indicates a problem.  Stock  standard solutions of the free acids degrade
      more quickly  and  should be replaced after  two  months,  or sooner  if
      comparison with check standards indicates a problem.

      5.14  Internal Standard Spiking Solution (if internal standard calibration
is used) - To use this  approach,  the  analyst must select one or more internal
standards that are similar in analytical  behavior to the  compounds of interest.
The  analyst  must further demonstrate  that the  measurement  of  the  internal
standard is not affected by  method or matrix interferences.  The compound 4,4'-
dibromooctafluorobiphenyl (DBOB)  has  been  shown  to be  an  effective  internal
standard, but other compounds,  such as 1,4-dichlorobenzene,  may be used.

            5.14.1  Prepare an  internal  standard spiking  solution by accurately
      weighing approximately 0.0025 g of pure DBOB.  Dissolve the DBOB in acetone
      and dilute to volume  in a 10 ml volumetric flask.  Transfer the internal
      standard spiking  solution to a  vial with  a Teflon lined screw-cap,  and
      store at room temperature.   Addition of  10 nl  of the internal  standard
      spiking solution  to 10 ml of sample extract results in a final  internal
      standard concentration of 0.25 M9/L.  The solution should be replaced if
      there is a change in  internal standard response greater than 20 percent
      of the original  response recorded.
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      5.15  Calibration standards - Calibration standards,  at a minimum of five
concentrations  for each  parameter of  interest,  should  be prepared  through
dilution of the stock standards with diethyl ether.   One of the concentrations
should be at a concentration near, but above, the method detection limit.  The
remaining  concentrations   should  correspond  to   the  expected   range   of
concentrations found in real samples or should define the working range of the
GC.   Calibration solutions must  be replaced  after  six months, or  sooner if
comparison with check standards indicates a problem.

            5.15.1  Derivatize each  calibration standard  prepared  from free
      acids  in  a  10  ml K-D  concentrator tube, according to  the  procedures
      beginning at Section 7.5.   If the calibration standards are prepared from
      salts or other esters, begin with the hydrolysis step  7.2.1.6, using a 250
      ml Erlenmeyer flask.

            5.15.2  Add a known constant amount of one or more internal standards
      to each derivatized calibration standard, and  dilute to  volume with  the
      solvent indicated in the derivative option used.

      5.16  Surrogate standards - The  analyst should monitor the performance of
the  extraction,  cleanup   (when   used),   and  determinative   step,   and  the
effectiveness of the method  in dealing with  each sample matrix, by spiking each
sample,  standard,   and  blank  with one  or  two herbicide surrogates  (e.g.,
herbicides that  are  not expected to be present in the  sample)  recommended to
encompass the range of the temperature program used in this method.  Deuterated
analogs of analytes should  not  be  used  as  surrogates  in  gas  chromatographic
analysis due to coelution  problems.  The surrogate standard  recommended for use
is 2,4-Dichlorophenylacetic acid (DCAA).

            5.16.1  Prepare  a  surrogate standard spiking solution by accurately
      weighing approximately 0.001 g of pure DCAA.  Dissolve the DCAA in acetone,
      and dilute to volume in  a 10 ml volumetric flask.   Transfer the surrogate
      standard spiking  solution  to a  vial with a Teflon lined  screw-cap,  and
      store at room temperature.  Addition  of 50 /iL  of the surrogate standard
      spiking solution to  1  L  of sample, prior to extraction, results  in a final
      concentration in the extract of 0.5 mg/L.

      5.17  pH Adjustment Solutions

            5.17.1  Sodium hydroxide,  NaOH,  6 N.

            5.17.2  Sulfuric acid, H2S04,  12 N.


6.0  SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1  See the  introductory  material  to this  chapter, Organic  Analytes,
Section 4.1.

      6.2  Extracts must be stored under refrigeration (4°C).
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7.0  PROCEDURE

      7.1  Preparation of High Concentration Waste Samples

            7.1.1 Extraction

                  7.1.1.1  Follow Method 3580, Waste Dilution, with the following
            exceptions:

               o  use diethyl ether as the dilution solvent,
               o  use acidified anhydrous sulfate, and acidified glass wool,
               o  spike  the sample  with surrogate  compound(s) according  to
                  Section 5.16.1.

                  7.1.1.2  Transfer 1.0 ml (a smaller volume or a dilution may
            be required if herbicide concentrations are large) to a 250 ml ground
            glass Erlenmeyer flask.  Proceed to Section 7.2.1.7 (hydrolysis).

      7.2  Preparation of Soil, Sediment, and Other Solid Samples

            7.2.1 Extraction

                  7.2.1.1  To a 400 mL,  thick-wall beaker add 30 g (dry weight)
            of the well-mixed solid sample.   Acidify  solids  in each beaker with
            85 mL of 0.1 M  phosphate  buffer  (pH  =2.5)  and  thoroughly mix the
            contents with a glass stirring rod. Spike the sample with surrogate
            compound(s) according to Section 5.16.1.

                  7.2.1.2  The ultrasonic extraction of solids must be optimized
            for each type of sample.   In order for the ultrasonic extractor to
            efficiently extract solid samples, the sample must be free flowing
            when the solvent is added.  Acidified anhydrous sodium sulfate should
            be added to clay type soils, or any other solid  that is not a free
            flowing sandy texture,  until a free flowing mixture is obtained.

                  7.2.1.3  Add  100  ml of  methylene   chloride  to the  beaker.
            Perform ultrasonic  extraction  for 3  minutes, with  output control
            knob set at 10  (full power) and with  mode switch on Pulse (pulsing
            energy rather than  continuous energy)  and percent-duty  cycle knob
            set at 50% (energy on 50% of time and off 50% of time).   Allow the
            solids  to  settle.   Transfer  the organic layer  into  a 500  ml
            centrifuge bottle.

                  7.2.1.4  Ultrasonically extract the sample twice  more  using
            100 mL of methylene chloride and the  same ultrasonic condition.

                  7.2.1.5  Combine  the three organic  extracts  from  the sample
            in the  centrifuge  bottle  and centrifuge   10 minutes  to  settle the
            fine particles.  Filter the  combined extract  through filter  paper
            (Whatman #1, or equivalent) into 500  mL 24/40 Erlenmeyer flask.

                  7.2.1.6  Add boiling chips and attach the macro Snyder column.
            Evaporate the methylene chloride on  the  water bath  to  a volume  of


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      approximately 25 ml.  Remove the flasks from the water bath and allow
      them to cool.

            7.2.1.7  Add 5 mL of 37%  aqueous  potassium hydroxide,  30 mL
      of water  and  40 ml  of methanol to  the extract.   Add additional
      boiling chips to the flask.  Reflux the mixture on a water bath at
      60-65°C for  2 hours.  Remove the flasks  from the water bath and cool
      to room temperature.

            7.2.1.8  Transfer the hydrolyzed aqueous  solution to a 500 mL
      separatory funnel and extract the solution three times with 100 ml
      portions  of methylene chloride.   Discard the methylene  chloride
      phase.  At  this point  the basic solution contains  the  herbicide
      salts.

            7.2.1.9  Adjust the pH of the solution to <2 with cold (4°C)
      sulfuric acid  (1+3)  and extract  three times with 100 ml portions of
      methylene chloride.  Combine the extracts and  pour them  through a
      pre-rinsed drying column containing 7 to  10 cm of acidified anhydrous
      sodium sulfate.  Collect the dried extracts  in a  500 mL  K-D flask
      fitted with a 10 mL concentrator tube.   Proceed to section 7.4 for
      extract concentration.

7.3  Preparation of  Aqueous Samples

      7.3.1  Separatory Funnel

            7.3.1.1   Using a graduated cylinder, measure  out a 1 liter of
      sample and  transfer  it into a  2  L separatory funnel.   Spike  the
      sample with surrogate compound(s) according  to Section 5.16.1.

            7.3.1.2   Add  250 g of NaCl to the sample, seal, and shake to
      dissolve the salt.

            7.3.1.3   Add  17 mL of 6 N NaOH to the sample,  seal, and shake.
      Check the  pH of the sample with pH paper; if the sample does not have
      a pH greater than or equal  to 12, adjust the pH by adding more 6 N
      NaOH.  Let the sample  sit  at room  temperature  for 1 hour,  shaking
      the separatory funnel and contents periodically.

            7.3.1.4   Add 60 mL of methylene chloride to the sample bottle
      to  rinse  the  bottle.    Transfer  the  methylene  chloride  to  the
      separatory funnel and extract the sample by  vigorously shaking the
      funnel  for  2  minutes,  with  periodic   venting  to  release  excess
      pressure.  Allow the organic  layer  to separate from the water phase
      for a minimum  of 10 minutes.  If the emulsion interface between the
      layers is  more than one-third the volume of  the solvent layer,  the
      analyst must  employ mechanical techniques  to complete the  phase
      separation.  The optimum technique  depends upon the sample,  but may
      include stirring, filtration  through glass wool, centrifugation, or
      other physical methods.  Discard the  methylene chloride phase.

            7.3.1.5   Add  a second 60 mL  volume of  methylene  chloride to
      the sample bottle and repeat the extraction procedure a second time,

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            discarding the methylene chloride layer.  Perform a third extraction
            in the same manner.

                  7.3.1.6  Add 17 ml of  cold  (4°C)  12 N sulfuric  acid  to the
            sample, seal, and shake to  mix.  Check the pH of the sample with pH
            paper:  if the sample does not have a pH less  than  or equal to 2,
            adjust the pH by adding more acid.

                  7.3.1.7  Add 120 ml  diethyl  ether to the sample,  seal,  and
            extract the sample by vigorously shaking the funnel  for 2 min with
            periodic venting  to  release excess pressure.   Allow  the  organic
            layer to separate from the  water phase for a minimum of 10 min.  If
            the emulsion  interface  between  layers  is more  than one  third the
            volume of  the solvent layer, the  analyst must employ mechanical
            techniques to complete the phase separation.  The optimum techniques
            to complete the phase separation depends upon  the  sample,  but may
            include stirring,  filtration  through glass wool, centrifugation, or
            other physical methods.  Remove the  aqueous phase to a 2 L Erlenmeyer
            flask  and  collect the ether phase in  a 500 ml  Erlenmeyer flask
            containing approximately 10 g of acidified anhydrous sodium sulfate.
            Periodically, vigorously shake the extract and drying agent.

                  7.3.1.8  Return the  aqueous  phase  to  the separatory funnel,
            add 60 ml of diethyl  ether  to the sample, and repeat the extraction
            procedure  a  second  time,  combining the extracts  in  the  500  ml
            Erlenmeyer flask.  Perform a third extraction  with 60 ml diethyl
            ether in the  same  manner.  Allow the extract  to remain in contact
            with the sodium sulfate for approximately 2 hours.

Note: The drying  step is  very critical  to  ensuring complete  esterification.
      Any  moisture  remaining in  the  ether  will   result in  low  herbicide
      recoveries.  The amount  of  sodium sulfate is adequate  if some free flowing
      crystals are visible when swirling the  flask.   If all  of the sodium sulfate
      solidifies  in  a cake,  add a few  additional  grams of  acidified  sodium
      sulfate and again test by swirling. The  2 hour drying time is a minimum,
      however, the  extracts may  be  held in contact with the  sodium sulfate
      overnight.

                  7.3.1.9  Pour the dried extract through a funnel plugged with
            acid  washed  glass  wool,  and  collect  the  extract   in  the  K-D
            concentrator.  Use a glass rod  to crush any  caked  sodium sulfate
            during the transfer.   Rinse the  round bottom flask and funnel with
            20 to 30 ml of diethyl ether  to complete  the quantitative transfer.
            Proceed to section 7.4 for extract concentration.

      7.4  Extract Concentration

            7.4.1  Add one or  two clean  boiling chips to  the  flask and attach
      a three ball Snyder column.   Prewet the  Snyder column by adding about 1
      ml of diethyl ether to the  top of the column.   Place the K-D apparatus on
      a hot water bath (15-20°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,

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      to complete the concentration  in  10-20 minutes.   At the  proper  rate of
      distillation the  balls of  the column  will  actively  chatter,   but  the
      chambers will not  flood.  When the apparent volume  of liquid reaches 1 ml,
      remove the K-D apparatus from the water bath and allow it to drain and cool
      for at least 10 minutes.

            7.4.2  Remove the Snyder column and rinse the flask and its lower
      joints  into  the  concentrator tube with  1-2  ml of  diethyl  ether.   The
      extract may be further concentrated by using either the micro Snyder column
      technique (Section 7.4.3) or nitrogen blowdown technique (Section 7.4.4).

            7.4.3  Micro Snyder  Column Technique

                  7.4.3.1  Add another one or  two  clean boiling chips  to the
            concentrator tube and attach a two ball  micro Snyder  column.  Prewet
            the column  by adding about 0.5 ml of diethyl  ether to the top of the
            column.  Place the  K-D apparatus  in a  hot water  bath  so  that the
            concentrator tube is partially immersed  in  the hot  water.   Adjust
            the vertical position  of  the apparatus and  the water temperature,
            as required, to complete the  concentration in 5-10 minutes.  At the
            proper rate of distillation the balls  of the  column will  actively
            chatter,  but the chambers will not  flood.  When the apparent volume
            of liquid reaches 0.5  ml, remove the K-D apparatus  from the water
            bath and  allow it to drain and cool  for  at least 10 minutes.  Remove
            the Snyder column and rinse the flask and its  lower joints with about
            0.2 ml of diethyl ether and  add to the  concentrator tube.   Proceed
            to Section 7.4.5.

            7.4.4 Nitrogen Blowdown Technique

                  7.4.4.1  Place the  concentrator  tube  in a warm  water  bath
            (approximately 35°C) and evaporate the solvent volume to the required
            level using  a gentle stream of clean, dry  nitrogen  (filtered through
            a column  of activated carbon).

CAUTION:   Do not use plasticized tubing between the carbon trap  and the sample.

                  7.4.4.2  The internal  wall of the  tube must  be  rinsed  down
            several times  with  diethyl  ether  during the  operation.   During
            evaporation, the  solvent  level  in the  tube must  be positioned to
            prevent water  from  condensing  into the  sample (i.e.,  the  solvent
            level should be  below  the level of the water  bath).  Under normal
            operating conditions,  the extract  should not  be  allowed to become
            dry.  Proceed to Section 7.4.5.

            7.4.5  Dilute the extract with 1  ml of isooctane  and 0.5 ml of
      methanol.  Dilute  to a final volume of 4 ml with  diethyl  ether.  The sample
      is now ready for methylation with diazomethane.  If PFB derivation  is being
      performed, dilute to 4 mL with acetone.

      7.5  Esterification - For diazomethane derivatization proceed with Section
7.5.1.  For PFB derivatization proceed with Section 7.5.2.
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            7.5.1  Diazomethane Derivatization  -  Two methods may  be  used for
      the generation of diazomethane:  the bubbler method (see Figure 1), Section
      7.5.1.1, and the Diazald kit method, Section 7.5.1.2.

CAUTION:  Diazomethane is a carcinogen and can explode under certain conditions.

      The bubbler  method  is suggested  when  small batches of  samples (10-15)
      require esterification.  The bubbler method works well with samples that
      have low concentrations of herbicides (e.g., aqueous samples)  and is safer
      to use than the Diazald kit procedure.  The Diazald kit  method is good for
      large quantities of samples needing esterification.  The Diazald kit method
      is more effective than the bubbler method for  soils or samples  that may
      contain high concentrations of herbicides (e.g.,  samples such as soils that
      may result  in  yellow extracts following  hydrolysis may  be difficult to
      handle by the bubbler method).   The diazomethane derivatization  (U.S.EPA,
      1971) procedures,  described below, will  react efficiently with all of the
      chlorinated  herbicides described  in this  method and should be used only
      by experienced analysts,  due  to the potential hazards associated with its
      use.  The following precautions should be taken:

            o  Use a safety screen.
            o  Use mechanical pipetting aides.
            o  Do not heat above 90°C -  EXPLOSION  may result.
            o  Avoid grinding  surfaces,  ground-glass joints,  sleeve  bearings,
               and glass stirrers - EXPLOSION may result.
            o  Store away from alkali metals - EXPLOSION may result.
            o  Solutions of  diazomethane  decompose rapidly  in  the presence of
               solid materials  such as  copper  powder,  calcium  chloride,  and
               boiling chips.

                   7.5.1.1  Bubbler  method  -  Assemble the diazomethane bubbler
            (see Figure 1).

                        7.5.1.1.1  Add 5 mL of diethyl ether to the first test
                   tube.   Add 1  mL of diethyl  ether, 1 mL  of carbitol,  1.5 mL of
                   37% KOH,  and 0.1-0.2  g of Diazald  to  the  second test tube.
                   Immediately  place  the exit tube into  the  concentrator tube
                   containing the sample extract. Apply nitrogen flow (10 mL/min)
                   to bubble  diazomethane  through the extract for 10 minutes or
                   until  the yellow color  of diazomethane persists.  The amount
                   of  Diazald   used  is   sufficient   for  esterification  of
                   approximately three sample  extracts.   An additional 0.1-0.2
                   g  of  Diazald  may be  added  (after  the initial  Diazald is
                   consumed) to  extend the generation of the diazomethane.  There
                   is sufficient KOH present in the original solution to perform
                   a maximum of  approximately 20 minutes of total esterification.

                        7.5.1.1.2  Remove the concentrator tube and seal  it with
                   a  Neoprene or Teflon  stopper.   Store at room temperature in
                   a  hood for 20 minutes.

                        7.5.1.1.3  Destroy any unreacted  diazomethane  by adding
                   0.1-0.2 g of silicic acid to the concentrator tube.  Allow to
                   stand until the evolution of nitrogen gas has  stopped.  Adjust

                                   8151  - 13                      Revision 0
                                                                 November 1990

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      the  sample volume  to  10.0  ml  with hexane.    Stopper the
      concentrator tube or transfer  1 ml of sample to a GC vial, and
      store refrigerated if further processing will not be performed
      immediately.  It is recommended that the methylated extracts
      be analyzed immediately to minimize the trans-esterification
      and other potential reactions  that may occur.  Analyze by gas
      chromatography.

            7.5.1.1.4  Extracts  should be  stored  at 4°C  away from
      light.  Preservation study results indicate that  most analytes
      are stable for 28  days; however,  it  is  recommended that the
      methylated extracts  be  analyzed  immediately to minimize the
      trans-esterification  and other  potential  reactions  that may
      occur.  Analyze by gas chromatography.

      7.5.1.2  Diazald   kit method  -  Instructions for  preparing
diazomethane are provided with the generator kit.

            7.5.1.2.1  Add 2 ml  of  diazomethane  solution  and let
      the sample  stand for  10  minutes with  occasional  swirling.
      The yellow color  of diazomethane  should  be evident and should
      persist for this period.

            7.5.1.2.2  Rinse the  inside wall of the  ampule with 700
      /iL  of   di ethyl   ether.    Reduce   the  sample  volume  to
      approximately 2 ml to remove excess diazomethane by allowing
      the solvent to evaporate  spontaneously  at room temperature.
      Alternatively, 10 mg of silicic acid can be added to destroy
      the excess diazomethane.

            7.5.1.2.3  Dilute the sample  to  10.0 ml  with  hexane.
      Analyze by gas chromatography.

7.5.2  PFB Method

      7.5.2.1  Add 30  /*L of 10% K2C03 and 200  /iL of  3%  PFBBr in
acetone.  Close the tube  with a  glass  stopper and mix on a vortex
mixer.  Heat the tube at 60°C for 3  hours.

      7.5.2.2  Evaporate the solution to 0.5 ml with a  gentle stream
of nitrogen.   Add 2 ml  of hexane and repeat evaporation  just to
dryness at ambient temperature.

      7.5.2.3  Redissolve  the residue in  2  ml  of toluene:hexane
(1:6) for column cleanup.

      7.5.2.4  Top the  silica column with 0.5 cm of anhydrous sodium
sulfate.  Prewet  the column with 5 ml hexane and let the solvent
drain to  the  top of the adsorbent.   Quantitatively  transfer the
reaction  residue to   the column  with  several   rinsings  of  the
toluene:hexane solution (total 2-3 ml).
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                  7.5.2.5  Elute the column  with sufficient toluene:hexane  to
            collect 8 ml of eluent.  Discard this fraction which contains  excess
            reagent.

                  7.5.2.6  Elute the column with toluenerhexane (1:9) to collect
            8 mL  of eluent containing  PFB  derivatives  in  a 10 ml  volumetric
            flask.  Dilute to 10 ml with hexane.  Analyze by 6C/ECD.

7.6  Gas chromatographic conditions (recommended):

            7.6.1  Narrow Bore

                  7.6.1.1  Primary Column 1:
            Temperature program:  60°C to 300°C,  at  4°C/min
            Helium carrier flow:  30 cm/sec
            Injection volume:  2 /ul_, splitless,  45  sec delay
            Injector temperature:  250°C
            Detector temperature:  320°C

                  7.6.1.2  Primary Column la:
            Temperature program:  60°C to 300°C,  at  4°C/min
            Helium carrier flow:  30 cm/sec
            Injection volume:  2 /nL. splitless,  45  sec delay
            Injector temperature:  250°C
            Detector temperature:  320°C

                  7.6.1.3  Column 2:
            Temperature program:  60°C to 300PC,  at  4°C/min
            Helium carrier flow:  30 cm/sec
            Injection volume:  2 /itL, splitless,  45  sec delay
            Injector temperature:  250°C
            Detector temperature:  320°C

                  7.6.1.4  Confirmation Column:
            Temperature program:  60°C to 300°C,  at  4°C/irin
            Helium carrier flow:  30 cm/sec
            Injection volume:  2 pi, splitless,  45  sec delay
            Injector temperature:  250°C
            Detector temperature:  320°C

            7.6.2  Megabore

                  7.6.2.1  Primary Column:
            Temperature program:  0.5 minute at 150°C,  150°C  to 270°C at 5°C/min
            Helium carrier flow:  7 mL/min
            Injection volume:  1 ^L

                  7.6.2.2  Confirmatory Column:
            Temperature program:  0.5 minute at 150°C,  150°C  to 270°C at 5°C/min
            Helium carrier flow:  7 mL/min
            Injection volume:  1 pi
                                   8151 - 15                     Revision 0
                                                                 November 1990

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      7.7  Calibration

            7.7.1  The procedure  for internal  or external  calibration may be
      used.  Refer to Method  8000  for a description of each  of these procedures.
      Use Table 1 for guidance on  selecting the  lowest point on the calibration
      curve.

      7.8  Gas chromatographic analysis

            7.8.1  Refer to Method 8000.   If the internal standard calibration
      technique is used, add 10 nl of internal standard to the sample prior to
      injection.

            7.8.2  Follow Method 8000 for instructions on the analysis sequence,
      appropriate  dilutions,  establishing  daily  retention time  windows,  and
      identification criteria.  Include  a mid-concentration standard after each
      group of 10 samples in the analysis  sequence.

            7.8.3  An example of a chromatogram for a methylated chlorophenoxy
      herbicide is shown in  Figure 2.   Tables  2 and 3 present retention times
      for  the target  analytes  after esterification,  using the  diazomethane
      derivatization   procedure  and   the   PFB   derivatization   procedure,
      respectively.

            7.8.4  Record the  sample volume injected  and  the  resulting  peak
      sizes (in area units or peak heights).

            7.8.5  Using either the internal or external calibration procedure
      (Method 8000),  determine the identity and  quantity of each component peak
      in the  sample  chromatogram  which  corresponds to  the  compounds  used  for
      calibration purposes.

            7.8.6  If calibration  standards have been analyzed in the same manner
      as the samples (e.g. have undergone hydrolysis and esterification),  then
      the  calculation  of concentration  given  in  Method 8000 should  be used.
      However, if calibration is performed using standards made from methyl ester
      compounds (compounds not esterified by application of this method),  then
      the  calculation of  concentration must   include  a  correction  for  the
      molecular weight of the methyl  ester versus the acid  herbicide.

            7.8.7  If peak detection  and  identification are prevented  due to
     interferences,  further  cleanup  is  required.    Before using any  cleanup
     procedure, the  analyst  must  process  a series  of standards through  the
     procedure to  validate elution  patterns and the  absence  of interferences
     from reagents.


8.0  QUALITY CONTROL

      8.1  Refer to Chapter One for specific quality control  procedures.  Quality
control  to  validate  sample extraction  is  covered  in  Method  3500 and  in  the
extraction method utilized.   If  extract  cleanup was  performed, follow the QC in
Method 3600 and in the specific cleanup  method.


                                  8151  - 16                    Revision 0
                                                                November 1990

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      8.2  Procedures to check the GC system operation are found in Method 8000.

            8.2.1  Select a representative spike concentration for each compound
      (acid or ester) to be measured.  Using stock standards, prepare a quality
      control check  sample  concentrate, in acetone,  that  is 1000  times more
      concentrated than the selected concentrations.  Use this  quality control
      check sample concentrate to prepare quality control  check samples.

            8.2.2  Tables 4  and  5 present bias and precision data for water and
      clay matrices,  using the diazomethane derivatization  procedure.  Table 6
      presents relative  recovery data generated using the  PFB  derivatization
      procedure and water samples. Compare the results obtained with the results
      given in these Tables to determine if the data quality is acceptable.

      8.3  Calculate   surrogate  standard recovery on all  standards,  samples,
blanks,  and spikes.    Determine if  the recovery  is within  limits  (limits
established by performing QC procedures outlined in  Method  8000).

            8.3.1  If recovery is not within  limits,  the  following procedures
      are required:

                  8.3.1.1 Check to  be  sure there  are  no errors in calculations,
            surrogate solutions and internal standards.  Also, check instrument
            performance.

                  8.3.1.2 Recalculate  the data and/or reanalyze the extract if
            any of the above checks reveal  a problem.

                  8.3.1.3 Reextract and  reanalyze the sample if none of the above
            are a problem or flag the data as "estimated concentration."

      8.4  GC/MS confirmation

            8.4.1  GC/MS techniques should be judiciously employed to support
      qualitative identifications made with this method.   Refer to Method 8270
      for the appropriate GC/MS operating conditions and analysis procedures.

            8.4.2  When  available,  chemical  ionization  mass  spectra  may be
      employed to aid the qualitative identification process.

            8.4.3  Should these  MS procedures   fail  to  provide  satisfactory
      results, additional steps  may be taken before  reanalysis.   These steps
      may  include the  use  of  alternate packed  or  capillary  GC  columns or
      additional cleanup.


9.0  METHOD PERFORMANCE

      9.1  In single  laboratory  studies using organic-free  reagent water and
clay/still bottom samples, the mean recoveries presented in Tables 4 and 5 were
obtained for diazomethane derivatization. The  standard deviations of the percent
recoveries of these measurements are also in Tables  4 and 5.
                                   8151  -  17                      Revision 0
                                                                 November 1990

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      9.2  Table 6 presents relative  recoveries of the target analytes obtained
using the PFB derivatization procedure with spiked water samples.


10.0 REFERENCES

1.   Fed. Reg. 1971, 38, No. 75, Pt.  II.

2.   Goerlitz, D. G.; Lamar, W.L.,  "Determination of Phenoxy Acid Herbicides in
     Water by Electron Capture  and  Microcoulometric Gas Chromatography,".  U.S.
     Geol. Survey Water Supply Paper 1967, 1817-C.

3.   Burke,  J.  A.  "Gas  Chromatography for  Pesticide  Residue  Analysis;  Some
     Practical Aspects, J. Assoc. Off Anal. Chem.  1965,  48, 1037.

4.   "Extraction and Cleanup Procedures for  the Determination  of Phenoxy Acid
     Herbicides in Sediment"; U.S. Environmental Protection Agency. EPA Toxicant
     and Analysis Center: Bay St. Louis, MS,  1972.

5.   Shore, F.L.; Amick, E.N.;  Pan, S. T.  "Single Laboratory Validation of EPA
     Method 8151 for the Analysis of Chlorinated Herbicides  in Hazardous Waste";
     U.S. Environmental  Protection Agency.  Environmental  Monitoring  Systems
     Laboratory.  Office  of  Research and  Development,  Las  Vegas,  NV,  1985;
     EPA-60014-85-060.

6.   Method  515.1,  "Determination  of Chlorinated  Acids  in  Water  by  Gas
     Chromatography  with  an Electron Capture Detector", Revision  4.0,  USEPA,
     Office  of  Research  and  Development,  Environmental  Monitoring  Systems
     Laboratory, Cincinnati, Ohio.

7.   Method 1618, "Organo-halide and Organo-phosphorus Pesticides and Phenoxy-
     acid Herbicides by Wide  Bore Capillary Column  Gas  Chromatography  with
     Selective  Detectors",   Revision  A,  July  1989,  USEPA, Office of  Water
     Regulations and Standards, Washington, DC.
                                   8151  -  18                     Revision 0
                                                                 November 1990

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                                   Figure 1
                            DIAZOMETHANE GENERATOR
    nitrogen
rubber  stopper
                                                                 gloss tubing
                     tube 1
tube 2
                                  8151  - 19
                    Revision 0
                    November 1990

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                                    TABLE  1
              ESTIMATED METHOD DETECTION LIMITS FOR METHOD 8151,
                          DIAZOMETHANE DERIVATIZATION
Analyte
Aqueous Samples
GC/ECD
Estimated
Detection
Limit8
(Mg/L)
Soil
GC/ECD
Estimated
Detection
Limitb
(WJ/Kg)
Samples
GC/MS
Estimated
Identification
Limit0
(ng)
Acifluorfen
Bentazon
Chloramben
2,4-D
Dalapon
2,4-DB
DCPA diacid6
Dicamba
3,5-Dichlorobenzoic acid
Dichlorprop
Dinoseb
5-Hydroxydicamba
MCPP
MCPA
4-Nitrophenol
Pentachlorophenol
Picloram
2,4,5-T
2,4,5-TP
0.096
0.2
0.093
0.2
1.3
0.8
0.02
0.081
0.061
0.26
0.19
0.04
0.09d
0.056d
0.13
0.076
0.14
0.08
0.075
4.0
0.11
0.12
0.38
66
43
0.34
0.16
0.28
1.7
1.25
0.5
0.65
0.43
0.3
0.44
1.3
4.5
a  EDL = estimated detection limit;  defined  as either the MDL (40 CFR Part 136,
   Appendix B,  Revision 1.11  ),  or  a  concentration of  analyte in  a  sample
   yielding  a  peak  in the  final   extract  with  signal-to-noise  ratio  of
   approximately 5, whichever value is higher.

b  Detection limits determined from standard solutions  corrected back to 50 g
   samples,  extracted  and  concentrated  to  10  ml,   with  5  /xL  injected.
   Chromatography   using   narrow  bore  capillary   column,  0.25  urn   film,
   5% phenyl/95% methyl silicone.

c  The minimum amount of analyte to give a  Finnigan  INCOS  FIT  value of 800 as
   the methyl  derivative vs. the  spectrum obtained from  50 ng of the respective
   free acid herbicide.
   40 CFR Part  136,  Appendix B (49 FR 43234).
   capillary column.
                    Chromatography using megabore
   DCPA monoacid and diacid metabolites  included  in  method scope;  DCPA diacid
   metabolite used for validation studies.  DCPA is a dimethyl ester.
                                   8151  -  20
                                    Revision 0
                                    November 1990

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                                 TABLE  2
RETENTION TIMES (MINUTES) OF METHYL DERIVATIVES OF CHLORINATED HERBICIDES


Analyte
Dalapon
3,5-Dichlorobenzoic
4-Nitrophenol
DCAA (surrogate)
Dicamba
Dichlorprop
2,4-D
DBOB (internal std.)
Pentachlorophenol
Chloramben
2,4,5-TP
5-Hydroxydicamba
2,4,5-T
2,4-DB
Dinoseb
Bentazon
Picloram
DCPA diacidc
Acifluorfen
MCPP
MCPA
Narrow
Primary8
Column
3.4
acid 18.6
18.6
22.0
22.1
25.0
25.5
27.5
28.3
29.7
29.7
30.0
30.5
32.2
32.4
33.3
34.4
35.8
41.5


Bore Columns
Confirmation3
Col umn
4.7
17.7
20.5
14.9
22.6
25.6
27.0
27.6
27.0
32.8
29.5
30.7
30.9
32.2
34.1
34.6
37.5
37.8
42.8


Megabore
Primary"
Col umn




4.39
5.15
5.85



6.97

7.92
8.74





4.24
4.74
Columns
Confirmation"
Col umn




4.39
5.46
6.05



7.37

8.20
9.02





4.55
4.94
                                8151  - 21
Revision 0
November 1990

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                           TABLE 2 (continued)
Primary Column:      5% phenyl/95% methyl silicone
Confirmation Column: 14% cyanopropyl phenyl silicone

         Temperature program:    60°C to 300°C, at 4°C/min
         Helium carrier flow:    30 cm/sec
         Injection volume:       2 /iL,  splitless, 45 sec delay
         Injector temperature:   250°C
         Detector temperature:   320°C

Primary Column:      DB-608
Confirmatory Column: 14% cyanopropyl phenyl silicone

         Temperature program:    0.5 minute at 150°C,
                                 150°C to 270°C, at 5°C/nrin
         Helium carrier flow:    7 mL/min
         Injection volume:       1 nl
DCPA monoacid and diacid metabolites included in method scope; DCPA diacid
metabolite used for validation studies.  DCPA is a dimethyl ester.
                                8151 -  22                     Revision 0
                                                              November 1990

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                                    TABLE 3
    RETENTION TIMES (MINUTES) OF PFB DERIVATIVES OF CHLORINATED HERBICIDES


                	Gas chromatoqraphic column	
Herbicide       Thin-film DB-5aSP-2250"Thick-film DB-5C
Dalapon
MCPP
Dicamba
MCPA
Dichlorprop
2,4-D
Silvex
2,4,5-T
Dinoseb
2,4-DB
10.41
18.22
18.73
18.88
19.10
19.84
21.00
22.03
22.11
23.85
12.94
22.30
23.57
23.95
24.10
26.33
27.90
31.45
28.93
35.61
13.54
22.98
23.94
24.18
24.70
26.20
29.02
31.36
31.57
35.97
   DB-5 capillary column, 0.25 jum  film thickness, 0.25 mm  ID  x 30 m  long.
   Column temperature, programmed: 70°C for 1 minute, program 10°C/min.  to
   240°C,  hold for 17 minutes.

   SP-2550 capillary column,  0.25  pm  film  thickness,  0.25  mm  ID  x 30 m  long.
   Column temperature, programmed: 70°C for 1 minute, program 10°C/min.  to
   240°C,  hold for 10 minutes.

   DB-5 capillary column, 1.0 urn film thickness, 0.32 mm ID x 30 m long.
   Column temperature, programmed: 70°C for 1 minute, program 10°C/min.  to
   240°C,  hold for 10 minutes.
                                   8151 - 23                     Revision 0
                                                                 November 1990

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                               TABLE  4
               ACCURACY  AND  PRECISION FOR METHOD 8151
   DIAZOMETHANE DERIVATIZATION, ORGANIC-FREE REAGENT WATER MATRIX
Spike
Concentration
Analyte (M9/L)
Acifluorfen
Bentazon
Chloramben
2,4-D
Dalapon
2,4-DB
DCPA diacidb
Dicamba
3,5-Dichlorobenzoic Acid
Dichlorprop
Dinoseb
5-Hydroxydicamba
4-Nitrophenol
Pentachlorophenol
Picloram
2,4,5-TP
2,4,5-T
0.2
1
0.4
1
10
4
0.2
0.4
0.6
2
0.4
0.2
1
0.04
0.6
0.4
0.2
Mean8 Standard
Percent Deviation of
Recovery Percent Recovery
121
120
111
131
100
87
74
135
102
107
42
103
131
130
91
117
134
15.7
16.8
14.4
27.5
20.0
13.1
9.7
32.4
16.3
20.3
14.3
16.5
23.6
31.2
15.5
16.4
30.8
Mean percent recovery calculated from 7-8 determinations of spiked
organic-free reagent water.

DCPA monoacid and diacid metabolites included in method scope; DCPA
diacid metabolite used for validation studies.  DCPA is a dimethyl ester.
                              8151  -  24
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November 1990

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                                  TABLE  5
                  ACCURACY AND PRECISION FOR METHOD  8151
                 DIAZOMETHANE DERIVATIZATION, CLAY MATRIX
Analyte
     Mean8
Percent Recovery
   Linear"
Concentration
   Range
   (ng/g)
    Percent
   Relative0
Standard Deviation
    (n-20)
Dicamba
MCPP
MCPA
Dichlorprop
2,4-D
2,4,5-TP
2,4,5-T
2,4-DB
Dinoseb
95.7
98.3
96.9
97.3
84.3
94.5
83.1
90.7
93.7
0.52
620
620
1.5
1.2
0.42
0.42
4.0
0.82
- 104
- 61,800
- 61,200
- 3,000
- 2,440
- 828
- 828
- 8,060
- 1,620
7.5
3.4
5.3
5.0
5.3
5.7
7.3
7.6
8.7
   Mean percent recovery calculated from 10 determinations of spiked clay
   and clay/still bottom samples over the linear concentration range.

   Linear concentration range was determined on standard solutions and
   corrected to 50 g solid samples.

   Percent relative standard deviation was calculated on standard solutions,
   10 samples high in the linear concentration range, and 10 samples low in
   the range.
                                 8151  -  25
                                            Revision  0
                                            November  1990

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                                            TABLE 6
                      RELATIVE  RECOVERIES  OF  PFB DERIVATIVES OF HERBICIDES8
Std.concn,
Analyte
MCPP
Dicamba
MCPA
Dichlorprop
2,4-D
Si 1 vex
2,4,5-T
2,4-DB
Mean
Mg/mL
5
3
10
6
9
10
12
20

.1
.9
.1
.0
.8
.4
.8
.1

1
95.6
91.4
89.6
88.4
55.6
95.3
78.6
99.8
86.8
2
88.8
99.2
79.7
80.3
90.3
85.8
65.6
96.3
85.7
Relative recoveries, %
3
97.1
100
87.0
89.5
100
91.5
69.2
100
91.8
4
100
92.7
100
100
65.9
100
100
88.4
93.4
5
95.5
84.0
89.5
85.2
58.3
91.3
81.6
97.1
85.3
6
97.2
93.0
84.9
87.9
61.6
95.0
90.1
92.4
89.0
7
98.1
91.1
92.3
84.5
60.8
91.1
84.3
91.6
87.1
8
98.2
90.1
98.6
90.5
67.6
96.0
98.5
91.6
91.4
Mean
96.3
92.7
90.2
88.3
70.0
93.3
83.5
95.0

Percent recovery determinations made using spiked water samples.
                            8151 - 26
Revision 0
November 1990

-------
                                      METHOD 8151
CHLORINATED HERBICIDES  BY GC USING METHYLATION OR PENTAFLUOROBENZYLATIQN
                   PERIVATIZATION; CAPILLARY  COLUMN TECHNIQUE
        7.1.1 1  Follow
         method 3580
        waste dilution
        unrig the given
         exceptions
Soil

7.2 1.1 Heigh
sample and add
to beaker ; add
buffer and
spike ; mix wel 1
                                                    7.3.1.1 Measure
                                                     1L of sample
                                                    and transfer to
                                                       a 2L sap.
                                                        funnel.
 7.3.1.2 Add
2SOg NaCI to
 •ample and
  shake to
  dissolve
7.1.1.2
Transfer 1 0 ml
to flask and
proceed to step
7.2.1.7
















7.2.1.2
Opti-
mize ultrasonic
solid OK trac-
tion for each
ma t r i K .
,














7.2.1
HeCl to

3 Add
sample
and extract 3
mm ; let settle
and decant MeCl

72.1

4 & 5
Ul trasonically
extract
2 more

7.2.1.5
sample
times

Combine
organic
ex tracts ,
centrifuge, and
filter ex t rac t .

7 2.1.7 Add
KOH. water, and

for 2 hours and
allow to cool
7 2

1 6
Concentrate
MeCl to

25 ml with
Snyder column.
                                       8151  -  27
                                                    7.3.1.3 Add 6N
                                                    NaOH to sample
                                                    and shake. Add
                                                     until pH>12.
                                                    Let stand 1 hr.
                                                      7.3.1.4 Add
                                                     MeCl and ex-
                                                     tract by sha-
                                                    king for 2 min.
                                                     Discard MeCl.
No



7 3.1.5
Repeat
ex tract ion
twice more .
Discard MeCl .
                                                      7.3  1.6 Add
                                                     12N sulfuric
                                                       acid and
                                                      shake. Add
                                                      until pH<2.
                                                                     Yes
                     Employ  mechanical
                       techniques to
                      complete phase
                     separation (e.g.
                    stirring,  filteration
                     through  glass wool,
                     centrifugalion,  or
                    other physical meth-
                     ods).  Discard MeCl.
                       Revision 0
                       November 1990

-------
METHOD 8151
(continued)


















7 3.1
7 Add
die thy 1 ether
to sampl e and
ex t rac
L Save
both phases .

/
/

I
X
/Does \
/ difficult X. Ye
emulsion j—
\ form? /
\
\
X.
No

7.3.1.8
/
/
/


Re turn
aqueous phase to
separator/


ex tracts ,
extract to
funnel and

and allow
remain in
contact with sodium
sulfate for 2 hours.


















73.1.9 Pour
extract through
proseed to Step
7 .1












1.












7.2.18
Trans-
f er to sep fun-
nel and
extract
3x with MeCl
Discard MeCl .

Employ mechanical
techniques to com-
plete phase separ-
s ation (e.g. sti r r ing ,
> filtration through
glass wool, centfi-
f uga tion. or other
physical methods )
Save both phases.
•






7.2.1.9 Adjust to
pH<2 »ith cold
sul fur ic acid ,
extract
3x tilth

MeCl, dry MeCl on
sodium sulfate
column, transfer to
K-D apparatus for
concentration .
1




I















741 Place K-D
apparatus in
concentrate ,
and cool .







7.4.2

74.4















Complete
concentration vith
micro Snyder column
or nitrogen bloM
dot

*n .
•
7 45 Dilute
extract
• ith 1
ml isooctane
and 0
S ml
methanol







8151 - 28
Revision 0
November 1990

-------
                                      METHOD  8151
                                      (continued)
                                                   7 4 5 Diluta
                                                   axtract  to 4
                                                      ml »ith
                                            ma than*    diathy1
                                                      ether
                        7  5 1 1 1 Add  5ml to
                        1st test tub*   Add 1
                        ml diethyl •that. 1ml
                         carbitol. 1  5 ml of
                        37% KOH. and  0 1-0 2
                         9 of Diaxald  to the
                        2nd tub*  Bubble -ith
                         nitrogan for  10 mm
                         or yal1ow persists.
ml diaiomathana
                                                                          7 5 1 2  2 Rins
                                                                        ampule with
                                                                        ether and  evaporat
                                                                         to 2 ml to remove
                                                                           diazomethane
                                                                          Alterna 1iv»ly,
                                                                        silicic acid may b
                                                                              added
 7  5  2 6 Discard 1st

 elution vith enough
toluene hexane (1:9)
 to codlect 8nl  more
aluent  Transfer to a
10ml  volumatric  flask
  and dilute to  the
  mark with Havana
                        7  S  1.1.3 Add silicic
                        to concentrator  tuba
                         and  let stand until
                         nitrogen evolution
                         has  stopped  Adjust
                         sample volume to  10
                        ml with hexana  Stop-
                        per   Immediate analy-
                                       8151  -  29
          Revision  0
          November  1990

-------
                               METHOD  8151
                                (continued)
   7.7 Internal  or
      • M terna.1
   calibration may
    be used.  (See
    Method  8000)
                          7.8.1  Add  lOul
                             internal
                          standard to the
                          sample prior to
                             infection
78.2  See  Method 8000
  for  analysis se-
 quence, appropriate
dilution*,  establish-
 ing daily  retenion
  time windoMS, and
   identification
criteria.  Check stds
  every 10  samples
    7  8,4  Record
       volume
    injected and
    the resulting
     peak  sizes
7.8.S Determine
 the identity
 and quantify
   component
    peaks.
                        Calculate  the
                       correction  for
                        molecular  wt.
                       of methyl ester
                        vs herbicide
7 86  Calculate
 concentration
using  procedure
in Method  8000
 7.8.7  Perform
    further
  cleanup if
  necessary.
                                                    Stop
                                 8151  -  30
                          Revision
                          November
0
1990

-------
                                 METHOD 8240B

      VOLATILE ORGANICS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS):
                            PACKED  COLUMN  TECHNIQUE

1.0  SCOPE AND APPLICATION

      1.1  Method 8240  is used to  determine  volatile organic compounds  in a
variety of solid waste matrices.  This  method  is applicable to nearly all types
of samples, regardless of water content, including ground water, aqueous sludges,
caustic  liquors,  acid  liquors,  waste  solvents,  oily wastes, mousses,  tars,
fibrous  wastes,  polymeric  emulsions,  filter  cakes,  spent  carbons,  spent
catalysts, soils, and sediments.  The following compounds can be determined by
this method:
Analyte
CAS No.
  Appropriate Technique
                  Direct
Purge-and-Trap    Injection
Acetone
Acetonitrile
Acrolein
Acrylonitrile
Ally! alcohol
Allyl chloride
Benzene
Benzyl chloride
Bromoacetone
Bromochloromethane (I.S.)
Bromodi chl oromethane
4-Bromofluorobenzene (surr.)
Bromoform
Bromomethane
2-Butanone
Carbon disulfide
Carbon tetrachloride
Chloral hydrate
Chlorobenzene
Chlorobenzene-ds (I.S.)
Chl orodi bromomethane
Chloroethane
2-Chloroethanol
bis-(2-Chloroethyl) sulfide
2-Chloroethyl vinyl ether
Chloroform
Chl oromethane
Chloroprene
3-Chloropropionitrile
1 , 2-Di bromo-3-chl oropropane
1,2-Dibromoethane
Di bromomethane
67-64-1
75-05-8
107-02-8
107-13-1
107-18-6
107-05-1
71-43-2
100-44-7
598-31-2
74-97-5
75-27-4
460-00-4
75-25-2
74-83-9
78-93-3
75-15-0
56-23-5
75-87-6
108-90-7
3114-55-4
124-48-1
75-00-3
107-07-3
505-60-2
110-75-8
67-66-3
74-87-3
126-99-8
542-76-7
96-12-8
106-93-4
74-95-3
PP
PP
PP
PP
PP
a
a
PP
PP
a
a
a
a
a
PP
PP
a
PP
a
a
a
a
PP
PP
a
a
a
a
ND
PP
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
pc
pc
a
a
a
                                   8240B  -  1
                              Revision 2
                              November 1990

-------
               Appropriate Technique
Analyte
l,4-Dichloro-2-butene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
l,2-Dichloroethane-d4(surr.)
1,1-Dichloroethene
trans- 1,2-Di chl oroethene
1 , 2-Di chl oropropane
l,3-Dichloro-2-propanol
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
l,2:3,4-Diepoxybutane
1,4-Difluorobenzene (I.S.)
1,4-Dioxane
Epichlorohydrin
Ethanol
Ethyl benzene
Ethyl ene oxide
Ethyl methacryl ate
2-Hexanone
2-Hydroxypropionitrile
lodomethane
Isobutyl alcohol
Malononitrile
Methacrylonitrile
Methyl ene chloride
Methyl iodide
Methyl methacryl ate
4-Methyl -2-pentanone
Pentachloroethane
2-Picoline
Propargyl alcohol
b-Propiolactone
Propionitrile
n-Propylamine
Pyridine
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachl oroethene
Toluene
Toluene-dB (surr.)
1 , 1 , 1-Tri chl oroethane
1 , 1 , 2-Tri chl oroethane
Tri chl oroethene
Tri chl orof 1 uoromethane
1,2,3-Trichloropropane
CAS No.b
764-41-0
75-71-8
75-34-3
107-06-2
107-06-2
75-35-4
156-60-5
78-87-5
96-23-1
10061-01-5
10061-02-6
1464-53-5
540-36-3
123-91-1
106-89-8
64-17-5
100-41-4
75-21-8
97-63-2
591-78-6
78-97-7
74-88-4
78-83-1
109-77-3
126-98-7
75-09-2
74-88-4
80-62-6
108-10-1
76-01-7
109-06-8
107-19-7
57-57-8
107-12-0
107-10-8
110-86-1
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
2037-26-5
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
Purge-and-Trap
PP
a
a
a
a
a
a
a
PP
a
a
a
a
PP
i
i
a
PP
a
PP
ND
a
PP
PP
PP
a
a
a
PP
i
PP
PP
PP
PP
a
i
a
a
a
a
a
a
a
a
a
a
a
Direct
Injection
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
pc
a
a
a
a
a
a
a
a
pc
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
8240B - 2
Revision 2
November 1990

-------
                                                  Appropriate Technique
                                                                  Direct
Analyte                             CAS No."    Purge-and-Trap    Injection
Vinyl acetate
Vinyl chloride
Xylene (Total)
108-05-4
75-01-4
1330-20-7
a
a
a
a
a
a
a   Adequate response by this technique.
b   Chemical Abstract Services Registry Number.
pp  Poor purging efficiency resulting in high EQLs.
i   Inappropriate technique for this analyte.
pc  Poor chromatographic behavior.


      1.2  Method 8240 can  be used to quantitate most volatile organic compounds
that have boiling points below 200°C and that are insoluble or slightly soluble
in water.  Volatile water-soluble compounds can be included in this analytical
technique.   However,  for the more soluble  compounds,  quantitation limits are
approximately ten times higher because of poor purging efficiency.  The method
is also limited to compounds that elute as sharp peaks from a GC column packed
with graphitized carbon lightly coated with  a carbowax.  Such compounds include
low molecular  weight  halogenated hydrocarbons, aromatics,  ketones,  nitriles,
acetates, acrylates,  ethers,  and  sulfides.  See Table 1 for a list of compounds,
retention times, and  their characteristic ions that  have  been  evaluated  on a
purge-and-trap GC/MS system.

      1.3  The  estimated  quantitation  limit   (EQL)  of  Method 8240  for  an
individual  compound  is approximately 5 jig/Kg   (wet  weight)  for soil/sediment
samples, 0.5 mg/Kg (wet  weight)  for  wastes, and 5 /xg/L  for  ground water (see
Table 2).  EQLs will  be proportionately higher for sample extracts and samples
that require dilution or reduced sample size  to avoid saturation of the detector.

      1.4  Method 8240 is based upon a purge-and-trap, gas chromatographic/mass
spectrometric (GC/MS) procedure.   This method is restricted to use  by, or under
the supervision of, analysts experienced  in the use of purge-and-trap systems
and gas chromatograph/mass spectrometers,  and skilled in the interpretation of
mass spectra and their use as a quantitative tool.

      1.5  To increase purging  efficiencies of acrylonitrile and  acrolein, refer
to Methods 5030 and 8030 for proper purge-and-trap conditions.


2.0  SUMMARY OF METHOD

      2.1  The volatile compounds are introduced into the gas chromatograph by
the purge-and-trap method  or  by  direct injection  (in  limited  applications).
The components are  separated via the gas chromatograph and detected  using a mass
spectrometer,  which   is  used  to provide  both  qualitative  and  quantitative
information.    The  chromatographic  conditions,   as  well  as   typical   mass


                                  8240B - 3                      Revision 2
                                                                  November 1990

-------
spectrometer operating parameters, are given.

      2.2  If the  above  sample introduction techniques are  not  applicable,  a
portion of the sample is  dispersed in  methanol to dissolve the volatile organic
constituents.  A portion  of  the  methanolic  solution is combined  with organic-
free reagent water in a specially designed purging chamber.   It is then analyzed
by purge-and-trap GC/MS following the normal water method.

      2.3  The purge-and-trap  process - An  inert  gas is bubbled  through the
solution at  ambient  temperature,  and the volatile  components  are  efficiently
transferred  from  the aqueous  phase  to  the vapor phase.   The vapor  is  swept
through  a  sorbent column  where  the  volatile components  are trapped.   After
purging is completed, the  sorbent  column  is heated  and backflushed with  inert
gas  to  desorb the components onto  a  gas  chromatographic  column.   The  gas
chromatographic column is  heated  to elute  the components,  which  are detected
with a mass spectrometer.


3.0  INTERFERENCES

      3.1  Interferences  purged  or  coextracted  from the  samples will  vary
considerably from  source to source,  depending upon the particular  sample or
extract being tested.   The  analytical  system, however,  should be  checked to
ensure freedom from interferences, under the analysis conditions,  by analyzing
method blanks.

      3.2  Samples  can   be  contaminated  by  diffusion of  volatile  organics
(particularly methylene chloride and fluorocarbons) through the septum seal into
the sample during  shipment and storage.   A  trip  blank, prepared  from organic-
free reagent water and carried through the sampling and handling  protocol, can
serve as a check on such contamination.

      3.3  Cross contamination can occur  whenever  high-concentration and low-
concentration  samples  are  analyzed  sequentially.    Whenever  an  unusually
concentrated  sample  is   analyzed,  it should  be  followed by the  analysis of
organic-free reagent water to check for cross contamination.  The purge-and-trap
system may require extensive bake-out and cleaning  after  a  high-concentration
sample.

      3.4  The  laboratory where  volatile  analysis  is  performed  should  be
completely free of solvents.

      3.5  Impurities in the purge gas  and  from  organic  compounds  out-gassing
from the plumbing  ahead  of the trap  account for  the majority of  contamination
problems.    The  analytical  system  must  be demonstrated   to  be  free  from
contamination under the  conditions of the analysis  by running  calibration and
reagent blanks.   The  use  of  non-TFE  plastic coating,  non-TFE thread sealants,
or flow  controllers with  rubber  components in  the purging device  should be
avoided.
                                   8240B  -  4                       Revision 2
                                                                  November 1990

-------
4.0  APPARATUS AND MATERIALS

      4.1  Microsyringes - 10 /A, 25 p.L, 100 jitL, 250 /iL, 500 juL, and 1,000 ni.
These syringes should be equipped with a 20 gauge (0.006 In. ID) needle having
a length sufficient to extend from the sample  Inlet  to within 1 cm of the glass
frit In the purging device.  The needle length will  depend upon the dimensions
of the purging device employed.

      4.2  Syringe valve - Two-way, with Luer ends (three each), if applicable
to the purging device.

      4.3  Syringe - 5 ml, gas-tight with shutoff valve.

      4.4  Balances - Analytical, 0.0001 g, and top-loading, 0.1 g.

      4.5  Glass scintillation vials - 20 ml,  with screw caps and Teflon liners
or glass culture tubes with a screw cap and Teflon liner.

      4.6  Volumetric flasks,  Class A - 10  ml and  100 ml,  with ground-glass
stoppers.

      4.7  Vials - 2 ml, for GC autosampler.

      4.8  Spatula - Stainless steel.

      4.9  Disposable pipets - Pasteur.

      4.10  Heater or heated  oil  bath - Should be  capable  of  maintaining the
purging chamber to within 1°C over the temperature range of  ambient to  100°C.

      4.11  Purge-and-trap device - The purge-and-trap device consists of three
separate pieces of equipment:  the sample purger, the trap,  and the desorber.
Several complete devices are commercially available.

            4.11.1  The recommended purging chamber is designed to accept 5 ml
      samples with a  water  column at least 3  cm deep.   The gaseous headspace
      between the water  column and the trap  must have a total  volume of less than
      15 ml.  The  purge  gas must pass through the water column as finely divided
      bubbles with a diameter of.less than  3  mm at  the  origin.  The purge gas
      must be introduced no more  than 5  mm from the base of the water column.
      The sample purger, illustrated  in Figure  1, meets these design criteria.
      Alternate  sample  purge  devices  may be  utilized,  provided  equivalent
      performance  is demonstrated.

            4.11.2  The trap  must be  at least 25  cm long  and  have an inside
      diameter of  at  least  0.105 in.  Starting from the  inlet,  the trap must
      contain the following amounts  of adsorbents: 1/3 of 2,6-diphenylene oxide
      polymer, 1/3 of silica gel, and 1/3 of coconut charcoal. It is recommended
      that 1.0 cm of methyl  silicone coated packing  be inserted at the inlet to
      extend the  life of  the  trap (see Figure  2).  If  it is not necessary to
      analyze for dichlorodifluoromethane  or other fluorocarbons  of  similar
      volatility,  the charcoal can  be eliminated  and  the polymer increased to
      fill 2/3  of the trap.   If only compounds boiling above  35°C are  to be


                                   8240B -  5                      Revision 2
                                                                  November 1990

-------
analyzed, both  the silica gel and  charcoal  can be eliminated   and the
polymer increased to fill the entire trap.  Before initial use, the trap
should be conditioned overnight at 180°C by backflushing with an inert gas
flow of at least 20  mL/min.   Vent the  trap effluent  to the room, not to
the analytical column.   Prior  to daily use, the trap should be conditioned
for 10 minutes at 180°C  with backflushing.  The  trap may be vented to the
analytical column during daily conditioning.   However,  the column must be
run through the temperature program prior to analysis of samples.
                               *
      4.11.3  The desorber should be capable of rapidly heating the trap
to 180°C for desorption.  The polymer  section  of  the  trap should not be
heated higher  than  180°C,  and the remaining  sections  should  not exceed
220°C  during  bake out mode.   The desorber design illustrated in Figure 2
meets these criteria.

      4.11.4  The  purge-and-trap  device may be assembled  as  a separate
unit or may be coupled to a gas chromatograph, as shown in Figures 3 and 4.

      4.11.5  Trap Packing Materials

            4.11.5.1  2,6-Diphenylene   oxide  polymer  -   60/80  mesh,
      chromatographic grade (Tenax GC or equivalent).

            4.11.5.2  Methyl silicone packing - OV-1 (3%) on Chromosorb-W,
      60/80 mesh or equivalent.

            4.11.5.3  Silica  gel  -  35/60  mesh,  Davison,  grade 15  or
      equivalent.

            4.11.5.4  Coconut charcoal  -  Prepare from Barnebey  Cheney,
      CA-580-26, lot #M-2649, by  crushing  through  26 mesh  screen (or
      equivalent).

4.12  Gas chromatograph/mass spectrometer system

     4.12.1  Gas chromatograph  -  An analytical  system complete  with  a
temperature programmable gas  chromatograph and all  required accessories
including syringes, analytical columns, and gases.

      4.12.2  Column  -  6 ft  x 0.1 in.  ID  glass,  packed with  1% SP-1000
on Carbopack-B (60/80 mesh) or equivalent.

      4.12.3  Mass  spectrometer  - Capable  of scanning from  35-260 amu
every 3 seconds or less, using 70 volts (nominal) electron energy in the
electron  impact  mode and producing  a  mass spectrum that meets  all the
criteria in Table 3 when 50 ng of 4-bromofluorobenzene  (BFB) are injected
through the gas chromatograph inlet.

      4.12.4  GC/MS  interface  -  Any  GC-to-MS  interface  that  gives
acceptable calibration points at 50 ng or less per injection for each of
the analytes and achieves all acceptable performance criteria (see Table 3)
may be used. GC-to-MS interfaces  constructed entirely of glass or of glass-
lined materials are  recommended.  Glass  can be deactivated by  silanizing
with dichlorodimethylsilane.

                            8240B -  6                       Revision 2
                                                            November 1990

-------
            4.12.5  Data system - A computer system that allows the continuous
      acquisition and  storage on machine  readable  media of  all  mass spectra
      obtained throughout the duration  of  the  chromatographic program must be
      interfaced to the mass spectrometer.  The  computer must have software that
      allows searching  any  GC/MS data  file  for  ions of a  specified  mass and
      plotting such ion abundances versus time or scan number.  This type of plot
      is defined as an  Extracted  Ion Current  Profile  (EICP). Software must also
      be available that allows integrating the abundances  in  any EICP between
      specified  time or scan number  limits.  The most  recent version  of the
      EPA/NIST Mass Spectral Library should also be available.


5.0  REAGENTS

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

      5.2  Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3  Stock solutions - Stock  solutions  may  be prepared from pure standard
materials or purchased  as certified solutions.  Prepare stock standard solutions
in methanol, using assayed liquids or gases,  as appropriate.

            5.3.1  Place about 9.8 ml  of methanol  in a 10 mL tared ground-glass-
      stoppered  volumetric  flask.  Allow  the flask  to stand,  unstoppered, for
      about 10 minutes or until  all alcohol wetted surfaces have dried.  Weigh
      the flask to the nearest 0.0001 g.

            5.3.2  Add the assayed reference material, as described below.

                  5.3.2.1  Liquids -  Using a  100 /iL syringe,  immediately add
            two or more drops of assayed reference material to the flask; then
            reweigh.   The  liquid must  fall directly  into  the alcohol without
            contacting the neck of the  flask.

                  5.3.2.2  Gases - To prepare  standards for any compounds that
            boil below 30°C  (e.g. bromomethane, chloroethane, chloromethane, or
            vinyl  chloride),  fill  a  5  mL valved  gas-tight  syringe  with the
            reference  standard to  the 5.0 mL mark.    Lower  the  needle to 5 mm
            above the methanol meniscus. Slowly introduce the reference standard
            above the surface  of the liquid. The heavy gas will rapidly dissolve
            in the methanol.  Standards  may also  be prepared by using a lecture
            bottle  equipped with a  Hamilton  Lecture Bottle  Septum  (#86600).
            Attach Teflon tubing to the side-arm relief valve and direct a gentle
            stream of gas into the methanol meniscus.

            5.3.3  Reweigh, dilute  to  vofume, stopper, and then mix by inverting
      the flask  several times.   Calculate  the  concentration in milligrams per


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      liter (mg/L) from the net gain in weight.  When compound purity  is assayed
      to  be  96%  or greater, the weight  may be  used without  correction to
      calculate the concentration of the stock standard.  Commercially prepared
      stock standards may be used at any concentration  if they are certified by
      the manufacturer or by an independent source.

            5.3.4  Transfer the  stock standard solution into a Teflon sealed
      screw cap bottle.   Store,  with minimal  headspace, at  -10°C to -20°C and
      protect from light.

            5.3.5  Prepare fresh standards every two months for gases.  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.  Both gas  and  liquid  standards  must be  monitored closely by
      comparison to the initial  calibration curve  and by comparison to QC check
      standards.  It may  be  necessary  to replace the standards more frequently
      if either check exceeds a 25% difference.

      5.4  Secondary dilution  standards - Using stock standard solutions, prepare
in methanol,  secondary dilution  standards containing the compounds of interest,
either singly or  mixed  together.   Secondary dilution standards  must  be stored
with minimal  headspace and should be checked frequently  for  signs of degradation
or evaporation, especially  just  prior to preparing calibration standards from
them.

      5.5  Surrogate  standards  -  The  surrogates recommended are toluene-da,
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 5.3,  and  a
surrogate  standard spiking solution  should be prepared  from the stock  at  a
concentration  of  250  /ug/10  ml  in methanol.   Each sample  undergoing  GC/MS
analysis must be  spiked  with  10  /iL of the surrogate spiking solution prior to
analysis.

      5.6  Internal   standards   -   The   recommended  internal  standards  are
bromochloromethane, 1,4-difluorobenzene, and chlorobenzene-ds.  Other compounds
may be used as internal  standards as long as they  have retention times similar
to the compounds being detected by GC/MS.   Prepare internal  standard stock and
secondary  dilution standards in  methanol  using  the procedures  described in
Sections 5.3 and  5.4.   It  is  recommended that the secondary dilution standard
should be  prepared at  a concentration of  25 mg/L  of each  internal standard
compound.  Addition of 10 p.1 of this standard to 5.0 ml  of sample or calibration
standard would be the equivalent of 50 M9/L-

      5.7  4-Bromofluorobenzene (BFB) standard - A standard solution containing
25 ng/jiL of BFB in methanol should be prepared.

      5.8  Calibration  standards  -  Calibration  standards  at a minimum of five
concentrations should be prepared from the secondary dilution of  stock standards
(see Sections  5.3 and 5.4).  Prepare these solutions  in  organic-free reagent
water. One of the concentrations should be  at a concentration near, but above,
the method detection  limit. The remaining concentrations  should correspond to
the expected range of concentrations found in real  samples  but should  not exceed


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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  target analytes may be
included). Calibration standards must be prepared daily.

      5.9  Matrix spiking standards - Matrix spiking standards should  be prepared
from volatile organic  compounds  which will be representative of the compounds
being   investigated.      The   suggested  compounds   are  1,1-dichloroethene,
trichloroethene, chlorobenzene,  toluene, and  benzene.   The standard should be
prepared  in  methanol,  with  each  compound  present  at  a   concentration  of
250 jug/10.0 ml.

      5.10  Great care must be taken to maintain the integrity of all standard
solutions.  It is recommended that all  standards in  methanol  be  stored  at  -10°C
to -20°C in screw cap amber bottles  with Teflon liners.

      5.11  Methanol, CH3OH.  Pesticide quality or equivalent. Store apart from
other solvents.

      5.12  Reagent Tetraglyme - Reagent tetraglyme  is defined as tetraglyme in
which interference is  not observed  at the  method  detection limit of compounds
of interest.

            5.12.1  Tetraglyme  (tetraethylene glycol dimethyl  ether,  Aldrich
      #17, 240-5 or equivalent),  C8H1805.  Purify by  treatment at reduced pressure
      in a rotary evaporator. The tetraglyme should have a peroxide content of
      less  than  5 ppm as indicated by  EM Quant  Test  Strips (available  from
      Scientific Products Co., Catalog No. P1126-8 or equivalent).

CAUTION;   Glycol ethers  are suspected carcinogens. All solvent handling should
           be done in a hood while using proper protective equipment  to minimize
           exposure to liquid and vapor.

           Peroxides may  be removed by passing the tetraglyme through a column
      of activated alumina.  The tetraglyme is placed in  a round bottom flask
      equipped with a standard taper joint, and the flask is affixed  to a rotary
      evaporator. The flask is  immersed  in a water bath at 90-100°C and a vacuum
      is maintained  at <  10 mm  Hg  for at least  two hours  using a two stage
      mechanical pump. The vacuum system is  equipped with an all  glass trap,
      which is maintained in a dry ice/methanol  bath.  Cool  the tetraglyme to
      ambient temperature and add 0.1 mg/mL of 2,6-di-tert-butyl-4-methyl-phenol
      to prevent peroxide formation. Store the tetraglyme in a tightly sealed
      screw cap  bottle in an area that is not contaminated by solvent vapors.

            5.12.2   In order to demonstrate that all  interfering volatiles have
      been removed from the tetraglyme,  an organic-free reagent water/tetraglyme
      blank must be analyzed.

      5.13  Polyethylene  glycol,  H(OCH2CH2)nOH.   Free of  interferences  at the
detection limit of the analytes.
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6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

     6.1   See  the  Introductory material  to  this chapter,  Organic Analytes,
Section 4.1.
7.0  PROCEDURE

      7.1  Direct Injection -  In very limited applications (e.g. aqueous process
wastes), direct  Injection of the  sample  Into the GC/MS system  with a  10 ML
syringe may be  appropriate.   One such application is  for verification  of the
alcohol content  of an  aqueous  sample prior  to  determining if the  sample is
ignitable  (Methods  1010 or 1020).   In this case,  it  is  suggested that  direct
injection be used.  The detection limit is very  high  (approximately 10,000 M9/L);
therefore, 1t  is only permitted when concentrations in  excess of 10,000 ng/L are
expected or for water soluble compounds that do not purge.  The system must be
calibrated by direct injection (bypassing the purge-and-trap device).

      7.2  Initial calibration for purge-and-trap procedure

            7.2.1 Recommended GC/MS operating conditions

      Electron energy:               70 volts (nominal).
      Mass range:                   35-260 amu.
      Scan time:                    To give 5  scans/peak,  but  not to exceed 7
                                    sec/scan.
      Initial  column temperature:   45°C.
      Initial  column holding time:  3 minutes.
      Column temperature program:   8°C/minute.
      Final column temperature:      220°C.
      Final column holding time:    15 minutes.
      Injector temperature:         200-225°C.
      Source temperature:           According to manufacturer's specifications.
      Transfer line temperature:    250-300°C.
      Carrier gas:                  Hydrogen at 50 cm/sec or helium at  30 cm/sec.

            7.2.2  Each GC/MS  system must be hardware tuned to meet the criteria
      in Table 3 for a  50 ng injection or purging of 4-bromofluorobenzene (2 pi
      injection  of the BFB standard).   Analyses  must not begin  until  these
      criteria are met.

            7.2.3  Assemble a  purge-and-trap device that meets the specification
      in Section 4.11.   Condition the  trap  overnight at 180°C in the purge mode
      with an  inert gas  flow of at least 20 mL/min.  Prior to use,  condition the
      trap daily for 10  min while backflushing  at  180°C with the  column at 220°C.

            7.2.4  Connect the purge-and-trap device to a gas chromatograph.

            7.2.5  Prepare  the   final   solutions  containing  the   required
      concentrations of  calibration standards, including surrogate standards,
      directly in the purging  device (use freshly prepared  stock solutions when
      preparing  the calibration  standards  for the initial  calibration.)   Add
      5.0 mL of organic-free reagent water  to the purging device.   The organic-


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free reagent  water is added  to  the purging  device  using a  5  ml glass
syringe fitted  with  a 15 cm,  20  gauge needle.  The  needle  Is  Inserted
through the sample Inlet shown In  Figure 1.  The Internal diameter of the
14 gauge needle that forms the sample Inlet will permit Insertion of the
20 gauge needle.  Next,  using  a 10 nl or 25 ML mlcrosyrlnge equipped with
a  long  needle  (Section  4.1),  take a  volume  of the  secondary  dilution
solution containing appropriate concentrations of the calibration standards
(Section 5.6).  Add  the  aliquot of calibration solution directly to the
organic-free reagent water in the purging device by inserting the needle
through  the  sample  inlet.    When discharging   the  contents  of  the
microsyringe, be sure that the end of the syringe needle is well beneath
the surface of  the organic-free reagent water.   Similarly,  add  10 /uL of
the internal  standard  solution (Section 5.4).  Close  the  2  way syringe
valve at the sample inlet.

      7.2.6  Carry out the purge-and-trap analysis  procedure as described
in Section 7.4.1.

      7.2.7 Tabulate the  area response of the  characteristic ions (see
Table  1)   against  concentration  for  each  compound  and each  internal
standard.  Calculate response factors (RF) for each compound relative to
one of  the internal  standards.  The internal  standard selected for the
calculation of the RF for a compound should be  the  internal standard that
has a  retention time  closest to  the  compound being  measured  (Section
7.5.2).  The RF is calculated as follows:

      RF = (AXC1S)/(A1SCX)

where:

AX  =  Area of the characteristic ion for the compound being measured.
A,s = Area of the characteristic ion for the specific internal standard.
C,s = Concentration of the specific internal  standard.
Cx  =  Concentration of the compound being measured.

      7.2.8  The average RF must be calculated  for each compound.  A system
performance check  should  be made  before this  calibration curve  is used.
Five compounds  (the System Performance Check Compounds, or  SPCCs)  are
checked  for  a  minimum  average response factor.   These  compounds  are
chloromethane,  1,1-dichloroethane, bromoform,  1,1,2,2-tetrachloroethane,
and chlorobenzene.  The  minimum acceptable average  RF for these compounds
should be 0.300 (0.250 for bromoform).  These compounds  typically have RFs
of 0.4-0.6 and  are used to check compound instability and  to check for
degradation caused by contaminated  lines or active sites in the system.
Examples of these occurrences are:

            7.2.8.1  Chloromethane  -  This compound  is the  most  likely
      compound  to be lost if the purge  flow is too fast.

            7.2.8.2  Bromoform -  This  compound is one  of the compounds
      most likely to be purged very poorly if  the purge flow is too slow.
      Cold spots and/or active sites in the transfer lines may adversely
      affect  response.   Response of the quantitation ion  (m/z  173)  is


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      directly  affected  by  the  tuning  of BFB  at  ions  m/z  174/176.
      Increasing the m/z 174/176 ratio may improve bromoform response.

            7.2.8.3  Tetrachloroethane  and  1,1-dichloroethane  -  These
      compounds are degraded  by contaminated transfer lines in purge-and-
      trap systems and/or active sites in trapping materials.

      7.2.9  Using the  RFs  from the  initial calibration,  calculate the
percent relative standard deviation (%RSD) for Calibration Check Compounds
(CCCs).

                   SD
           %RSD	x 100
where:

RSD = relative standard deviation.
x = mean of 5 initial RFs for a compound.
SD  = standard deviation of average RFs for a compound.
      SD
                N   (x,  -
                i=l   N - 1
      The %RSD  for  each individual  CCC should be  less  than 30 percent.
This criterion must be met in order for the individual calibration to be
valid.  The CCCs are:

     1,1-Dichloroethene,
     Chloroform,
     1,2-Dichloropropane,
     Toluene,
     Ethyl benzene, and
     Vinyl chloride.

7.3  Daily GC/MS calibration

      7.3.1  Prior to the analysis  of  samples,  inject or purge 50 ng of
the 4-bromofluorobenzene  standard.   The resultant mass  spectra for the
BFB must meet all of the criteria given in Table 3 before sample analysis
begins.  These criteria must be demonstrated each 12 hour shift.

      7.3.2  The initial calibration curve (Section 7.2) for  each compound
of interest must be checked and verified once every 12 hours of analysis
time.  This  is  accomplished  by  analyzing  a  calibration standard that is
at a concentration near the midpoint concentration for the working range
of the GC/MS by  checking the SPCC (Section 7.3.3)  and CCC  (Section 7.3.4).

      7.3.3  System  Performance  Check  Compounds   (SPCCs)   -  A  system
performance check must  be made  each 12 hours.   If the SPCC criteria are
met, a comparison of response factors is made for all  compounds.  This is
the same  check  that is applied during  the  initial  calibration.   If the

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minimum response factors are not met,  the  system must be evaluated,  and
corrective action must be taken before sample analysis begins.  The minimum
response factor for volatile SPCCs is 0.300 (0.250 for Bromoform).  Some
possible problems are standard mixture degradation, injection port inlet
contamination, contamination at the  front  end  of the analytical  column,
and active sites in the column or chromatographic system.

      7.3.4  Calibration  Check  Compounds   (CCCs):    After  the  system
performance check is met, CCCs listed in Section 7.2.9 are used to check
the validity of the initial calibration.  Calculate the percent difference
using:

                           RF,  - RF
            % Difference = —= -   x 100
                             RF,
where:
RF, =  average response factor from initial calibration.
RFC  =  response factor from current verification check standard.

      If the percent difference for any compound is greater than 20, the
laboratory should consider this a warning limit.  If the percent difference
for each CCC is  less than 25%,  the  initial  calibration is assumed to be
valid.  If the criterion  is not met (> 25% difference), for any one CCC,
corrective action MUST be taken.  Problems similar to those listed under
SPCCs could affect  this  criterion.   If no source  of the  problem can be
determined  after corrective  action  has  been  taken,  a  new  five point
calibration  MUST be  generated.   This criterion  MUST  be met  before
quantitative sample analysis begins.

      7.3.5  The  internal standard responses and  retention times in the
check calibration standard must be evaluated immediately after or during
data acquisition.  If the  retention time for any internal standard changes
by more than 30  seconds  from  the last  check calibration  (12 hours), the
chromatographic system must  be inspected for malfunctions and corrections
must  be made,  as required.   If the EICP  area for any of the internal
standards changes by a  factor  of two (- 50% to + 100%) from  the last daily
calibration standard check, the mass  spectrometer must be inspected for
malfunctions  and  corrections  must   be  made,  as  appropriate.    When
corrections are made,  reanalysis of samples  analyzed while  the system was
malfunctioning are necessary.

7.4  GC/MS analysis

      7.4.1  Water samples

            7.4.1.1  Screening  of the  sample  prior  to  purge-and-trap
      analysis  will provide  guidance  on  whether  sample dilution  is
      necessary  and will  prevent contamination  of the  purge-and-trap
      system.   Two  screening  techniques  that can  be used  are:   the
      headspace  sampler   (Method  3810)  using  a gas chromatograph  (GC)
      equipped with a  photo ionization  detector (PID)  in  series with an
      electrolytic  conductivity detector  (HECD);  and  extraction  of the

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sample with hexadecane and analysis of  the  extract  on a GC with a
FID and/or an ECD (Method 3820).

      7.4.1.2  All samples and  standard  solutions must be allowed
to warm to ambient temperature before analysis.

      7.4.1.3  Set up the GC/MS system as outlined in Section 7.2.1.

      7.4.1.4  BFB  tuning  criteria  and  daily GC/MS  calibration
criteria must be met (Section 7.3) before analyzing  samples.

      7.4.1.5  Adjust  the  purge  gas  (helium)  flow  rate to  25-
40 mL/min on the purge-and-trap device.   Optimize the flow rate to
provide the best response for  chloromethane  and bromoform, if these
compounds are analytes.  Excessive flow rate reduces chloromethane
response, whereas insufficient flow reduces  bromoform response (see
Section 7.2.8).

      7.4.1.6  Remove the plunger from a 5 ml syringe and attach a
closed syringe  valve.   Open  the sample  or  standard  bottle,  which
has been allowed to  come to ambient temperature, and carefully pour
the sample  into  the syringe  barrel  to just short of overflowing.
Replace  the  syringe plunger  and  compress  the  sample.   Open  the
syringe valve and vent any residual  air while adjusting the sample
volume to 5.0 ml.  This process of taking an aliquot destroys the
validity of the  liquid sample for future  analysis;  therefore,  if
there is only one VOA vial, the analyst should fill a second syringe
at this time to protect against possible loss of sample integrity.
This  second  sample  is maintained  only  until  such  time  when  the
analyst  has  determined that  the  first  sample has   been  analyzed
properly.  Filling one  20 ml syringe would allow the use of only one
syringe.  If a  second analysis is needed  from  a syringe, it must be
analyzed within  24 hours.  Care must  be  taken to  prevent air from
leaking into the syringe.

      7.4.1.7  The following  procedure is appropriate for diluting
purgeable samples.  All steps must be performed without  delays until
the diluted sample is in a gas tight  syringe.

            7.4.1.7.1  Dilutions may be  made  in volumetric flasks
      (10 to 100 ml).  Select the volumetric flask that will allow
      for the  necessary  dilution.   Intermediate dilutions  may be
      necessary for extremely large dilutions.

            7.4.1.7.2  Calculate the approximate volume of organic-
      free reagent water to be added to the volumetric flask selected
      and  add  slightly less  than this  quantity of organic-free
      reagent water to the flask.

            7.4.1.7.3  Inject the proper aliquot of  samples from
      the  syringe prepared  in Section  7.4.1.6  into the  flask.
      Aliquots of less than  1 ml  are  not recommended.   Dilute the
      sample to the mark with organic-free reagent water.  Cap the
      flask, invert, and  shake three times.  Repeat above procedure

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      for additional dilutions.

            7.4.1.7.4  Fill a 5 ml syringe with the diluted sample
      as in Section 7.4.1.6.

      7.4.1.8  Add 10.0 /iL  of  surrogate  spiking solution (Section
5.3) and 10 /iL of internal standard spiking solution (Section 5.4)
through the valve bore of  the  syringe; then  close the  valve.   The
surrogate and internal  standards may  be mixed and  added as a single
spiking solution.  The addition  of 10 juL of the surrogate spiking
solution to  5 ml of  sample is  equivalent  to  a  concentration  of
50 /itg/L of each surrogate standard.

      7.4.1.9  Attach  the  syringe-syringe  valve  assembly  to  the
syringe valve on the purging device.  Open  the syringe valves and
inject the sample into the purging chamber.

      7.4.1.10  Close  both  valves  and purge  the sample for 11.0 ±
0.1 minutes at ambient temperature.

      7.4.1.11  At  the conclusion of the purge  time,  attach  the
trap to the  chromatograph,  adjust the device  to  the  desorb mode,
and begin the gas chromatographic temperature program and GC/MS data
acquisition.  Concurrently,  introduce the trapped  materials to the
gas chromatographic  column by rapidly heating the trap to 180°C while
backflushing  the trap  with  inert gas between  20 and 60 mL/min for
4 minutes.   If this rapid heating requirement cannot be met, the gas
chromatographic column must be used as a secondary trap by cooling
it  to  30°C  (or  subambient,  if  problems  persist)  instead  of  the
recommended initial  program temperature of 45°C.

      7.4.1.12  While  the  trap is  being desorbed  into  the  gas
chromatograph, empty the purging chamber.  Wash the chamber with a
minimum of  two  5  ml  flushes  of  organic-free reagent  water  (or
methanol followed by organic-free reagent water) to avoid carryover
of pollutant  compounds into subsequent analyses.

      7.4.1.13  After   desorbing  the   sample   for   4   minutes,
recondition the trap by returning the purge-and-trap device to the
purge mode.   Wait 15 seconds;  then close the  syringe  valve on the
purging device  to  begin  gas  flow through  the  trap.    The  trap
temperature should be maintained at 180°C.  Trap temperatures up to
220°C may be  employed;  however,  the higher temperature will shorten
the useful  life of the trap.   After  approximately 7 minutes,  turn
off the trap heater and open the syringe  valve  to  stop the gas flow
through the trap.  When cool, the trap is  ready  for the next sample.

      7.4.1.14   If the initial  analysis  of  a  sample or a dilution
of  the  sample has  a  concentration of  analytes  that  exceeds  the
initial calibration  range,  the sample must be reanalyzed at a higher
dilution.   Secondary ion quantitation is allowed only when there are
sample interferences with the primary ion. When a sample is analyzed
that has  saturated  ions  from  a  compound,  this  analysis  must  be


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      followed  by  a blank organic-free reagent water  analysis.   If the
      blank  analysis  is not free  of interferences, the  system  must be
      decontaminated.   Sample  analysis  may  not resume  until a blank can
      be analyzed that  is free of interferences.

            7.4.1.15   For matrix spike  analysis, add 10 /nL  of the matrix
      spike solution  (Section  5.7)  to the 5 ml of  sample to be purged.
      Disregarding  any  dilutions,  this  is equivalent to a  concentration
      of 50 M9/L of each matrix spike standard.

            7.4.1.16   All dilutions should keep the  response of the major
      constituents  (previously saturated peaks) in the upper half of the
      linear range of the curve.   Proceed  to Sections 7.5.1  and 7.5.2 for
      qualitative and quantitative analysis.

      7.4.2 Water miscible liquids

            7.4.2.1  Water miscible liquids  are analyzed as  water samples
      after first diluting them at least 50 fold with organic-free reagent
      water.

            7.4.2.2  Initial  and  serial  dilutions  can  be  prepared  by
      pipetting  2  ml  of  the sample  to a 100  ml  volumetric flask and
      diluting  to   volume  with organic-free  reagent  water.   Transfer
      immediately to a  5 ml gas tight syringe.

            7.4.2.3  Alternatively, prepare dilutions directly in a 5 ml
      syringe filled with organic-free  reagent  water by adding  at least
      20 MU  but  not  more than 100 /iL  of liquid sample.   The sample is
      ready for addition of internal and surrogate standards.

      7.4.3  Sediment/soil and waste  samples  -  It  is highly recommended
that all  samples  of this type  be  screened prior to the  purge-and-trap
GC/MS analysis.   The  headspace method  (Method 3810)  or  the hexadecane
extraction and screening method (Method 3820) may be used for  this purpose.
These samples may contain percent  quantities  of purgeable organics that
will contaminate the purge-and-trap system, and require extensive cleanup
and instrument downtime.  Use the screening data to determine whether to
use the  low-concentration method (0.005-1 mg/Kg)  or the high-concentration
method (> 1 mg/Kg).

            7.4.3.1  Low-concentration  method  -  This   is  designed  for
      samples containing individual  purgeable  compounds of < 1 mg/Kg.  It
      is limited to sediment/soil  samples and waste that is of a similar
      consistency (granular and porous). The low-concentration method is
      based on purging  a heated sediment/soil  sample mixed with  organic-
      free reagent water containing  the  surrogate and internal standards.
      Analyze all reagent blanks and standards under the same conditions
      as the  samples.   See  Figure 5 for an illustration  of a low soils
      impinger.

                  7.4.3.1.1  Use a 5 g sample if the expected concentration
            is < 0.1  mg/Kg  or a 1 g  sample for expected  concentrations


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                  between 0.1 and 1 mg/Kg.

                        7.4.3.1.2  The GC/MS  system  should  be  set  up  as  in
                  Sections 7.4.1.2-7.4.1.4.  This should  be  done prior to the
                  preparation of  the  sample to  avoid loss of  volatiles from
                  standards and samples.   A heated purge calibration curve must
                  be prepared  and used  for the quantitation  of  all  samples
                  analyzed with the low-concentration method.  Follow the initial
                  and daily calibration  instructions,  except  for the addition
                  of a 40°C purge  temperature.

                        7.4.3.1.3  Remove the plunger  from a 5 ml Luerlock type
                  syringe  equipped  with  a  syringe   valve  and  fill  until
                  overflowing with water.  Replace the plunger and compress the
                  water to vent trapped air. Adjust the volume to 5.0 ml.  Add
                  10 /uL  each  of surrogate  spiking solution  (Section 5.3) and
                  internal standard solution (Section 5.4) to the syringe through
                  the valve.  (Surrogate  spiking  solution and internal standard
                  solution may be  mixed together.)  The addition of  10 /uL  of the
                  surrogate  spiking  solution   to   5   g  of  sediment/soil  is
                  equivalent to 50 M9/K9  of each surrogate standard.

                        7.4.3.1.4  The sample (for volatile organics) consists
                  of the  entire contents of the sample container.  Do not discard
                  any  supernatant liquids.   Mix the  contents of the  sample
                  container with  a narrow metal spatula.   Weigh the  amount
                  determined in Section  7.4.3.1.1  into a  tared  purge device.
                  Note and record the actual weight to the nearest 0.1 g.

                        7.4.3.1.5  Determine  the percent  dry  weight of the
                  soil/sediment sample.   This includes waste samples that are
                  amenable to percent  dry weight determination.   Other wastes
                  should be reported on a wet-weight basis.

                              7.5.3.1.5.1  Immediately after weighing the  sample
                        for extraction, weigh 5-10 g of the sample  into a tared
                        crucible.  Determine the % dry weight of the sample by
                        drying overnight  at 105°C. Allow to cool in  a desiccator
                        before  re-weighing.    Concentrations  of  individual
                        analytes  are  reported  relative to the dry  weight  of
                        sample.

WARNING;   The drying oven should  be contained in a  hood or vented.  Significant
           laboratory  contamination  may  result from a   heavily  contaminated
           hazardous waste sample.


                    % dry  weight  = q of  dry sample x  100
                                    g of  sample

                        7.4.3.1.6  Add the spiked  water  to  the  purge device,
                  which contains the weighed amount of sample, and connect the
                  device to the purge-and-trap system.


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NOTE; Prior to the attachment of  the  purge  device,  the procedures in Sections
      7.4.3.1.4 and.7.4.3.1.6 must be performed rapidly and without interruption
      to avoid loss of volatile organics.   These  steps must be performed in a
      laboratory free of solvent fumes.

                        7.4.3.1.7  Heat the sample to  40°C ± 1°C and purge the
                  sample for 11.0 ± 0.1 minute.

                        7.4.3.1.8  Proceed  with  the  analysis  as outlined  in
                  Sections 7.4.1.11-7.4.1.16.   Use 5 mL of the same organic-free
                  reagent water as  in the reagent blank.   If  saturated peaks
                  occurred or would occur if  a 1 g  sample  were analyzed, the
                  high-concentration method must be followed.

                        7.4.3.1.9  For  low-concentration  sediment/soils  add
                  10 /iL of the matrix spike solution (Section 5.7) to the 5 ml
                  of  organic-free reagent  water  (Section  7.4.3.1.3).    The
                  concentration for a  5 g sample would be equivalent to 50 M9/Kg
                  of each matrix spike standard.

                  7.4.3.2  High-concentration  method -  The  method  is based on
            extracting the sediment/soil with methanol.  A waste  sample is either
            extracted  or  diluted, depending  on  its solubility  in  methanol.
            Wastes (i.e.  petroleum and  coke  wastes)   that  are  insoluble  in
            methanol  are diluted with reagent tetraglyme or possibly polyethylene
            glycol (PEG).  An aliquot  of  the  extract is added  to organic-free
            reagent water containing  internal standards.   This is  purged  at
            ambient temperature.   All  samples  with an expected concentration of
            > 1.0 mg/Kg should be analyzed by  this method.

                        7.4.3.2.1  The sample  (for volatile organics) consists
                  of the entire contents of the sample container.  Do not discard
                  any  supernatant  liquids.    Mix the  contents of  the  sample
                  container with a narrow  metal  spatula.  For sediment/soil and
                  solid wastes that are insoluble  in methanol,  weigh 4  g (wet
                  weight) of sample into a tared 20 ml  vial.  Use a top loading
                  balance.  Note and  record the actual  weight  to 0.1 gram and
                  determine the  percent  dry  weight of  the sample  using the
                  procedure in Section 7.4.3.1.5.   For  waste that is soluble in
                  methanol,  tetraglyme, or  PEG, weigh  1  g  (wet weight)  into a
                  tared scintillation  vial or culture tube or a  10 ml volumetric
                  flask.  (If  a  vial  or  tube is  used,  it  must  be  calibrated
                  prior to use.  Pipet 10.0 ml  of solvent into the vial and mark
                  the bottom of the meniscus.   Discard this solvent.)

                        7.4.3.2.2  Quickly add 9.0 ml  of appropriate solvent;
                  then add 1.0 ml of the surrogate spiking solution to the vial.
                  Cap and shake for 2  minutes.

NOTE; Sections 7.4.3.2.1  and  7.4.3.2.2 must be performed rapidly  and  without
      interruption to  avoid  loss  of  volatile  organics.   These  steps must  be
      performed in a laboratory free from solvent fumes.
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      7.4.3.2.3  Pi pet approximately 1 mi  of the extract to
a GC vial for storage, using a disposable pipet. The remainder
may be disposed of. Transfer approximately 1 ml of appropriate
solvent to a separate GC  vial  for  use as the method blank for
each set of samples.  These extracts may be  stored at 4°C in
the dark,  prior to  analysis.  The addition of a 100 /iL aliquot
of each of  these extracts in Section  7.4.3.2.6  will  give a
concentration  equivalent  to  6,200  M9/Kg  of  each  surrogate
standard.

      7.4.3.2.4  The  GC/MS system  should  be  set  up as in
Sections 7.4.1.2-7.4.1.4.  This should be  done prior to the
addition of the solvent extract to  organic-free reagent water.

      7.4.3.2.5  Table 4 can be used to determine the volume
of solvent extract to add to the 5 ml of organic-free reagent
water for  analysis.   If a screening procedure  was followed
(Method 3810  or 3820),  use  the  estimated  concentration to
determine the  appropriate volume.  Otherwise,  estimate the
concentration range of the sample from the low-concentration
analysis to determine the appropriate volume.  If the sample
was submitted as a high-concentration sample, start with 100
p.1.   All  dilutions  must keep  the response of  the  major
constituents (previously  saturated  peaks)  in the upper half
of the linear range of the curve.

      7.4.3.2.6  Remove  the  plunger from a  5.0  ml Luerlock
type  syringe  equipped with a  syringe  valve  and  fill  until
overflowing with 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 pi of internal
standard solution.   Also add the volume of solvent extract
determined in Section 7.4.3.2.5 and  a volume of extraction or
dissolution solvent  to total  100 /LiL  (excluding  methanol in
standards).

      7.4.3.2.7  Attach the syringe-syringe valve assembly to
the  syringe  valve  on the purging device.   Open  the syringe
valve and inject the organic-free reagent water/methanol sample
into the purging chamber.

      7.4.3.2.8  Proceed  with the  analysis  as  outlined in
Section 7.4.1.11-7.4.1.16. Analyze  all reagent blanks on the
same instrument  as that  use  for the samples.  The standards
and blanks should also contain 100 n\. of solvent to simulate
the sample conditions.

      7.4.3.2.9  For a matrix spike  in  the high-concentration
sediment/soil  samples,  add 8.0  mL  of  methanol,   1.0 ml of
surrogate spike  solution  (Section 5.3), and  1.0 ml of matrix
spike solution (Section  5.7)  as  in  Section 7.4.3.2.2.   This
results in a 6,200 M9/Kg concentration of  each matrix spike

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            standard when added to a 4 g sample.  Add a 100 /iL aliquot of
            this extract to 5 ml of organic-free reagent water for purging
            (as per Section 7.4.3.2.6).

7.5  Data interpretation

      7.5.1  Qualitative analysis

            7.5.1.1  The qualitative identification of compounds determined
      by this method is based  on  retention time, and on comparison of the
      sample   mass   spectrum,    after   background   correction,   with
      characteristic ions in a reference mass spectrum. The reference mass
      spectrum must be generated  by  the laboratory  using the conditions
      of this method.   The  characteristic ions from the reference mass
      spectrum are  defined  to  be the three  ions  of greatest  relative
      intensity,  or any ions over 30% relative intensity if less than three
      such  ions  occur in the  reference spectrum.   Compounds  should be
      identified as present when the criteria below are met.

              7.5.1.1.1 The intensities of the  characteristic  ions of a
            compound maximize  in the same scan or within one scan of each
            other.  Selection  of a peak by a data system target compound
            search routine where  the search  is  based on  the presence of
            a target chromatographic peak containing ions  specific for the
            target compound  at a  compound-specific retention time will be
            accepted as meeting this criterion.

              7.5.1.1.2 The RRT of the sample component is within ± 0.06
            RRT units of the RRT of the standard component.

              7.5.1.1.3 The relative  intensities  of the characteristic
            ions agree within 30% of the relative intensities  of these ions
            in the  reference  spectrum.   (Example:   For an ion  with an
            abundance of 50% in the reference spectrum,  the corresponding
            abundance in a sample  spectrum can range  between  20% and 80%.)

              7.5.1.1.4 Structural isomers that  produce very similar mass
            spectra should be  identified  as individual  isomers  if they
            have sufficiently different GC  retention times.  Sufficient
            GC resolution is achieved if the height of the valley between
            two isomer peaks is less than  25% of the sum of the two peak
            heights.   Otherwise, structural  isomers  are identified as
            isomeric pairs.

              7.5.1.1.5'Identification is hampered when sample components
            are not resolved chromatographically and produce mass spectra
            containing ions contributed by more than one analyte.   When
            gas chromatographic peaks obviously represent more  than one
            sample component (i.e., a broadened peak with shoulder(s) or
            a valley  between two  or  more maxima),  appropriate  selection
            of  analyte  spectra   and  background spectra is  important.
            Examination of extracted ion current profiles of appropriate
            ions can aid in the selection  of spectra,  and in qualitative


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      identification of compounds.  When analytes coelute (i.e., only
      one  chromatographic  peak  is apparent),  the  identification
      criteria can be  met, but  each  analyte spectrum will contain
      extraneous ions contributed by the coeluting compound.

      7.5.1.2  For samples containing components not associated with
the calibration  standards,  a library search  may be made for the
purpose of tentative identification.  The necessity to perform this
type of identification will  be  determined  by  the type of analyses
being conducted.  Guidelines for making tentative identification are:

      (1)   Relative  intensities  of major  ions in  the reference
spectrum (ions > 10% of the most  abundant ion)  should be present in
the sample spectrum.

      (2)   The relative  intensities of  the  major ions should agree
within + 20%.   (Example:  For an ion with an  abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%).

      (3)   Molecular ions  present in the reference spectrum should
be present in the sample  spectrum.

      (4)   Ions  present  in  the  sample spectrum but  not  in  the
reference  spectrum  should  be  reviewed for   possible  background
contamination or presence of coeluting compounds.

      (5)   Ions present in  the  reference  spectrum  but not in the
sample spectrum  should be  reviewed for  possible subtraction  from
the sample spectrum because of background contamination or coeluting
peaks.  Data system library reduction programs  can sometimes create
these discrepancies.

      Computer generated  library  search routines  should  not  use
normalization routines that would misrepresent the library or unknown
spectra when compared to  each other.  Only after visual comparison
of sample with the nearest library searches will the mass spectral
interpretation specialist assign a tentative identification.

7.5.2  Quantitative analysis

      7.5.2.1  When a compound has been identified, the quantitation
of that compound will be  based on  the integrated  abundance from the
EICP of the primary characteristic ion.  Quantitation  will take place
using the  internal standard technique.  The internal standard used
shall  be  the one  nearest  the  retention time  of that  of a given
analyte (e.g. see Table 5).

      7.5.2.2  Calculate the concentration of each identified analyte
in the sample as follows:
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            Water

                                       (AJdJ
            concentration  (M9/L)  =
                                    (Als)(RF)(V0)

           where:

            A,, =  Area of characteristic  ion  for  compound  being  measured.
            Is =  Amount of  internal  standard injected  (ng).
            Als=   Area of characteristic  ion  for  the  internal  standard.
            RF =  Response factor  for compound  being  measured  (Section  7.3.3).
            V0 =  Volume of  water purged  (ml),  taking  into consideration  any
                  dilutions  made.
            Sediment/Soil Sludge (on a dry-weight basis) and Waste (normally on
            a wet-weight basis)
                                       (AJ(Is)(Vt)
            concentration  (Mg/Kg)  =
                                    (AJ(RF)(V,)(H.)(D)
            where:

            A,,,  Is, Als, RF, = Same as for water.
            V, = Volume of total extract (pi) (use 10,000 /xL or a factor of this
            when dilutions are made).
            V, =   Volume of extract added  (/nL)  for  purging.
            Ws  =  Weight of sample extracted or purged  (g).
            D  =  % dry weight of sample/100, or 1  for  a wet-weight  basis.

                  7.6.2.3  Where applicable,  an estimate of concentration  for
            noncalibrated components in the sample should be made.  The formulae
            given above  should be used with  the  following modifications:  The
            areas A,,  and  Als should be from  the total  ion chromatograms,  and  the
            RF for the compound  should be  assumed  to be 1.  The concentration
            obtained  should  be reported indicating (1) that  the  value  is  an
            estimate  and (2)  which  internal standard  was used  to  determine
            concentration.     Use   the  nearest  internal   standard   free   of
            interferences.

8.0  QUALITY CONTROL

      8.1   Refer  to  Chapter  One and Method  8000  for specific quality  control
procedures.

      8.2  Required instrument QC is found in the following sections:

            8.2.1  The GC/MS  system must be tuned to meet the BFB specifications
      in Section 7.2.2.

            8.2.2  There must be an initial calibration of the GC/MS  system as


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      specified in Section 7.2.

            8.2.3  The  GC/MS  system must meet the  SPCC  criteria specified in
      Section 7.3.3 and the CCC criteria in Section 7.3.4, each 12 hours.

     8.3 To establish the ability to generate acceptable accuracy and precision,
the analyst must perform the following operations.

            8.3.1   A  quality control  (QC)  reference  sample concentrate  is
      required containing each  analyte at a concentration of 10 mg/L in methanol.
      The QC  reference  sample concentrate  may be prepared  from  pure standard
      materials  or purchased  as certified  solutions.   If  prepared by  the
      laboratory, the QC reference sample concentrate must be made using stock
      standards prepared independently from those used for calibration.

            8.3.2  Prepare  a  QC reference sample  to contain 20  M9/L of each
      analyte by adding 200 /LtL of QC reference sample concentrate to 100 ml of
      organic-free reagent water.

            8.3.3  Four 5 ml aliquots  of the well mixed QC reference sample are
      analyzed according to the method beginning in Section 7.4.1.

            8.3.4  Calculate the average recovery  (x) in p.g/1, and the standard
      deviation of the  recovery  (s)  in M9/U for each analyte using the four
      results.

            8.3.5   For each  analyte  compare s  and x with  the  corresponding
      acceptance criteria_for precision and accuracy, respectively,  found in
      Table 6.   If s and  x  for all  analytes  meet the acceptance  criteria,  the
      system performance is  acceptable and analysis of actual  samples can_begin.
      If any individual  s exceeds the  precision limit or any  individual x falls
      outside the range for accuracy, then the system performance is unacceptable
      for that analyte.

NOTE: The large number of analytes  in  Table 6 present a substantial probability
      that one or more will fail at least  one  of the acceptance  criteria when
      all analytes of a given  method are determined.

            8.3.6  When one  or more  of the analytes  tested fail at least one of
      the acceptance criteria,  the  analyst must proceed  according  to Section
      8.3.6.1 or 8.3.6.2.

                  8.3.6.1   Locate  and correct the  source of the problem  and
            repeat the test for all  analytes beginning with Section 8.3.2.

                  8.3.6.2   Beginning with Section  8.3.2,  repeat  the test only
            for those analytes that  failed to meet criteria.  Repeated failure,
            however,  will  confirm a general  problem with the measurement system.
            If this occurs, locate  and correct the  source  of  the problem  and
            repeat the  test  for all compounds of interest beginning with Section
            8.3.2.
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      8.4   For  aqueous  and soil  matrices,  laboratory  established  surrogate
control limits  should  be compared with the control limits  listed  in Table 8.
The limits given in Table 8 are  multilaboratory  performance  based limits for
soil and aqueous samples, and therefore,  the single laboratory limits must fall
within those given  in Table 8 for these matrices.

            8.4.1   If  recovery  is not  within  limits,  the following procedures
      are required.

                  8.4.1.1   Check to be  sure  that there are no  errors  in the
            calculations, surrogate solutions  or internal standards.  If errors
            are  found, recalculate the data accordingly.

                  8.4.1.2   Check  instrument  performance.    If  an instrument
            performance problem  is identified,  correct the problem and re-analyze
            the  extract.

                  8.4.1.3  If no problem is found,  re-extract and  re-analyze the
            sample.

                  8.4.1.4  If, upon re-analysis,  the recovery is again not within
            limits, flag the data as "estimated concentration".

            8.4.2  At a minimum,  each laboratory should  update surrogate recovery
      limits on  a matrix-by-matrix basis, annually.


9.0  METHOD PERFORMANCE

      9.1  The   method  detection  limit  (MDL)   is  defined  as  the  minimum
concentration  of  a substance   that  can  be  measured  and  reported  with  99%
confidence that  the value  is above  zero.  The MDL concentrations  listed in
Table 1 were obtained  using  organic-free  reagent  water.   Similar results were
achieved using representative wastewaters.  The MDL actually  achieved  in a given
analysis will vary depending on  instrument sensitivity and matrix effects.

      9.2  This method was tested by 15 laboratories using organic-free reagent
water, drinking water, surface water,  and industrial  wastewaters spiked at six
concentrations over the  range 5-600 M9/L-  Single operator  precision,  overall
precision,  and  method  accuracy  were  found  to  be  directly related  to  the
concentration of the analyte and essentially  independent of the  sample matrix.
Linear equations to describe these relationships are presented in Table 7.


10.0  REFERENCES

1.   U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
     Analysis  of   Pollutants   Under   the  Clean  Water  Act,   Method  624,"
     October 26, 1984.

2.   U.S.  EPA  Contract  Laboratory  Program,  Statement  of Work  for  Organic
     Analysis, July 1985, Revision.
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                                                                  November 1990

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3.   Bellar, T.A., and J.J.  Lichtenberg,  J.  Amer.  Water Works Assoc., 66(12),
     739-744, 1974.

4.   Bellar, T.A., and J.J. Lichtenberg, "Semi-Automated Headspace Analysis of
     Drinking  Waters and  Industrial  Waters for  Purgeable  Volatile Organic
     Compounds,"  in  Van Hall,  ed.,  Measurement  of  Organic Pollutants in Water
     and Wastewater, ASTM STP 686, pp. 108-129, 1979.

5.   Budde, W.L.  and J.W.  Eichelberger,  "Performance Tests for the Evaluation
     of  Computerized  Gas   Chromatography/Mass Spectrometry  Equipment  and
     Laboratories,"  EPA-600/4-79-020,  U.S.  Environmental  Protection Agency,
     Environmental Monitoring  and  Support  Laboratory,  Cincinnati,  Ohio 45268,
     April 1980.

6.   Eichelberger, J.W.,  L.E.  Harris,  and W.L. Budde,  "Reference  Compound to
     Calibrate Ion Abundance Measurement in Gas Chromatography-Mass Spectrometry
     Systems," Analytical  Chemistry, 47, 995-1000,  1975.

7.   "Method Detection Limit for Methods 624 and 625," Olynyk, P.,  W.L. Budde,
     and J.W. Eichelberger, Unpublished report, October 1980.

8.   "Interlaboratory Method Study for EPA Method 624-Purgeables," Final Report
     for EPA Contract 68-03-3102.

9.   "Method Performance Data for Method  624," Memorandum  from R. Slater and T.
     Pressley, U.S.  Environmental  Protection Agency, Environmental  Monitoring
     and Support  Laboratory, Cincinnati, Ohio 45268, January  17, 1984.

10.  Gebhart,  J.E.;  Lucas,  S.V.;  Naber,  S.J.; Berry,  A.M.;  Danison,  T.H.;
     Burkholder, H.M. "Validation of SW-846 Methods  8010,  8015, and 8020"; U.S.
     Environmental  Protection  Agency,  Environmental  Monitoring and Support
     Laboratory, Cincinnati, Old 45268, July 1987,  Contract No. 68-03-1760.

11.  Lucas, S.V.;  Kornfeld,  R.A. "GC-MS Suitability Testing  of RCRA Appendix
     VIII and Michigan List  Analytes ";  U.S. Environmental Protection Agency,
     Environmental Monitoring  and Support  Laboratory,  Cincinnati,  OH 45268,
     February 20, 1987, Contract No. 68-03-3224.
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                                   TABLE 1.
        RETENTION TIMES AND CHARACTERISTIC IONS FOR VOLATILE COMPOUNDS
Compound
Retention
Time (minutes)
Primary Ion  Secondary Ion(s)
Ethyl ene oxide
Chloromethane
Di chl orodi f 1 uoromethane
Bromomethane
Vinyl chloride
Acetonitrile
Chloroethane
Methyl iodide
Methyl ene chloride
Carbon disulfide
Tri chl orofl uoromethane
Propionitrile
Ally! chloride
1,1-Dichloroethene
Bromochloromethane (I.S.)
Allyl alcohol
trans- 1,2-Di chl oroethene
1,2-Dichloroethane
Propargyl alcohol
Chloroform
1,2-Di chl oroethane-d4(surr)
2-Butanone
Methacrylonitrile
Dibromomethane
2-Chloroethanol
b-Propiolactone
Epichlorohydrin
1,1,1-Trichloroethane
Carbon tetrachloride
1,4-Dioxane
Isobutyl alcohol
Bromodichloromethane
Chloroprene
l,2:3,4-Diepoxybutane
1,2-Dichloropropane
Chloral hydrate (b)
cis-l,3-Dichloropropene
Bromoacetone
Tri chl oroethene
Benzene
trans - 1 , 3 -Di chl oropropene
1 , 1 , 2-Trichl oroethane
3-Chloropropionitrile
1,2-Di bromoethane
Pyridine
1.30
2.30
2.47
3.10
3.80
3.97
4.60
5.37
6.40
7.47
8.30
8.53
8.83
9.00
9.30
9.77
10.00
10.10
10.77
11.40
12.10
12.20
12.37
12.53
12.93
13.00
13.10
13.40
13.70
13.70
13.80
14.30
14.77
14.87
15.70
15.77
15.90
16.33
16.50
17.00
17.20
17.20
17.37
18.40
18.57
44
50
85
94
62
41
64
142
84
76
101
54
76
96
128
57
96
62
55
83
65
72
41
93
49
42
57
97
117
88
43
83
53
55
63
82
75
136
130
78
75
97
54
107
79
44, 43, 42
52, 49
85, 87, 101, 103
96, 79
64, 61
41, 40, 39
66, 49
142, 127, 141
49, 51, 86
76, 78, 44
103, 66
54, 52, 55, 40
76, 41, 39, 78
61, 98
49, 130, 51
57, 58, 39
61, 98
64, 98
55, 39, 38, 53
85, 47
102
43, 72
41, 67, 39, 52, 66
93, 174, 95, 172, 176
49, 44, 43, 51, 80
42, 43, 44
57, 49, 62, 51
99, 117
119, 121
88, 58, 43, 57
43, 41, 42, 74
85, 129
53, 88, 90, 51
55, 57, 56
62, 41
44, 84, 86, 111
77, 39
43, 136, 138, 93, 95
95, 97, 132
52, 71
77, 39
83, 85, 99
54, 49, 89, 91
107, 109, 93, 188
79, 52, 51, 50
                                  8240B  -  26
                                      Revision 2
                                      November 1990

-------
                                   TABLE 1.
                                  (Continued)
Compound
Retention
Time (minutes)
Primary Ion  Secondary Ion(s)
2-Chloroethyl vinyl ether
2-Hydroxypropi oni tri 1 e
1,4-Difluorobenzene (I.S.)
Malononitrile
Methyl methacrylate
Bromoform
1,1,1 , 2-Tetrachl oroethane
l,3-Dichloro-2-propanol
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
1,2, 3 -Tri chl oropropane
l,4-Dichloro-2-butene
n-Propylamine
2-Picoline
Toluene
Ethyl methacrylate
Chlorobenzene
Pentachl oroethane8
Ethyl benzene
1 , 2-Di bromo-3-chl oropropane
4-Bromofluorobenzene (surr.)
Benzyl chloride
Styrene
bis-(2-Chloroethyl) sulfide(b)
Acetone
Acrolein
Acrylonitrile
Chlorobenzene-d5 (I.S.)
Chl orodi bromomethane
1,1-Dichloroethane
Ethanol
O llnir-i^n^ir-i
fc-nexanone
lodomethane
4-Methyl -2-pentanone
Toluene-d8 (surr.)
Vinyl acetate
Xylene (Total)
18.60
18.97
19.60
19.60
19.77
19.80
20.33
21.83
22.10
22.20
22.20
22.73
23.00
23.20
23.50
23.53
24.60
24.83
26.40
27.23
28.30
29.50
30.83
33.53
--
--
--
--
--
--
--
--
--
--
--
--
~ ••
63
44
114
66
69
173
131
79
83
164
75
75
59
93
92
69
112
167
106
157
95
91
104
109
43
56
53
117
129
63
31
43
142
43
98
43
106
65,106
44,43,42,53
63,88
66,39,65,38
69,41,100,39
171,175,252
131,133,117,119,95
79,43,81,49
85,131,133
129,131,166
75,77,110,112,97
75,53,77,124,89
59,41,39
93,66,92,78
91,65
69,41,99,86,114
114,77
167,130,132,165,169
91
157,75,155,77
174,176
91,126,65,128
104,103,78,51,77
111, 158, 160
58
55,58
52,51
82,119
208,206
65,83
45,27,46
58,57, 100
127,141
58,57,100
70,100
86
91
a The  base  peak at m/e  117  was  not used due to  an  interference at that mass
  with a nearly coeluting  internal  standard,  chlorobenzene-d5.

b  Response factor judged to be too low  (less than 0.02) for practical use.
                                  8240B - 27
                                      Revision 2
                                      November 1990

-------
                         TABLE 2.
ESTIMATED QUANTITATION LIMITS  (EQL) FOR VOLATILE  ORGANICS"
                            Estimated
                           Quantitation
                             Limits"
Ground water
Volatiles ng/l
Acetone
Acetonitrile
Allyl chloride
Benzene
Benzyl chloride
Bromodichloromethane
Bromoform
Bromomethane
2-Butanone
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chi orodi bromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Chloroprene
1 , 2-Di bromo-3-chl oropropane
1,2-Dibromoethane
Oi bromomethane
l,4-Dichloro-2-butene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1 Dichloroethene
trans- 1, 2-Di chl oroethene
1 , 2 -Di chl oropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Ethyl benzene
Ethyl methacrylate
2-Hexanone
Isobutyl alcohol
Methacrylonitrile
Methyl ene chloride
Methyl iodide
Methyl methacrylate
4-Methyl -2-pentanone
Pentachloroethane
100
100
5
5
100
5
5
10
100
100
5
5
5
10
10
5
10
5
100
5
5
100
5
5
5
5
5
5
5
5
5
5
50
100
100
5
5
5
50
10
Low Soil/Sediment
M9/K9
100
100
5
5
100
5
5
10
100
100
5
5
5
10
10
5
10
5
100
5
5
100
5
5
5
5
5
5
5
5
5
5
50
100
100
5
5
50
50
10
                        8240B - 28
Revision 2
November  1990

-------
                                   TABLE 2.
                                  (Continued)
                                      Estimated
                                     Quantltatlon
                                       Limits"
                            Ground water        Low Soil/Sediment
   Volatlles                    M9/L                 M9/Kg
Propionitrile
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachl oroethene
Toluene
1,1,1 -Tr1 chl oroethane
1 , 1 ,2-Tr1chloroethane
Trl chl oroethene
1,2,3-Trichloropropane
Vinyl acetate
Vinyl chloride
Xylene (Total)
100
5
5
5
5
5
5
5
5
5
50
10
5
100
5
5
5
5
5
5
5
5
5
50
10
5
a Sample EQLs are highly matrix dependent.   The  EQLs listed herein are provided
  for guidance and may not always be achievable.  See the following Information
  for further guidance on matrix dependent  EQLs.

b EQLs  listed  for soil/sediment  are based on  wet  weight.   Normally  data Is
  reported on a dry weight basis; therefore, EQLs will be higher, based on the
  percent dry weight of each sample.
               Other Matrices                      Factor0
               Water miscible liquid waste             50
               High-concentration soil and sludge     125
               Non-water miscible waste               500
  °EQL =  [EQL  for  low soil sediment  (Table 2)] X  [Factor].  For non-aqueous
          samples, the factor is on a wet weight basis.
                                  8240B - 29                      Revision 2
                                                                  November 1990

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                                TABLE 3.
                     BFB KEY ION ABUNDANCE CRITERIA
    Mass             Ion Abundance Criteria
    50               15 to 40% of mass 95
    75               30 to 60% of mass 95
    95               base peak, 100% relative abundance
    96               5 to 9% of mass 95
   173               less than 2% of mass 174
   174               greater than 50% of mass 95
   175               5 to 9% of mass 174
   176               greater than 95% but less than 101% of mass 174
   177               5 to 9% of mass 176
                                TABLE 4.
          QUANTITY OF METHANOL  EXTRACT  REQUIRED FOR ANALYSIS
                 OF HIGH-CONCENTRATION  SOILS/SEDIMENTS
       Approximate                               Volume of
   Concentration Range                        Methanol  Extract8
      500- 10,000 M9/Kg                            100 ML
    1,000- 20,000 M9/Kg                             50 juL
    5,000-100,000 M9/Kg                             10 pi
   25,000-500,000 M9/Kg                            100 /jL of 1/50 dilution"
Calculate  appropriate  dilution  factor for  concentrations exceeding  this
table.

a  The volume of methanol  added to 5 mL of water being purged should be kept
   constant. Therefore, add to the 5 mL syringe whatever volume of methanol
   is necessary to maintain a volume of 100 /iL added to the syringe.

b  Dilute  and  aliquot  of  the methanol extract  and then  take 100 /xL  for
   analysis.

                               8240B - 30                      Revision 2
                                                               November 1990

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                                   TABLE 5.
       VOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES ASSIGNED
                               FOR QUANTITATION
Bromochloromethane

Acetone
Acrolein
Acrylonitrile
Bromomethane
Carbon disulfide
Chloroethane
Chloroform
Chioromethane
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
l,2-Dichloroethane-d4 (surrogate)
1,1-Dichloroethene
trans-1,2-Di chloroethene
lodomethane
Methylene chloride
Tri chlorof1uoromethane
Vinyl chloride
1.4-Di f1uorobenzene

Benzene
Bromodi chloromethane
Bromoform
2-Butanone
Carbon tetrachloride
Chlorodi bromomethane
2-Chloroethyl vinyl ether
Dibromomethane
1,4-Dichloro-2-butene
1,2-Di chloropropane
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
1,1,1-Tri chloroethane
1,1,2-Trichloroethane
Trichloroethene
Vinyl acetate
                        Chlorobenzene-ds
                        Bromofluorobenzene (surrogate)
                        Chlorobenzene
                        Ethyl benzene
                        Ethyl  methacrylate
                        2-Hexanone
                        4-Methyl-2-pentanone
                        Styrene
                        1,1,2,2-Tetrachloroethane
                        Tetrachloroethene
                        Toluene
                        Toluene-d8 (surrogate)
                        1,2,3-Trichloropropane
                        Xylene
                                  8240B  - 31
                    Revision 2
                    November 1990

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                                   TABLE 6.
                    CALIBRATION AND QC ACCEPTANCE CRITERIA8
Parameter
Benzene
Bromodi chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
2-Chloroethylvinyl ether
Chloroform
Chl oromethane
Di bromochl oromethane
1,2-Dichlorobenzene
1 , 3-Di chl orobenzene
1,4-Dichlorobenzene
1,1-Dichloroethane
1,2-Dichl oroethane
1,1-Dichloroethene
trans- 1,2-Dichl oroethene
1,2-Dichloropropane
cis-1, 3-Di chl oropropene
trans-l,3-Dichloropropene
Ethyl benzene
Methyl ene chloride
1,1,2 , 2-Tetrachl oroethane
Tetrachl oroethene
Toluene
1,1,1-Trichloroethane
1 , 1 ,2-Tri chl oroethane
Tri chl oroethene
Tri chl orof 1 uoromethane
Vinyl chloride
Range
for Q
(M9/L)
12.8-27.2
13.1-26.9
14.2-25.8
2.8-37.2
14.6-25.4
13.2-26.8
D-44.8
13.5-26.5
D-40.8
13.5-26.5
12.6-27.4
14.6-25.4
12.6-27.4
14.5-25.5
13.6-26.4
10.1-29.9
13.9-26.1
6.8-33.2
4.8-35.2
10.0-30.0
11.8-28.2
12.1-27.9
12.1-27.9
14.7-25.3
14.9-25.1
15.0-25.0
14.2-25.8
13.3-26.7
9.6-30.4
0.8-39.2
Limit
for s
6.9
6.4
5.4
17.9
5.2
6.3
25.9
6.1
19.8
6.1
7.1
5.5
7.1
5.1
6.0
9.1
5.7
13.8
15.8
10.4
7.5
7.4
7.4
5.0
4.8
4.6
5.5
6.6
10.0
20.0
Range
for x
(M9/L)
15.2-26.0
10.1-28.0
11.4-31.1
D-41.2
17.2-23.5
16.4-27.4
D-50.4
13.7-24.2
D-45.9
13.8-26.6
11.8-34.7
17.0-28.8
11.8-34.7
14.2-28.4
14.3-27.4
3.7-42.3
13.6-28.4
3.8-36.2
1.0-39.0
7.6-32.4
17.4-26.7
D-41.0
13.5-27.2
17.0-26.6
16.6-26.7
13.7-30.1
14.3-27.1
18.5-27.6
8.9-31.5
D-43.5
Range
P,PS
37-151
35-155
45-169
D-242
70-140
37-160
D-305
51-138
D-273
53-149
18-190
59-156
18-190
59-155
49-155
D-234
54-156
D-210
D-227
17-183
37-162
D-221
46-157
64-148
47-150
52-162
52-150
71-157
17-181
D-251
Q = Concentration measured in QC check sample, in M9/L.
s = Standard deviation of four recovery measurements, in M9/L-
x = Average recovery for four recovery measurements, in M9/L.
p, ps = Percent recovery measured.
D = Detected; result must be greater than zero.

a  Criteria from 40 CFR Part 136 for Method 624 and were calculated assuming a
   QC check sample concentration of 20  M9/L.   These  criteria are based directly
   upon the method performance data  in Table 7.  Where necessary, the limits for
   recovery  have been  broadened to  assure  applicability of  the limits  to
   concentrations below those used to develop Table 7.
                                  8240B - 32
Revision 2
November 1990

-------
                                   TABLE 7.
         METHOD ACCURACY AND PRECISION AS  FUNCTIONS OF CONCENTRATION8
  Parameter
Accuracy, as
recovery, x'
   (M9/L)
Single analyst
precision, s/
    (Mg/L)
 Overall
precision,
 S' (M9/L)
Benzene
Bromodi chl oromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethyl vinyl ether8
Chloroform
Chl oromethane
Di bromochl oromethane
1 , 2-Di chl orobenzene"
1,3-Dichlorobenzene
l,4-Dichlorobenzeneb
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans- 1 , 2 , -Di chl oroethene
1 , 2-Di chl oropropane8
cis-l,3-Dichloropropene8
trans -1,3-Di chl oropropene8
Ethyl benzene
Methyl ene chloride
1,1,2 , 2-Tetrachl oroethane
Tetrachl oroethene
Toluene
1 , 1 , 1-Trichloroethane
1 , 1 , 2-Tri chl oroethane
Tri chl oroethene
Tr i chl orof 1 uoromethane
Vinyl chloride
0.93C+2.00
1.03C-1.58
1.18C-2.35
l.OOC
1.10C-1.68
0.98C+2.28
1.18C+0.81
l.OOC
0.93C+0.33
1.03C-1.81
1.01C-0.03
0.94C+4.47
1.06C+1.68
0.94C+4.47
1.05C+0.36
1.02C+0.45
1.12C+0.61
- 1.05C+0.03
l.OOC
l.OOC
l.OOC
0.98C+2.48
0.87C+1.88
0.93C+1.76
1.06C+0.60
0.98C+2.03
1.06C+0.73
0.95C+1.71
1.04C+2.27
0.99C+0.39
l.OOC
0.26X-1.74
0.15x+0.59
0.12X+0.34
0.43x
0.12X+0.25
0.16X-0.09
0.14X+2.78
0.62x
0.16X+0.22
0.37X+2.14
0.17X-0.18
0.22X-1.45
0.14X-0.48
0.22X-1.45
0.13X-0.05
0.17X-0.32
0.17X+1.06
0.14X+0.09
0.33x
0.38x
0.25x
0.14X+1.00
0.15X+1.07
0.16X+0.69
0.13X-0.18
0.15X-0.71
0.12X-0.15
0.14X+0.02
0.13X+0.36
0.33X-1.48
0.48x
0.25X-1.33
0.20X+1.13
O.Ux+1.38
0.58x
O.llx+0.37
0.26x-1.92
0.29X+1.75
0.84x
O.lSx+0.16
0.58X+0.43
0.17X+0.49
0.30X-1.20
O.lSx-0.82
0.30X-1.20
O.lSx+0.47
0.21X-0.38
0.43X-0.22
0.19X+0.17
0.45x
0.52x
0.34x
0.26X-1.72
0.32X+4.00
0.20X+0.41
0.16X-0.45
0.22X-1.71
0.21X-0.39
0.18X+0.00
0.12X+0.59
0.34X-0.39
0.65x
x' =  Expected  recovery  for  one or more measurements of a sample containing a
      concentration  of C,  in M9/L.
sr'  =  Expected  single analyst standard  deviation of measurements at an average
      concentration  of x,  in ng/L.
S1  = Expected  interlaboratory_ standard deviation of measurements at an average
      concentration  found  of x,  in  /ng/L.
C   = True value  for the concentration,  in /ig/L.
x  =  Average   recovery   found   for  measurements  of  samples  containing  a
      concentration  of C,  in M9/L-
a  Estimates based upon the performance in a single laboratory.
b  Due to chromatographic resolution problems,  performance statements for these
   isomers are  based upon the sums  of their concentrations.
                                  8240B - 33
                                    Revision 2
                                    November 1990

-------
                                   TABLE 8.
      SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
                                      Low/High               Low/High
   Surrogate Compound                   Water              Soil/Sediment
4-Bromofluorobenzene                    86-115                 74-121
l,2-Dichloroethane-d4                   76-114                 70-121
Toluene-d8                              88-110                 81-117
                                  8240B - 34                      Revision 2
                                                                  November 1990

-------
      FIGURE  1.
   PURGING CHAMBER
OVt W M 04
       t7 CM » OMAC STWNOC NCIOU
                       _     00
                     /^ STAMUU STHk
     8240B  -  35
Revision  2
November 1990

-------
                FIGURE 2.
TRAP PACKINGS AND  CONSTRUCTION TO INCLUDE
    DESORB CAPABILITY  FOR METHOD 8240
                           CONSTRUCTION OCTA«.
     TMFMLffT
                8240B - 36
Revision 2
November 1990

-------
                            FIGURE 3.
  SCHEMATIC OF PURGE-AND-TRAP DEVICE - PURGE MODE FOR METHOD 8240
CAJWCftOAS
FlOW COMTMQL
uouo
   - OOUJMNOVfN
                                   jinrP
                                                         COUJMM
                                              AMAimCAL COLUMN
                             OPTIONAL+*OffT COLUMN
                             SCLfCTWN VALVf
                                     TftAPMlfT
13X
                               PUMOINQ
                               ocvcc
             NOTI.
             AU UNO •CTWflN TWA*
             AMO QC SHOULD M MCATO
                            8240B - 37
                          Revision  2
                          November 1990

-------
                            FIGURE 4.
 SCHEMATIC  OF PURGE-AND-TRAP DEVICE - DESORB MODE FOR METHOD 8240
CAJWfUQAt
                                                 ANALYTICAL COLUMN
                              OPTIONAL*
                              SfLfCnON VALVt

                                               NOT1;
                                               ALL UNfS ITOMEN
                                               ANOOCSMOUL0M
                                               TOVO
                           8240B - 38
Revision 2
November 1990

-------
                      FIGURE 5.
                 LOW SOILS  IMPINGER
 PURGE INLET FITTING
 SAMPLE OUTLET HTTING
3  • 6mm o o  GLASS TUBING
            40ml VIAL
                                    SEPTUM
                                       CAP
                     8240B - 39
Revision 2
November 1990

-------
                        METHOD 8240B
GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR VOLATILE ORGANICS
 Purge-and-trap
              7.1
            Select
         procedure for
          introducing
          sample into
            CC/MS.
           7.2.1 Set
             CC/MS
           operating
          conditions
         7.2.4 Connect
        purge-and-trap
         device to CC.
         7.2.6 Perform
        purge-and-trap
           analysis.
    72.8
Calculate RFs
for 5 SPCCs.
 7.3 Perform
    daily
 calibration
 using SPCCs
  and CCCs.
            7
                         8240B - 40
                       Revision 2
                       November 1990

-------
                                                   METHOD 8240
                                                   (continued)
                                      Soil/sediment
                                        and  waste
   7421
Dilute sample
 at least  50
  fold with
   water
                            7 4.1 1
                         Screen sample
                         us ing Method
                         3810 or 3820
                            7417
                            Per form
                           seconda ry
                          dilutions
                          7 4.1.8 Add
                        internal standard
                         and surrogate
                       spiking solutions.
7 4.1.10
Perform
purge-and- trap
procedure


   7.4.3.1.3 Add
 interna1  standard
   and  surrogate
spiking solutions
                                                     7  4.3.1.5
                                                     Determine
                                                    percent dry
                                                     weight of
                                                      sample.
                                                     7.4.3.1.7
                                                      Perf o rm
                                                  purge-and-trap
                                                    procedure.
   sample us ing
    Method 3810
      or 3820
     7  4.3 I*
   concentration
       mg/Kg?
   9ize  based on
     es tima ted
  concentra tion
                       7 4 1 11
                      Attach trap
                       to CC and
                        per fo rm
                       analysis
7432  Choose
  solvent  for
 ex t raction  or
dilution  Weigh
    sample
 7511  Identify
    analytes by
   comparing the
 sample  retention
  time and  samp 1e
   mass  spect ra
 7.4.32  2  Add
   sol vent.
    shake
 752.2  Calculate
 the concentration
of each  identified
     ana 1y te
   7 4 3 2.7
    Perform
purge-and - trap
  pr ocedure.
      7.5  2  4
    Report all
     results
                                                    Stop
                                                   8240B  - 41
                                              Revision  2
                                              November 1990

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                                  METHOD  8250A

SEMIVOLATILE ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS):
                            PACKED COLUMN TECHNIQUE
 1.0   SCOPE  AND  APPLICATION

       1.1   Method  8250 is used to determine the concentration of  semivolatile
 organic  compounds  in  extracts  prepared  from  all  types  of  solid waste  matrices,
 soils, and  ground  water.   Direct injection of a sample may be used in  limited
 applications.   The following compounds  can be  determined  by this method:
Compounds
CAS No"
Appropriate Preparation Techniques

  3510     3520  3540  3550  3580
Acenaphthene
Acenaphthene-d10 (I.S.)
Acenaphthylene
Acetophenone
Aldrin
4-Aminobiphenyl
Aniline
Anthracene
Aroclor - 1016
Aroclor - 1221
Aroclor - 1232
Aroclor - 1242
Aroclor - 1248
Aroclor - 1254
Aroclor - 1260
Benzidine
Benzoic acid
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(g,h,i)perylene
Benzo(a)pyrene
Benzyl alcohol
a-BHC
0-BHC
6-BHC
T-BHC (Lindane)
Bi s (2-chl oroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
83-32-9

208-96-8
98-86-2
309-00-2
92-67-1
62-53-3
120-12-7
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
92-87-5
65-85-0
56-55-3
205-99-2
207-08-9
191-24-2
50-32-8
100-51-6
319-84-6
319-85-7
319-86-8
58-89-9
111-91-1
111-44-4
108-60-1
117-81-7
101-55-3
85-68-7
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
ND
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
ND
ND
X
X
X
X
X
X
X
X
CP
ND
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
ND
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
                                   8250A - 1
                                 Revision 1
                                 November 1990

-------
         Appropriate  Preparation  Techniques
Compounds
Chlordane
4-Chloroaniline
1-Chloronaphthalene
2-Chl oronaphthal ene
4-Chl oro-3-methyl phenol
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Chrysene-d12 (I.S.)
4,4'-DDD
4,4'-DDT
Dibenz(a,j)acridine
Dibenz (a, h) anthracene
Dibenzofuran
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
l,4-Dichlorobenzene-d4 (I.S)
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dieldrin
Diethyl phthalate
Dimethyl ami noazobenzene
7,12-Dimethylbenz(a)-
anthracene
a,a-Dimethylphenethylamine
2,4-Dimethylphenol
Dimethyl phthalate
4, 6-Dinitro-2-methyl phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di phenyl ami ne
1 , 2-Di phenyl hydrazi ne
Di-n-octyl phthalate
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
Ethyl methanesulfonate
Fluoranthene
Fluorene
CAS Noa
57-74-9
106-47-8
90-13-1
91-58-7
59-50-7
95-57-8
7005-72-3
218-01-9

72-54-8
50-29-3
224-42-0
53-70-3
132-64-9
84-74-2
95-50-1
541-73-1
106-46-7
3855-82-1
91-94-1
120-83-2
87-65-0
60-57-1
84-66-2
60-11-7
57-97-6

122-09-8
105-67-9
131-11-3
534-52-1
51-28-5
121-14-2
606-20-2
122-39-4
122-66-7
117-84-0
959-98-8
33213-65-9
1031-07-8
72-20-8
7421-93-4
53494-70-5
62-50-0
206-44-0
86-73-7
3510
X
X
X
X

X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP(45)

ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
3520
X
ND
X
X

X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
ND
X
X
ND
ND

ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
3540
X
ND
X
X

X
X
X
X
X
X
ND
X
ND
X
X
X
X
X
X
X
ND
X
X
ND
ND

ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
ND
X
X
3550
X
ND
X
X

X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
ND
X
X
ND
ND

ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
3580
X
X
X
X

X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP

X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
8250A - 2
Revision 1
November 1990

-------
AooroDriate Preparation Techniaues
Compounds
2-Fluorobiphenyl (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachloroethane
Indeno(l,2,3-cd)pyrene
Isophorone
Methoxychlor
3-Methyl chol anthrene
Methyl methanesulfonate
2-Methyl naphthalene
2-Methyl phenol
4-Methyl phenol
Naphthalene
Naphthalene-de (I.S.)
1-Naphthylamine
2-Naphthylamine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
Nitrobenzene-d5 (surr.)
2-Nitrophenol
4-Nitrophenol
N-Nitrosodi butyl ami ne
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi -n-propylamine
N-Nitrosopiperidine
Pentachl orobenzene
Pentachl oroni trobenzene
Pentachl orophenol
Perylene-d12 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-d10 (I.S.)
Phenol
Phenol -d6 (surr.)
2-Picoline
Pronamide
Pyrene
Terphenyl-d14(surr.)
1,2,4, 5-Tetrachl orobenzene
2,3,4,6-Tetrachlorophenol
CAS No"
321-60-8
367-12-4
76-44-8
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
193-39-5
78-59-1
72-43-5
56-49-5
66-27-3
91-57-6
95-48-7
106-44-5
91-20-3
1146-65-2
134-32-7
91-59-8
88-74-4
99-09-2
100-01-6
98-95-3
4165-60-0
88-75-5
100-02-7
924-16-3
62-75-9
86-30-6
621-64-7
100-75-4
608-93-5
82-68-8
87-86-5
198-55-0
62-44-2
85-01-8

108-95-2
13127-88-3
109-06-8
23950-58-5
129-00-0

u95-94-3
58-90-2
3510
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
OS(44)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
DC(28)
DC(28)
ND
X
X
X
X
X
3520
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
X
ND
ND
X
X
ND
ND
X
X
X
X
X
X
X
ND
X
X
X
ND
ND
ND
X
X
ND
X
X
X
X
ND
ND
X
X
ND
ND
3540
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
ND
ND
X
X
X
X
ND
X
X
X
ND
ND
ND
X
X
ND
X
X
X
X
ND
ND
X
ND
ND
ND
3550
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
X
ND
ND
X
X
ND
ND
X
X
X
X
X
X
X
ND
X
X
X
ND
ND
ND
X
X
ND
X
X
X
X
ND
ND
X
X
ND
ND
3580
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
8250A - 3
Revision 1
November 1990

-------
                                            Appropriate Preparation Techniques

Compounds                        CAS Noa      3510     3520  3540  3550  3580
Toxaphene
2,4,6-Tribromophenol (surr.)
1,2,4-Trichlorobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
8001-35-2
118-79-6
120-82-1
95-95-4
88-06-2
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
a    Chemical Abstract Service Registry Number.

CP = Nonreproducible chromatographic performance.
DC = Unfavorable  distribution  coefficient  (number  in parenthesis  is  percent
     recovery).
ND = Not determined.
OS = Oxidation during storage (number in parenthesis is percent stability).
X =  Greater than 70 percent recovery by this technique.

Percent Stability = Average Recovery (Day 7) x 100/Average Recovery (Day 0).


      1.2  Method 8250 can be used to quantitate most neutral,  acidic, and basic
organic compounds that are  soluble  in methylene  chloride  and capable of being
eluted without derivatization as sharp peaks from a gas chromatographic packed
column.  Such compounds include polynuclear aromatic hydrocarbons, chlorinated
hydrocarbons  and  pesticides,   phthalate  esters,   organophosphate  esters,
nitrosamines,  halpethers,  aldehydes,  ethers,  ketpnes,   anilines,  pyridines,
quinolines, aromatic nitro compounds,  and  phenols,  including nitrophenols.  See
Table 1 for  a list  of compounds and their  characteristic ions that have been
evaluated on the  specified GC/MS system.

      1.3  The  following  compounds  may require  special  treatment  when being
determined by this method.  Benzidine  can  be subject  to oxidative losses during
solvent concentration.    Also,  chromatography  is  poor.   Under  the alkaline
conditions of the extraction step, a-BHC, T-BHC, endosulfan I  and II, and endrin
are subject to decomposition.  Neutral extraction should be performed if these
compounds  are   expected   and   are  not  being  determined  by  Method  8080.
Hexachlorocyclopentadiene  is subject  to thermal  decomposition in the inlet of
the gas chromatograph, chemical  reaction in  acetone solution,  and photochemical
decomposition.  N-nitrosodimethylamine is difficult to separate from  the solvent
under  the   chromatographic conditions  described.     N-nitrosodiphenylamine
decomposes  in  the  gas chromatographic inlet  and  cannot  be  separated  from
diphenylamine. Pentachlorophenol,2,4-dinitrophenol, 4-nitrophenol, 4,6-dinitro-
2-methylphenol,   4-chloro-3-methylphenol,    benzoic  acid,   2-nitroaniline,  3-
nitroaniline,  4-chloroaniline,   and  benzyl  alcohol  are   subject   to  erratic
chromatographic behavior,  especially if  the  GC system is contaminated with high
boiling material.
                                   8250A -  4                      Revision 1
                                                                  November 1990

-------
      1.4  The estimated quantitation limit (EQL) of Method 8250 for determining
an individual compound is approximately 1 mg/Kg (wet weight) for soil/sediment
samples, 1-200 mg/Kg for wastes (dependent on matrix and method of preparation),
and  10  /zg/L  for  ground  water  samples   (see  Table  2).    EQLs  will  be
proportionately  higher for  sample extracts  that  require  dilution to  avoid
saturation of the detector.

      1.5  This  method  is restricted  to  use by  or under the  supervision  of
analysts experienced  in  the use  of gas chromatograph/mass  spectrometers and
skilled in the interpretation of  mass  spectra.   Each analyst must demonstrate
the ability to generate acceptable results with this method.


2.0  SUMMARY OF METHOD

      2.1  Prior  to using  this  method, the samples should be  prepared for
chromatography using  the  appropriate  sample preparation and cleanup methods.
This  method  describes  chromatographic  conditions  that  will  allow for the
separation of the compounds in the extract.


3.0  INTERFERENCES

      3.1  Raw GC/MS data from all blanks, samples, and spikes must be evaluated
for interferences.  Determine if the source of interference is in the preparation
and/or  cleanup  of  the  samples  and take corrective  action to eliminate the
problem.

      3.2  Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially analyzed.  To reduce carryover, the
sample  syringe must be rinsed  out between samples  with  solvent.   Whenever  an
unusually concentrated  sample  is  encountered,  it  should  be followed  by the
analysis of solvent to check for cross contamination.


4.0  APPARATUS AND MATERIALS

      4.1  Gas chromatograph/mass spectrometer system

            4.1.1 Gas  chromatograph  -  An  analytical system complete with  a
      temperature-programmable gas chromatograph suitable for splitless injection
      and all required accessories,  including syringes, analytical  columns, and
      gases.

            4.1.2 Columns

                  4.1.2.1 For base/neutral compound  detection - 2  m x  2 mm  ID
            stainless  or  glass,  packed with  3%  SP-2250-DB  on  100/120  mesh
            Supelcoport or equivalent.

                  4.1.2.2 For acid  compound  detection -  2 m x  2  mm ID glass,
            packed with 1% SP-1240-DA on 100/120 mesh Supelcoport or equivalent.
                                  8250A  -  5                       Revision 1
                                                                  November 1990

-------
            4.1.3 Mass spectrometer  -  Capable of scanning from 35  to 500 amu
      every 1 second or  less,  using  70 volts  (nominal)  electron  energy in the
      electron impact ionization mode.   The mass spectrometer must be capable
      of  producing  a mass  spectrum for  decafluorotriphenylphosphine (DFTPP)
      which meets all of the criteria in Table 3 when 1  /iL of the GC/MS tuning
      standard is injected through the GC (50 ng of DFTPP).

            4.1.4 GC/MS interface - Any GC-to-MS interface that gives acceptable
      calibration points at 50  ng per  injection  for each compound of interest
      and achieves acceptable tuning performance criteria may be used.  GC-to-
      MS interfaces constructed entirely of glass or glass-lined materials are
      recommended.      Glass    may   be  deactivated    by   silanizing   with
      dichlorodimethylsi 1ane.

            4.1.5 Data system - A computer system must be interfaced  to the mass
      spectrometer.  The system must  allow the continuous  acquisition  and storage
      on machine-readable  media of  all  mass  spectra obtained throughout the
      duration of the chromatographic program.  The computer must have software
      that can search any GC/MS data file for ions of a  specific mass and that
      can plot such ion abundances versus time  or  scan number.  This type of plot
      is defined as an Extracted  Ion Current Profile (EICP).  Software  must also
      be available that  allows  integrating the abundances in  any  EICP between
      specified time  or  scan-number limits.    The most   recent version  of the
      EPA/NIH Mass Spectral Library should also be available.

      4.2  Syringe -  10 /iL.


5.0  REAGENTS

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

      5.2  Organic-free reagent water.   All  references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3  Stock standard  solutions  (1.00  M9/ML) - Standard  solutions  can be
prepared from pure standard materials or purchased as certified solutions.

            5.3.1 Prepare stock standard solutions by accurately weighing about
      0.0100 g of  pure  material.  Dissolve the  material  in pesticide quality
      acetone  or other  suitable solvent  and  dilute  to  volume  in  a  10  ml
      volumetric flask.  Larger  volumes can be used at  the convenience of the
      analyst.  When  compound  purity  is  assayed to be 96% or greater, the weight
      may be used without correction to calculate the concentration of  the stock
      standard.   Commercially  prepared stock  standards may  be  used  at any
      concentration  if  they   are  certified  by  the manufacturer or  by  an
      independent source.
                                   8250A -  6                      Revision 1
                                                                  November 1990

-------
            5.3.2 Transfer the stock standard solutions into bottles with Teflon
      lined screw-caps  or crimp tops.   Store at 4°C and  protect from light.
      Stock  standard solutions  should  be checked  frequently  for  signs  of
      degradation or evaporation, especially just prior to preparing calibration
      standards from them.

            5.3.3 Stock  standard  solutions must  be  replaced after  1 year or
      sooner  if comparison  with  quality  control check  samples  indicates  a
      problem.

      5.4  Internal standard solutions - The internal  standards recommended are
l,4-dichlorobenzene-d4,    naphthalene-d8,   acenaphthene-d10,   phenanthrene-d10,
chrysene-d12, and perylene-d12.  Other compounds may be used  as internal  standards
as long as the requirements given  in Section 7.3.2 are met.   Dissolve  200 mg of
each compound  with  a small volume  of carbon  disulfide.  Transfer  to a 50 mL
volumetric flask and dilute to volume  with  methylene chloride so that  the final
solvent is approximately 20% carbon disulfide.  Most of the  compounds are also
soluble in small volumes of methanol,  acetone, or  toluene, except  for  perylene-
d12.  The  resulting solution will  contain  each  standard at a concentration of
4,000 ng//iL.  Each 1 ml  sample extract undergoing analysis  should be spiked with
10 ML  of the  internal  standard  solution,  resulting  in a  concentration of 40
ng//nL of each  internal  standard.  Store  at 4°C or less when not being used.

      5.5  GC/MS  tuning standard  - A methylene  chloride  solution containing
50 ng//iL  of  decafluorotriphenylphosphine  (DFTPP)  should  be  prepared.   The
standard should also contain 50 ng/jiL each of 4,4'-DDT, pentachlorophenol, and
benzidine to verify  injection port  inertness and GC column  performance.  Store
at 4°C  or less when not  being used.

      5.6  Calibration  standards -  Calibration  standards  at a minimum of five
concentrations should be prepared.  One  of the calibration  standards  should be
at a concentration near, but above, the method detection limit; the  others should
correspond to the range of concentrations found in real samples but should not
exceed the working range of the GC/MS system.   Each standard should contain each
analyte for detection by this method  (e.g. some or all of the compounds listed
in Table 1 may be included).  Each  1 ml  aliquot of calibration standard should
be spiked with 10 /xL of the internal  standard solution prior to analysis.  All
standards should be stored at -10°C  to -20°C and  should be  freshly  prepared once
a year, or sooner if check standards indicate  a  problem.  The daily calibration
standard should be  prepared weekly  and stored at 4°C.

      5.7  Surrogate  standards  -   The recommended  surrogate   standards are
phenol-d6,     2-fluorophenol,    2,4,6-tribromophenol,    nitrobenzene-d5,    2-
fluorobiphenyl, and p-terphenyl-d14.  See Method  3500 for the instructions on
preparing the  surrogate standards.  Determine what  concentration should be in
the  blank  extracts  after all extraction,  cleanup,   and  concentration steps.
Inject  this  concentration into the GC/MS  to determine recovery  of  surrogate
standards in  all  blanks,  spikes,  and  sample extracts.  Take into account all
dilutions of sample extracts.

      5.8  Matrix spike  standards - See Method 3500 for instructions on  preparing
the matrix spike standard.  Determine  what  concentration should be in  the blank
extracts after  all  extraction, cleanup,  and  concentration steps.   Inject this

                                  8250A -  7                       Revision 1
                                                                  November  1990

-------
concentration into the GC/MS  to  determine  recovery  of standards in all  matrix
spikes.  Take into account all dilutions of sample extracts.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See  the  introductory material  to  this chapter,  Organic  Analytes,
Section 4.1.


7.0  PROCEDURE

      7.1  Sample preparation -  Samples must be prepared by one of the following
methods prior to GC/MS analysis.

           Matrix                                Methods
           Water                                 3510, 3520
           Soil/sediment                         3540, 3550
           Waste                                 3540, 3550, 3580

            7.1.1 Direct  injection  -   In  very   limited  applications  direct
      injection of the sample into the  GC/MS system with a  10  juL syringe may
      be  appropriate.    The detection  limit   is  very  high  (approximately
      10,OOOM9/L);  therefore,  it  is only permitted where  concentrations  in
      excess of 10,000 ng/l are expected.   The  system must be calibrated  by
      direct injection.

      7.2  Extract cleanup - Extracts may be  cleaned up  by any of the following
methods prior to GC/MS analysis.

           Compounds                                  Methods
           Phenols                                    3630, 3640, 8040a
           Phthalate esters                           3610, 3620, 3640
           Nitrosamines                               3610, 3620, 3640
           Organochlorine pesticides & PCBs           3620, 3640, 3660
           Nitroaromatics and cyclic ketones          3620, 3640
           Polynuclear aromatic hydrocarbons          3611, 3630, 3640
           Haloethers                                 3620, 3640
           Chlorinated hydrocarbons                   3620, 3640
           Organophosphorus pesticides                3620
           Petroleum waste                            3611, 3650
           All  basic, neutral, and acidic
                Priority Pollutants                    3640


aMethod 8040 includes a derivatization technique followed  by GC/ECD analysis,
if interferences are encountered on GC/FID.
                                   8250A -  8                      Revision 1
                                                                  November  1990

-------
      7.3  Recommended GC/MS operating conditions

Electron energy: 70 volts (nominal)
Mass range: 35-500 amu
Scan time: 1 sec/scan
Injector temperature: 250-300°C
Transfer line temperature: 250-300°C
Source temperature: According to manufacturer's specifications
Injector: Grob-type, splitless
Sample volume: 1-2 juL
Carrier gas: Helium at 30 mL/min

Conditions for base/neutral analysis (3% SP-2250-DB)

      Initial column temperature and hold time: 50°C for 4 minutes
      Column temperature program: 50-300°C at 8°C/min
      Final column temperature hold: 300°C for 20 minutes

Conditions for acid analysis (1% SP-1240-DA)

      Initial column temperature and hold time: 70°C for 2 minutes
      Column temperature program: 70-200°C at 8°C/min
      Final column temperature hold: 200°C for 20 minutes

      7.4 Initial calibration

            7.4.1 Each GC/MS system must be hardware-tuned to meet the criteria
      in Table 3 for a 50 ng injection of DFTPP.  Analyses should not begin until
      all  these   criteria   are  met.     Background   subtraction  should  be
      straightforward and designed only to eliminate column bleed  or instrument
      background ions.  The GC/MS tuning standard should also be used to assess
      GC column performance  and  injection port inertness.  Degradation of DDT
      to DDE  and  DDD should not exceed 20%.   Benzidine and  pentachlorophenol
      should be present  at  their normal  responses, and no peak tailing should
      be visible.   If degradation  is  excessive  and/or poor chromatography is
      noted, the injection port may require cleaning.

            7.4.2 The internal standards  selected  in Section  5.1  should permit
      most of  the  components of interest  in  a chromatogram to have retention
      times of  0.80-1.20 relative to one of  the  internal  standards.   Use the
      base peak ion from the specific  internal standard as the  primary ion for
      quantitation (see Table 1).  If interferences are noted, use  the next most
      intense ion as the quantitation  ion  (i.e.  for l,4-dichlorobenzene-d4 use
      m/z 152 for quantitation).

            7.4.3 Analyze 1 /uL of each calibration standard (containing internal
      standards) and tabulate the area  of the primary characteristic ion against
      concentration  for  each compound  (as  indicated  in  Table  1).  Calculate
      response factors (RFs) for each  compound as  follows:


                               RF = (AXC|S)/(A1SCX)
                                   8250A - 9                      Revision  1
                                                                  November 1990

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where:

      Ax = Area of the characteristic  ion for the compound being measured.
      Als = Area  of  the  characteristic  ion for  the  specific  internal
           standard.
      Cx = Concentration of the compound being measured  (ng//ul_).
      Cls = Concentration of the specific internal standard  (ng//il_).

      7.4.4 The average RF should  be  calculated  for each compound.  The
percent relative standard deviation  (%RSD  =  100[SD/RF]) should also be
calculated for each compound.  The %RSD should be less than 30% for each
compound.  However, the %RSD for each individual  Calibration Check Compound
(CCC) (see Table 4) must be less than 30%.   The relative retention times
of each compound  in each calibration run should  agree within  0.06 relative
retention  time units.   Late-eluting compounds usually  have much better
agreement.

      7.4.5 A system performance check  must be performed to ensure that
minimum average response factors are met before the calibration curve is
used.  For semivolatiles, the System Performance Check Compounds (SPCCs)
are:      N-nitroso-di-n-propylamine;    hexachlorocyclopentadiene;   2,4-
dinitrophenol; and 4-nitrophenol.  The minimum acceptable average RF for
these is  0.050.   These SPCCs typically have very  low RFs  (0.1-0.2) and
tend  to  decrease in  response as  the  chromatographic system  begins  to
deteriorate  or the  standard material  begins  to deteriorate.   They are
usually the  first  to show poor performance.   Therefore,  they must meet
the minimum requirement when the system is calibrated.

7.5  Daily GC/MS calibration

      7.5.1 Prior to analysis of samples, the GC/MS tuning  standard must
be analyzed.  A 50 ng  injection  of DFTPP must  result  in a mass spectrum
for DFTPP which meets the  criteria  given in  Table 3.  These  criteria must
be demonstrated during each 12 hour shift.

      7.5.2 A calibration standard(s)  at mid-concentration containing all
semivolatile analytes,  including all required surrogates, must be performed
every 12 hours during analysis.  Compare the response factor  data from the
standards every 12 hours with the average response factor  from the initial
calibration for a specific instrument  as per SPCC (Section 7.4.3) and CCC
(Section 7.4.4) criteria.

      7.5.3 System  Performance  Check  Compounds  (SPCCs)  -  A  system
performance check must be made during every 12 hour shift.   If the SPCC
criteria  are met,  a comparison of response  factors is  made for  all
compounds.   This  is  the same  check  that is applied  during the  initial
calibration.  If the minimum response factors are not met, the system must
be evaluated, and corrective action must be taken before sample analysis
begins.  The minimum RF for  semivolatile SPCCs is  0.050.  Some possible
problems   are  standard   mixture  degradation,  injection   port   inlet
contamination,  contamination at the front  end  of the  analytical  column,
and active sites  in the column or chromatographic  system.  This check must
be met before analysis begins.


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      7.5.4 Calibration  Check  Compounds  (CCCs):    After  the  system
performance check  is  met,  CCCs  listed in Table 4 are  used  to check the
validity of the  initial  calibration.  Calculate  the percent difference
using:
                    RF,   - RFC
     % Difference =	 x 100
where:
                       RF,
      RF, =   Average response factor from initial calibration.
      RFC =   Response factor from current verification check standard.

     If the percent difference  for  any  compound  is  greater than 20, the
laboratory should consider this a warning limit.  If the percent difference
for each CCC is  less than 30%,  the  initial  calibration  is assumed to be
valid.   If the criterion  is  not met (>  30% difference)  for any one CCC,
corrective action must be taken.  Problems similar to those listed under
SPCCs could affect  these  criteria.   If no source of  the  problem can be
determined  after corrective  action has  been taken,  a  new  five-point
calibration must be generated.  This criterion must be met before sample
analysis begins.

      7.5.5 The  internal  standard  responses and retention  times  in the
calibration check standard must be evaluated immediately after or during
data acquisition.  If the  retention time for any internal standard changes
by more than 30  seconds from the last  check calibration (12 hours), the
chromatographic system must  be inspected for malfunctions and corrections
must be  made,  as required.   If the EICP  area  for  any of the internal
standards changes by a factor of two (-50% to +100%) from the last daily
calibration standard check,  the  mass spectrometer must  be inspected for
malfunctions and corrections must be made, as appropriate.

7.6  GC/MS analysis

      7.6.1 It is  highly  recommended that the extract  be  screened  on a
GC/FID or  GC/PID using the  same type  of column.   This  will  minimize
contamination of the GC/MS system from  unexpectedly high  concentrations
of organic compounds.

      7.6.2 Spike the 1 ml extract obtained from sample preparation with
10 pi of the internal standard solution just prior to analysis.

      7.6.3 Analyze the 1  ml  extract by  GC/MS using the appropriate column
(as  specified  in   Section  4.1.2).    The recommended  GC/MS  operating
conditions to be used are specified in  Section 7.3.

      7.6.4 If the response for any quantitation ion exceeds the initial
calibration curve range of the  GC/MS system,  extract  dilution must take
place.  Additional  internal standard must  be added to the diluted extract
to maintain  the  required 40  ng//iL of each internal  standard  in  the
extracted volume.  The diluted extract  must be reanalyzed.
                            8250A - 11                      Revision 1
                                                            November 1990

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      7.6.5 Perform  all  qualitative  and  quantitative  measurements  as
described  in  Section 7.7.   Store the  extracts at 4°C,  protected  from
light in screw-cap vials equipped with unpierced Teflon lined septa.

7.7  Data interpretation

      7.7.1 Qualitative analysis

            7.7.1.1 The qualitative identification of compounds determined
      by this method is  based  on  retention  time, and on comparison of the
      sample   mass   spectrum,    after   background   correction,   with
      characteristic ions in a reference mass spectrum. The reference mass
      spectrum must be generated  by the  laboratory using  the conditions
      of this method.   The characteristic ions from  the  reference  mass
      spectrum are  defined to  be the three  ions of greatest  relative
      intensity,  or any ions over 30% relative intensity if  less than three
      such  ions  occur in  the reference  spectrum.  Compounds  should  be
      identified as present when the criteria below are met.

                  7.7.1.1.1 The  intensities  of the characteristic  ions
            of a compound  maximize in  the same  scan or within one scan of
            each other.   Selection of  a peak  by a data  system target
            compound  search  routine  where  the search  is based on  the
            presence  of  a target  chromatographic peak containing  ions
            specific  for   the  target  compound at a  compound-specific
            retention time will  be accepted as meeting this criterion.

                  7.7.1.1.2 The  RRT of the sample component is within ±
            0.06 RRT units of the RRT of the standard component.

                  7.7.1.1.3 The relative  intensities of the characteristic
            ions agree within 30% of the relative intensities of these ions
            in the  reference  spectrum.   (Example:   For  an  ion  with  an
            abundance of 50% in  the reference spectrum, the corresponding
            abundance in a  sample  spectrum can range between  20% and 80%.)

                  7.7.1.1.4 Structural isomers that produce very similar
            mass spectra should be identified as individual  isomers if they
            have sufficiently different  GC retention  times.  Sufficient
            GC resolution  is achieved  if  the height of the valley between
            two isomer peaks is less than 25% of the sum of the two peak
            heights.   Otherwise,  structural  isomers  are  identified  as
            isomeric pairs.

                  7.7.1.1.5 Identification   is  hampered   when   sample
            components are not  resolved  chromatographically and produce
            mass spectra  containing  ions  contributed  by  more  than  one
            analyte.  When gas chromatographic peaks obviously represent
            more than one  sample  component (i.e.,  a broadened  peak with
            shoulder(s)  or  a  valley  between  two  or  more  maxima),
            appropriate selection of analyte spectra and background spectra
            is important.   Examination of extracted ion current profiles
            of appropriate ions can aid in the selection of spectra, and
            in qualitative  identification  of compounds.   When analytes

                            8250A  - 12                      Revision 1
                                                            November 1990

-------
      coelute (I.e., only one chromatographic peak Is apparent), the
      identification criteria can be met, but each analyte spectrum
      will contain  extraneous ions contributed  by the  coeluting
      compound.

      7.7.1.2 For samples containing components not associated with
the calibration  standards,  a library  search  may be made  for the
purpose of tentative identification.  The necessity to perform this
type of  identification  will be  determined  by the purpose  of the
analyses being conducted.  Computer generated library search routines
should not use normalization  routines  that  would misrepresent the
library or unknown spectra when compared to each other.  For example,
the RCRA  permit  or waste  delisting  requirements may  require the
reporting of  nontarget analytes.  Only after visual  comparison of
sample  spectra  with the  nearest library searches  will  the  mass
spectral interpretation specialist assign a tentative identification.
Guidelines for making tentative identification are:

(1)  Relative  intensities of  major ions  in  the reference spectrum
(ions > 10% of the most abundant ion) should be present in the sample
spectrum.

(2)  The relative intensities  of  the major ions should agree within
+  20%.    (Example:   For an  ion  with   an abundance  of 50%  in the
standard  spectrum, the corresponding sample ion  abundance  must be
between 30 and 70%.)

(3)   Molecular ions present  in  the  reference spectrum  should be
present in sample the spectrum.

(4)  Ions present in the  sample  spectrum but not in  the  reference
spectrum  should  be  reviewed for  possible  background  contamination
or presence of coeluting compounds.

(5)  Ions present in the  reference spectrum but  not  in the sample
spectrum should be reviewed  for possible subtraction from the sample
spectrum  because  of background contamination or coeluting peaks.
Data system library reduction  programs can  sometimes  create these
discrepancies.

7.7.2 Quantitative analysis

      7.7.2.1 When a compound has been  identified, the quantitation
of that compound will  be  based on  the integrated  abundance from the
EICP of the primary characteristic ion.  Quantitation will take place
using the internal standard technique.   The internal  standard used
shall  be  the  one nearest  the retention  time  of that of  a given
analyte (e.g.  see Table 5).

      7.7.2.2 Calculate the concentration of each  identified analyte
in the sample as follows:
                      8250A - 13                      Revision 1
                                                      November 1990

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            Water
                                        (AJ(Is)(Vt)
            concentration (M9/L)  =
                                      (Als)(RF)(V0}(V,)

            where:

            Ax =  Area of characteristic ion for compound  being measured.
            Is =  Amount of internal  standard injected  (ng).
            Vt =  Volume of total extract, taking  into  account dilutions  (i.e.
                  a l-to-10 dilution of a 1 ml extract will mean Vt =  10,000 /zL.
                  If half the base/neutral extract  and half the acid extract are
                  combined, V, = 2,000).
            A,s=   Area of characteristic ion for the internal standard.
            RF =  Response factor for compound being measured (Section  7.3.3).
            V0 =  Volume of water extracted (ml).
            V, =   Volume of extract injected
            Sediment/Soil Sludge (on a dry-weight basis) and Waste (normally on
            a wet-weight basis

                                          (Ax)(IJ(Vt)
            concentration (jug/Kg)
                                      (A|S)(RF)(V,)(WS)(D)

            where:

            A,,,  Is, Vt,  Als,  RF,  V, = Same as for water.
            Ws =  Weight of sample extracted or diluted  in grams.
            D  =  % dry weight of sample/100, or  1 for a wet-weight  basis.

                  7.7.2.3  Where  applicable,  an estimate  of concentration  for
            noncalibrated components in the sample should be made.  The formulas
            given above should  be  used with  the following modifications:   The
            areas Ax and Als should be from the total  ion chromatograms  and  the
            RF for the  compound  should be assumed to be 1.  The concentration
            obtained should  be reported  indicating  (1)  that  the  value is  an
            estimate and   (2)  which  internal  standard  was  used  to  determine
            concentration.     Use   the  nearest  internal  standard   free   of
            interferences.

                  7.7.2.4  Quantitation   of  multicomponent   compounds   (e.g.
            Aroclors) is beyond the scope of Method 8250.  Normally,  quantitation
            is performed using a GC/ECD by Method 8080.


8.0  QUALITY CONTROL

      8.1  Refer to  Chapter  One and Method  8000  for specific quality  control
procedures.

      8.2  Required instrument QC is found in the following  section:


                                  8250A -  14                       Revision  1
                                                                   November 1990

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            8.2.1 The GC/MS system must be tuned to meet the DFTPP specifications
      in Sections 7.4.1 and 7.4.1.

            8.2.2 There must be an  initial  calibration of  the GC/MS system as
      specified in Section 7.4.

            8.2.3 The  GC/MS  system must  meet  the SPCC criteria  specified in
      Section 7.5.3 and the CCC criteria in Section 7.5.4,  each 12 hours.

      8.3  To  establish  the  ability  to  generate  acceptable  accuracy  and
precision, the analyst must perform the following operations.

            8.3.1 A  quality (QC)  reference  sample  concentrate  is  required
      containing each analyte at a concentration of 100 nq/ml in acetone.  The
      QC  reference  sample  concentrate  may be  prepared  from pure  standard
      materials  or purchased  as   certified solutions.   If  prepared by  the
      laboratory, the QC reference sample concentrate must  be made using stock
      standards prepared independently from those used for  calibration.

            8.3.2 Using a pipet, prepare QC reference samples  at a concentration
      of 100 /xg/L by adding 1.00 ml of QC reference sample  concentrate to each
      of four 1 L aliquots of water.

            8.3.3 Analyze the well-mixed QC reference samples according to the
      method beginning in Section  7.1 with extraction of the samples.

            8.3.4 Calculate the average recovery (x) in p.g/1, and the  standard
      deviation of the recovery(s)  in M9/U for each analyte of interest using
      the four results.

            8.3.5 For  each  analyte  compare s  and x  with  the  corresponding
      acceptance criteria _for  precision and accuracy,  respectively,  found in
      Table 6.   If s  and x  for all  analytes of  interest meet  the  acceptance
      criteria, the  system performance  is  acceptable and  analysis of actual
      samples can  begin.   If any  individual s exceeds  the  precision  limit or
      any individual x falls outside the range for accuracy,  then  the system
      performance is unacceptable  for that analyte.

NOTE: The large number of analytes  in Table  6 present a substantial probability
      that one or more will  fail at  least one  of the  acceptance criteria when
      all analytes of a given method are analyzed.

            8.3.6 When one or more of the analytes tested fail at least one of
      the acceptance criteria,  the analyst must  proceed according  to Section
      8.3.6.1 or 8.3.6.2.

                  8.3.6.1 Locate and correct  the source  of the problem  and
            repeat the test for all  analytes of interest beginning with Section
            8.3.2.

                  8.3.6.2 Beginning  with  Section  8.3.2, repeat the test only
            for those analytes  that failed to meet criteria.  Repeated  failure,
            however, will confirm a general problem with the measurement system.


                                  8250A - 15                      Revision 1
                                                                  November  1990

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            If this  occurs,  locate and correct the source  of the problem and
            repeat the test for all compounds of interest beginning with Section
            8.3.2.

      8.4  For  aqueous and  soil   matrices,  laboratory  established  surrogate
control limits should  be  compared with the control limits  listed in Table 8.
The limits given  in  Table 8 are  multilaboratory  performance  based  limits for
soil and aqueous samples,  and therefore, the single laboratory limits must fall
within those given in Table 8 for these matrices.

            8.4.1 If recovery  is  not within limits,  the following  procedures
      are required.

                  8.4.1.1 Check to be sure  that there  are no errors  in the
            calculations, surrogate solutions  or internal  standards.  If errors
            are found, recalculate the data accordingly.

                  8.4.1.2 Check  instrument  performance.   If  an  instrument
            performance problem is identified, correct the problem and re-analyze
            the extract.

                  8.4.1.3 If no problem is found,  re-extract and re-analyze the
            sample.

                  8.4.1.4 If, upon re-analysis,  the recovery is again not within
            limits, flag the data as "estimated concentration".

            8.4.2 At a minimum, each laboratory should  update surrogate recovery
      limits on a matrix-by-matrix basis,  annually.


9.0  METHOD PERFORMANCE

      9.1  Method 8250 was tested  by  15 laboratories using organic-free reagent
water, drinking water, surface water, and industrial  wastewaters spiked at six
concentrations over  the  range  5-1,300 /ig/L.    Single  operator  accuracy and
precision,  and method  accuracy  were  found  to  be  directly  related  to  the
concentration of the analyte and essentially independent of the sample matrix.
Linear equations to describe these relationships are presented in Table 7.


10.0 REFERENCES

1.   U.S. EPA 40 CFR Part  136,  "Guidelines  Establishing Test Procedures for the
     Analysis of Pollutants Under  the Clean Water Act, Method 625," October 26,
     1984.

2.   U.S.  EPA Contract  Laboratory  Program,  Statement  of Work  for  Organic
     Analysis, July 1985,  Revision.

3.   Eichelberger, J.W.,  L.E.  Harris,  and W.L. Budde,  "Reference Compound  to
     Calibrate Ion Abundance Measurement in Gas Chromatography-Mass Spectrometry
     Systems," Analytical  Chemistry,  47,  995-1000, 1975.


                                  8250A -  16                      Revision 1
                                                                  November 1990

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"Method Detection Limit for Methods 624 and 625," Olynyk, P., W.L. Budde,
and J.W. Eichelberger, Unpublished report, October 1980.

"Inter!aboratory Method Study for EPA Method 625-Base/Neutrals,  Acids, and
Pesticides," Final Report for EPA Contract 68-03-3102  (in preparation).

Burke,  J.A.  "Gas  Chromatography  for Pesticide  Residue Analysis;  Some
Practical  Aspects,"  Journal  of the  Association  of  Official   Analytical
Chemists, 48, 1037, 1965.
                             8250A - 17                      Revision 1
                                                             November 1990

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                        TABLE 1.
CHROMATOGRAPHIC CONDITIONS, METHOD DETECTION LIMITS, AND
     CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS
Retention
Compound Time (min)
Acenaphthene 17.8
Acenaphthene-d10 (I.S.)
Acenaphthylene 17.4
Acetophenone
Aldrin 24.0
4-Aminobiphenyl
Aniline
Anthracene 22.8
Aroclor-1016b 18-30
Aroclor-1221b 15-30
Aroclor-1232b 15-32
Aroclor-1242b 15-32
Aroclor-1248b 12-34
Aroclor-1254b 22-34
Aroclor-1260b 23-32
Benzidine" 28.8
Benzoic acid
Benzo(a)anthracene 31.5
Benzo(b)fluoranthene 34.9
Benzo(k)fluoranthene 34.9
Benzo(g,h,i)perylene 45.1
Benzo(a)pyrene 36.4
Benzyl alcohol
«-BHCa 21.1
6-BHC 23.4
*-BHC 23.7
T-BHC (Lindane)8 22.4
Bis(2-chloroethoxy)methane 12.2
Bis(2-chloroethyl) ether 8.4
Bis(2-chloroisopropyl) ether 9.3
Bis(2-ethylhexyl) phthalate 30.6
4-Bromophenyl phenyl ether 21.2
Butyl benzyl phthalate 29.9
Chlordane" 19-30
4-Chloroaniline
1-Chloronaphthalene
2-Chloronaphthalene 15.9
4-Chloro-3-methylphenol 13.2
2-Chlorophenol 5.9
4-Chlorophenyl phenyl ether 19.5
Chrysene 31.5
Chrysene-d12 (I.S.)
4,4'-DDD 28.6
4,4'-DDT 29.3
Method
detection
limit (/ag/L)
1.9
--
3.5
--
1.9
--
--
1.9
--
30
--
--
--
36
--
44
--
7.8
4.8
2.5
4.1
2.5
--
--
4.2
3.1
--
5.3
5.7
5.7
2.5
1.9
2.5
--
--
--
1.9
3.0
3.3
4.2
2.5
--
2.8
4.7
Primary
Ion
154
164
152
105
66
169
93
178
222
190
190
222
292
292
360
184
122
228
252
252
276
252
108
183
181
183
183
93
93
45
149
248
149
373
127
162
162
107
128
204
228
240
235
235
Secondary
Ion(s)
153, 152
162, 160
151, 153
77, 51
263, 220
168, 170
66, 65
176, 179
260, 292
224, 260
224, 260
256, 292
362, 326
362, 326
362, 394
92, 185
105, 77
229, 226
253, 125
253, 125
138, 277
253, 125
79, 77
181, 109
183, 109
181, 109
181, 109
95, 123
63, 95
77, 121
167, 279
250, 141
91, 206
375, 377
129
127, 164
127, 164
144, 142
64, 130
206, 141
226, 229
120, 236
237, 165
237, 165
                        8250A -  18
Revision 1
November 1990

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TABLE 1.
(Continued)
Retention
Compound Time (min)
Dibenz(a,j)acridine
Dibenz (a, h) anthracene
Dibenzofuran
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
--
43.2
--
24.7
8.4
7.4
7.8
Method
detection
Primary
limit (jug/L) Ion
--
2.5
--
2.5
1.9
1.9
4.4
l,4-Dichlorobenzene-d4 (I.S.) --
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dieldrin
Diethyl phthalate
p-Dimethyl aminoazobenzene
32.2
9.8
--
27.2
20.1
--
16.5
2.7
--
2.5
1.9
--
7,12-0imethylbenz(a)anthracene --
a-, a -Dimethyl phenethyl ami ne
2, 4-Dimethyl phenol
Dimethyl phthalate
4, 6-Dinitro-2-methyl phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
1 , 2-Di phenyl hydrazi ne
Di-n-octyl phthalate
Endosulfan I"
Endosulfan IIa
Endosulfan sulfate
Endrin8
Endrin aldehyde
Endrin ketone
Ethyl methanesulfonate
Fluoranthene
Fluorene
2-Fluorobiphenyl (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachl orobutadi ene
Hexachl orocycl opentadi enea
Hexachl oroethane
Indeno(l,2,3-cd)pyrene
Isophorone
Methoxychlor
--
9.4
18.3
16.2
15.9
19.8
18.7
--
--
32.5
26.4
28.6
29.8
27.9
--
--
--
26.5
19.5
--
--
23.4
25.6
21.0
11.4
13.9
8.4
42.7
11.9
--
--
2.7
1.6
24
42
5.7
1.9
--
--
2.5
--
--
5.6
--
--
--
--
2.2
1.9
--
--
1.9
2.2
1.9
0.9
--
1.6
3.7
2.2
--
279
278
168
149
146
146
146
152
252
162
162
79
149
120
256
58
122
163
198
184
165
165
169
77
149
195
337
272
263
67
317
79
202
166
172
112
100
353
284
225
237
117
276
82
227
Secondary
Ion(s)
280,
139,
139
150,
148,
148,
148,
150,
254,
164,
164,
263,
177,
225,
241,
91,
107,
194,
51,
63,
63,
63,
168,
105,
167,
339,
339,
387,
82,
345,
67,
109,
101,
165,
171
64
272,
355,
142,
223,
235,
201,
138,
95,
228
111
279

104
111
111
111
115
126
98
98
279
150
77
257
42
121
164
105
154
89
89
167
182
43
341
341
422
81
250
319
97
203
167


274
351
249
227
272
199
227
138

8250A - 19
Revision 1
November 1990

-------
TABLE 1.
(Continued)
Retention
Compound Time (min)
3-Methylcholanthrene
Methyl methanesulfonate
2-Methyl naphthalene
2-Methyl phenol
4-Methyl phenol
Naphthalene
Naphthalene-dB (I.S.)
1-Naphthylamine
2-Naphthylamine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
Nitrobenzene-d5 (surr.)
2-Nitrophenol
4-Nitrophenol
N-Nitroso-di-n-butylamine
N-Nitrosodimethylaminea
N-Nitrosodiphenylaminea
N-Nitroso-di-N-propylamine
N-Nitrosopiperidine
Pentachlorobenzene
Pentachloronitrobenzene
Pentachlorophenol
Perylene-d12 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-d10 (I.S.)
Phenol
Phenol -d6 (surr.)
2-Picoline
Pronamide
Pyrene
Terphenyl-d14 (surr.)
1,2,4,5-Tetrachlorobenzene
2,3,4,6-Tetrachlorophenol
--
--
--
--
--
12.1
--
--
--
--
--
--
11.1
--
6.5
20.3
--
--
20.5
--
--
--
--
17.5
--
--
22.8
--
8.0
--
--
--
27.3
--
--
--
Method
detection
Primary
limit (/ig/L) Ion
--
--
--
--
--
1.6
--
--
--
--
--
--
1.9
--
3.6
2.4
--
--
1.9
--
--
--
--
3.6
--
--
5.4
--
1.5
--
--
--
1.9
--
--
--
Toxaphene" 25-34
2,4,6-Tribromophenol (surr,
1,2,4-Trichlorobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
. ) --
11.6
--
11.8
--
1.9
--
2.7
268
80
142
108
108
128
136
143
143
65
138
138
77
82
139
139
84
42
169
70
42
250
295
266
264
108
178
188
94
99
93
173
202
244
216
232
159
330
180
196
196
Secondary
Ion(s)
253,
79,
141
107,
107,
129,
68
115,
115,
92,
108,
108,
123,
128,
109,
109,
57,
74,
168,
130,
114,
252,
237,
264,
260,
109,
179,
94,
65,
42,
66,
175,
200,
122,
214,
230,
231,
332,
182,
198,
198,
267
65

79
79
127

116
116
138
92
92
65
54
65
65
41
44
167
42
55
248
142
268
265
179
176
80
66
71
92
145
203
212
218
131
233
141
145
200
200
aSee Section 1.3
"These compounds are mixtures of various isomers.
                                   8250A -  20
Revision 1
November 1990

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                                   TABLE 2.
             DETERMINATION OF ESTIMATED QUANTITATION LIMITS (EQL)
                             FOR VARIOUS MATRICES8
    Matrix                                                        Factor"
Ground water                                                           10
Low-concentration soil by ultrasonic extraction with GPC cleanup      670
High-concentration soil and sludges by ultrasonic extraction       10,000
Non-water miscible waste                                          100,000


a    Sample EQLs are highly matrix-dependent.  The EQLs listed herein are provided
    for guidance  and  may  not always be  achievable.

b    EQL = [Method detection limit  (Table 1)]  X [Factor  (Table  2)].   For non-
    aqueous  samples,  the  factor is  on  a wet-weight  basis.
                                  8250A - 21                      Revision 1
                                                                  November 1990

-------
                                   TABLE 3.
                  DFTPP KEY  IONS AND  ION ABUNDANCE CRITERIA8
       Mass              Ion Abundance Criteria
       51               30-60% of mass 198

       68               < 2% of mass 69
       70               < 2% of mass 69

      127               40-60% of mass 198

      197               < 1% of mass 198
      198               Base peak, 100% relative abundance
      199               5-9% of mass 198

      275               10-30% of mass 198

      365               > 1% of mass 198

      441               Present but less than mass 443
      442               > 40% of mass 198
      443               17-23% of mass 442
aSee  Reference 4.
                                  8250A - 22                      Revision 1
                                                                  November 1990

-------
                             TABLE 4.
                    CALIBRATION CHECK COMPOUNDS
Base/Neutral Fraction                   Acid Fraction
Acenaphthene                            4-Chloro-3-methylphenol
1,4-Dichlorobenzene                     2,4-Dichlorophenol
Hexachlorobutadiene                     2-Nitrophenol
N-Nitroso-di-n-phenylamine              Phenol
Di-n-octyl phthalate                    Pentachlorophenol
Benzo(a)pyrene                          2,4,6-Trichlorophenol
                            8250A - 23                      Revision 1
                                                            November  1990

-------
                                   TABLE 5.
          SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
                           ASSIGNED FOR QUANTITATION
Phenanthrene-d
              10
Chrysene-d12
Perylene-d12
4-Aminobiphenyl
Anthracene
4-Bromophenyl phenyl ether
Di-n-butyl phthalate
4,6-Dinitro-2-methylphenol
Diphenylamine
1,2-Di phenylhydrazi ne
Fluoranthene
Hexachlorobenzene
N-Nitrosodiphenylamine
Pentachlorophenol
Pentachloroni trobenzene
Phenacetln
Phenanthrene
Pronamide
 Benzidine
 Benzo(a)anthracene
 Bis(2-ethylhexyl)  phthalate
 Butyl  benzyl  phthalate
 Chrysene
 3,3'-Dichlorobenzidine
 p-Dimethylami noazobenzene
 Pyrene
 Terphenyl-d14 (surr.)
  Benzo(b)fluor-
    anthene
   Benzo(k)fluor-
      anthene
  Benzo(g,h,i)-
    perylene
  Benzo(a)pyrene
  Dibenz(a,j)acridine
 Dibenz(a,h)-
    anthracene
  7,12-Dimethylbenz-
    (a)anthracene
  Di-n-octyl  phthalate
  Indeno(l,2,3-cd)-
    pyrene
  3-Methylchol-
   anthrene
(surr.) = surrogate
                                  8250A  -  24
                                      Revision 1
                                      November 1990

-------
                                   TABLE 5.
          SEMIVOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
                           ASSIGNED FOR QUANTITATION
                                  (Continued)
l,4-Dichlorobenzene-D4
Naphthalene-d8
Acenaphthene-d
                                                                    10
Aniline
Benzyl alcohol
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether   4-Chloroaniline
Acetophenone              Acenaphthene
Benzoic acid              Acenaphthylene
Bis(2-chloroethoxy)methanel-Chloronaphthalene
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Di chlorobenzene
Ethyl methanesulfonate
2-Fluorophenol (surr.)
Hexachloroethane
Methyl methanesulfonate
2-Methylphenol
4-Methylphenol
N-Nitrosodimethylamine
N-Nitroso-di-n-propylamine
Phenol
Phenol-d6 (surr.)
2-Picoline
4-Chloro-3-methylphenol
2,4-Dichlorophenol
2,6-Dichlorophenol
o,a-Dimethyl-
    phenethylamine
2,4-Dimethylphenol
Hexachlorobutadiene
Isophorone
2-Methylnaphthalene
Naphthalene
Nitrobenzene
Nitrobenzene-d8 (surr.)
2-Chloronaphthalene
4-Chlorophenyl
    phenyl ether
Dibenzofuran
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Fluorene
2-Fluorobiphenyl
  (surr.)
Hexachlorocyclo-
  pentadiene
2-Nitrophenol
N-Nitroso-di-n-butylamine 1-Naphthylamine
N-Nitrosopiperi dine       2-Naphthylamine
1,2,4-Trichlorobenzene    2-Nitroaniline
                          3-Nitroaniline
                          4-Nitroaniline
                          4-Nitrophenol
                          Pentachlorobenzene
                          1,2,4,5-Tetra-
                            chlorobenzene
(surr.) = surrogate
                                  8250A - 25
                                      Revision 1
                                      November 1990

-------
       TABLE 6.
QC ACCEPTANCE CRITERIA3
Test
cone.
Compound (M9/L)
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benzo(a)anthracene
Benzo(b)fl uoranthene
Benzo(k)fl uoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Butyl benzyl phthalate
6-BHC
i-BHC
Bis(2-chloroethyl) ether
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl) ether
Bis(Z-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dibenzo( a, h) anthracene
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
Dieldrin
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfan sulfate
Endrin aldehyde
Fl uoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachloroethane
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
.100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(M9/L)
27.6
40.2
39.0
32.0
27.6
38.8
32.3
39.0
58.9
23.4
31.5
21.6
55.0
34.5
46.3
41.1
23.0
13.0
33.4
48.3
31.0
32.0
61.6
70.0
16.7
30.9
41.7
32.1
71.4
30.7
26.5
23.2
21.8
29.6
31.4
16.7
32.5
32.8
20.7
37.2
54.7
24.9
26.3
24.5
Range
for x
(M9/L)
60.1-132.3
53.5-126.0
7.2-152.2
43.4-118.0
41.8-133.0
42.0-140.4
25.2-145.7
31.7-148.0
D-195.0
D-139.9
41.5-130.6
D-100.0
42.9-126.0
49.2-164.7
62.8-138.6
28.9-136.8
64.9-114.4
64.5-113.5
38.4-144.7
44.1-139.9
D-134.5
19.2-119.7
D-170.6
D-199.7
8.4-111.0
48.6-112.0
16.7-153.9
37.3-105.7
8.2-212.5
44.3-119.3
D-100.0
D-100.0
47.5-126.9
68.1-136.7
18.6-131.8
D-103.5
D-188.8
42.9-121.3
71.6-108.4
D-172.2
70.9-109.4
7.8-141.5
37.8-102.2
55.2-100.0
Range
P» Ps
(%)
47-145
33-145
D-166
27.133
33-143
24-159
11-162
17-163
D-219
D-152
24-149
D-110
12-158
33-184
36-166
8-158
53-127
60-118
25-158
17-168
D-145
4-136
D-203
D-227
1-118
32-129
D-172
20-124
D-262
29-136
D-114
D-112
39-139
50-158
4-146
D-107
D-209
26-137
59-121
D-192
26.155
D-152
24-116
40-113
       8250A -  26
Revision 1
November  1990

-------
                                   TABLE 6.
                            QC ACCEPTANCE CRITERIA8
                                  (Continued)
Compound
Test
cone.
(M9/L)
Limit
for s
(M9/L)
Range
for x
(M9/L)
Range
P. Ps
(%)
Indeno(l,2,3-cd)pyrene      100       44.6
Isophorone                  100       63.3
Naphthalene                 100       30.1
Nitrobenzene                100       39.3
N-Nitroso-di-n-propylamine  100       55.4
PCB-1260                    100       54.2
Phenanthrene                100       20.6
Pyrene                      100       25.2
1,2,4-Trichlorobenzene      100       28.1
4-Chloro-3-methylphenol     100       37.2
2-Chlorophenol              100       28.7
2,4-Chlorophenol            100       26.4
2,4-Dimethylphenol          100       26.1
2,4-Dinitrophenol           100       49.8
2-Methyl-4,6-dinitrophenol  100       93.2
2-Nitrophenol               100       35.2
4-Nitrophenol               100       47.2
Pentachlorophenol           100       48.9
Phenol                      100       22.6
2,4,6-Trichlorophenol       100       31.7
D-150.9
46.6-180.2
35.6-119.6
54.3-157.6
13.6-197.9
19.3-121.0
65.2-108.7
69.6-100.0
57.3-129.2
40.8-127.9
36.2-120.4
52.5-121.7
41.8-109.0
D-172.9
53.0-100.0
45.0-166.7
13.0-106.5
38.1-151.8
16.6-100.0
52.4-129.2
D-171
21-196
21-133
35-180
D-230
D-164
54-120
52-115
44-142
22-147
23-134
39-135
32-119
D-191
D-181
29-182
D-132
14-176
5-112
37-144
s =


X =


P» Ps

D =
Standard deviation of four recovery measurements, in M9/L.

Average recovery for four recovery measurements, in M9/L.

Percent recovery measured.

Detected; result must be greater than zero.
   Criteria from  40  CFR Part  136  for Method 625.   These  criteria  are based
   directly on the method  performance data in Table 7.   Where necessary,  the
   limits for  recovery have been broadened to assure applicability of the limits
   to concentrations  below those used to develop Table  7.
                                  8250A - 27
                                                           Revision 1
                                                           November 1990

-------
                                 TABLE 7.
       METHOD ACCURACY AND PRECISION AS  FUNCTIONS OF CONCENTRATION8
Parameter
                            Accuracy, as
                            recovery, x'
Single analyst    Overall
precision, s/    precision,
    (M9/L)        S'  (M9/L)
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benzo(a)anthracene
Chloroethane
Benzo(b)f 1 uoranthene
Benzo ( k) f 1 uoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Butyl benzyl phthalate
B-BHC
«-BHC
Bis(2-chloroethyl) ether
Bi s (2-chl oroethoxy)methane
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dibenzo(a,h) anthracene
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1 , 4-Di chl orobenzene
3,3'-Dichlorobenzidine
Dieldrin
Diethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfan sulfate
Endrin aldehyde
Fl uoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachlorobutadiene
Hexachl oroethane
0.96C+0.19
0.89C+0.74
0.78C+1.66
0.80C+0.68
0.88C-0.60
0.99C-1.53
0.93C-1.80
0.87C-1.56
0.90C-0.13
0.98C-0.86
0.66C-1.68
0.87C-0.94
0.29C-1.09
0.86C-1.54
1.12C-5.04
1.03C-2.31
0.84C-1.18
0.91C-1.34
0.89C+0.01
0.91C+0.53
0.93C-1.00
0.56C-0.40
0.70C-0.54
0.79C-3.28
0.88C+4.72
0.59C+0.71
0.80C+0.28
0.86C-0.70
0.73C-1.47
1.23C-12.65
0.82C-0.16
0.43C+1.00
0.20C+1.03
0.92C-4.81
1.06C-3.60
0.76C-0.79
0.39C+0.41
0.76C-3.86
0.81C+1.10
0.90C-0.00
0.87C-2.97
0.92C-1.87
0.74C+0.66
0.71C-1.01
0.73C-0.83
0.15X-0.12
0.24X-1.06
0.27X-1.28
0.21X-0.32
0.15X+0.93
0.14X-0.13
0.22X+0.43
0.19X+1.03
0.22X+0.48
0.29x+2.40
O.lSx+0.94
0.20X-0.58
0.34X+0.86
0.35X-0.99
0.16X+1.34
0.24X+0.28
0.26X+0.73
O.lSx+0.66
0.07X+0.52
0.20X-0.94
0.28X+0.13
0.29X-0.32
0.26X-1.17
0.42X+0.19
0.30X+8.51
0.13x+1.16
0.20X+0.47
0.25X+0.68
0.24X+0.23
0.28X+7.33
0.20X-0.16
0.28X+1.44
0.54X+0.19
0.12X+1.06
0.14X+1.26
0.21X+1.19
0.12X+2.47
0.18x+3.91
0.22X-0.73
0.12X+0.26
0.24X-0.56
0.33X-0.46
O.lSx-0.10
0.19X+0.92
0.17x+0.67
0.21X-0.67
0.26X-0.54
0.43X+1.13
0.27X-0.64
0.26X-0.21
0.17X-0.28
0.29X+0.96
0.35X+0.40
0.32X+1.35
0.51X-0.44
0.53X+0.92
0.30X+1.94
0.93X-0.17
0.35X+0.10
0.26X-I-2.01
0.25X+1.04
0.36X+0.67
0.16X+0.66
0.13X+0.34
0.30X-0.46
0.33X-0.09
0.66X-0.96
0.39X-1.04
0.65X-0.58
0.59X+0.25
0.39X+0.60
0.24X+0.39
0.41X+0.11
0.29X+0.36
0.47X+3.45
0.26X-0.07
0.52X+0.22
l.OSx-0.92
0.21X+1.50
0.19X+0.35
0.37X+1.19
0.63X-1.03
0.73X-0.62
0.28X-0.60
0.13X+0.61
0.50X-0.23
0.28X+0.64
0.43X-0.52
0.26X+0.49
0.17X+0.80
                                8250A - 28
                  Revision 1
                  November 1990

-------
                                   TABLE 7.
         METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION8
                                  (Continued)
Parameter
Indeno(l,2,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Nitroso-di-n-propylamine
PCB-1260
Phenanthrene
Pyrene
1 , 2 , 4-Tri chl orobenzene
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2, 4-Dimethyl phenol
2,4-Dinitrophenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Accuracy, as
recovery, x'
(M9/L)
0.78C-3.10
1.12C+1.41
0.76C+1.58
1.09C-3.05
1.12C-6.22
0.81C-10.86
0.87C+0.06
0.84C-0.16
0.94C-0.79
0.84C+0.35
0.78C+0.29
0.87C-0.13
0.71C+4.41
0.81C-18.04
1.04C-28.04
0.07C-1.15
0.61C-1.22
0.93C+1.99
0.43C+1.26
0.91C-0.18
Single analyst
precision, s/
(M9/L)
0.29X+1.46
0.27X+0.77
0.21X-0.41
0.19X+0.92
0.27X+0.68
0.35X+3.61
0.12X+0.57
0.16x+0.06
O.lBx+0.85
0.23X+0.75
O.lSx+1.46
O.lSx+1.25
0.16X+1.21
0.38X+2.36
O.lOx+42.29
O.lSx+1.94
0.38X+2.57
0.24X+3.03
0.26X+0.73
0.16X+2.22
Overall
precision,
S' (M9/L)
O.BOx-0.44
0.33X+0.26
0.30X-0.68
0.27X+0.21
0.44X+0.47
0.43X+1.82
O.lSx+0.25
O.lBx+0.31
0.21X+0.39
0.29X+1.31
0.28X+0.97
0.21x+1.28
0.22X+1.31
0.42X+26.29
0.26X+23.10
0.27X+2.60
0.44X+3.24
O.SOx+4.33
0.35X+0.58
0.22X+1.81
X' =



s,'-


S' =
Expected recovery for one or more measurements of a sample containing a
concentration of C, in M9/L.

Expected single analyst standard deviation  of measurements at an average
concentration of x, in M9/L.

Expected interlaboratory_standard deviation of measurements at an average
concentration found of x, in M9/L.

True value for the concentration, in jug/l.

Average  recovery  found  for  measurements  of  samples  containing  a
concentration of C, in
                                  8250A - 29
                                                           Revision 1
                                                           November 1990

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                                   TABLE 8.
  SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
                                    Low/Medium             Low/Medium
   Surrogate Compound                  Water              Soil/Sediment
Nitrobenzene-d5                       35-114                 23-120
2-Fluorobiphenyl                      43-116                 30-115
p-Terphenyl -d14                        33-141                 18-137

Phenol-d6                              10-94                 24-113
2-Fluorophenol                        21-100                 25-121
2,4,6-Tribromophenol                  10-123                 19-122
                                  8250A  - 30                       Revision  1
                                                                   November 1990

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                                    METHOD 8250A
SEMIVOLATILE ORGANIC  COMPOUNDS BY  GAS CHROMATOGRAPHY/MASS SPECTROMETRY fGC/HSl:
                              PACKED COLUMN TECHNIQUE
            7.1 Prepare
           sample using
            Method 3540
             or 3550.
  7 . 1  Prepare
 sample  using
  Method 3510
   or  3520.
                                     7.1 Prepare
                                    sample using
                                    Method 3540,
                                      3550,  or
                                        3580.
                                     7 . 2 Cleanup
                                      ex tract.
                                         7.3
                                     Recommended
                                        CC/MS
                                      operating
                                     condi tions.
  7.4  Initial
 calibration.
   7.5  Daily
 calibration-
Tune CC/MS  with
TFTPP and check
  SPCC  & CCC.
                                     8250A - 31
             Revision 1
             November  1990

-------
METHOD 8250A
  continued
   7 6 1 Scrt«n
 ••tract in CC/FID
   or CC/PID to
 eliminat* too-high
  concentration*
  7 7.1 Identify
   compound* by
 comparing sample
 retention time and
 •ample mass spectra
   to standards
  8250A  -  32
Revision  1
November 1990

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                                 METHOD 8260A

  VOLATILE ORGANIC COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY fGC/MSl:
                          CAPILLARY COLUMN TECHNIQUE


1.0  SCOPE AND APPLICATION

      1.1  Method  8260  Is used to  determine volatile organic  compounds  in a
variety of solid waste matrices.  This method is applicable to nearly all types
of samples, regardless of water content, including ground water, aqueous sludges,
caustic  liquors,  acid  liquors,  waste solvents,  oily wastes,  mousses,  tars,
fibrous  wastes,  polymeric  emulsions,   filter  cakes,  spent  carbons,  spent
catalysts, soils, and sediments.  The following compounds can be determined by
this method:
Analyte
CAS No.b
  Appropriate Technique
                  Direct
Purge-and-Trap    Injection
Benzene
Bromobenzene
Bromochl oromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chi oromethane
2-Chlorotoluene
4-Chlorotoluene
Di bromochl oromethane
1 , 2-Di bromo-3-chl oropropane
1,2-Dibromoethane
Dibromomethane
1 , 2-Dichl orobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1 -Di chloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-1, 2-Di chl oroethene
trans- 1 , 2-Di chl oroethene
1,2-Dichloropropane
1,3-Dichloropropane
71-43-2
108-86-1
74-97-5
75-27-4
75-25-2
74-83-9
104-51-8
135-98-8
98-06-6
56-23-5
108-90-7
75-00-3
67-66-3
74-87-3
95-49-8
106-43-4
124-48-1
96-12-8
106-93-4
74-95-3
95-50-1
541-73-1
106-46-7
75-71-8
75-34-3
107-06-2
75-35-4
156-59-2
156-60-5
78-87-5
142-28-9
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
PP
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
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a
                                   8260A -  1
                               Revision  1
                               November 1990

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                                     Appropriate Technique
                                                      Direct
Analyte                            CAS No.b     Purge-and-Trap    Injection
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachl orobutadi ene
Isopropyl benzene
p-Isopropyl toluene
Methylene chloride
Naphthalene
n-Propyl benzene
Styrene
1,1,1, 2 -Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachl oroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1-Trichl oroethane
1,1,2-Trichloroethane
Trichloroethene
Tr i chl orof 1 uoromethane
1,2,3-Trichloropropane
1,2, 4-Trimethyl benzene
1, 3, 5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
a Adequate response by thi
594-20-7
563-58-6
100-41-4
87-68-3
98-82-8
99-87-6
75-09-2
91-20-3
103-65-1
100-42-5
630-20-6
79-34-5
127-18-4
108-88-3
87-61-6
120-82-1
71-55-6
79-00-5
79-01-6
75-69-4
96-18-4
95-63-6
108-67-8
75-01-4
95-47-6
108-38-3
106-42-3
s technique.
a
a
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a

a
a
a
a
a
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a
a
a
a
a
a
a

b Chemical Abstract Services Registry Number.
pp Poor purging efficiency
i Inappropriate technique
resulting in high EQLs.
for this analyte.




pc Poor chromatographic behavior.
      1.2  Method 8260 can be used to quantitate most volatile organic compounds
that have boiling points below 200°C  and that are insoluble or slightly soluble
in water.  Volatile water-soluble compounds can be included in this analytical
technique.  However,  for the more soluble  compounds,  quantitation limits are
approximately  ten times  higher  because  of  poor  purging  efficiency.    Such
compounds  include low-molecular-weight  halogenated  hydrocarbons,  aromatics,
ketones, nitriles, acetates, acrylates,  ethers, and sulfides.  See Tables 1 and
2 for lists of analytes and  retention times that have been  evaluated on a purge-
and-trap  GC/MS  system.   Also,  the method  detection  limits for 25  ml  sample
volumes are presented.

      1.3  The  estimated  quantitation  limit   (EQL)  of  Method 8260  for  an

                                   8260A -  2                      Revision 1
                                                                  November 1990

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 individual  compound is approximately  5 /ig/Kg  (wet  weight)  for soil/sediment
 samples,  0.5  mg/Kg (wet weight) for wastes, and  5 /ig/L for ground water  (see
 Table 3).   EQLs will be proportionately higher  for sample extracts and samples
 that require dilution or reduced sample size to avoid saturation of the detector.

      1.4   Method 8260 is based upon a  purge-and-trap, gas chromatographic/mass
 spectrometric (GC/MS) procedure.  This method is restricted  to  use by, or under
 the supervision of,  analysts experienced  in the use of purge-and-trap systems
 and gas chromatograph/mass spectrometers,  and skilled in the interpretation of
 mass spectra  and their  use as  a quantitative tool.


 2.0  SUMMARY OF METHOD

      2.1   The volatile compounds are  introduced  into the gas chromatograph by
 the purge-and-trap method or  by  direct injection  (in  limited applications).
 Purged  sample components are  trapped  in  a tube containing  suitable  sorbent
 materials.  When purging is complete, the sorbent tube is heated and backflushed
 with helium to  desorb  trapped sample  components.  The analytes  are desorbed
 directly  to a large bore capillary or cryofocussed on a  capillary precolumn
 before  being  flash evaporated to a narrow bore capillary for  analysis.   The
 column is temperature programmed to separate the  analytes which are then detected
 with a mass spectrometer  (MS)  interfaced  to the gas  chromatograph.   Wide bore
 capillary columns require a jet separator, whereas narrow bore capillary columns
 can be directly interfaced to  the ion  source.

      2.2   If the  above sample introduction techniques are  not  applicable,  a
 portion of  the sample is dispersed  in  solvent to dissolve the volatile organic
 constituents.  A portion of  the solution is combined with organic-free reagent
 water  in  the purge chamber.   It  is  then  analyzed  by purge-and-trap  GC/MS
 following the normal water method.

      2.3   Qualitative  identifications are  confirmed  by analyzing  standards
 under the same conditions used for samples  and comparing resultant mass spectra
 and GC retention times.   Each  identified  component  is  quantitated  by relating
 the MS response  for an appropriate selected ion produced by that compound to the
 MS response for another ion  produced by an internal  standard.


 3.0  INTERFERENCES

      3.1  Major contaminant sources are  volatile materials  in the laboratory
 and impurities in  the  inert  purging gas and in the sorbent trap.   The  use of
 non-polytetrafluoroethylene  (PTFE)  thread  sealants,  plastic  tubing, or  flow
 controllers with rubber components  should be avoided since such materials out-
gas organic compounds which  will  be concentrated  in  the trap during the purge
 operation.  Analyses of  calibration  and reagent blanks provide information about
 the presence  of contaminants.   When potential  interfering peaks are  noted in
 blanks, the analyst should  change  the  purge  gas  source  and regenerate  the
molecular sieve purge  gas filter (Figure  1).   Subtracting blank  values  from
 sample results is not permitted.  If reporting values not  corrected for blanks
 result in  what the laboratory feels is a false positive for a sample, this should
 be fully explained in text accompanying the uncorrected data.


                                  8260A -  3                       Revision 1
                                                                  November  1990

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      3.2  Interfering contamination  may occur when  a sample  containing  low
concentrations of  volatile  organic  compounds is analyzed  immediately  after a
sample  containing  high  concentrations  of  volatile organic  compounds.    The
preventive technique  is  rinsing  of the purging apparatus  and sample syringes
with two portions of organic-free reagent water between  samples.  After analysis
of a sample containing high  concentrations  of volatile organic compounds,  one
or more calibration blanks should  be analyzed  to check for cross contamination.
For  samples  containing  large  amounts of water  soluble materials,  suspended
solids,  high  boiling  compounds  or   high  concentrations  of compounds  being
determined, it may  be  necessary to wash the purging  device with a soap solution,
rinse it with  organic-free reagent water,  and  then  dry the purging device in an
oven at  105°C.   In extreme  situations,  the  whole  purge  and trap  device  may
require dismantling and cleaning.   Screening of the samples prior to purge and
trap GC/MS analysis is highly recommended to prevent contamination of the system.
This  is  especially  true  for  soil   and  waste  samples.     Screening  may  be
accomplished with an automated headspace technique or by Method 3820 (Hexadecane
Extraction and Screening of Purgeable Organics).

      3.3  Special  precautions must be taken to analyze for methylene chloride.
The analytical and sample storage area should be isolated from all  atmospheric
sources of methylene chloride.  Otherwise  random background levels will  result.
Since  methylene   chloride   will   permeate   through  PTFE   tubing,   all   gas
chromatography carrier gas lines  and  purge  gas  plumbing  should be  constructed
from stainless steel or copper tubing. Laboratory  clothing worn by the analyst
should be clean  since  clothing previously exposed  to methylene chloride  fumes
during   liquid/liquid  extraction   procedures   can   contribute   to   sample
contamination.

      3.4  Samples  can  be  contaminated  by  diffusion of  volatile  organics
(particularly methylene chloride and fluorocarbons) through  the septum seal into
the sample during shipment and storage.  A trip blank prepared  from organic-free
reagent water and carried through the sampling and handling protocol can  serve
as a check on  such contamination.
4.0  APPARATUS AND MATERIALS

      4.1  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.

            4.1.1  The recommended purging chamber  is designed to accept 5 mL
      (and 25 mL if  the lowest detection limit is required)  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  (i.e. needle spargers), may be utilized, provided equivalent
      performance is demonstrated.

            4.1.2  The trap must  be  at  least 25 cm  long and have  an inside
      diameter  of at  least  0.105  in.  Starting  from the  inlet,  the trap must

                                   8260A -  4                       Revision 1
                                                                  November 1990

-------
      contain the following amounts  of  adsorbents: 1/3 of 2,6-diphenylene oxide
      polymer, 1/3 of silica gel, and 1/3 of coconut charcoal.  It is recommended
      that 1.0 cm of methyl  silicone-coated packing be inserted at the inlet to
      extend the  life of  the  trap (see Figure 2).   If  it  is  not  necessary to
      analyze  for dichlorodifluoromethane or  other  fluorocarbons  of  similar
      volatility, the charcoal can  be  eliminated  and the  polymer  increased to
      fill 2/3 of the  trap.   If  only  compounds boiling above 35°C  are  to be
      analyzed,  both  the  silica  gel  and  charcoal can  be eliminated  and  the
      polymer increased to fill the entire trap.  Before initial  use, the trap
      should be conditioned overnight at 180°C by backflushing  with an inert gas
      flow of at  least 20 mL/min.   Vent the  trap  effluent  to  the  room,  not to
      the analytical column.   Prior to daily use, the  trap should be conditioned
      for 10 minutes at 180°C  with backflushing.  The trap may be vented to the
      analytical  column during daily conditioning; however, the column must be
      run through the temperature program prior to analysis of samples.   Traps
      normally last 2-3 months when used daily.  Some signs of a deteriorating
      trap are: uncharacteristic recoveries of surrogates, especially  toluene-d8;
      a loss of the response of the internal  standards during  a 12 hour shift;
      and/or a rise in the baseline in the early portion of the scan.

            4.1.3  The desorber should be capable of rapidly  heating the trap
      to 180°C for desorption.  The  trap bake-out temperature should not exceed
      220°C.   The desorber design  illustrated in Figure 2 meets these criteria.

            4.1.4  The purge-and-trap device may be assembled as a separate unit
      or may be coupled to a gas chromatograph, as shown in Figures 3 and 4.

            4.1.5 Trap Packing Materials

                  4.1.5.1   2,6-Diphenylene   oxide  polymer   -   60/80   mesh,
            chromatographic grade (Tenax GC or equivalent).

                  4.1.5.2  Methyl silicone packing -  OV-1 (3%) on Chromosorb-W,
            60/80 mesh or equivalent.

                  4.1.5.3  Silica  gel   -  35/60  mesh,  Davison,  grade  15  or
            equivalent.

                  4.1.5.4  Coconut charcoal  - Prepare from Barnebey Cheney, CA-
            580-26  lot #M-2649   by  crushing  through  a  26  mesh   screen  (or
            equivalent).

      4.2  Heater  or  heated oil   bath  - Should be capable  of maintaining  the
purging chamber to within 1°C  over the  temperature range of ambient  to  100°C.

      4.3  Gas chromatography/mass spectrometer/data system

            4.3.1  Gas chromatograph  - An analytical  system  complete with a
      temperature-programmable gas chromatograph suitable for splitless injection
      and all required accessories,  including syringes, analytical columns, and
      gases.  The GC should be equipped with variable  constant differential flow
      controllers so that the column flow rate will  remain constant throughout
      desorption   and   temperature   program   operation.    For   some  column
      configuration, the  column  oven must be  cooled to <  30°C,  therefore, a

                                  8260A -  5                       Revision 1
                                                                  November  1990

-------
 subambient oven controller may be required.  The capillary column should
 be directly coupled to the source.

             4.3.1.1  Capillary precolumn  interface  when using cryogenic
       cooling - This device interfaces  the purge and trap concentrator to
       the  capillary gas  chromatograph.    The  interface condenses  the
       desorbed.sample components  and focuses  them  into  a narrow band on
       an uncoated fused silica capillary  precolumn.   When the interface
       is  flash heated,  the  sample is  transferred  to the  analytical
       capillary column.

                   4.3.1.1.1  During the cryofocussing step, the  temperature
             of the fused silica in the interface is maintained at -150°C
             under a  stream of  liquid  nitrogen.   After  the  desorption
             period,  the interface must be capable of rapid heating to 250°C
             in 15 seconds or less to complete the transfer of analytes.

       4.3.2  Gas chromatographic columns

             4.3.2.1  Column 1  -  60 m x  0.75 mm ID capillary column coated
       with VOCOL (Supelco), 1.5 urn film thickness, or equivalent.

             4.3.2.2  Column 2  -  30 m x  0.53 mm ID capillary column coated
       with  DB-624  (J&W  Scientific)   or   VOCOL  (Supelco),  3  /im  film
       thickness, or equivalent.

             4.3.2.3  Column 3  -  30 m x  0.32 mm ID capillary column coated
       with DB-5 (J&W Scientific) or SE-54  (Supelco), 1 /xm film thickness,
       or equivalent.

       4.3.3  Mass spectrometer -  Capable  of  scanning  from 35  to 300  amu
 every 2  sec  or less,  using  70 volts  (nominal)  electron energy  in  the
 electron impact ionization mode. The mass  spectrometer must be capable of
 producing a mass spectrum for  Bromofluorobenzene (BFB) which meets all of
 the criteria in Table 4 when 50 ng of the GC/MS tuning standard (BFB) is
 injected through the GC.  To ensure sufficient precision of mass spectral
 data, the  desirable MS  scan  rate allows  acquisition  of at  least  five
 spectra while a sample component elutes from the GC.

       4.3.4  GC/MS interface - The GC  is interfaced to the MS with an all
glass enrichment device and an  all  glass transfer line, but any enrichment
device or transfer line  can  be used  if   the  performance specifications
described in Section 8.2 can be  achieved.  Any GC-to-MS interface that gives
acceptable calibration points at 50  ng  or  less per  injection for each of
the analytes and achieves  all  acceptable performance criteria  (see Table
4) may be used.  GC-to-MS  interfaces constructed entirely of glass or of
glass-lined materials  are  recommended.    Glass  can  be deactivated  by
silanizing with dichlorodimethylsilane.  This  interface is only needed for
the wide bore columns (> 0.53 mm ID).

       4.3.5  Data system  - A  computer  system that  allows the continuous
 acquisition and  storage on machine-readable  media of  all  mass spectra
 obtained throughout  the duration  of the chromatographic program must be


                             8260A - 6                       Revision 1
                                                             November  1990

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      interfaced to the mass spectrometer.  The computer must have software that
      allows searching any  6C/MS data file  for  ions of a specified  mass and
      plotting such ion abundances versus time or  scan number.   This type of plot
      is defined as an  Extracted  Ion Current Profile (EICP).  Software must also
      be available that allows integrating  the abundances  in  any EICP between
      specified time or  scan-number limits.   The  most recent version  of the
      EPA/NIST Mass Spectral Library should also  be available.

      4.5  Microsyringes - 10, 25, 100, 250, 500, and 1,000 nl.

      4.6  Syringe valve - Two-way, with Luer ends (three each),  if applicable
to the purging device.

      4.7  Syringes - 5,  10, or 25 ml, gas-tight  with shutoff valve.

      4.8  Balance - Analytical,  0.0001 g, and top-loading,  0.1 g.

      4.9  Glass scintillation vials  - 20 ml,  with  Teflon  lined  screw-caps or
glass culture tubes with Teflon lined screw-caps.

      4.10 Vials - 2 ml,  for GC autosampler.

      4.11 Disposable pipets - Pasteur.

      4.12  Volumetric flasks, Class  A -  10 ml  and  100  ml,  with ground-glass
stoppers.

      4.13  Spatula - Stainless steel.


5.0  REAGENTS

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

      5.2  Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined  in Chapter One.

      5.3  Methanol, CH3OH - Pesticide quality or  equivalent,  demonstrated to
be free of analytes.  Store apart from other solvents.

      5.4  Reagent Tetraglyme - Reagent tetraglyme is defined as tetraglyme in
which interference  is  not observed  at the method detection  limit of compounds
of interest.

CAUTION;   Glycol ethers  are suspected carcinogens.  All solvent handling should
           be done in a hood while using proper protective equipment to minimize
           exposure to liquid and vapor.
                                   8260A -  7                       Revision 1
                                                                  November 1990

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            5.4.1  Tetraglyme (tetraethylene glycol dimethyl ether, Aldrich #17,
      240-5 or equivalent), C8H1805  -  Purify  by treatment at reduced pressure in
      a rotary evaporator.  The tetraglyme should have a peroxide content of less
      than 5 ppm as indicated by EM Quant Test Strips  (available from Scientific
      Products Co., Catalog No. P1126-8 or  equivalent).

                  5.4.1.1  Peroxides may  be removed  by passing the tetraglyme
            through a column of activated alumina.  The tetraglyme is placed in
            a round bottom flask equipped with a standard taper joint,  and the
            flask is affixed to a rotary evaporator.  The flask is immersed in
            a water bath at 90-100°C and a vacuum is maintained at < 10 mm Hg for
            at least two hours using a two-stage mechanical  pump.  The vacuum
            system is equipped with  an all-glass trap,  which is maintained in
            a dry ice/methanol  bath.  Cool the tetraglyme to ambient temperature
            and  add  100 mg/L of 2,6-di-tert-butyl-4-methyl-phenol  to  prevent
            peroxide formation. Store  the tetraglyme in a  tightly  sealed screw-
            cap bottle  in an area that is not contaminated by solvent vapors.

            5.4.2  In order to demonstrate  that all interfering volatiles have
      been removed from  the tetraglyme, an organic-free reagent water/tetraglyme
      blank must be analyzed.

      5.5  Polyethylene  glycol,  H(OCH2CH2)nOH -  Free  of  interferences  at  the
detection limit of the  target analytes.

      5.6  Hydrochloric acid (1:1  v/v), HC1 - Carefully add a measured volume
of concentrated HC1 to  an equal volume of organic-free reagent water.

      5.7  Stock solutions - Stock  solutions may be prepared  from  pure standard
materials or purchased as certified solutions.  Prepare  stock  standard solutions
in methanol, using assayed liquids or gases, as appropriate.

            5.7.1  Place about 9.8  mL of methanol in a 10 ml tared ground-glass-
      stoppered volumetric flask.  Allow  the flask to stand, unstoppered,  for
      about 10 minutes  or until all  alcohol-wetted surfaces have dried.  Weigh
      the flask to the  nearest 0.0001 g.

            5.7.2  Add  the assayed reference material, as described below.

                  5.7.2.1  Liquids - Using  a 100 nl  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.

                  5.7.2.2  Gases - To prepare standards for any compounds that
            boil below 30°C (e.g. bromomethane, chloroethane, chloromethane, or
            vinyl  chloride),  fill  a 5 ml  valved  gas-tight syringe  with  the
            reference standard to  the  5.0 ml mark.  Lower the needle  to 5 mm
            above the methanol meniscus. Slowly introduce the reference standard
            above the surface of the liquid.   The heavy gas  will  rapidly dissolve
            in the methanol.   Standards may  also be prepared  by  using a  lecture
            bottle equipped  with a  Hamilton Lecture Bottle  Septum (#86600).
            Attach Teflon tubing to the side arm  relief valve and direct  a gentle


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            stream of gas Into the methanol meniscus.

            5.7.3  Reweigh, dilute to volume, stopper, and then mix by inverting
      the flask  several  times.   Calculate the  concentration in milligrams per
      liter (mg/L) from the net gain  in weight.   When compound purity is assayed
      to  be 96%  or greater,  the weight  may  be  used  without  correction to
      calculate the concentration of the stock  standard.  Commercially prepared
      stock standards may be used at any concentration if they  are certified by
      the manufacturer or by an  independent source.

            5.7.4  Transfer the  stock standard solution into  a  bottle  with a
      Teflon lined screw-cap.  Store, with minimal headspace, at -10°C to  -20°C
      and protect from light.

            5.7.5  Prepare fresh standards for  gases every two  months or sooner
      if comparison with check standards indicates  a problem.   Reactive compounds
      such as 2-chloroethyl  vinyl ether  and styrene may need  to  be prepared more
      frequently.   All  other  standards must be replaced after six  months, or
      sooner if comparison with  check standards indicates a problem.  Both gas
      and liquid standards must be monitored closely  by comparison to the initial
      calibration curve  and by  comparison to  QC  check  standards.  It  may be
      necessary to replace  the standards more frequently  if either check exceeds
      a 25% difference.

      5.8  Secondary dilution standards - Using stock standard solutions, prepare
in methanol, secondary dilution  standards containing the compounds of interest,
either singly or mixed together.  Secondary  dilution standards must be stored
with minimal headspace and should be checked frequently for signs of degradation
or evaporation, especially  just  prior to preparing  calibration standards from
them.  Store in a vial with no headspace for one week only.

      5.9  Surrogate  standards   -  The surrogates recommended  are toluene-de,
4-bromofluorobenzene, and dibromofluoromethane.  Other compounds may be used as
surrogates, depending upon the analysis requirements.  A stock surrogate solution
in methanol  should  be prepared  as  described  in Section 5.7,  and a surrogate
standard spiking solution should be prepared from the stock at a concentration
of 50-250 M9/10 ml in methanol.  Each sample undergoing  GC/MS analysis must be
spiked with 10 /iL of the surrogate spiking solution  prior to analysis.

      5.10  Internal  standards  -  The  recommended  internal  standards  are
chlorobenzene-d5,     1,4-difluorobenzene,    l,4-dichlorobenzene-d4,     and
pentafluorobenzene.  Other compounds may be used as  internal standards as long
as they have retention times similar to the compounds being detected by GC/MS.
Prepare internal  standard  stock and  secondary dilution standards  in  methanol
using the procedures described  in Sections 5.7 and 5.8.  It  is recommended that
the secondary dilution standard should be prepared at a concentration of 25 mg/L
of each  internal  standard compound.   Addition  of  10 /xL  of this standard to
5.0 ml of sample or calibration  standard would  be the equivalent of 50 M9/L.

      5.11  4-Bromofluorobenzene (BFB) standard - A standard  solution containing
25 ng/jLtL of BFB in methanol should be prepared.
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      5.12  Calibration standards - Calibration standards at a minimum of five
concentrations should be prepared from the secondary dilution of stock standards
(see Sections 5.7  and 5.8).   Prepare these  solutions  in organic-free reagent
water.   One of the  concentrations  should  be at a concentration near, but above,
the method detection limit.  The remaining concentrations should correspond to
the expected range  of concentrations found in real  samples but should not exceed
the working range of the GC/MS system.  Each standard should contain each analyte
for detection by this* method  (e.g.  some or all of the compounds listed in Table
1 may be included).  Calibration standards must be prepared daily.

      5.13  Matrix  spiking  standards  -  Matrix  spiking  standards  should  be
prepared from volatile  organic  compounds which will be  representative  of the
compounds being investigated.   At a minimum, the  matrix spike  should include
1,1-dichloroethene, trichloroethene, chlorobenzene, toluene, and benzene.   It
is desirable to perform a matrix spike using compounds found in samples.  Some
permits may require spiking specific compounds of interest,  especially if they
are polar  and would  not  be  represented  by  the  above listed compounds.   The
standard  should  be  prepared in  methanol,  with  each compound  present  at  a
concentration of 250 /ig/10.0 mL.

      5.14  Great care must be taken to maintain the integrity of all  standard
solutions.  It is  recommended all  standards  in  methanol  be stored  at -10°C to
-20°C  in amber bottles with Teflon lined  screw-caps.


6.0  SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1  See the  introductory material to this chapter, Organic  Analytes,
Section 4.1.
7.0  PROCEDURE

      7.1  Direct injection -  In very limited applications (e.g. aqueous process
wastes) direct  injection of  the  sample into  the  GC/MS  system  with a  10  ;xL
syringe may be  appropriate.   One such application is  for verification  of the
alcohol content  of an  aqueous  sample prior to  determining if  the  sample  1s
ignitable (Methods  1010 or 1020).   In this case,  it  is  suggested that  direct
injection  be  used.     The   detection   limit   is   very  high   (approximately
10,000 Mg/L).   Therefore,  it is only permitted  when  concentrations  in  excess
of 10,000 jig/L are expected, or for water-soluble compounds that do not purge.
The system must be calibrated by direct injection using the same solvent (e.g.
water) for standards as  the sample matrix (bypassing the purge-and-trap device).


      7.2  Chromatographic conditions

            7.2.1 General:
     Injector temperature:         200-225°C
     Transfer line temperature:    250-300°C
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      7.2.2  Column 1 (A sample chromatogram is presented in Figure 5)
Carrier gas (He) flow rate:  15 mL/min
                             10°C,  hold for 5 minutes
                             6°C/min to 160°C
                             160°C,  hold until all expected compounds have
                             eluted.
Initial temperature:
Temperature program:
Final temperature:
      7.2.3  Column  2,  Cryogenic  cooling  (A  sample  chromatogram  is
presented in Figure 6)
Carrier gas (He) flow rate:  15 mL/min
                             10°C, hold for 5 minutes
                             6°C/min to 160°C
                             160°C,  hold until all expected compounds have
                             eluted.
Initial temperature:
Temperature program:
Final temperature:
      7.2.4  Column 2,  Non-cryogenic cooling (A  sample  chromatogram is
presented in Figure 7)
Carrier gas flow rate:  It is recommended that carrier gas  flow  and split
                        and  make-up  gases  be set using  performance of
                        standards as guidance.  Set the carrier gas head
                        pressure to » 10  psi and the split to » 30 mL/min.
                        Optimize the  make-up  gas  flow for the  separator
                        (approximately 30  mL/min)  by  injecting BFB, and
                        determining the optimum response when varying the
                        make-up gas.   This will require several injections
                        of  BFB.   Next,  make  several   injections  of the
                        volatile working standard with  all  analytes of
                        interest.  Adjust the  carrier and split to provide
                        optimum chromatography and response.  This is an
                        especially critical adjustment for the volatile
                        gas analytes.  The head pressure should optimize
                        between  8-12 psi  and  the  split  between  20-60
                        mL/min.  The  use of the splitter is  important to
                        minimize the effect of water on analyte  response,
                        to  allow  the use  of  a larger volume  of helium
                        during trap desorption, and to slow  column flow.
Initial temperature:
Temperature program:
Final temperature:
                             45°C, hold for 2 minutes
                             8°C/min to 200°C
                             200°C, hold for 6 minutes,
A trap preheated to 150°C prior to  trap desorption  is required to provide
adequate chromatography  of the gas analytes.
      7.2.5  Column 3 (A sample chromatogram is presented in Figure 8)
Carrier gas (He) flow rate:  4 mL/min
                             10°C, hold for 5 minutes
                             6°C/min to 70°C, then  15°C/min to  145°C
                             145°C, hold until all expected compounds have
                             eluted.
Initial temperature:
Temperature program:
Final temperature:
7.3  Initial calibration for purge-and-trap procedure

      7.3.1  Each GC/MS system must be hardware-tuned to meet the criteria
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in Table 4 for a 50 ng  injection or purging of 4-bromofluorobenzene (2 /xL
injection of  the BFB  standard).   Analyses  must  not begin  until  these
criteria are met.

      7.3.2  Assemble a purge-and-trap device that meets the specification
in Section 4.1.  Condition the trap overnight at  180°C in the purge mode
with an inert g*s flow  of at least 20 mL/min.   Prior  to use, condition the
trap daily for  10 minutes while backflushing at 180°C with the column at
220°C.

      7.3,3  Connect the purge-and-trap device to a gas chromatograph.

      7.3.4  A  set of at least five calibration standards containing the
method analytes  is needed.  One calibration standard should contain each
analyte  at   a   concentration  approaching  but  greater  than   the  method
detection  limit  (Table 1)  for that  compound;  the other  calibration
standards should contain analytes  at concentrations  that define the range
of the method.  The purging efficiency for 5 ml of water is greater than
for 25 mL.  Therefore,  develop  the  standard  curve with whichever volume
of sample that  will be  analyzed.  To prepare a calibration standard, add
an appropriate  volume  of a  secondary  dilution standard  solution  to an
aliquot  of  organic-free reagent  water  in  a volumetric  flask.    Use a
microsyringe and rapidly inject the alcoholic standard into the expanded
area of  the  filled volumetric flask.   Remove the  needle  as  quickly as
possible after  injection.  Mix  by  inverting  the flask three  times only.
Discard the contents contained in the neck of the flask.  Aqueous standards
are not  stable  and should be  prepared  daily.   Transfer 5.0 ml (or 25 ml
if lower detection limits are required)  of each standard to  a gas tight
syringe along with 10 /iL of internal standard.  Then  transfer the contents
to a purging device.

      7.3.5  Carry out the purge-and-trap analysis procedure as described
in Section 7.5.1.

      7.3.6  Tabulate the area response  of the characteristic ions (see
Table  5) against  concentration  for   each  compound  and each  internal
standard.  Calculate response factors  (RF)  for each compound relative to
one of the  internal  standards.   The internal  standard  selected  for the
calculation of  the RF for a  compound should be the internal standard that
has a  retention time  closest to the  compound being  measured  (Section
7.6.2).  The RF  is calculated as follows:

      RF = (AXC,S)/(A,SCX)

     where:

      A,   =   Area  of  the  characteristic  ion  for  the   compound  being
             measured.
      Als =   Area  of  the characteristic  ion for the  specific  internal
             standard.
      Cls =   Concentration of the specific internal standard.
      Cx   =   Concentration of the compound being  measured.
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      7.3.7  The  average  RF must  be calculated  and  recorded  for  each
compound.    A  system  performance  check  should  be  made  before  this
calibration curve is used.  Five compounds (the System Performance Check
Compounds, or SPCCs) are  checked  for a  minimum average  response factor.
These compounds  are chloromethane; 1,1-dichloroethane; bromoform; 1,1,2,2-
tetrachloroethane; and chlorobenzene.  The minimum acceptable average RF
for these compounds should be 0.300 (0.250 for bromoform).  These compounds
typically have RFs of 0.4-0.6 and are used to check compound instability
and to check for degradation caused by contaminated lines or active sites
in the system.  Examples of these occurrences are:

            7.3.7.1  Chloromethane  -  This compound  is  the most  likely
      compound to be lost if the purge flow is too fast.

            7.3.7.2  Bromoform -  This compound is one of  the compounds
      most likely to be purged  very poorly if  the  purge flow is too slow.
      Cold spots and/or active sites in the transfer lines may adversely
      affect  response.   Response of  the  quantitation  ion  (m/z  173)  is
      directly  affected  by the  tuning  of   BFB  at ions  m/z  174/176.
      Increasing  the m/z  174/176 ratio relative  to m/z 95 may improve
      bromoform response.

            7.3.7.3  Tetrachloroethane  and  1,1-dichloroethane  -  These
      compounds are degraded by contaminated transfer lines in purge-and-
      trap systems and/or active sites in trapping materials.

      7.3.8  Using the  RFs  from  the  initial  calibration,  calculate the
percent relative standard  deviation (%RSD)  for Calibration Check Compounds
(CCCs).  Record  the %RSDs for all compounds.  The percent RSD is calculated
as follows:
                  SD
          %RSD = —^x 100
                   x
     where:

      RSD = Relative standard deviation.
      x =   Mean of 5 initial RFs for a compound.
      SD  = Standard deviation of average RFs for a compound.
                    N  (x,  - x)5
      SD
                   i=l  N - 1

The %RSD  for each individual  CCC must be  less  than 30  percent.   This
criterion must be  met for the individual  calibration to  be  valid.   The
CCCs are:

     1,1-Dichloroethene,
     Chloroform,
     1,2-Dichloropropane,
     Toluene,
     Ethyl benzene, and
     Vinyl chloride.

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7.4  Daily GC/MS calibration

      7.4.1  Prior to the  analysis of  samples,  inject or purge 50 ng of
the 4-bromofluorobenzene  standard.   The resultant mass  spectra for the
BFB must meet all  of the criteria  given in Table 4 before sample analysis
begins.  These criteria must be demonstrated each 12-hour shift.

      7.4.2  The initial calibration curve (Section 7.3) for each compound
of interest must be checked and verified once every 12 hours of analysis
time.  This  is accomplished by  analyzing  a  calibration standard that is
at a concentration near the midpoint concentration for the working range
of the GC/MS by checking the SPCC (Section  7.4.3) and CCC  (Section 7.4.4).

      7.4.3  System  Performance  Check Compounds  (SPCCs)  -  A  system
performance check must  be  made  each 12 hours.   If the SPCC  criteria are
met, a comparison of response  factors  is made for all  compounds.  This is
the same check that  is  applied during  the  initial calibration.   If the
minimum response factors are not  met,  the system  must be evaluated, and
corrective action must be taken before sample analysis begins.  The minimum
response factor for volatile SPCCs is  0.300  (0.250 for Bromoform).  Some
possible problems are standard mixture degradation,  injection port inlet
contamination, contamination at the front end  of  the  analytical column,
and active sites in the column or chromatographic system.

      7.4.4  Calibration  Check  Compounds   (CCCs)  -   After  the  system
performance check is met, CCCs listed  in Section 7.3.8 are used to check
the validity of the initial calibration. Calculate the percent difference
using the following equation:
                    RF,  - RF
                           c
     % Difference = 	-	   x 100

where:
RF,
     RF, =    Average response factor from initial calibration.
     RFC  =    Response factor from current verification check standard.

If  the percent  difference for  any compound  is greater  than  20,  the
laboratory should consider  this a warning limit.  If the percent difference
for each CCC is  less than  25%,  the  initial  calibration  is  assumed to be
valid.  If the criterion is not met (> 25% difference),  for any one CCC,
corrective action must be taken.  Problems similar to those listed under
SPCCs could affect  this  criterion.   If no source of the problem can be
determined  after corrective  action has  been taken,  a new  five-point
calibration  must be  generated.    This criterion  must be  met  before
quantitative sample  analysis begins.  If the CCCs are  not required analytes
by  the permit,  then all  required analytes must  meet  the  25% difference
criterion.

      7.4.5  The  internal  standard  responses  and retention times in the
check calibration standard must be evaluated immediately after or during
data acquisition. If the retention time for any internal standard changes
by more than 30  seconds  from  the last  check calibration (12 hours), the
chromatographic system must be inspected for malfunctions and corrections

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must be  made,  as required.   If the EICP  area for any  of  the internal
standards changes by a factor of two (-50% to +100%) from the last daily
calibration standard check, the mass  spectrometer must be inspected for
malfunctions  and  corrections  must  be made,  as  appropriate.    When
corrections are made, reanalysis of samples  analyzed while the system was
malfunctioning are necessary.

7.5  GC/MS analysis

     7.5.1  Water samples

            7.5.1.1  Screening  of  the  sample  prior   to  purge-and-trap
      analysis  will   provide  guidance  on  whether sample  dilution  is
      necessary  and  will  prevent  contamination  of the  purge-and-trap
      system.  Two screening techniques that can be used are the headspace
      sampler (Method 3810) using  a gas chromatograph  (GC) equipped with
      a photo  ionization  detector (PID) in series with  an  electrolytic
      conductivity detector  (HECD), and extraction of the  sample  with
      hexadecane and analysis  of the extract on a  GC with a FID and/or an
      ECD (Method 3820).

            7.5.1.2  All samples and standard  solutions  must be allowed
      to warm to ambient temperature before analysis.

            7.5.1.3  Set up the GC/MS  system as outlined in  Sections 4.3
      and 7.2.

            7.5.1.4  BFB  tuning  criteria  and  daily  GC/MS  calibration
      criteria must be met (Section 7.4) before analyzing samples.

            7.5.1.5  Adjust the  purge  gas  (helium)  flow  rate  to  25-
      40 mL/min on the purge-and-trap  device.   Optimize the  flow rate to
      provide the best response  for chloromethane  and bromoform, if these
      compounds are analytes.   Excessive flow rate reduces chloromethane
      response, whereas insufficient flow reduces  bromoform response (see
      Section 7.3.7).

            7.5.1.6  Remove the plunger from a 5 ml syringe  and attach a
      closed syringe valve.  If lower  detection limits  are required, use
      a 25 ml  syringe.  Open the sample or standard bottle, which has been
      allowed to come to ambient temperature, and carefully pour the sample
      into the syringe barrel  to just  short of overflowing.   Replace the
      syringe plunger and compress the sample.   Open the syringe valve and
      vent any residual air while  adjusting the sample  volume to 5.0 ml.
      This process of taking an aliquot destroys the validity of the liquid
      sample for future analysis; therefore,  if there is  only one VOA vial,
      the analyst should  fill a second syringe at this  time to protect
      against possible loss of sample  integrity.   This second  sample is
      maintained only until such time when the analyst has determined that
      the first sample  has been analyzed properly.   Filling one  20 ml
      syringe would  allow the  use of  only  one  syringe.   If  a  second
      analysis is needed from a syringe,  it must be analyzed  within 24
      hours.  Care must be taken   to  prevent  air from leaking  into the
      syringe.

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      7.5.1.7  The following procedure is appropriate for diluting
purgeable samples.  All steps must be performed without delays until
the diluted sample is in a gas-tight syringe.

            7.5.1.7.1  Dilutions may be  made in volumetric flasks
      (10 to 100 ml).  Select the volumetric flask that will allow
      foe the  necessary  dilution.    Intermediate  dilutions  may be
      necessary for extremely large dilutions.

            7.5.1.7.2  Calculate the approximate volume of organic-
      free reagent water to be added to the volumetric flask selected
      and  add  slightly  less  than  this  quantity  of  organic-free
      reagent water to the flask.

            7.5.1.7.3  Inject the proper  aliquot of sample from the
      syringe prepared in Section 7.5.1.6 into the  flask.  Aliquots
      of less than 1 ml are not recommended.  Dilute the sample to
      the mark  with  organic-free reagent  water.   Cap  the  flask,
      invert, and shake  three times.  Repeat above  procedure for
      additional dilutions.

            7.5.1.7.4  Fill a 5 ml syringe with the diluted sample
      as in Section 7.5.1.6.

      7.5.1.8  Compositing samples prior to GC/MS analysis

            7.5.1.8.1  Add  5  ml or  equal  larger  amounts of  each
      sample (up to  5 samples are allowed) to a 25 ml glass syringe.
      Special precautions must  be made to maintain zero headspace
      in the syringe.

            7.5.1.8.2  The samples must be cooled at 4°C during this
      step to minimize volatilization losses.

            7.5.1.8.3  Mix  well  and draw out  a 5 ml  aliquot for
      analysis.

            7.5.1.8.4  Follow  sample  introduction,  purging,  and
      desorption steps described in the method.

            7.5.1.8.5  If  less  than five  samples  are used  for
      compositing, a  proportionately smaller syringe may  be  used
      unless a 25 ml sample is to be purged.

      7.5.1.9  Add   10.0   nl  of   surrogate   spiking   solution
(Section 5.9)  and  10  p,L  of  internal  standard  spiking  solution
(Section 5.10)  through  the valve bore of  the  syringe;  then close
the valve.  The  surrogate  and internal  standards  may be mixed and
added as a single spiking  solution.  The addition  of 10 /uL of the
surrogate spiking  solution to 5 ml  of sample  is  equivalent  to a
concentration of 50 /ig/L of each surrogate  standard.

      7.5.1.10  Attach the syringe-syringe valve  assembly  to the


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syringe valve on the purging device.   Open the syringe valves and
inject the sample into the purging chamber.

      7.5.1.11  Close both valves and  purge  the  sample for 11.0 ±
0.1 minutes at ambient temperature.  Be sure the trap  is cooler than
25°C.
        «
      7.5.1.12  Sample desorption - The  mode of  sample desorption
is  determined by the type of capillary column  employed  for the
analysis.   When using  a wide bore  capillary column,  follow the
desorption conditions of Section 7.5.1.13.  The conditions for using
narrow bore columns are described in Section 7.5.1.14.

      7.5.1.13  Sample desorption for  wide bore  capillary column.
Under most  conditions,  this  type of column  must  be  interfaced to
the MS through an all glass jet separator.

            7.5.1.13.1   After the 11 minute purge, attach the trap
      to the chromatograph, adjust the  purge  and trap system to the
      desorb  mode (Figure  4) and  initiate the temperature program
      sequence of the gas chromatograph and start data acquisition.
      Introduce the trapped materials  to the GC  column by rapidly
      heating the trap  to 180°C while backflushing the trap with an
      inert gas at 15 mL/min for  4  minutes.   If  the non-cryogenic
      cooling technique is followed, the trap must be preheated to
      150°C just prior to trap desorption  at 180°C.  While the purged
      analytes are being introduced into the gas chromatograph, empty
      the  purging  device  using  the sample  syringe  and  wash the
      chamber with two 5 ml or 25 ml portions of organic-free reagent
      water depending on  the size of the purge device.  After the
      purging device has been emptied,  leave  the syringe valve open
      to allow the purge gas to vent  through the sample introduction
      needle.

            7.5.1.13.2  Hold the  column  temperature at  10°C for
      5 minutes, then program at 6°C/min to 160°C and  hold until all
      analytes elute.

            7.5.1.13.3  After desorbing  the  sample  for 4 minutes,
      condition the trap by returning the purge-and-trap system to
      the purge mode.  Wait 15 seconds,  then close the syringe valve
      on the  purging  device to  begin  gas flow through  the trap.
      Maintain the trap temperature at 180°C.  After approximately
      7 minutes,  turn off the trap heater and open the syringe valve
      to stop the gas flow through the trap.  When  the trap is cool,
      the next sample can be analyzed.

      7.5.1.14  Sample desorption for narrow  bore capillary column.
Under normal operating conditions, most  narrow bore capillary columns
can be interfaced directly to the MS without a jet separator.

            7.5.1.14.1  After the 11 minute purge, attach the trap
      to the  cryogenically cooled interface  at  -150°C and adjust
      the  purge-and-trap system  to  the  desorb  mode  (Figure 4).

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      Introduce the trapped materials to  the  interface by rapidly
      heating the trap to 180°C while backflushing the trap with an
      inert gas  at  4 mL/min for  5  minutes.   While  the extracted
      sample  is  being  introduced into the  interface,  empty  the
      purging device using the  sample syringe and rinse the chamber
      with two 5 ml  or 25 ml portions of organic-free reagent water
      depending on the size of the  purging device. After the purging
      device has been  emptied, leave the syringe  valve open to allow
      the purge gas  to vent through the sample introduction needle.
      After desorbing  for 5  minutes,  flash heat the interface to
      250°C and quickly introduce  the sample on the chromatographic
      column.  Start the temperature program sequence, and initiate
      data acquisition.

            7.5.1.14.2  Hold the  column  temperature at  10°C  for
      5 minutes, then program at 6°C/min  to 70°C and  then at 15°C/min
      to  145°C.     After  desorbing  the  sample  for  5  minutes,
      recondition the trap by  returning the  purge-and-trap system
      to the purge  mode.   Wait  15 seconds, then close the syringe
      valve on the purging device to begin gas  flow through the trap.
      Maintain the trap temperature at 180°C.   After approximately
      15 minutes,  turn off the trap heater and  open the syringe valve
      to stop the gas  flow through the trap.  When the trap is cool,
      the next sample can be analyzed.

      7.5.1.15  If the initial  analysis of sample or a dilution of
the sample has a concentration  of  analytes that exceeds the initial
calibration  range,  the  sample must  be  reanalyzed  at a  higher
dilution.  Secondary ion  quantitation is allowed  only  when there are
sample interferences with the primary ion.  When a sample is analyzed
that  has  saturated  ions  from  a  compound, this analysis  must be
followed by  a  blank organic-free  reagent  water  analysis.   If the
blank analysis is not free of interferences,  the system  must be
decontaminated.   Sample analysis  may  not resume until  the blank
analysis is demonstrated to be free of interferences.

      7.5.1.16  For matrix spike analysis, add 10 /xL of the matrix
spike solution  (Section  5.13)  to  the 5  ml of  sample  to be purged.
Disregarding any dilutions, this  is  equivalent  to  a concentration
of 50 ng/l of  each  matrix  spike standard.

      7.5.1.17  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 Sections  7.6.1 and 7.6.2 for
qualitative and quantitative analysis.

7.5.2  Water-miscible liquids

      7.5.2.1  Water-miscible liquids are  analyzed as water samples
after first diluting them at least 50 fold  with organic-free reagent
water.

      7.5.2.2   Initial  and serial  dilutions can  be  prepared by


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      pipetting  2  ml of  the sample  to  a  100  ml volumetric  flask and
      diluting  to  volume  with  organic-free  reagent  water.    Transfer
      immediately to a 5 ml gas-tight syringe.

            7.5.2.3  Alternatively, prepare dilutions directly in a 5 ml
      syringe filled with organic-free reagent  water by adding at least
      20 ML,  but not more than 100 /iL of  liquid  sample.   The sample is
      ready for addition of internal and surrogate standards.

      7.5.3  Sediment/soil and waste  samples  -  It is highly recommended
that all  samples of this type  be screened prior to the purge-and-trap
GC/MS analysis.   The headspace  method  (Method 3810)  or  the  hexadecane
extraction and screening method (Method 3820) may used for this purpose.
These samples may contain percent quantities  of purgeable organics that
will contaminate the purge-and-trap system,  and  require extensive cleanup
and instrument downtime.  Use the screening data to determine whether to
use the  low-concentration method (0.005-1 mg/Kg)  or the high-concentration
method (> 1 mg/Kg).

            7.5.3.1  Low-concentration  method  -  This  is designed  for
      samples containing individual purgeable compounds of < 1 mg/Kg.  It
      is limited to sediment/soil samples and waste that is of a similar
      consistency (granular and porous).  The  low-concentration method is
      based on purging a heated sediment/soil sample mixed with organic-
      free reagent water containing the surrogate  and internal  standards..
      Analyze all blanks  and  standards  under the  same conditions as the
      samples.  See Figure 9 for an illustration of a low soils impinger.

                  7.5.3.1.1  Use a 5 g sample if the expected concentration
            is < 0.1  mg/Kg  or a  1 g  sample for expected concentrations
            between 0.1 and 1 mg/Kg.

                  7.5.3.1.2  The  GC/MS  system  should  be  set up  as  in
            Sections 7.5.1.3-7.5.1.4.  This should  be  done prior to the
            preparation of  the sample to  avoid loss  of  volatile* from
            standards and samples.  A heated purge calibration curve must
            be  prepared  and  used for the  quantitation of all  samples
            analyzed with  the low-concentration method.  Follow  the initial
            and daily calibration instructions, except for the addition
            of a 40°C purge  temperature.

                  7.5.3.1.3  Remove the plunger from a  5 mL Luerlock type
            syringe  equipped  with  a  syringe  valve  and  fill  until
            overflowing with water.  Replace the plunger and compress the
            water to vent trapped air.  Adjust the volume  to 5.0 mL.  Add
            10 /iL  each  of surrogate  spiking  solution  (Section 5.9) and
            internal  standard solution  (Section  5.10)  to the  syringe
            through  the  valve (surrogate  spiking solution and Internal
            standard  solution  may be mixed together).   The  addition of
            10 juL   of  the   surrogate  spiking   solution  to  5  g  of
            sediment/soil is  equivalent to  50  M9/Kg  of  each surrogate
            standard.
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                        7.5.3.1.4  The sample (for volatile organics) consists
                  of the entire contents of the sample container.  Do not discard
                  any  supernatant  liquids.   Mix the  contents of  the  sample
                  container  with  a  narrow metal spatula.   Weigh  the  amount
                  determined  in  Section  7.5.3.1.1 into a  tared purge device.
                  Note and record the actual weight to the nearest 0.1 g.

                        7.5.3.1.5  Determine  the percent  dry  weight of the
                  soil/sediment sample.   This includes  waste  samples that are
                  amenable to percent dry weight determination.  Other wastes
                  should be reported on a wet-weight basis.

                              7.5.3.1.5.1  Immediately after weighing the sample
                        for extraction,  weigh 5-10 g of  the sample  into a tared
                        crucible.  Determine the % dry weight of the sample by
                        drying overnight  at 105°C. Allow to cool in  a desiccator
                        before  re-weighing.    Concentrations  of   individual
                        analytes are reported relative to  the dry  weight of
                        sample.

WARNING;   The drying oven should be  contained in a hood  or vented.  Significant
           laboratory  contamination  may  result   from  a heavily  contaminated
           hazardous waste sample.

                        % dry weight = q of dry sample x 100
                                         g of sample

                        7.5.3.1.6  Add the spiked organic-free  reagent water to
                  the  purging device, which contains  the  weighed  amount of
                  sample, and connect the device to the purge-and-trap system.

NOTE: Prior to the attachment of the purge device,  the  procedures  in Sections
      7.5.3.1.4 and 7.5.3.1.6 must be performed rapidly and without interruption
      to avoid loss of volatile organics.   These steps  must  be performed in a
      laboratory free of solvent fumes.

                        7.5.3.1.7  Heat the  sample to 40°C ± 1°C and purge the
                  sample for  11.0 ±  0.1  minutes.  Be sure the trap is  cooler
                  than 25°C.

                        7.5.3.1.8  Proceed  with  the analysis  as  outlined in
                  Sections 7.5.1.12-7.5.1.17. Use 5 ml of the same organic-free
                  reagent water as in the blank.   If  saturated peaks occurred
                  or would  occur if a   1  g sample were  analyzed,  the  high-
                  concentration method must be followed.

                        7.5.3.1.9  For  low-concentration  sediment/soils,  add
                  10 /iL of the matrix spike  solution (Section 5.7)  to the 5 ml
                  of  organic-free  reagent  water  (Section 7.5.3.1.3).    The
                  concentration for a 5 g sample would be equivalent to 50 M9/Kg
                  of each matrix spike standard.

                  7.5.3.2  High-concentration method -  The method  is based on


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           extracting the sediment/soil  with methanol.  A waste sample  Is either
           extracted or diluted, depending on its  solubility in methanol.  Wastes
           (i.e. petroleum and coke wastes) that are insoluble in methanol are
           diluted with  tetraglyme  or possibly polyethylene  glycol  (PEG).  An
           aliquot  of  the  extract  is   added  to  organic-free  reagent  water
           containing  surrogate  and internal  standards.   This  is  purged at
           ambient temperature.  All samples with an expected concentration of
           > 1.0 mg/Kg should be analyzed by this method.

                        7.5.3.2.1  The sample  (for volatile organics) consists
                  of the entire contents of the  sample container.  Do not discard
                  any  supernatant  liquids.   Mix the  contents of the  sample
                  container with a narrow metal spatula.  For sediment/soil and
                  solid wastes that  are insoluble in methanol weigh  4  g (wet
                  weight) of sample into a tared  20 ml vial.  Use a top-loading
                  balance.  Note and record the  actual  weight to 0.1  gram and
                  determine the  percent  dry  weight  of  the  sample using the
                  procedure in Section 7.5.3.1.5. For waste that is soluble in
                  methanol, tetraglyme,  or PEG,  weigh  1  g  (wet weight)  into a
                  tared scintillation vial  or culture tube or a 10 ml volumetric
                  flask.   (If a  vial or  tube  is used,  it must  be  calibrated
                  prior to use.  Pipet 10.0 ml of solvent into  the vial and mark
                  the bottom of the meniscus.  Discard this solvent.)

                        7.5.3.2.2  Quickly add 9.0 ml  of appropriate  solvent;
                  then add 1.0 ml of the surrogate spiking solution to the vial.
                  Cap and shake for 2 minutes.

NOTE: Sections 7.5.3.2.1  and  7.5.3.2.2  must be  performed  rapidly  and without
      interruption to  avoid  loss  of volatile  organics.   These  steps must be
      performed in a laboratory free from solvent fumes.

                        7.5.3.2.3  Pipet approximately 1 ml of the  extract to
                  a GC vial for storage,  using a disposable pipet.  The remainder
                  may be disposed.  Transfer approximately 1 ml of appropriate
                  solvent to a separate  GC vial for use as the method blank for
                  each set of samples.   These  extracts may be stored at 4°C in
                  the dark,  prior to analysis.  The addition of a 100 pi aliquot
                  of each of  these  extracts  in  Section  7.5.3.2.6 will  give a
                  concentration equivalent  to  6,200 jug/Kg of each  surrogate
                  standard.

                        7.5.3.2.4  The   GC/MS  system should  be  set  up   as  in
                  Sections 7.5.1.3-7.5.1.4.  This should be done prior  to the
                  addition of  the solvent extract to organic-free reagent water.

                        7.5.3.2.5  The  information in Table 10 can be used to
                  determine the volume of solvent extract to add to the 5 ml of
                  organic-free reagent  water  for  analysis.    If a  screening
                  procedure was followed (Method 3810 or 3820),  use the estimated
                  concentration to determine the appropriate volume.  Otherwise,
                  estimate the concentration range of the sample  from the low-
                  concentration analysis to determine  the  appropriate volume.


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            If the sample was  submitted  as  a high-concentration sample,
            start with 100 ML.  All  dilutions must keep the response of
            the major  constituents  (previously saturated  peaks)  in the
            upper half of the linear range of the curve.

                  7.5.3.2.6  Remove the  plunger  from a  5.0  ml Luerlock
            type syringe  equipped with  a  syringe valve and  fill  until
            overflowing with 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 /uL of internal
            standard solution.  Also add the volume  of solvent extract
            determined in  Section  7.5.3.2.5  and a  volume  of extraction or
            dissolution solvent to  total 100  juL  (excluding  solvent  in
            standards).

                  7.5.3.2.7  Attach the syringe-syringe  valve assembly to
            the syringe valve  on  the purging device.   Open  the syringe
            valve and  inject  the  water/solvent sample  into  the purging
            chamber.

                  7.5.3.2.8  Proceed with  the analysis  as  outlined  in
            Sections 7.5.1.12-7.5.1.17.  Analyze  all  blanks  on the same
            instrument as that used for  the samples.  The  standards and
            blanks  should also contain 100 /*L of the dilution solvent to.
            simulate the sample conditions.

                  7.5.3.2.9  For a matrix spike in the high-concentration
            sediment/soil  samples,  add  8.0  ml of  methanol,   1.0  ml  of
            surrogate spike solution (Section 5.9), and   1.0 ml of matrix
            spike solution (Section 5.13) as in Section  7.5.3.2.2.   This
            results in a 5,200 jug/Kg  concentration of each matrix spike
            standard when  added to a  4 g  sample.  Add a 100 pi aliquot of
            this extract to 5 ml of organic-free reagent  water for purging
            (as per Section 7.5.3.2.6).

7.6  Data interpretation

     7.6.1  Qualitative analysis

            7.6.1.1  The qualitative identification of compounds  determined
      by this method is based on retention time, and on comparison of the
      sample   mass   spectrum,    after   background   correction,   with
      characteristic ions  in a reference mass spectrum. The reference mass
      spectrum must be generated  by  the  laboratory using the conditions
      of thi-s  method.   The characteristic  ions from  the reference mass
      spectrum are  defined to  be the three ions of greatest relative
      intensity,  or any ions over 30% relative intensity if less  than three
      such  ions  occur in the  reference  spectrum.  Compounds  should  be
      identified as present when the criteria below are  met.

                  7.6.1.1.1  The  intensities  of  the characteristic ions
            of a compound maximize in the same scan  or within one scan of

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      each other.   Selection of  a  peak by  a data  system  target
      compound search  routine where  the  search  is  based on  the
      presence of  a target  chromatographlc  peak containing  ions
      specific for the  target  compound  at  a  compound-specific
      retention time will  be accepted as meeting this criterion.

            7.6.1.1.2  The RRT of the sample  component is within  ±
      0.06 RRT units of the RRT of the standard component.

            7.6.1.1.3  The relative intensities of the  characteristic
      ions agree within 30% of the relative intensities of these ions
      in the  reference  spectrum.   (Example:    For an ion with  an
      abundance of 50% in  the  reference spectrum, the corresponding
      abundance in a sample spectrum can range between 20% and 80%.)

            7.6.1.1.4  Structural  isomers that produce very similar
      mass spectra should be identified as individual isomers if they
      have sufficiently different GC  retention  times.   Sufficient
      GC resolution is achieved  if the height of the valley between
      two isomer peaks is  less than 25% of the sum of the two peak
      heights.   Otherwise, structural  isomers  are  identified  as
      isomeric pairs.

            7.6.1.1.5  Identification  is  hampered   when  sample
      components are not  resolved chromatographically and produce.
      mass spectra  containing ions contributed  by  more  than  one
      analyte.  When gas chromatographic peaks obviously represent
      more than one sample  component  (i.e.,  a broadened  peak with
      shoulder(s)  or  a  valley  between  two  or  more  maxima),
      appropriate selection of analyte  spectra and background spectra
      is important.  Examination of extracted ion current profiles
      of appropriate ions  can aid in the selection of spectra,  and
      in qualitative  identification  of compounds.   When analytes
      coelute (i.e., only one chromatographic  peak is  apparent), the
      identification criteria can  be met, but each analyte spectrum
      will contain extraneous  ions  contributed by  the  coeluting
      compound.

      7.6.1.2  For samples containing components not associated with
the calibration  standards,  a library  search  may be  made for  the
purpose of tentative identification.   The necessity to perform this
type of  identification will  be  determined by the type of analyses
being conducted.  Guidelines for making tentative identification are:

      (1)   Relative  intensities  of  major  ions in  the  reference
spectrum (ions > 10% of the most abundant ion) should  be present in
the sample spectrum.

      (2)   The relative intensities of the major  ions should agree
within ± 20%.   (Example:   For  an ion with an abundance of  50% in the
standard spectrum,  the corresponding  sample  ion abundance must be
between 30 and 70%).

      (3)   Molecular ions present in  the reference spectrum should

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 be present In the sample spectrum.

       (4)   Ions  present  in  the  sample spectrum  but not  in the
 reference  spectrum  should  be  reviewed  for  possible  background
 contamination or presence of coeluting compounds.

       (5)   Ions present in the reference  spectrum but not in the
 sample spectrum  should be  reviewed for  possible subtraction from
 the sample spectrum because of background contamination or coeluting
 peaks.  Data system library  reduction  programs  can sometimes create
 these discrepancies.

       Computer generated  library search  routines should  not use
 normalization routines that would misrepresent the library or unknown
 spectra when compared to each other.  Only after visual comparison
 of sample with the nearest library searches will the mass spectral
 interpretation specialist assign a tentative identification.

 7.6.2  Quantitative analysis

       7.6.2.1  When a compound has been identified, the quantitation
 of that compound  will  be based on  the  integrated  abundance from the
 EICP of the primary characteristic  ion.  Quantitation will take place
 using the internal standard technique.  The internal standard used
 shall be  the one  nearest  the retention time  of that of  a given
 analyte (e.g. see Table 6).

       7.6.2.2  Calculate the concentration of each identified analyte
 in the sample as follows:

 Water

                          (AJd.)
 concentration (jug/L) =
                        (Als)(RF)(V0)

where:

 A,, =   Area of characteristic ion for compound being measured.
 Is =   Amount of internal standard injected (ng).
 Als=   Area of characteristic ion for the internal standard.
 RF =  Response factor for compound being measured (Section 7.3.3).
 V0 =   Volume of water  purged (ml), taking  into consideration any
       dilutions made.
 Sediment/Soil Sludge (on a dry-weight  basis) and Waste  (normally on
 a wet-weight basis)
                           (Ax)(Is)(Vt)
 concentration (M9/Kg) =
                        (AJ(RF)(Y,)(H.)(D)
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            where:

            A,,,  I8, Als, RF, = Same as for water.
            Vt = Volume of total extract (/iL) (use 10,000 /iL or a factor of this
            when dilutions are made).
            V, =   Volume of extract added (/iL)  for  purging.
            W8  =  Weight of sample extracted or purged  (g).
            D  =  % dry weight of sample/100, or 1  for  a wet-weight basis.

                  7.6.2.3  Where applicable,  an estimate of concentration for
            noncalibrated components in the  sample should be made. The  formulae
            given above  should be  used with  the  following modifications:  The
            areas A,, and  A,s should be from the total  ion chromatograms,  and the
            RF for the compound  should be  assumed  to be 1.  The concentration
            obtained  should  be reported indicating (1) that  the value is an
            estimate  and (2)  which  internal standard  was used to determine
            concentration.     Use  the  nearest  internal   standard   free  of
            interferences.
8.0  QUALITY CONTROL

      8.1  Refer to  Chapter One and Method 8000  for specific quality control
procedures.

      8.2  Required instrument QC is found in the following sections:

            8.2.1  The 6C/MS system must  be tuned to meet the BFB specifications
      in Section 7.3.1.

           ,8.2.2  There must be an initial calibration of the GC/MS system as
      specified in Section  7.3.

            8.2.3  The GC/MS  system must meet the  SPCC criteria specified in
      Section 7.4.3 and the CCC criteria in Section  7.4.4, each 12 hours.

      8.3  To  establish  the  ability  to  generate  acceptable   accuracy  and
precision, the analyst must perform the following operations.

            8.3.1  A  quality  control  (QC)  reference  sample concentrate is
      required containing each analyte at a  concentration of 10 mg/L in methanol.
      The QC reference  sample concentrate may be  prepared  from  pure standard
      materials  or purchased  as  certified  solutions.   If  prepared  by  the
      laboratory, the QC reference sample concentrate must be made using stock
      standards prepared independently from those used  for calibration.

            8.3.2  Prepare  a  QC reference sample  to contain 20  /ig/L  of  each
      analyte by adding 200 /iL of QC reference sample concentrate to 100 mL of
      organic-free reagent water.

            8.3.3  Four 5 mL aliquots of the well  mixed  QC reference sample are
      analyzed according to the method beginning in  Section 7.5.1.
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            8.3.4  Calculate the  average recovery (x) in M9/U and the standard
      deviation  of the recovery  (s)  in M9/U  for each analyte  using the four
      results.


            8.3.5  Tables  7  and 8  provide  single laboratory recovery  and
      precision  data  obtained for  the  method  analytes  from water.   Similar
      results from dosed water should be expected by  any experienced laboratory.
      Compare s and x   (Section 8.3.4) for each analyte to the single laboratory
      recovery and  precision data.   Results are comparable  if  the calculated
      standard deviation of  the  recovery  does  not exceed  2.6 times the single
      laboratory RSD or 20%,  whichever is greater,  and  the mean recovery lies
      within the interval  x ± 3S or x ±  30%, whichever  is  greater.

NOTE: The large  number of  analytes  in  Tables  7 and  8 present  a  substantial
      probability that one  or more will  fail  at  least one  of  the acceptance
      criteria when all analytes of a given method  are  determined.

            8.3.6  When one  or more of the analytes tested are  not comparable
      to the data in Table 7  or 8, the analyst  must proceed according to Section
      8.3.6.1 or 8.3.6.2.

                  8.3.6.1   Locate and correct the   source  of the  problem  and
            repeat the test for all  analytes beginning  with Section 8.3.2.

                  8.3.6.2   Beginning with  Section 8.3.2, repeat the  test only
            for  those  analytes  that  are   not  comparable.    Repeated  failure,
            however, will confirm a general problem with the measurement system.
            If this occurs,  locate  and  correct the  source of the  problem  and
            repeat the test  for all compounds of interest beginning with Section
            8.3.2.

      8.4  For aqueous  and  soil matrices,  laboratory  established  surrogate
control  limits should  be compared with the control limits  listed in Table 9.

            8.4.1  If  recovery is not within  limits, the  following procedures
      are required.

                  8.4.1.1   Check to be  sure that there are  no  errors  in  the
            calculations,  surrogate  solutions  or internal standards.  If errors
            are found, recalculate the data accordingly.

                  8.4.1.2   Check  instrument performance.     If  an  instrument
            performance problem is identified, correct the problem and re-analyze
            the extract.

                  8.4.1.3   If no  problem is found, re-extract  and re-analyze the
            sample.

                  8.4.1.4   If, upon re-analysis, the  recovery is again not within
            limits, flag the data as "estimated concentration".

            8.4.2  At  a minimum, each laboratory should update surrogate recovery


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      limits on a matrix-by-matrix basis, annually.


9.0  METHOD PERFORMANCE

      9.1  The  method  detection  limit  (MDL)  is  defined  as  the  minimum
concentration  of a  substance  that  can  be  measured  and  reported with  99%
confidence that the value is above zero.  The MDL actually achieved in a given
analysis will vary depending on instrument sensitivity and matrix effects.

      9.2  This  method  has been  tested in  a single laboratory  using spiked
water.  Using a wide-bore capillary column, water was spiked at concentrations
between 0.5  and  10  M9/L.   Single laboratory accuracy and  precision  data are
presented for the method analytes  in  Table  7.  Calculated MDLs are presented in
Table 1.

      9.3  The method was tested using  water spiked at 0.1  to 0.5 M9/L and
analyzed on a cryofocussed narrow-bore  column. The accuracy and precision data
for these compounds are presented in Table 8.  MDL values were also calculated
from these data and are presented in Table 2.


10.0  REFERENCES

1.   Methods for  the  Determination  of Organic Compounds in  Finished  Drinking
     Water and  Raw  Source Water  Method 524.2; U.S.  Environmental  Protection
     Agency.  Office of Research Development. Environmental  Monitoring  and Support
     Laboratory: Cincinnati, OH 1986.

2.   U.S.  EPA Contract  Laboratory  Program,  Statement  of  Work for  Organic
     Analysis, July 1985, Revision.

3.   Bellar,  T.A.; Lichtenberg, J.J.  jh Amer. Water Works Assoc. 1974,  66(12).
     739-744.

4.   Bellar,   T.A.;  Lichtenberg,  J.J.   "Semi-Automated  Headspace Analysis  of
     Drinking  Waters  and  Industrial  Waters  for  Purgeable Volatile  Organic
     Compounds"; in Van Hall,  Ed.; Measurement of  Organic  Pollutants  in Water
     and Wastewater.  ASTM STP 686, pp 108-129, 1979.

5.   Budde, W.L.; Eichelberger, J.W. "Performance  Tests  for  the Evaluation of
     Computerized   Gas   Chromatography/Mass   Spectrometry   Equipment   and
     Laboratories";   U.S.   Environmental   Protection  Agency.   Environmental
     Monitoring and Support Laboratory. Cincinnati, OH 45268, April  1980; EPA-
     600/4-79-020.

6.   Eichelberger, J.W.;  Harris,  L.E.; Budde,  W.L.  "Reference Compound  to
     Calibrate Ion Abundance Measurement in  Gas Chromatography-Mass Spectrometry
     Systems"; Analytical Chemistry 1975, 47, 995-1000.

7.   Olynyk,  P.;  Budde,  W.L.;  Eichelberger,  J.W.  "Method Detection Limit for
     Methods  624 and  625"; Unpublished  report, October 1980.
                                  8260A - 27                      Revision 1
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8.   Non Cryogenic Temperatures Program and Chromatogram, Private Communications;
     Myron Stephenson and Frank Allen, EPA Region  IV Laboratory, Athens,  GA.
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                             TABLE 1.
CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (MDL)
  FOR VOLATILE ORGANIC COMPOUNDS ON WIDE BORE CAPILLARY COLUMNS
ANALYTE
Di chl orodi f 1 uoromethane
Chloromethane
Vinyl Chloride
Bromomethane
Chloroethane
Tri chl orof 1 uoromethane
1,1-Dichloroethene
Methyl ene chloride
trans- 1 , 2-Dichl oroethene
1,1-Dichl oroethane
2,2-Dichloropropane
cis-1, 2-Dichl oroethene
Chloroform
Bromochl oromethane
1,1,1 -Tri chl oroethane
Carbon tetrachloride
1,1-Dichloropropene
Benzene
1,2-Dichloroethane
Tri chl oroethene
1,2-Dichloropropane
Bromodi chl oromethane
Dibromomethane
trans- 1,3-Di chl oropropene
Toluene
cis- 1,3-Di chl oropropene
1,1,2-Tri chl oroethane
Tetrachl oroethene
1,3-Dichloropropane
Di bromochl oromethane
1,2-Dibromoethane
1-Chlorohexane
Chlorobenzene
1,1,1 , 2-Tetrachl oroethane
Ethyl benzene
p-Xylene
m-Xylene
o-Xylene
Styrene
Bromoform
Isopropyl benzene
1,1,2, 2-Tetrachl oroethane
RETENTION TIME
(minutes)
Column la
1.55
1.63
1.71
2.01
2.09
2.27
2.89
3.60
3.98
4.85
6.01
6.19
6.40
6.74
7.27
7.61
7.68
8.23
8.40
9.59
10.09
10.59
10.65
--
12.43
--
13.41
13.74
14.04
14.39
14.73
15.46
15.76
15.94
15.99
16.12
16.17
17.11
17.31
17.93
18.06
18.72
Column 2b
0.70
0.73
0.79
0.96
1.02
1.19
1.57
2.06
2.36
2.93
3.80
3.90
4.80
4.38
4.84
5.26
5.29
5.67
5.83
7.27
7.66
8.49
7.93
--
10.00
--
11.05
11.15
11.31
11.85
11.83
13.29
13.01
13.33
13.39
13.69
13.68
14.52
14.60
14.88
15.46
16.35
Column 2'
3.13
3.40
3.93
4.80
--
6.20
7.83
9.27
9.90
10.80
11.87
11.93
12.60
12.37
12.83
13.17
13.10
13.50
13.63
14.80
15.20
15.80
15.43
16.70
17.40
17.90
18.30
18.60
18.70
19.20
19.40
--
20.67
20.87
21.00
21.30
21.37
22.27
22.40
22.77
23.30
24.07
MDLd
(WJ/L)
c
0.10
0.13
0.17
0.11
0.10
0.08
0.12
0.03
0.06
0.04
0.35
0.12
0.03
0.04
0.08
0.21
0.10
0.04
0.06
0.19
0.04
0.08
0.24
--
0.11
--
0.10
0.14
0.04
0.05
0.06
0.05
0.04
0.05
0.06
0.13
0.05
0.11
0.04
0.12
0.15
0.04
                            8260A - 29
Revision 1
November 1990

-------
                                   TABLE 1.
                                  (Continued)
ANALYTE
         RETENTION TIME
	(minutes)
Column la   Column 2b
                                                            Column 2'
 MDL"
Bromobenzene                        18.95       15.86       24.00
1,2,3-Trichloropropane              19.02       16.23       24.13
n-Propylbenzene                     19.06       16.41       24.33
2-Chlorotoluene                     19.34       16.42       24.53
1,3,5-Trimethylbenzene              19.47       16.90       24.83
4-Chlorotoluene                     19.50       16.72       24.77
tert-Butylbenzene                   20.28       17.57       26.60
1,2,4-Trimethylbenzene              20.34       17.70       31.50
sec-Butyl benzene                    20.79       18.09       26.13
p-Isopropyltoluene                  21.20       18.52       26.50
1,3-Dichlorobenzene                 21.22       18.14       26.37
1,4-Dichlorobenzene                 21.55       18.39       26.60
n-Butylbenzene                      22.22       19.49       27.32
1,2-Dichlorobenzene                 22.52       19.17       27.43
l,2-Dibromo-3-chloropropane         24.53       21.08
1,2,4-Trichlorobenzene              26.55       23.08       31.50
Hexachlorobutadiene                 26.99       23.68       32.07
Naphthalene                         27.17       23.52       32.20
1,2,3-Trichlorobenzene              27.78       24.18       32.97

INTERNAL STANDARDS/SURROGATES

4-Bromofluorobenzene                18.63       15.71       23.63
                                     0.03
                                    0.32
                                    0.04
                                    0.04
                                    0.05
                                    0.06
                                    0.14
                                    0.13
                                    0.13
                                    0.12
                                    0.12
                                    0.03
                                    0.11
                                     .03
                                     .26
                                    0.04
                                    0.11
                                    0.04
                                    0.03
0.
0.
   Column 1 - 60 meter x 0.75 mm ID VOCOL capillary.  Hold at 10°C  for 5 minutes,
   then program  to 160°C at 6°/min.

   Column 2-30 meter x 0.53 mm  ID DB-624 wide-bore capillary using cryogenic
   oven.  Hold at 10°C for 5 minutes,  then program to 160°C at  6°/min.

   Column 2' - 30 meter x 0.53 mm  ID DB-624 wide-bore capillary, cooling  GC oven
   to  ambient temperatures.  Hold  at 10°C for 6 minutes,  program to  70°C at
   107min> program to 120°C at  5°/nnn,  then program to 180°C at 8°/nrin.

   MDL based  on  a 25  ml sample volume.
                                  8260A  - 30
                              Revision  1
                              November 1990

-------
                             TABLE 2.
CHROMATOGRAPHIC RETENTION TIMES AND METHOD DETECTION LIMITS (MDL)
 FOR VOLATILE ORGANIC COMPOUNDS ON NARROW BORE CAPILLARY COLUMNS
ANALYTE
Di chl orodi f 1 uoromethane
Chloromethane
Vinyl chloride
Bromomethane
Chloroethane
Tr i chl orof 1 uoromethane
1,1-Dichloroethene
Methyl ene chloride
trans- 1,2-Di chl oroethene
1,1-Dichloroethane
cis- 1,2-Di chl oroethene
2,2-Dichloropropane
Chloroform
Bromochl oromethane
1,1,1 -Tri chl oroethane
1,2-Dichloroethane
1 , 1 -Di chl oropropene
Carbon tetrachloride
Benzene
1 , 2-Di chl oropropane
Tri chl oroethene
Dibromomethane
Bromodi chl oromethane
Toluene
1,1,2-Trichloroethane
1,3-Dichloropropane
Di bromochl oromethane
Tetrachl oroethene
1,2-Dibromoethane
Chlorobenzene
1,1,1 , 2-Tetrachl oroethane
Ethyl benzene
p-Xylene
m-Xylene
Bromoform
o-Xylene
Styrene
1,1,2, 2-Tetrachl oroethane
1, 2, 3-Tri chl oropropane
I sopropyl benzene
RETENTION TIME
(minutes)
Column 3a
0.88
0.97
1.04
1.29
1.45
1.77
2.33
2.66
3.54
4.03
5.07
5.31
5.55
5.63
6.76
7.00
7.16
7.41
7.41
8.94
9.02
9.09
9.34
11.51
11.99
12.48
12.80
13.20
13.60
14.33
14.73
14.73
15.30
15.30
15.70
15.78
15.78
15.78
16.26
16.42
MDLb
(M9/L)
0.11
0.05
0.04
0.06
0.02
0.07
0.05
0.09
0.03
0.03
0.06
0.08
0.04
0.09
0.04
0.02
0.12
0.02
0.03
0.02
0.02
0.01
0.03
0.08
0.08
0.08
0.07
0.05
0.10
0.03
0.07
0.03
0.06
0.03
0.20
0.06
0.27
0.20
0.09
0.10
                           8260A  -  31
Revision 1
November 1990

-------
                                   TABLE 2.
                                  (Continued)
ANALYTE
RETENTION TIME
  (minutes)
  Column 3a
MDLb
(M9/L)
Bromobenzene
2-Chlorotoluene
n-Propyl benzene
4-Chlorotoluene
1,3, 5-Trimethyl benzene
tert-Butyl benzene
1, 2, 4-Trimethyl benzene
sec-Butyl benzene
1,3-Oichlorobenzene
p-Isopropyl toluene
1,4-Dichlorobenzene
1 , 2-Di chl orobenzene
n-Butyl benzene
1 , 2-Di bromo-3-chl oropropane
1,2, 4-Tri chl orobenzene
Naphthalene
Hexachlorobutadiene
1, 2, 3-Tri chl orobenzene
16.42
16.74
16.82
16.82
16.99
17.31
17.31
17.47
17.47
17:63
17.63
17.79
17.95
18.03
18.84
19.07
19.24
19.24
0.11
0.08
0.10
0.06
0.06
0.33
0.09
0.12
0.05
0.26
0.04
0.05
0.10
0.50
0.20
0.10
0.10
0.14
a  Column 3-30 meter x 0.32 mm ID DB-5 capillary with 1 urn film thickness.

b  MDL based on a 25 ml sample volume.
                                  8260A  - 32
                              Revision 1
                              November  1990

-------
                                 TABLE 3.
            ESTIMATED  QUANTITATION  LIMITS  FOR  VOLATILE ANALYTES8
                                            Estimated
                                           Quantitation
                                              Limits
                                  Ground water         Low Soil/Sediment"
                                      M9/L                  Aig/Kg
Volume of water purged
All analytes in Table 1
5 ml
5
25 mL
1
5
   Estimated Quantitation Limit  (EQL) - The lowest concentration that can be
   reliably  achieved within specified limits of precision and  accuracy during
   routine  laboratory operating  conditions. The EQL is generally 5 to 10 times
   the MDL.  However,  it  may be nominally chosen within these guidelines to
   simplify data  reporting. For many analytes the EQL analyte concentration.
   is selected  for  the  lowest  non-zero  standard  in  the calibration curve.
   Sample  EQLs  are  highly    matrix-dependent.  The  EQLs listed  herein  are
   provided for guidance and may  not always be achievable. See the  following
   information for further guidance  on matrix-dependent EQLs.

   EQLs listed  for  soil/sediment are based on wet weight.  Normally data is
   reported on a dry weight basis;  therefore,  EQLs will  be higher, based on
   the percent dry weight in each sample.
             Other Matrices                      Factor0
             Water miscible liquid waste             50
             High-concentration soil and sludge     125
             Non-water miscible waste               500
°EQL =  [EQL  for  low soil  sediment  (Table 3)] X  [Factor].  For non-aqueous
        samples, the factor is on a wet-weight basis.
                                8260A - 33                      Revision 1
                                                                November  1990

-------
                             TABLE 4.
    BFB MASS - INTENSITY SPECIFICATIONS (4-BROMOFLUOROBENZENE)
Mass              Intensity Required (relative abundance)
 50               15 to 40% of mass 95
 75               30 to 60% of mass 95
 95               base peak, 100% relative abundance
 96               5 to 9% of mass 95
173               less than 2% of mass 174
174               greater than 50% of mass 95
175               5 to 9% of mass 174
176               greater than 95% but less than 101% of mass 174
177               5 to 9% of mass 176
                            8260A  - 34                       Revision  1
                                                             November 1990

-------
                             TABLE 5.
    CHARACTERISTIC MASSES (M/Z)  FOR PURGEABLE ORGANIC COMPOUNDS
Analyte
  Primary
Characteristic
    Ion
  Secondary
Characteristic
    Ion(s)
Benzene
Bromobenzene
Bromochloromethane
Bromodi chl oromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chl oromethane
2-Chlorotoluene
4-Chlorotoluene
1 , 2-Di bromo-3-chl oropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1,2-Dichlorobenzene
1,3-Di chlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-1, 2-Di chl oroethene
trans- 1, 2-Di chl oroethene
1,2-Dichloropropane
1,3-Di chl oropropane
2 , 2-Di chl oropropane
1,1-Dichloropropene
Ethyl benzene
Hexachl orobutadi ene
Isopropyl benzene
p-Isopropyl toluene
Methylene chloride
Naphthalene
n-Propyl benzene
Styrene
1,1,1 , 2-Tetrachl oroethane
78
156
128
83
173
94
91
105
119
117
112
64
83
50
91
91
75
129
107
93
146
146
146
85
63
62
96
96
96
63
76
77
75
91
225
105
119
84
128
91
104
131

77,
49,
85,
175,
96
92,
134
91,
119
77,
66
85
52
126
126
155,
127
109,
95,
111,
111,
111,
87
65,
98
61,
61,
61,
112
78
97
110,
106
223,
120
134,
86,
-
120
78
133,

158
130
127
254

134

134

114





157

188
174
148
148
148

83

63
98
98



77

227

91
49



119
                            8260A  - 35
                              Revision 1
                              November 1990

-------
                                   TABLE 5.
                                  (Continued)
      Analyte
  Primary
Characteristic
    Ion
  Secondary
Characteristic
    Ion(s)
1 , 1 , 1 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1 , 2 ,3-Tri chl orobenzene
1,2,4-Trichlorobenzene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chl orof 1 uoromethane
1,2,3-Trichloropropane
1 , 2 , 4-Trimethyl benzene
1,3, 5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
83
166
92
180
180
97
83
95
101
75
105
105
62
106
106
106
131,
168,
91
182,
182,
99,
97,
130,
103
77
120
120
64
91
91
91
85
129

145
145
61
85
132








INTERNAL STANDARDS/SURROGATES

      4-Bromof1uorobenzene
      Di bromofl uoromethane
      Toluene-d8
      Pentaf1uorobenzene
      1,4-Di f1uorobenzene
      Chlorobenzene-d5
      l,4-Dichlorobenzene-d4
    95
   113
    98
   168
   114
   117
   152
   174, 176
                                  8260A - 36
                              Revision 1
                              November 1990

-------
                                   TABLE 6.
            VOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
                           ASSIGNED FOR QUANTITATION
Pentafluorobenzene   ,

Acetone
Acrolein
Acrylonitrile
Bromochloromethane
Bromomethane
2-Butanone
Carbon disulfide
Chloroethane
Chloroform
Chioromethane
D1chlorodi fluoromethane
1,1-01chloroethane
1,1-Dichloroethene
cis-l,2-D1chloroethene
trans-1, 2-Di chloroethene
2,2-Di chloropropane
lodomethane
Methylene chloride
1,1,1-Tri chloroethane
Tri chlorof1uoromethane
Vinyl acetate
Vinyl chloride

Chlorobenzene-d;

Bromoform
Chlorodi bromomethane
Chlorobenzene
1,3-Dichloropropane
Ethyl benzene
2-Hexanone
Styrene
1,1,1,2-Tetrachloroethane
Tetrachloroethene
Xylene
1.4-Difluorobenzene

Benzene
Bromodichloromethane
Bromofluorobenzene (surrogate)
Carbon tetrachloride
2-Chloroethyl vinyl ether
1,2-Dibromoethane
Dibromomethane
1,2-Dichloroethane
1,2-Dichloroethane-d4 (surrogate)
1,2-Dichloropropane
1,1-Dichloropropene
cis-1,3-Dichloropropene
trans-1,3-Di chloropropene
4-Methyl-2-pentanone
Toluene
Toluene-dB (surrogate)
1,1,2-Trichloroethane
Trichloroethene

1,4-Dichlorobenzene-d^

Bromobenzene
n-Butylbenzene
sec-Butyl benzene
tert-Butylbenzene
2-Chlorotoluene
4-Chlorotoluene
1,2-Di bromo-3-chloropropane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Di chlorobenzene
Hexachlorobutadiene
Isopropyl benzene
p-Isopropyltoluene
Naphthalene
n-Propylbenzene
1,1,2,2-Tetrachloroethane
1,2,3-Trichlorobenzene
1,2,4-Tri chlorobenzene
1,2,3-Tri chloropropane
1,2,4-Trimethylbenzene
1,3,5-Trimethylbenzene
                                  8260A - 37
                              Revision 1
                              November 1990

-------
                         TABLE 7.
SINGLE LABORATORY ACCURACY AND PRECISION DATA FOR VOLATILE
    ORGANIC  COMPOUNDS  IN  WATER DETERMINED  WITH  A WIDE
                   BORE CAPILLARY COLUMN
Analyte
Benzene
Bromobenzene
Bromochl oromethane
Bromodichloromethane
Bromoform
Bromomethane
n- Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chi oromethane
2-Chlorotoluene
4-Chlorotoluene
1 , 2-Di bromo-3-Chl oropropane
Di bromochl oromethane
1,2-Dibromoethane
Dibromomethane
1, 2-DI chlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1 -Di chlorobenzene
1, 2-Di chlorobenzene
1,1-Dichloroethene
cis-l,2-Dichloroethene
trans- 1, 2-Di chl oroethene
1,2-Dichl oropropane
1,3-Di chl oropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachl orobutadi ene
I sopropyl benzene
p- I sopropyl toluene
Methyl ene chloride
Naphthalene
n-Propyl benzene
Cone. Number
Range, of Recovery,8
/ig/L Samples %
0.1
0.1
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.5
0.5
0.5
0.1
0.1
0.5
0.1
0.5
0.5
0.1
0.5
0.2
0.5
0.5
0.1
0.1
0.5
0.1
0.1
0.1
0.5
0.5
0.1
0.5
0.5
0.1
0.1
0.1
0.1
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 20
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
-100
- 10
31
30
24
30
18
18
18
16
18
24
31
24
24
23
31
31
24
31
24
24
31
24
31
18
24
31
34
18
30
30
31
12
18
31
18
16
23
30
31
31
97
100
90
95
101
95
100
100
102
84
98
89
90
93
90
99
83
92
102
100
93
99
103
90
96
95
94
101
93
97
96
86
98
99
100
101
99
95
104
100
Standard Percent
Deviation tel. Std.
of Recovery" Dev.
6.5
5.5
5.7
5.7
6.4
7.8
7.6
7.6
7.4
7.4
5.8
8.0
5.5
8.3
5.6
8.2
16.6
6.5
4.0
5.6
5.8
6.8
6.6
6.9
5.1
5.1
6.3
6.7
5.2
5.9
5.7
14.6
8.7
8.4
6.8
7.7
6.7
5.0
8.6
5.8
5.7
5.5
6.4
6.1
6.3
8.2
7.6
7.6
7.3
8.8
5.9
9.0
6.1
8.9
6.2
8.3
19.9
7.0
3.9
5.6
6.2
6.9
6.4
7.7
5.3
5.4
6.7
6.7
5.6
6.1
6.0
16.9
8.9
8.6
6.8
7.6
6.7
5.3
8.2
5.8
                        8260A - 38
Revision 1
November 1990

-------
                                    TABLE  7.
                                  (Continued)
Analyte
Cone.   Number
Range,    of
M9/L    Samples
Recovery,8
   %
  Standard
  Deviation
of Recovery"
Percent
Rel. Std.
Dev.
Styrene
1,1,1, 2 -Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachl oroethene
Toluene
1 , 2 , 3 -Tr i chl orobenzene
1,2,4-Trichlorobenzene
1,1,1 -Tri chl oroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chl orof 1 uoromethane
1,2,3-Trichloropropane
1, 2, 4-Trimethyl benzene
1 , 3 , 5-Tri methyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene
0.1
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.5
-100
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 10
- 31
- 10
- 10
39
24
30
24
18
18
18
18
18
24
24
16
18
23
18
18
31
18
102
90
91
89
102
109
108
98
104
90
89
108
99
92
98
103
97
104
7.3
6.1
5.7
6.0
8.1
9.4
9.0
7.9
7.6
6.5
7.2
15.6
8.0
6.8
6.5
7.4
6.3
8.0
7.2
6.8
6.3
6.8
8.0
8.6
8.3
8.1
7.3
7.3
8.1
14.4
8.1
7.4
6.7
7.2
6.5
7.7
a  Recoveries were calculated using internal standard method.  Internal  standard
   was fluorobenzene.

b  Standard deviation was calculated by pooling data form three concentrations.
                                  8260A  - 39
                                      Revision 1
                                      November 1990

-------
                     TABLE 8.
SINGLE LABORATORY ACCURACY AND PRECISION DATA FOR
 VOLATILE ORGANIC  COMPOUNDS  IN WATER DETERMINED
       WITH A NARROW BORE CAPILLARY COLUMN
Analyte
Benzene
Bromobenzene
Bromochloromethane
Bromodichloromethane
Bromoform
Bromomethane
n-Butyl benzene
sec-Butyl benzene
tert-Butyl benzene
Carbon tetrachloride
Chlorobenzene
Chloroethane
Chloroform
Chloromethane
2-Chlorotoluene
4-Chlorotoluene
1 , 2-Di bromo-3-chl oropropane
Di bromochl oromethane
1,2-Dibromoethane
Di bromomethane
1, 2-Di Chlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Di chl orodi f 1 uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
cis-1, 2-Di chl oroethene
trans- 1, 2-Di chl oroethene
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
1,1-Dichloropropene
Ethyl benzene
Hexachlorobutadiene
I sopropyl benzene
p-Isopropyl toluene
Methyl ene chloride
Naphthalene
n-Propyl benzene
Cone.
M9/L
0.1
0.5
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.5
0.1
0.5
0.5
0.1
0.1
0.1
0.1
0.5
0.1
0.1
0.1
0.1
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
Number
of
Samples
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Recovery,"
%
99
97
97
100
101
99
94
110
110
108
91
100
105
101
99
96
92
99
97
93
97
101
106
99
98
100
95
100
98
96
99
99
102
99
100
102
113
97
98
99
Standard
Deviation
of Recovery
6.2
7.4
5.8
4.6
5.4
7.1
6.0
7.1
2.5
6.8
5.8
5.8
3.2
4.7
4.6
7.0
10.0
5.6
5.6
5.6
3.5
6.0
6.5
8.8
6.2
6.3
9.0
3.7
7.2
6.0
5.8
4.9
7.4
5.2
6.7
6.4
13.0
13.0
7.2
6.6
Percent
Rel. Std.
Dev.
6.3
7.6
6.0
4.6
5.3
7.2
6.4
6.5
2.3
6.3
6.4
5.8
3.0
4.7
4.6
7.3
10.9
5.7
5.8
6.0
3.6
5.9
6.1
8.9
6.3
6.3
9.5
3.7
7.3
6.3
5.9
4.9
7.3
5.3
6.7
6.3
11.5
13.4
7.3
6.7
                    8260A - 40
Revision 1
November 1990

-------
TABLE 8.
(Continued)


Analyte
Styrene
1,1,1 , 2-Tetrachl oroethane
1,1,2 , 2-Tetrachl oroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene
1,2,4-Trichlorobenzene
1,1,1-Trichloroethane
1,1,2-Trichl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
1,2,3-Trichloropropane
1,2, 4-Trimethyl benzene
1,3, 5-Trimethyl benzene
Vinyl chloride
o-Xylene
m-Xylene
p-Xylene

Cone.
M9/L
0.5
0.5
0.5
0.1
0.5
0.5
0.5
0.5
0.5
0.1
0.1
0.5
0.5
0.5
0.1
0.5
0.5
0.5
Number
of
Samples
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7

Recovery,8
%
96
100
100
96
100
102
91
100
102
104
97
96
96
101
104
106
106
97
Standard
Deviation
of Recovery
19.0
4.7
12.0
5.0
5.9
8.9
16.0
4.0
4.9
2.0
4.6
6.5
6.5
4.2
0.2
7.5
4.6
6.1
Percent
Rel. Std.
Dev.
19.8
4.7
12.0
5.2
5.9
8.7
17.6
4.0
4.8
1.9
4.7
6.8
6.8
4.2
0.2
7.1
4.3
6.3
Recoveries were calculated using internal standard method.  Internal  standard
was fluorobenzene.
                                8260A  -  41
Revision 1
November 1990

-------
                                   TABLE 9.
      SURROGATE  SPIKE  RECOVERY  LIMITS  FOR WATER AND SOIL/SEDIMENT SAMPLES
                                    Low/High          Low/High
      Surrogate Compound            Water             Soil/Sediment
      4-Bromofluorobenzenea         86-115             74-121
      Dibromofluoromethane3         86-118             80-120
      Toluene-d8a                    88-110             81-117
   Single laboratory data for guidance only.
                                   TABLE  10.

                 QUANTITY OF EXTRACT REQUIRED FOR ANALYSIS OF
                          HIGH-CONCENTRATION SAMPLES
Approximate                                     Volume of
Concentration Range                             Extract8


   500 -  10,000 Aig/Kg                          100 nl
 1,000 -  20,000 jug/Kg                           50 nl
 5,000 - 100,000 jug/Kg                           10 nl
25,000 - 500,000 ^g/Kg                          100 ML of 1/50 dilution"
Calculate appropriate dilution factor for concentrations exceeding this table.

a     The volume of solvent added to 5 ml of water being purged should be kept
      constant.  Therefore, add to the 5 mL syringe whatever volume of solvent
      is necessary to maintain a volume of 100 /iL added to the syringe.

b     Dilute  an aliquot  of the  solvent extract  and  then  take  100 pi for
      analysis.
                                  8260A - 42                      Revision 1
                                                                  November 1990

-------
                     FIGURE  1.
                  PURGING DEVICE
EXIT 1M IN. O.O
                       EXIT 1M IN OJ>.
                     » U MM 0.0.
                        INLET IM IN. 0.0.
10 MM GLASS FNT
MEDIUM PONosny
SAMPLE INLET

*WAV SYNNQC VALVt

17 CM » OAUQC STWNQE NEEDLE


6 MM 0.0  RUeSEN SEPTUM


INLET 1M IN. 0.0.
                                                      me IN. 0.0.
                                                   /^STAINLESS STEEL
                                                     IK
                                                     MOLECULAR SIEVE
                                                     PUHOE GAS HLTER
                                                       n.OWOONTIVX
                   8260A  - 43
                            Revision  1
                            November 1990

-------
                            FIGURE 2.
TRAP  PACKING  AND CONSTRUCTION TO  INCLUDE  DESORB  CAPABILITY
      PACKING DETAIL



         Z^- 5 MM QLA38 WOOL
CONSTRUCTION OTTAJL
                                                  FTTTMQNVr
                                                  AND I
           77 CM SIUCA GCL
           19 CM TENAX QC
           •- 1 CM 3% OV-1
             9MMOLAMWOOL
             u FT rn/FOOT
             ncssTANceww
             MWAPPCDSOUO
                                                  THEMMCOUPLB
                                                  CONTROLLER
                                                  SCN80M
                                                   ELECTMOMC
                                                   TIMPBMTUMi
                                                   OOMTMOLANO
                                                  a 106 M. LO
                                                  0.1B M OA
                                                  ST,
                           8260A  -  44
                           Revision  1
                           November 1990

-------
                         FIGURE 3.
      SCHEMATIC OF PURGE-AND-TRAP DEVICE  - PURGE MODE
CARWERGAS
F10W CONTROL
PRESSURE
REGULATOR
                              SELECTION VALVE
PURGE QAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
UOWO INJECTION PORTS

     COLUMN OVEN
    .A/IT--,
    JUUV
                                               CONFIRMATORY COLUMN
                                              TO DETECTOR
                                               ANALYTICAL COLUMN
                                      TRAP INLET
                                PURGING
                                DEVICE
             NOTE:
             ALL LINES BETWEEN TRAP
             AND OC SHOULD BE HEATED
             TOWC.
                        8260A - 45
                       Revision 1
                       November 1990

-------
                           FIGURE 4.
       SCHEMATIC OF PURGE-AND-TRAP DEVICE -  DESORB MODE
CARRCRQAB
FLO* CONTROL
PRESSURE
REGULATOR
LIQUID INJECTION PORTS

   r- COLUMN OVEN

               CONFIRMATORY COLUMN
    JUUvP
                                              TO DETECTOR
                                               ANALYTICAL COLUMN
PURGE GAS
FLOWCONT
13X MOLECULAR
SIEVE FILTER
                              OPTIONAL 4PORT COLUMN
                              SELECTION VALVE
                                       TRAP INLET
                                     TRAP
                                     200-C
                                              NOTE
                                              ALL LINES BETWEEN TRAP
                                              AND OC SHOULD BE HEATED
                                              TO «TC.
                         8260A - 46
                        Revision 1
                        November 1990

-------
                      FIGURE 5.

        GAS CHROMATOGRAM OF VOLATILE ORGANICS
o_
T
M
                           • » »1
      3N3;N3aO«01M3  *. -C'3
 3N3TOMlMdt»N


3N3ZN380«OTH3IM1  -» '<
  S   5

  o   r
      n


  c   o
  UJ   (k

  ^   u


  2   2
                          3NVH13UOM01H3 I aOWOUf
                                          t 'T 'T
                           3NOHl30U01H3ia -t '
                           3QXW01H3 3N31AM13W


                                         -I 'T



                                      •\ANXA
                                                 J
                                                      n
                                                      (VI
                                                  •
-------
                 FIGURE 6.
    GAS CHROMATOGRAM OF VOLATILE ORGANICS
a
c
®
M
                    3N3ZKG8CM01H3XU1 -Ł**'<
                    3N3ZN3gOUGlH3UU -«*J'
«

<«
            3N3ZN380H01H3XO  -3  I

               -«••
      3N3WA1S  *  JN1-UX  -O
»
    -    -2
    II  i*
    2s  J?
    ?- '  u tf

         OS
    ^    «• y
     I      •
     i
                      3N3H130M01H3IU1

                   3N3HJ.30M01H3IQ -«':




                          30IMOTM3  1ANIA
                                                    i
                                                    !
               8260A - 48
                                            Revision  1
                                            November 1990

-------
   00
   ro
   o»
  vo
Z 3D
O*
10 <
to
o
             F.1C
                                                              : 40"SCW2987  »843
                                                         CALI: 40».'S042987  13
RIC                                  DATA: 40U5CW2987 »843    SCkllS  125 TO  900
04/23/87  9:28:00
SAMPLE: 40UOASTD04
COHDS.: F4000.40-160X8.12,F4,38MLPURGE,TEt6ILGEL.G6624,SWEEP35,18FSI
RANGE: G    1.1200  LABEL:.H  8,  4.0  GUAM: A  0, 1.0 J  0  BASE:  U 20,   3
                                                                                                                 CM
                                                                                                                ^
                                                                                                                u
                                                                                                                 in
                                                                                             (N
                                                                                            ^
                                                                                            U
                                                                                                                                264132.
        260
"I	
 3*8
 5:06
                                                       6:40
"1	
 500
 8:20
                                                              16:08
11:43
  I
 SCO
13:20
                                                                                                                                     CO
                                                                                                                                     r>
                                                                                                                                     30
                                                                                            oc=
                                                                                            -n 30
                                                                                              m
                                                                                            o —i
                                                                                            i— •
                                                                                                                                    o
                                                                                                                                    30
                                                                                                                                    CT>
      SCHH
15:08 TIME

-------
                                                                           I. I.I
                                U
                                                              US MM. HI
00
ro
en
o
on
O
                              $
                              M
                                                                           M riMMOWXIM (Mt I1»)
                                                                cr>
                                                                CO
                                                                o
                                                                                                      '00
                                                                                                    X
                                                                                                    -H

                                                                                                    70
                  ••   « t   /
                 ULi
B
U
               V
              JL-
                                             SCMf
                                             IIP!

-------
                    FIGURE 9.
                LOU SOILS IMPINGER
PURGE INLET FITTING
SAMPLE OUTLET FITTING
 • 6r*m 00  GLASS TUBING
                                   SEPTUM
                                      CAP
           40ml VIAL
                          u

                   8260A -  51
Revision 1
November 1990

-------
                          METHOD 8260A
GAS  CHROMATOGRAPHY/MASS SPECTROMETRY FOR VOLATILE  ORGANICS
                  CAPILLARY COLUMN TECHNIQUE
                 Start
                           Direct
                  7  1
                Select
             procedure  for
              introducing
              sample into
                CC/MS
and - trap

7.2 Set CC/MS
. operating
condi tions .
              7.3.2  Tune
             CC/MS system
               xith  BFB
              73.2/733
               Assemble
            purge-and-trap
            device.  Connect
             device  to CC.
             7.3.4 Prepare
              calibration
              standards.
             7.3.6 Perform
            purge-and-trap
               analysis.
    7.37
Calculate RFs
for 5  SPCCs.
                                         738
                                       Calculate
                                      XRSD of RF
                                       for CCCs.
 7.4 Perform
    daily
calibration.
                          8260A -  52
                         Revision  1
                         November  1990

-------
                                   METHOD  8260A
                                    (Continued)
                                        High concentration
                                        soil/sediment
                                                                                       7
                   wa ter and  wate
                   miacible liquids
 75313  Prepare
aqueous  solution of
   sur roga te and
internal  standard*
               1
751/752 Screen
sample  using Method
   3810 or 3820
      (Dilute
  «a tar-miscible
liquids at l«*lt SO
      fold )
                             7.5.1.9  Add
                          internal  standard
                            and surrogate
                         •piking solutions.
 7.5.1.10/7.5  1.11
      Perform
  purge-and-trap
    procedure.
                                                     7  5 3 2 2 Add
                                                   solvent, internal
                                                     standard and
                                                   surrogate spiking
                                                   solutions. Shake.
                                                    7532  Store
                                                  portion of extract
                                                   for  re*analysis
                                                    Prepare method
                                                        blank.
                                                                        7 5 1 12 Desorb trap
                                                                        onto column  Analyze
                                                                              sample
                                                                        chroma tographically
 7611  Identify
    analytes by
   comparing the
sample  and standard
   mass spectra
                                                 7622 Calculate
                                                 the concentration
                                                of each identified
                                                    analyte
                                     8260A  -  53
                                                         Revision  1
                                                         November  1990

-------
                                 METHOD 8270B

                       SEMIVOLATILE ORGANIC  COMPOUNDS  BY
   GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS1; CAPILLARY COLUMN TECHNIQUE
1.0   SCOPE AND APPLICATION

      1.1  Method 8270 is used to  determine  the concentration of semivolatile
organic compounds in extracts prepared from all types of solid waste matrices,
soils, and ground water.  Direct injection of  a sample  may be used in limited
applications.  The following compounds can be determined by this method:
Compounds
CAS No8
Appropriate Preparation Techniques

     3510    3520  3540  3550  3580
Acenaphthene
Acenaphthene-d10 (I.S.)
Acenaphthylene
Acetophenone
2-Acetyl ami nof 1 uorene
l-Acetyl-2-thiourea
Aldrin
2-Aminoanthraquinone
Aminoazobenzene
4-Aminobiphenyl
3-Amino-9-ethylcarbazole
Anilazine
Aniline
o-Anisidine
Anthracene
Aramite
Aroclor - 1016
Aroclor - 1221
Aroclor - 1232
Aroclor - 1242
Aroclor - 1248
Aroclor - 1254
Aroclor - 1260
Azinphos-methyl
Barban
Benzidine
Benzoic acid
Benz(a)anthracene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo (g , h , i ) peryl ene
Benzo(a)pyrene
p-Benzoquinone
Benzyl alcohol
83-32-9

208-96-8
98-86-2
53-96-3
591-08-2
309-00-2
117-79-3
60-09-3
92-67-1
132-32-1
101-05-3
62-53-3
90-04-0
120-12-7
140-57-8
12674-11-2
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
86-50-0
101-27-9
92-87-5
65-85-0
56-55-3
205-99-2
207-08-9
191-24-2
50-32-8
106-51-4
100-51-6
X
X
X
X
X
LR
X
X
X
X
X
X
X
X
X
HS(43)
X
X
X
X
X
X
X
HS(62)
LR
CP
X
X
X
X
X
X
OE
X
X
X
X
ND
ND
ND
X
ND
ND
ND
X
ND
X
ND
X
ND
X
X
X
X
X
X
X
ND
ND
CP
X
X
X
X
X
X
ND
X
X
X
X
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
X
ND
X
X
X
X
X
X
X
ND
ND
CP
ND
X
X
X
X
X
ND
ND
X
X
X
ND
ND
ND
X
ND
ND
ND
ND
ND
X
ND
X
ND
X
X
X
X
X
X
X
ND
ND
CP
X
X
X
X
X
X
ND
X
X
X
X
X
X
LR
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
CP
X
X
X
X
X
X
X
X
                                   8270B -  1
                                    Revision 2
                                    November 1990

-------
      Appropriate  Preparation  Techniques
Compounds CAS Noa
o-BHC
0-BHC

-------
ADorooriate Preoaration Techniaues
Compounds
Dibenzofuran
Dibenzo(a,e)pyrene
1 , 2-Di bromo-3-chl oropropane
Di-n-butyl phthalate
Dichlone
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
l,4-Dichlorobenzene-d4 (I.S)
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos
Dicrotophos
Dieldrin
Di ethyl phthalate
Di ethyl stilbestrol
Di ethyl sulfate
Dihydrosaffrole
Dimethoate
3,3'-Dimethoxybenzidine
Dimethyl ami noazobenzene
7,12-Dimethylbenz(a)-
anthracene
3, 3* -Dimethyl benzi dine
a , a-Dimethyl phenethyl ami ne
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-Diphenylhydantoin
1 , 2 -Di phenyl hydrazi ne
Di-n-octyl phthalate
Disulfoton
Endosulfan I
Endosulfan II
Endosulfan sulfate
CAS Noa
132-64-9
192-65-4
96-12-8
84-74-2
117-80-6
95-50-1
541-73-1
106-46-7

91-94-1
120-83-2
87-65-0
62-73-7
141-66-2
60-57-1
84-66-2
56-53-1
64-67-5
56312-13-1
60-51-5
119-90-4
60-11-7
57-97-6

119-93-7
122-09-8
105-67-9
131-11-3
528-29-0
99-65-0
100-25-4
534-52-1
51-28-5
121-14-2
606-20-2
39300-45-3
88-85-7
78-34-2
122-39-4
57-41-0
122-66-7
117-84-0
298-04-4
959-98-8
33213-65-9
1031-07-8
3510
X
ND
X
X
OE
X
X
X
X
X
X
X
X
X
X
X
AW,OS(67)
LR
ND
HE,HS(31)
X
X
CP(45)

X
ND
X
X
X
X
HE(14)
X
X
X
X
CP,HS(28)
X
ND
X
X
X
X
X
X
X
X
3520
X
ND
X
X
ND
X
X
X
X
X
X
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND

ND
ND
X
X
ND
ND
ND
X
X
X
X
ND
ND
ND
X
ND
X
X
ND
X
X
X
3540
ND
ND
ND
X
ND
X
X
X
X
X
X
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND

ND
ND
X
X
ND
ND
ND
X
X
X
X
ND
ND
ND
X
ND
X
X
ND
X
X
X
3550
X
ND
ND
X
ND
X
X
X
X
X
X
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND

ND
ND
X
X
ND
ND
ND
X
X
X
X
ND
ND
ND
X
ND
X
X
ND
X
X
X
3580
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
ND
X
LR
X
CP

X
X
X
X
X
X
X
X
X
X
X
CP
X
ND
X
X
X
X
X
X
X
X
8270B - 3
Revision 2
November 1990

-------
ADDrooriate Preoaration Techniaues
Compounds
Endrin
Endrin aldehyde
Endrin ketone
EPN
Ethion
Ethyl carbamate
Ethyl methanesulfonate
Ethyl parathion
Famphur
Fensulfothion
Fenthion
Fluchloralin
Fluoranthene
Fluorene
2-Fluorobiphenyl (surr.)
2-Fluorophenol (surr.)
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachloroethane
Hexachl orophene
Hexachl oropropene
Hexamethyl phosphoramide
Hydroquinone
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
Isosafrole
Kepone
Leptophos
Malathion
Maleic anhydride
Mestranol
Methapyrilene
Methoxychlor
3-Methyl chol anthrene
4,4'-Methylenebis(2-chloranil
4,4'-Methylenebis
(N,N-dimethylaniline)
Methyl methanesulfonate
2-Methyl naphthal ene
2-Methyl-5-nitroaniline
Methyl parathion
2-Methyl phenol
3-Methyl phenol
CAS No"
72-20-8
7421-93-4
53494-70-5
2104-64-5
563-12-2
51-79-6
62-50-0
56-38-2
52-85-7
115-90-2
55-38-9
33245-39-5
206-44-0
86-73-7
321-60-8
367-12-4
76-44-8
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
70-30-4
1888-71-7
680-31-9
123-31-9
193-39-5
465-73-6
78-59-1
120-58-1
143-50-0
21609-90-5
121-75-5
108-31-6
72-33-3
91-80-5
72-43-5
56-49-5
ine) 101-14-4

101-61-1
66-27-3
91-57-6
99-55-8
298-00-0
95-48-7
108-39-4
3510
X
X
X
X
X
DC(28)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
AW,CP(62)
X
X
ND
X
X
X
DC(46)
X
X
HS(5)
HE
X
X
X
X
OE,OS(0)

X
X
X
X
X
X
X
3520
X
X
X
ND
ND
ND
ND
X
ND
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND

X
ND
X
X
ND
ND
ND
3540
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND

ND
ND
ND
ND
ND
ND
ND
3550
X
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
X
X
X
X
X
ND
ND
ND
ND
X
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND

ND
ND
X
ND
ND
ND
ND
3580
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
CP
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LR

ND
X
X
ND
X
X
X
8270B - 4
Revision 2
November 1990

-------
ADorooriate Preoaration Techniaues
Compounds
4-Methyl phenol
2-Methylpyridine
Mevinphos
Mexacarbate
Mi rex
Monocrotophos
Naled
Naphthalene
Naphthalene -de (I.S.)
1,4-Naphthoquinone
1-Naphthylamine
2-Naphthylamine
Nicotine
5-Nitroacenaphthene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
5-Nitro-o-anisidine
Nitrobenzene
Nitrobenzene-d5 (surr.)
4-Nitrobiphenyl
Nitrofen
2-Nitrophenol
4-Nitrophenol
5-Nitro-o-toluidine
Nitroquinol ine-1-oxide
N-Ni trosodi butyl ami ne
N-Ni trosodi ethyl ami ne
N-Ni trosodimethyl ami ne
N-Ni trosomethyl ethyl ami ne
N-Ni trosodi phenyl ami ne
N-Ni trosodi -n-propyl ami ne
N-Nitrosomorphol ine
N-Nitrosopiperidine
N-Nitrosopyrrol idine
Octamethyl pyrophosphoramide
4,4'-Oxydianiline
Parathion
Pentachlorobenzene
Pentachloronitrobenzene
Pentachlorophenol
Perylene-d12 (I.S.)
Phenacetin
Phenanthrene
Phenanthrene-d10 (I.S.)
Phenobarbital
Phenol
CAS No"
106-44-5
109-06-8
7786-34-7
315-18-4
2385-85-5
6923-22-4
300-76-5
91-20-3

130-15-4
134-32-7
91-59-8
54-11-5
602-87-9
88-74-4
99-09-2
100-01-6
99-59-2
98-95-3
92-93-3
1836-75-5
88-75-5
100-02-7
99-55-8
56-57-5
924-16-3
55-18-5
62-75-9
10595-95-6
86-30-6
621-64-7
59-89-2
100-75-4
930-55-2
152-16-9
101-80-4
56-38-2
608-93-5
82-68-8
87-86-5

62-44-2
85-01-8

50-06-6
108-95-2
3510
X
X
X
HE,HS(68)
X
HE
X
X
X
X
OS(44)
X
DE(67)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
ND
X
X
LR
X
X
X
X
X
X
X
X
X
X
DC(28)
3520
ND
X
ND
ND
ND
ND
ND
X
X
ND
ND
ND
ND
ND
X
X
X
ND
X
X
ND
ND
X
X
ND
ND
ND
ND
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
X
X
ND
X
3540
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
X
X
ND
ND
ND
ND
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
X
X
ND
X
3550
ND
ND
ND
ND
ND
ND
ND
X
X
ND
ND
ND
ND
ND
X
X
X
ND
X
X
ND
ND
X
X
ND
ND
ND
ND
X
ND
X
X
ND
ND
ND
ND
ND
ND
ND
ND
X
X
ND
X
X
ND
X
3580
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
X
X
X
X
X
X
X
X
X
X
X
8270B - 5
Revision 2
November 1990

-------
Appropriate Preparation Techniques
Compounds
Phenol -d6 (surr.)
1 , 4-Phenyl enedi ami ne
Phorate
Phosalone
Phosmet
Phosphamidon
Phthalic anhydride
2-Picoline
Piperonyl sulfoxide
Pronamide
Propylthiouracil
Pyrene
Pyridine
Resorcinol
Safrole
Strychnine
Sul fall ate
Terbufos
Terphenyl-d14(surr.)
1,2,4 , 5-Tetrachl orobenzene
2,3,4,6-Tetrachlorophenol
Tetrachlorvinphos
Tetraethyl dithiopyrophosphate
Tetraethyl pyrophosphate
Thionazine
Thiophenol (Benzenethiol)
Toluene diisocyanate
o-Toluidine
Toxaphene
2,4,6-Tribromophenol (surr.)
1 , 2 , 4-Tri chl orobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Trifluralin
2,4,5-Trimethylaniline
Trimethyl phosphate
1, 3, 5-Tri nitrobenzene
Tris(2,3-dibromopropyl) phosphate
Tri-p-tolyl phosphate
0,0,0-Triethyl phosphorothioate
CAS Noa

106-50-3
298-02-2
2310-17-0
732-11-6
13171-21-6
85-44-9
109-06-8
120-62-7
23950-58-5
51-52-5
129-00-0
110-86-1
108-46-3
94-59-7
60-41-3
95-06-7
13071-79-9

95-94-3
58-90-2
961-11-5
3689-24-5
107-49-3
297-97-2
108-98-5
584-84-9
95-53-4
8001-35-2

120-82-1
95-95-4
88-06-2
1582-09-8
137-17-7
512-56-1
99-35-4
126-72-7
78-32-0
126-68-1
3510
DC(28)
X
X
HS(65)
HS(15)
HE(63)
CP,HE(1)
ND
X
X
LR
X
ND
DC,OE(10)
X
AW,OS(55)
X
X
X
X
X
X
X
X
X
X
HE(6)
X
X
X
X
X
X
X
X
HE(60)
X
X
X
X
3520
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
X
ND
ND
ND
ND
ND
X
X
X
X
X
ND
ND
ND
ND
ND
ND
ND
3540
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
ND
X
ND
ND
ND
ND
ND
ND
ND
3550
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
X
ND
ND
ND
ND
ND
ND
ND
ND
ND
X
X
X
X
X
ND
ND
ND
ND
ND
ND
ND
3580
X
X
X
X
X
X
CP
ND
X
X
LR
X
ND
X
X
X
X
X
X
X
X
X
ND
X
X
X
X
X
X
X
X
X
X
X
X
X
X
LR
X
X
Chemical Abstract Service Registry  Number.
                              8270B - 6
Revision 2
November  1990

-------
AW = Adsorption to walls of glassware during extraction and storage.
CP = Nonreproducible chromatographic performance.
DC = Unfavorable  distribution  coefficient  (number  in parenthesis  is percent
     recovery).
HE = Hydrolysis during  extraction accelerated  by acidic or  basic conditions
     (number in parenthesis is percent recovery).
HS = Hydrolysis "during storage (number in parenthesis is percent stability).
LR = Low response.
NO = Not determined.
OE = Oxidation  during  extraction accelerated  by basic conditions  (number in
     parenthesis  is percent recovery).
OS = Oxidation during storage (number in parenthesis is percent stability).
X =  Greater than 70 percent recovery by this technique.

Percent Stability =  Average Recovery (Day 7)  x 100/Average  Recovery (Day 0).


      1.2  Method 8270 can be used to quantitate most neutral,  acidic,  and basic
organic compounds that are  soluble  in methylene chloride and capable of being
eluted without derivatization as sharp peaks from a gas chromatographic fused-
silica capillary column coated with a slightly polar silicone.  Such compounds
include  polynuclear  aromatic   hydrocarbons,   chlorinated   hydrocarbons  and
pesticides, phthalate esters, organophosphate  esters, nitrosamines, halpethers,
aldehydes,  ethers,  ketones, anilines,  pyridines, quinolines,  aromatic  nitro
compounds,  and  phenols,   including nitrophenols.   See Table  1 for  a list of
compounds and their characteristic ions that have been evaluated on the specified
GC/MS system.

      1.3  The  following  compounds may  require special  treatment  when  being
determined by this method.  Benzidine can be subject  to oxidative losses during
solvent  concentration.    Also,  chromatography  is poor.   Under  the alkaline
conditions of the extraction step, a-BHC, 7-BHC, endosulfan I and II, and endrin
are subject to decomposition.  Neutral extraction should be performed if these
compounds  are  expected.    Hexachlorocyclopentadiene  is subject   to  thermal
decomposition in the  inlet of the gas chromatograph, chemical  reaction in acetone
solution, and photochemical decomposition.   N-nitrosodimethylamine  is difficult
to  separate  from the solvent under  the  chromatographic  conditions described.
N-nitrosodiphenylamine decomposes  in  the gas  chromatographic inlet and cannot
be  separated   from   diphenylamine.     Pentachlorophenol,   2,4-dinitrophenol,
4-nitrophenol,4,6-dinitro-2-methylphenol,4-chloro-3-methylphenol, benzoicacid,
2-nitroaniline, 3-nitroaniline, 4-chloroaniline, and benzyl  alcohol  are subject
to erratic chromatographic behavior, especially  if the GC  system is contaminated
with high boiling material.

      1.4  The estimated quantitation limit  (EQL) of Method 8270 for determining
an individual compound is approximately  1 mg/Kg  (wet weight) for soil/sediment
samples, 1-200 mg/Kg for wastes (dependent on matrix and method  of preparation),
and  10  jug/L   for   ground  water  samples  (see  Table  2).    EQLs  will  be
proportionately  higher  for sample extracts  that  require  dilution  to  avoid
saturation of the detector.

      1.5  This  method  is  restricted  to use  by  or under  the supervision of
analysts  experienced in  the use of gas  chromatograph/mass  spectrometers and


                                   8270B  - 7                      Revision 2
                                                                  November 1990

-------
skilled in the  interpretation of mass  spectra.   Each analyst must demonstrate
the ability to generate acceptable results with this method.


2.0  SUMMARY OF METHOD

      2.1  Prior  to  using  this  method,  the  samples  should  be  prepared  for
chromatography  using  the  appropriate sample preparation  and  cleanup methods.
This  method  describes  chromatographic  conditions  that  will  allow for  the
separation of the compounds in the extract.


3.0  INTERFERENCES

      3.1  Raw GC/MS data  from all blanks, samples, and spikes must be evaluated
for interferences. Determine if the source of interference is in the preparation
and/or  cleanup  of the  samples  and  take corrective  action to  eliminate  the
problem.

      3.2  Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially analyzed.  To reduce carryover,  the
sample  syringe  must  be  rinsed  out between samples with  solvent.   Whenever an
unusually  concentrated  sample is  encountered,  it  should  be followed  by  the
analysis of solvent to check for cross  contamination.


4.0  APPARATUS AND MATERIALS

      4.1  Gas chromatograph/mass spectrometer system

            4.1.1  Gas  chromatograph  - An  analytical  system complete  with  a
      temperature-programmable gas chromatograph suitable for spl itless injection
      and all  required accessories,  including syringes, analytical columns, and
      gases.   The capillary column should be directly coupled to the source.

            4.1.2  Column  - 30 m  x 0.25 mm  ID  (or  0.32  mm  ID)  1 urn  film
      thickness silicone-coated fused-silica capillary column (J&W Scientific
      DB-5 or equivalent).

            4.1.3  Mass spectrometer -  Capable of scanning  from 35 to 500 amu
      every 1  sec or less,  using  70  volts  (nominal) electron  energy  in  the
      electron  impact ionization mode.   The mass  spectrometer must be capable
      of  producing  a mass  spectrum for  decafluorotriphenylphosphine (DFTPP)
      which meets all of the criteria in Table 3  when 1 pi of the GC/MS tuning
      standard  is injected through the GC (50 ng  of DFTPP).

            4.1.4  GC/MS interface  - Any GC-to-MS interface that gives acceptable
      calibration points  at 50 ng  per  injection  for each compound of interest
      and achieves acceptable tuning performance  criteria may be used.

            4.1.5  Data system  -  A computer system must  be interfaced  to the
      mass spectrometer.  The system must allow the continuous acquisition and
      storage on machine-readable media of all mass  spectra obtained throughout


                                   8270B - 8                      Revision 2
                                                                  November  1990

-------
      the duration  of the  chromatographic  program.   The computer  must  have
      software that can search any GC/MS data file for ions of a specific mass
      and that can plot such  ion  abundances  versus  time  or scan number.   This
      type  of  plot  is  defined as  an Extracted  Ion  Current  Profile  (EICP).
      Software must also be available that allows integrating the abundances in
      any EICP between specified  time or scan-number  limits.   The most recent
      version of the EPA/NIST Mass Spectral  Library should also be available.

      4.2  Syringe - 10 /nL.

      4.3  Volumetric flasks, Class A - 10 ml to 1000 ml.

      4.4  Balance - Analytical, 0.0001 g.

      4.5  Bottles - glass with Teflon-lined screw caps or crimp tops.

5.0  REAGENTS

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

      5.2  Organic-free reagent water - All  references to water in this method
refer to organic-free reagent water,  as defined in Chapter One.

      5.3  Stock  standard  solutions  (1000 mg/L)  -  Standard solutions can be
prepared from pure standard materials or purchased as certified solutions.

            5.3.1  Prepare stock standard solutions by accurately weighing about
      0.0100 g of pure  material.   Dissolve the material  in  pesticide  quality
      acetone  or other  suitable   solvent  and dilute  to  volume   in  a 10  ml
      volumetric flask.  Larger volumes can  be used at the convenience of the
      analyst.  When compound purity  is assayed to be 96%  or greater, the weight
      may be used without correction to calculate the concentration  of the stock
      standard.   Commercially  prepared  stock standards  may  be  used at any
      concentration  if  they  are  certified  by  the  manufacturer  or  by  an
      independent source.

            5.3.2  Transfer the stock standard solutions into bottles with Teflon
      lined screw-caps.  Store  at  4°C and protect  from light.   Stock standard
      solutions  should  be  checked  frequently  for  signs  of   degradation  or
      evaporation, especially just prior to preparing calibration standards from
      them.

            5.3.3  Stock standard  solutions  must  be replaced  after  1  year or
      sooner  if  comparison  with  quality  control   check  samples   indicates  a
      problem.

      5.4  Internal standard solutions - The  internal standards recommended are
l,4-dichlorobenzene-d4,   naphthalene-ds,    acenaphthene-d10,   phenanthrene-d10,


                                   8270B  - 9                       Revision 2
                                                                  November 1990

-------
chrysene-d12, and perylene-d12.  Other compounds may be used as  internal standards
as long as the  requirements  given  in Section 7.3.2 are met.   Dissolve 0.200 g
of each compound with a small volume of carbon disulfide.  Transfer to a 50 mL
volumetric flask and dilute to volume with  methylene  chloride so that the final
solvent is approximately 20% carbon disulfide.  Most of the compounds are also
soluble  in  small  volumes  of  methanol,   acetone,  or   toluene,  except  for
perylene-d12.    The  resulting   solution  will  contain   each  standard  at  a
concentration of  4,000  ng/jitL.   Each 1 ml  sample  extract undergoing analysis
should be spiked with 10 /*L  of the internal standard solution,  resulting in a
concentration of 40 ng//iL of each internal  standard.   Store at 4°C or less when
not being used.

      5.5  GC/MS  tuning  standard  -  A methylene chloride solution  containing
50 ng//iL  of decafluorotriphenylphosphine   (DFTPP)  should be  prepared.    The
standard should also contain 50 ng//uL each of 4,4'-DDT, pentachlorophenol, and
benzidine to verify injection port inertness and GC column performance.  Store
at 4°C or less  when not  being used.

      5.6  Calibration standards - A minimum of five calibration standards should
be prepared.  One of the calibration standards should be at a concentration near,
but above,  the method detection  limit; the others should correspond to the range
of concentrations found  in  real  samples but should  not  exceed the working range
of the GC/MS system.  Each  standard  should contain each  analyte for detection
by this  method  (e.g.  some or  all  of the  compounds  listed in Table 1  may be
included).    Each  1 ml aliquot  of  calibration standard  should  be  spiked with
10 /iL of the internal standard solution prior to analysis.  All standards should
be stored at  -10°C to -20°C  and should be freshly prepared  once a year, or sooner
if check standards indicate  a  problem.   The daily calibration standard should
be prepared weekly and stored at 4°C.

      5.7  Surrogate  standards  -   The  recommended  surrogate  standards  are
phenol-d6,    2-fluorophenol,     2,4,6-tribromophenol,    nitrobenzene-d5,
2-fluorobiphenyl, and p-terphenyl-d14.  See Method 3500 for the instructions on
preparing the surrogate standards.   Determine  what concentration  should be in
the blank  extracts after  all   extraction,  cleanup,  and  concentration  steps.
Inject this  concentration  into  the  GC/MS  to determine  recovery  of surrogate
standards in all  blanks, spikes, and sample extracts.   Take into  account all
dilutions of sample extracts.

      5.8  Matrix spike standards - See Method 3500 for instructions on preparing
the matrix spike standard.   Determine what  concentration  should be in the blank
extracts after  all extraction,  cleanup,  and concentration steps.   Inject this
concentration into the GC/MS to determine recovery of surrogate standards in all
matrix spikes.   Take into account all dilutions of sample extracts.

      5.9  Acetone, hexane,  methylene chloride, isooctane,  carbon  disulfide,
toluene, and other appropriate solvents - Pesticide quality or equivalent


6.0  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1  See  the  introductory material  to this chapter,  Organic  Analytes,
Section 4.1.

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7.0  PROCEDURE
      7.1  Sample preparation -  Samples must be prepared by one of the following
methods prior to GC/MS analysis.
     Matrix
     Water
     Soil/sediment
     Waste
Methods
3510, 3520
3540, 3550
3540, 3550, 3580
            7.1.1  Direct  injection  -  In  very  limited  applications  direct
      injection of the  sample  into the GC/MS system with  a  10  p,l syringe may
      be  appropriate.    The  detection   limit   is  very   high  (approximately
      10,000 Mg/L);  therefore,  it  is  only permitted where  concentrations in
      excess of  10,000  ng/l are expected.   The system must  be calibrated by
      direct injection.

      7.2  Extract cleanup - Extracts may  be cleaned up by  any of the following
methods prior to GC/MS analysis.
     Compounds
     Phenols
     Phthalate esters
     Nitrosamines
     Organochlorine pesticides & PCBs
     Nitroaromatics and cyclic ketones
     Polynuclear aromatic hydrocarbons
     Haloethers
     Chlorinated hydrocarbons
     Organophosphorus pesticides
     Petroleum waste
     All priority pollutant base,
         neutral, and acids
                        Methods
                        3630, 3640, 8040a
                        3610, 3620, 3640
                        3610, 3620, 3640
                        3620, 3660
                        3620, 3640
                        3611, 3630, 3640
                        3620, 3640
                        3620, 3640
                        3620
                        3611, 3650

                        3640
     Method 8040 includes a derivatization technique followed by GC/ECD analysis,
     if interferences are encountered on GC/FID.

      7.3  Initial calibration - The recommended GC/MS operating conditions:
      Mass range:
      Scan time:
      Initial temperature:
      Temperature program:
      Final temperature:

      Injector temperature:
      Transfer line temperature:
      Source temperature:
      Injector:
      Sample volume:
      Carrier gas:
                                                   has
35-500 amu
1 sec/scan
40°C,  hold for 4 minutes
40-270°C  at 10°C/min
270°C,  hold  until  benzo[g,h,i]perylene
eluted
250-300°C
250-300°C
According to manufacturer's specifications
Grob-type, splitless
1-2 juL
Hydrogen at 50 cm/sec or helium at 30 cm/sec
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      7.3.1  Each GC/MS system must be hardware-tuned to meet the criteria
in Table 3 for a 50 ng injection  of DFTPP.  Analyses should not begin until
all  these   criteria  are  met.     Background   subtraction   should  be
straightforward and designed only to  eliminate column bleed or instrument
background ions.  The GC/MS tuning  standard  should also  be used to assess
GC column performance  and  injection  port  inertness.   Degradation of DDT
to DDE  and  ODD  should not exceed 20%.   Benzidine and pentachlorophenol
should  be present  at  their normal  responses,  and no peak tailing should
be visible.   If degradation is  excessive and/or poor  chromatography is
noted, the injection port may require cleaning.   It may also be necessary
to break off the first 6-12 in.  of the capillary column.

      7.3.2  The internal standards selected in  Section  5.1 should permit
most of the  components of interest  in a  chromatogram  to have retention
times of 0.80-1.20  relative to one of  the internal standards.  Use the base
peak  ion from  the specific  internal  standard   as  the primary  ion for
quantitation (see Table 1).  If  interferences are noted,  use the next most
intense  ion as the quantitation  ion  (i.e. for l,4-dichlorobenzene-d4 use
m/z 152  for quantitation).

      7.3.3  Analyze  1  ML  of   each calibration standard  (containing
internal  standards)  and  tabulate the area of the primary characteristic
ion against  concentration  for each  compound (as  indicated  in  Table 1).
Figure  1  shows  a  chromatogram of  a  calibration standard  containing
base/neutral and acid analytes.  Calculate response factors (RFs) for each
compound as follows:

      RF = (AxCis)/(AisCJ

where:

Ax  =  Area of the characteristic ion for the compound being measured.

Ais = Area of the characteristic  ion  for the specific internal  standard.

Cis = Concentration of the  specific internal  standard (ng//iL).

Cx  =  Concentration of the compound  being measured
      7.3.4  The average RF should be calculated for each compound.  The
percent relative standard deviation  (%RSD  =   100[SD/RF])  should also be
calculated for each compound.  The %RSD should be less than 30% for each
compound.  However, the %RSD for each individual Calibration Check Compound
(CCC) (see Table 4) must be less than 30%.  The relative retention times
of each compound in each calibration run should agree within 0.06 relative
retention  time  units.   Late-eluting compounds usually  have  much better
agreement.

      7.3.5  A system performance check must be performed to ensure that
minimum average  RFs  are  met before the calibration curve  is  used.   For
semivolatiles,  the  System  Performance  Check  Compounds (SPCCs)  are:  N-
nitroso-di-n-propylamine; hexachlorocyclopentadiene; 2,4-dinitro-phenol ;
and 4-nitrophenol .   The minimum acceptable  average RF for these compounds


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SPCCs is 0.050.  These SPCCs typically have very low RFs  (0.1-0.2) and tend
to decrease in response as the chromatographic system begins to deteriorate
or the standard material begins to deteriorate.  They are usually the first
to  show  poor  performance.    Therefore,  they must  meet  the  minimum
requirement when the system is calibrated.

7.4  Daily GC/MS calibration

      7.4.1  Prior to analysis of samples, the GC/MS tuning standard must
be analyzed.  A 50 ng  injection  of  DFTPP must  result  in  a mass spectrum
for DFTPP which meets the criteria given  in Table 3.  These criteria must
be demonstrated during each 12 hour shift.

      7.4.2  A calibration  standard(s) at  mid-concentration,  containing
each  compound  of  interest, including  all  required surrogates,  must  be
performed every 12  hours during analysis.   Compare the  response factor
data  from the standards  every  12 hours with  the average  response factor
from  the  initial  calibration  for a specific instrument  as  per  the SPCC
(Section 7.4.3) and CCC (Section 7.4.4) criteria.

      7.4.3  System  Performance Check  Compounds   (SPCCs):    A  system
performance check must be made during  every  12  hour shift.   If the SPCC
criteria  are  met,  a comparison of response  factors  is  made  for  all
compounds.  This  is the  same  check that is applied during  the initial
calibration.  If the  minimum response factors are not met, the system must
be evaluated,  and corrective action must  be taken  before  sample analysis
begins.  The minimum RF  for semivolatile SPCCs  is  0.050.  Some possible
problems  are   standard   mixture  degradation,  injection   port  inlet
contamination,  contamination at  the front end  of  the  analytical column,
and active sites in the column or chromatographic system.  This check must
be met before analysis begins.

      7.4.4  Calibration  Check  Compounds   (CCCs):    After  the  system
performance check is met,  CCCs listed  in Table 4  are  used  to  check the
validity of the  initial  calibration.   Calculate the  percent difference
using:

                    RF,   - RFC
     % Difference = ——	x 100
                       RF,

where:

      RF, =   Average response  factor from initial  calibration.
      RFC =  Response factor from current verification check standard.

      If the percent difference for any compound is greater than 20, the
laboratory should  consider this a warning  limit.  If the percent difference
for each CCC is less than  30%,  the  initial  calibration is assumed to be
valid.   If the criterion  is not  met (> 30%  difference) for any one CCC,
corrective action must be taken.  Problems  similar to  those listed under
SPCCs could affect  this  criterion.   If no  source  of the problem can  be
determined  after  corrective  action has been  taken,   a  new  five-point


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calibration must be generated.  This criterion must be met before sample
analysis begins.

      7.4.5  The internal standard  responses  and  retention times in the
calibration check standard must be evaluated immediately after or during
data acquisition.  If the retention time for any internal standard changes
by more than 30  seconds  from  the  last  check calibration (12 hours), the
chromatographic system must  be inspected  for malfunctions and corrections
must be made,  as required.    If the EICP  area for any of the internal
standards changes by a factor of two (-50% to +100%) from the last daily
calibration standard check, the mass spectrometer must be inspected for
malfunctions and corrections must be made, as appropriate.

7.5  GC/MS analysis

      7.5.1  It  is highly recommended  that  the extract be screened on a
GC/FID or  GC/PID using  the  same  type of  capillary column.   This will
minimize  contamination  of   the  GC/MS  system from  unexpectedly  high
concentrations of organic compounds.

      7.5.2  Spike the 1  ml  extract  obtained from  sample preparation with
10 pi of the internal  standard solution  just prior  to analysis.

      7.5.3  Analyze the 1 ml extract by  GC/MS  using a  30 m x 0.25 mm (or
0.32 mm)  silicone-coated fused-silica capillary column.  The volume to be
injected should ideally contain 100  ng  of base/neutral  and  200 ng of acid
surrogates  (for  a  1  /xL  injection).   The  recommended GC/MS  operating
conditions to be used are specified in Section 7.3.

      7.5.4  If the response for any quantitation  ion exceeds the initial
calibration curve range  of  the  GC/MS system,  extract  dilution  must take
place.  Additional  internal  standard must be added to the diluted extract
to  maintain  the required 40  ng/^L of  each  internal  standard  in  the
extracted volume.  The diluted extract must be reanalyzed.

      7.5.5  Perform  all  qualitative  and  quantitative measurements  as
described  in  Section  7.6.   Store  the extracts  at 4°C,  protected from
light in screw-cap vials equipped with unpierced Teflon lined septa.

7.6  Data interpretation

     7.6.1  Qualitative analysis

            7.6.1.1  The qualitative identification of compounds  determined
      by this method is based on retention  time, and on comparison of the
      sample   mass   spectrum,    after   background  correction,   with
      characteristic ions in a reference mass spectrum.  The reference mass
      spectrum must be generated  by the  laboratory using  the conditions
      of this  method.   The  characteristic  ions from  the  reference mass
      spectrum  are  defined  to  be the three  ions  of  greatest relative
      intensity, or any ions over 30% relative intensity if less  than three
      such ions  occur in the  reference  spectrum.  Compounds  should  be
      identified as present when the criteria below are met.


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            7.6.1.1.1  The intensities of the  characteristic  ions
      of a compound maximize  in the same scan or within one scan of
      each other.   Selection of  a  peak by  a  data  system  target
      compound search  routine where  the  search  is  based on  the
      presence of  a target  chromatographic  peak containing  ions
      specific for  the  target  compound  at  a  compound-specific
      retention time will  be  accepted as meeting this criterion.

            7.6.1.1.2  The RRT of the sample  component is within  ±
      0.06 RRT units of the RRT of the standard component.

            7.6.1.1.3  The relative intensities of the  characteristic
      ions agree within 30% of the relative  intensities of these ions
      in the  reference  spectrum.   (Example:    For an ion with  an
      abundance of 50%  in  the  reference spectrum, the corresponding
      abundance in a sample spectrum can range between 20% and 80%.)

            7.6.1.1.4  Structural  isomers that produce very similar
      mass spectra should be identified as individual  isomers if they
      have sufficiently different GC  retention  times.   Sufficient
      GC resolution is  achieved if the height of the valley between
      two isomer peaks  is less than 25% of the  sum of the two peak
      heights.   Otherwise, structural  isomers  are  identified  as
      isomeric pairs.

            7.6.1.1.5  Identification  is   hampered   when  sample
      components  are not  resolved chromatographically and produce
      mass spectra  containing ions contributed  by  more  than  one
      analyte.  When gas chromatographic peaks  obviously represent
      more than one  sample component  (i.e., a  broadened  peak with
      shoulder(s)  or  a  valley  between   two   or  more  maxima),
      appropriate selection of analyte  spectra and background spectra
      is important.  Examination  of extracted ion current profiles
      of appropriate ions can aid in the selection of spectra,  and
      in qualitative identification  of compounds.   When analytes
      coelute (i.e., only one chromatographic  peak  is  apparent), the
      identification criteria can  be met, but each analyte spectrum
      will contain  extraneous ions  contributed by  the  coeluting
      compound.

      7.6.1.2  For samples containing components not associated with
the calibration  standards,  a library  search may  be  made  for  the
purpose of tentative identification.   The necessity to perform this
type of  identification  will   be determined by  the purpose  of  the
analyses being conducted.  Computer generated library search routines
should not use normalization  routines that would  misrepresent  the
library or unknown spectra when compared to each  other. For example,
the RCRA  permit  or  waste  deli sting  requirements may  require  the
reporting of  nontarget analytes.  Only  after visual  comparison of
sample  spectra with the  nearest  library  searches  will  the  mass
spectral interpretation specialist assign a tentative identification.
Guidelines for making tentative identification  are:
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(1) Relative  intensities  of major ions  in  the reference spectrum
(ions > 10% of the most abundant ion) should be present in the sample
spectrum.

(2) The relative intensities of the major ions should agree within
±  20%.   (Example:   For an  ion with an  abundance of  50%  in the
standard spectrum, the  corresponding  sample ion  abundance must be
between 30 and 70%.)

(3) Molecular ions  present  in the  reference spectrum should be
present in the sample spectrum.

(4) Ions present  in  the sample spectrum  but  not  in the reference
spectrum should be reviewed  for possible background contamination
or presence of coeluting compounds.

(5) Ions present  in  the reference spectrum but not in  the sample
spectrum should be reviewed for possible subtraction from the sample
spectrum because  of  background contamination  or  coeluting peaks.
Data system library  reduction  programs  can  sometimes create these
discrepancies.

7.6.2  Quantitative analysis

      7.6.2.1  When a compound has been identified,  the quantitation
of that compound will be based  on the  integrated abundance from the
EICP of the primary characteristic ion.  Quantitation will take place
using the internal standard technique.  The internal standard used
shall   be the  one nearest  the  retention  time  of  that  of  a given
analyte (e.g. see Table 5).

      7.6.2.2  Calculate the concentration of each identified analyte
in the sample as follows:

Water
                         (AJ(I.)(Vt)
concentration (/ig/L)
                       (AJ(RF)(V0)(V,)

where:

Ax =  Area of characteristic ion for compound being measured.
Is =  Amount of internal  standard injected (ng).
V, =  Volume of total extract, taking into account dilutions (i.e.
      a l-to-10 dilution  of a  1 ml extract will mean V, = 10,000 pi.
      If half the  base/neutral extract and half the acid extract are
      combined, Vt =  2,000  juL).
A|S =  Area of characteristic ion for the internal standard.
RF =  Response factor for compound being measured (Section 7.3.3).
V0 =  Volume of water extracted (ml).
V, =  Volume of extract injected (ML).
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            Sediment/Soil Sludge (on a dry-weight basis)  and Waste  (normally on
            a wet-weight basis

                                         (Ax)(Is)(Vt)
            concentration (jig/Kg) =
                                     (A,S)(RF)(V,)(WS)(D)

            where:

            A,,  Is, Vt,  A,..,  RF,  V, = Same as for water.
            Ws =  Weight of sample extracted or diluted in grams.
            D  =  % dry weight of sample/100, or 1 for a wet-weight basis.

               7.6.2.3  Where  applicable,  an  estimate  of  concentration for
            noncalibrated components in the sample should be made.  The formulas
            given above should  be  used with the  following modifications:  The
            areas A,,  and A.  should  be  from the total  ion chromatograms and the
            RF for the compound  should be assumed  to  be 1.  The concentration
            obtained should  be reported  indicating  (1)  that the  value   is an
            estimate and  (2)  which  internal  standard  was  used  to determine
            concentration.     Use   the  nearest   internal   standard  free  of
            interferences.

               7.6.2.4  Quantitation of multicomponent compounds (e.g. Aroclors)
            is  beyond  the scope  of Method  8270.   Normally,  quantitation is
            performed using a GC/ECD by Method 8080.


8.0  QUALITY CONTROL

      8.1  Refer  to  Chapter  One and Method  8000 for  specific quality control
procedures.

      8.2  Required instrument QC is found  in the following  sections:

            8.2.1 The GC/MS system must be tuned to meet the DFTPP  specifications
      in Sections 7.3.1 and 7.4.1.

            8.2.2 There must be  an  initial calibration of the GC/MS system as
      specified in Section 7.3.

            8.2.3 The  GC/MS  system must  meet  the  SPCC criteria specified in
      Section 7.4.3 and the CCC criteria  in  Section 7.4.4, each  12  hours.

      8.3   To  establish  the  ability  to  generate  acceptable  accuracy and
precision, the analyst must perform the following operations.

            8.3.1 A quality control (QC) reference sample concentrate is required
      containing  each analyte  at a concentration of 100 mg/L  in methanol.  The
      QC  reference  sample  concentrate  may  be  prepared  from  pure  standard
      materials  or purchased  as  certified solutions.    If prepared  by the
      laboratory, the QC reference sample  concentrate must be made  using  stock
      standards prepared independently  from  those used for calibration.


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            8.3.2 Using a pipet,  prepare QC reference samples at a concentration
      of 100 /-ig/L by adding 1.00 ml of QC reference sample concentrate to each
      of four 1 L aliquots of organic-free reagent water.

            8.3.3 Analyze the well-mixed QC reference samples according to the
      method beginning in Section 7.1 with extraction of the samples.

            8.3.4 Calculate the average recovery (x) in M9/U and the standard
      deviation of the recovery (s)  in ng/l,  for each analyte of interest using
      the four results.

            8.3.5 For  each  analyte, compare  s and  x  with  the  corresponding
      acceptance criteria_for  precision and accuracy,  respectively,  found in
      Table 6.  If s and  x  for  all  analytes  meet  the acceptance  criteria,  the
      system performance is  acceptable and analysis of actual  samples can_begin.
      If any individual s exceeds the precision limit or any individual x falls
      outside the range for accuracy, then the system performance is unacceptable
      for that analyte.

NOTE: The large number of analytes in Table 6 present a  substantial probability
      that one or more will fail  at least  one  of  the acceptance  criteria when
      all analytes of  a given method are determined.

            8.3.6 When one or more of the analytes tested fail  at least one of
      the acceptance criteria,  the analyst must proceed  according  to Section
      8.3.6.1 or 8.3.6.2.

               8.3.6.1  Locate and correct  the  source of the problem and repeat
            the test for all analytes beginning with Section 8.3.2.

               8.3.6.2  Beginning with Section 8.3.2, repeat the  test only for
            those analytes  that  failed to meet  criteria.   Repeated  failure,
            however,  will  confirm a general  problem with  the measurement system.
            If this occurs, locate  and  correct the source  of the problem  and
            repeat the test  for all compounds of interest beginning with Section
            8.3.2.

      8.4  For  aqueous and  soil  matrices,  laboratory established  surrogate
control  limits should  be  compared with  the control limits  listed  in  Table 8.
The limits given in  Table 8 are multilaboratory performance based  limits  for
soil and aqueous samples,  and therefore, the single laboratory limits must fall
within those given in Table 8 for these matrices.

            8.4.1  If recovery  is  not within limits, the  following  procedures
      are required.

               8.4.1.1  Check  to be  sure  that  there  are  no errors in  the
            calculations, surrogate solutions or internal  standards.  If errors
            are found,  recalculate the data accordingly.

               8.4.1.2  Check  instrument  performance.     If  an  instrument
            performance problem is identified, correct the problem and re-analyze
            the extract.


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               8.4.1.3  If no problem  is  found,  re-extract and re-analyze the
            sample.

               8.4.1.4  If, upon re-analysis, the recovery is again not within
            limits, flag the data as "estimated concentration".

            8.4.2 At a minimum, each laboratory should update surrogate recovery
      limits on a matrix-by-matrix basis, annually.


9.0  METHOD PERFORMANCE

     9.1   Method 8250 (the packed column version of Method 8270) was tested by
15 laboratories using Organic-free reagent water, drinking water, surface water,
and  industrial  wastewaters  spiked  at  six  concentrations over  the  range 5-
1,300 /xg/L.  Single operator accuracy  and precision, and method accuracy were
found to be directly related to the concentration of the  analyte and essentially
independent  of  the  sample  matrix.   Linear  equations  to  describe  these
relationships are presented in Table 7.  Method performance data for Method 8270
is being developed.


10.0 REFERENCES

1.   U.S. EPA 40 CFR Part  136, "Guidelines Establishing  Test Procedures for the
     Analysis of Pollutants Under the Clean  Water Act, Method 625," October 26,
     1984.

2.   U.S.  EPA   Contract  Laboratory  Program,  Statement of  Work for  Organic
     Analysis,  July 1985,  Revision.

3.   Eichelberger, J.W.,  L.E. Harris,  and W.L.  Budde,  "Reference  Compound to
     Calibrate Ion Abundance Measurement in Gas Chromatography-Mass Spectrometry
     Systems,"  Analytical  Chemistry, 47, 995-1000, 1975.

4.   "Method Detection Limit for Methods 624 and 625," Olynyk, P.,  W.L. Budde,
     and J.W. Eichelberger, Unpublished report, October 1980.

5.   "Interlaboratory Method Study for  EPA Method 625-Base/Neutrals, Acids, and
     Pesticides," Final  Report for EPA Contract 68-03-3102 (in preparation).

6.   Burke,  J.A.   "Gas  Chromatography  for  Pesticide  Residue Analysis;  Some
     Practical   Aspects,"  Journal  of  the Association of  Official  Analytical
     Chemists,  48, 1037, 1965.

7.   Lucas, S.V.;  Kornfeld,  R.A. "GC-MS  Suitability  Testing  of  RCRA Appendix
     VIII and Michigan  List  Analytes  ";  U.S.  Environmental Protection Agency,
     Environmental Monitoring  and Support  Laboratory,  Cincinnati,  OH 45268,
     February 20, 1987,  Contract No. 68-03-3224.

8.   Engel, T.M.;  Kornfeld,  R.A.;  Warner, J.S.; Andrews,  K.D.   "Screening of
     Semi volatile Organic  Compounds for Extractability and. Aqueous Stability by
     SW-846, Method 3510";  U.S.  Environmental Protection Agency, Environmental


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Monitoring  and  Support Laboratory,  Cincinnati,  OH 45268,  June 5,  1987,
Contract 68-03-3224.
                             8270B - 20                      Revision  2
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                                   TABLE 1.
                CHARACTERISTIC IONS FOR SEMIVOLATILE COMPOUNDS
Compound
Retention    Primary   Secondary
Time (min.)  Ion       Ion(s)
2-Picoline
Aniline
Phenol
Bis(2-chloroethyl) ether
2-Chlorophenol
1,3-Dichlorobenzene
l,4-Dichlorobenzene-d4 (I.S.)
1,4-Dichlorobenzene
Benzyl alcohol
1,2-Dichlorobenzene
N-Nitrosomethylethyl ami ne
Bis(2-chloroisopropyl) ether
Ethyl carbamate
Thiophenol (Benzenethiol)
Methyl methanesulfonate
N-Nitrosodi-n-propylamine
Hexachloroethane
Maleic anhydride
Nitrobenzene
Isophorone*
N-Nitrosodiethylamine
2-Nitrophenol
2,4-Dimethylphenol
p-Benzoquinone
Bis(2-chloroethoxy)methane
Benzole acid
2,4-Dichlorophenol
Trimethyl phosphate
Ethyl methanesulfonate
1,2,4-Tri chlorobenzene
Naphthalene-d8 (I.S.)
Naphthalene
Hexachlorobutadi ene
Tetraethyl pyrophosphate
Diethyl sulfate
4-Chloro-3-methylphenol
2-Methyl naphtha!ene
2-Methylphenol
Hexachloropropene
Hexachlorocyclopentadiene
N-Nitrosopyrrolidine
Acetophenone
4-Methylphenol
2,4,6-Trichlorophenol
o-Toluidine
3-Methylphenol
2-Chloronaphthalene
      ,75a
      ,68
      ,77
      ,82
      ,97
      ,27
      ,35
      ,40
      ,78
     6.85
     6.97
       22
       27
       42
       48
       55
       65
       65
       87
     8.53
     8.70
     8.75
     9.
     9.
     9.
     9.
     9.
     9.
     9.
       .03
       13
       ,23
       .38
       .48
       ,53
       .62
     9.67
     9.75
     9.82
    10.43
    11.07
    11.37
    11.68
    11.87
    12.40
    12.45
    12.60
    12.65
    12.67
    12.82
    12.85
    12.87
    12.93
    13.30

8270B - 21
 93     66,92
 93     66,65
 94     65,66
 93     63,95
128     64,130
146     148,111
152     150,115
146     148,111
108     79,77
146     148,111
 88     42,88,43,56
 45     77,121
 62     62,44,45,74
110     110,66,109,84
 80     80,79,65,95
 70     42,101,130
117     201,199
 54     54,98,53,44
 77     123,65
 82     95,138
102     102,42,57,44,56
139     109,65
122     107,121
108     54,108,82,80
 93     95,123
122     105,77
162     164,98
110     110,79,95,109,140
 79     79,109,97,45,65
180     182,145
136     68
128     129,127
225     223,227
 99     99,155,127,81,109
139     139,45,59,99,111,125
107     144,142
142     141
107     107,108,77,79,90
213     213,211,215,117,106,141
237     235,272
100     100,41,42,68,69
105     71,105,51,120
107     107,108,77,79,90
196     198,200
106     106,107,77,51,79
107     107,108,77,79,90
162     127,164

                  Revision  2
                  November 1990

-------
                                   TABLE 1.
                                  (Continued)
Compound
Retention
Time (min.)
Primary
Ion
Secondary
Ion(s)
N-Nitrosopiperidine
1,4-Phenylenediamine
1-Chloronaphthalene
2-Nitroaniline
5-Chloro-2-methylaniline
Dimethyl phthalate
Acenaphthylene
2,6-Dinitrotoluene
Phthalic anhydride
o-Anisidine
3-Nitroaniline
Acenaphthene-d10  (I.S.)
Acenaphthene
2,4-Dinitrophenol
2,6-Dinitrophenol
4-Chloroaniline
Isosafrole
Dibenzofuran
2,4-Diaminotoluene
2,4-Dinitrotoluene
4-Nitrophenol
2-Naphthylamine
1,4-Naphthoquinone
p-Cresidine
Dichlorovos
Diethyl phthalate
Fluorene
2,4,5-Trimethylaniline
N-Nitrosodibutylamine
4-Chlorophenyl phenyl ether
Hydroquinone
4,6-Dinitro-2-methylphenol
Resorcinol
N-Nitrosodiphenylamine
Safrole
Hexamethyl phosphoramide
3-(Chloromethyl)pyridine hydrochloride
Diphenylamine
1,2,4,5-Tetrachlorobenzene
1-Naphthylamine
l-Acetyl-2-thiourea
4-Bromophenyl phenyl ether
Toluene diisocyanate
2,4,5-Trichlorophenol
Hexachlorobenzene
Nicotine
Pentachlorophenol
    13.55     114      42,114,55,56,41
    13.62     108      108,80,53,54,52
    13.65a     162      127,164
    13.75      65      92,138
    14.28     106      106,141,140,77,89
    14.48     163      194,164
    14.57     152      151,153
    14.62     165      63,89
    14.62     104      104,76,50,148
    15.00     108      80,108,123,52
    15.02     138      108,92
    15.05     164      162,160
    15.13     154      153,152
    15.35     184      63,154
    15.47     162      162,164,126,98,63
    15.50     127      127,129,65,92
    15.60     162      162,131,104,77,51
    15.63     168      139
    15.78     121      121,122,94,77,104
    15.80     165      63,89
    15.80     139      109,65
    16.00*     143      115,116
    16.23     158      158,104,102,76,50,130
    16.45     122      122,94,137,77,93
    16.48     109      109,185,79,145
    16.70     149      177,150
    16.70     166      165,167
    16.70     120      120,135,134,91,77
    16.73      84      84,57,41,116,158
    16.78     204      206,141
    16.93     110      110,81,53,55
    17.05     198      51,105
    17.13     110      110,81,82,53,69
    17.17     169      168,167
    17.23     162      162,162,104,77,103,135
    17.33     135      135,44,179,92,42
      17.50     92      92,127,129,65,39
    17.54a     169      168,167
    17.97     216      216,214,179,108,143,218
    18.20     143      143,115,89,63
    18.22     118      43,118,42,76
    18.27     248      250,141
    18.42     174      174,145,173,146,132,91
    18.47     196      196,198,97,132,99
    18.65     284      142,249
    18.70      84      84,133,161,162
    19.25     266      264,268
                                  8270B - 22
                                Revision  2
                                November 1990

-------
                                   TABLE 1.
                                  (Continued)
Compound
Retention
Time (min.)
Primary   Secondary
Ion       Ion(s)
5-Nitro-o-toluidine
Thionazine
4-Nitroaniline
Phenanthrene-d10(i.s.)
Phenanthrene
Anthracene
1,4-Dinitrobenzene
Mevinphos
Naled
1,3-Dinitrobenzene
Diallate (cis or trans)
1,2-Dinitrobenzene
Diallate (trans or cis)
Pentachlorobenzene
5-Nitro-o-anisidine
Pentachloron i trobenzene
4-Nitroquinoline-1-oxide
Di-n-butyl phthalate
2,3,4,6-Tetrachlorophenol
Dihydrosaffrole
Demeton-o
Fluoranthene
1,3,5-Trinitrobenzene
Dicrotophos
Benzidine
Trifluralin
Bromoxynil
Pyrene
Monocrotophos
Phorate
Sulfall ate
Demeton-s
Phenacetin
Dimethoate
Phenobarbital
Carbofuran
Octamethyl pyrophosphoramide
4-Aminobiphenyl
Dioxathion
Terbufos
o,o-Dimethylphenylamine
Pronamide
Aminoazobenzene
Dichlone
Dinoseb
Disulfoton
    19.27     152     77,152,79,106,94
    19.35     107     96,107,97,143,79,68
    19.37     138     138,65,108,92,80,39
    19.55     188     94,80
    19.62     178     179,176
    19.77     178     176,179
    19.83     168     168,75,50,76,92,122
    19.90     127     127,192,109,67,164
    20.03     109     109,145,147,301,79,189
    20.18     168     168,76,50,75,92,122
    20.57      86     86,234,43,70
    20.58     168     168,50,63,74
    20.78      86     86,234,43,70
    21.35     250     250,252,108,248,215,254
    21.50     168     168,79,52,138,153,77
    21.72     237     237,142,214,249,295,265
    21.73     174     174,101,128,75,116
    21.78     149     150,104
    21.88     232     232,131,230,166,234,168
    22.42     135     135,64,77
    22.72      88     88,89,60,61,115,171
    23.33     202     101,203
    23.68      75     75,74,213,120,91,63
    23.82     127     127,67,72,109,193,237
    23.87     184     92,185
    23.88     306     306,43,264,41,290
    23.90     277     277,279,88,275,168
    24.02     202     200,203
    24.08     127     127,192,67,97,109
    24.10      75     75,121,97,93,260
    24.23     188     188,88,72,60,44
    24.30      88     88,60,81,89,114,115
    24.33     108     180,179,109,137,80
    24.70      87     87,93,125,143,229
    24.70     204     204,117,232,146,161
    24.90     164     164,149,131,122
    24.95     135     135,44,199,286,153,243
    25.08     169     169,168,170,115
    25.25      97     97,125,270,153
    25.35     231     231,57,97,153,103
    25.43      58     58,91,65,134,42
    25.48     173     173,175,145,109,147
    25.72     197     92,197,120,65,77
    25.77     191     191,163,226,228,135,193
    25.83     211     211,163,147,117,240
    25.83      88     88,97,89,142,186
                                  8270B - 23
                                Revision 2
                                November 1990

-------
                                   TABLE 1.
                                  (Continued)
Compound
Retention
Time (min.)
Primary   Secondary
Ion       Ion(s)
Mexacarbate
4,4'-Oxydianiline
Butyl benzyl phthalate
4-Nitrobiphenyl
Phosphamidon
2-Cyclohexyl-4,6-Dinitrophenol
Methyl parathion
Carbaryl
Di methyl ami noazobenzene
Propylthiouracil
Benz(a)anthracene
Chrysene-d12  (I.S.)
3,3'-Dichlorobenzidine
Chrysene
Malathion
Kepone
Fenthion
Parathion
Anilazine
Bis(2-ethylhexyl) phthalate
3,3'-Dimethylbenzidine
Carbophenothion
5-Nitroacenaphthene
Methapyrilene
Isodrin
Captan
Chlorfenvinphos
Crotoxyphos
Phosmet
EPN
Tetrachlorvinphos
Di-n-octyl phthalate
2-Aminoanthraquinone
Barban
Aramite
Benzo(b)fluoranthene
Nitrofen
Benzo(k)fluoranthene
Chiorobenzilate
Fensulfothion
Ethion
Diethylstilbestrol
Famphur
Tri-p-tolyl  phosphate"
Benzo(a)pyrene
Perylene-d12  (I.S.)
7,12-Dimethylbenz(a)anthracene
    26.02     165     165,150,134,164,222
    26.08     200     200,108,171,80,65
    26.43     149     91,206
    26.55     199     199,152,141,169,151
    26.85     127     127,264,72,109,138
    26.87     231     231,185,41,193,266
    27.03     109     109,125,263,79,93
    27.17     144     144,115,116,201
    27.50     225     225,120,77,105,148,42
    27.68     170     170,142,114,83
    27.83     228     229,226
    27.88     240     120,236
    27.88     252     254,126
    27.97     228     226,229
    28.08     173     173,125,127,93,158
    28.18     272     272,274,237,178,143,270
    28.37     278     278,125,109,169,153
    28.40     109     109,97,291,139,155
    28.47     239     239,241,143,178,89
    28.47     149     167,279
    28.55     212     212,106,196,180
    28.58     157     157,97,121,342,159,199
    28.73     199     199,152,169,141,115
    28.77      97     97,50,191,71
    28.95     193     193,66,195,263,265,147
    29.47      79     79,149,77,119,117
    29.53     267     267,269,323,325,295
    29.73     127     127,105,193,166
    30.03     160     160,77,93,317,76
    30.11     157     157,169,185,141,323
    30.27     329     109,329,331,79,333
    30.48     149     167,43
    30.63     223     223,167,195
    30.83     222     222,51,87,224,257,153
    30.92     185     185,191,319,334,197,321
    31.45     252     253,125
    31.48     283     283,285,202,139,253
    31.55     252     253,125
    31.77     251     251,139,253,111,141
    31.87     293     293,97,308,125,292
    32.08     231     231,97,153,125,121
    32.15     268     268,145,107,239,121,159
    32.67     218     218,125,93,109,217
    32.75     368     368,367,107,165,198
    32.80     252     253,125
    33.05     264     260,265
    33.25     256     256,241,239,120
                                  8270B  - 24
                                Revision 2
                                November 1990

-------
                                   TABLE 1.
                                  (Continued)
Compound
Retention
Time (min.)
Primary   Secondary
Ion       Ion(s)
5,5-Di phenylhydantoi n
Captafol
Dinocap
Methoxychlor
2-Acetylaminofl uorene
4,4'-Methylenebis(2-chloroaniline)
3,3'-Dimethoxybenzidine
3-Methylcholanthrene
Phosalone
Azinphos-methyl
Leptophos
Mi rex
Tris(2,3-dibromopropyl) phosphate
Dibenz(a,j)acridine
Mestranol
Coumaphos
Indeno(l,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene
l,2:4,5-Dibenzopyrene
Strychnine
Piperonyl sulfoxide
Hexachlorophene
Aldrin
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
a-BHC
/3-BHC
S-BHC
7-BHC (Lindane)
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dieldrin
1,2-Di phenylhydrazi ne
Endosulfan  I
Endosulfan  II
Endosulfan  sulfate
Endrin
Endrin  aldehyde
Endrin  ketone
    33.40     180     180,104,252,223,209
    33.47      79     79,77,80,107
    33.47      69     69,41,39
    33.55     227     227,228,152,114,274,212
    33.58     181     181,180,223,152
    34.38     231     231,266,268,140,195
    34.47     244     244,201,229
    35.07     268     268,252,253,126,134,113
    35.23     182     182,184,367,121,379
    35.25     160     160,132,93,104,105
    35.28     171     171,377,375,77,155,379
    35.43     272     272,237,274,270,239,235
    35.68     201     137,201,119,217,219,199
    36.40     279     279,280,277,250
    36.48     277     277,310,174,147,242
    37.08     362     362,226,210,364,97,109
    39.52     276     138,227
    39.82     278     139,279
    41.43     276     138,277
    41.60     302     302,151,150,300
    45.15     334     334,335,333
    46.43     162     162,135,105,77
    47.98     196     196,198,209,211,406,408
               66     263,220
              222     260,292
              190     224,260
              190     224,260
              222     256,292
              292     362,326
              292     362,326
              360     362,394
              183     181,109
              181     183,109
              183     181,109
              183     181,109
              235     237,165
              246     248,176
              235     237,165
               79     263,279
               77     105,182
              195     339,341
              337     339,341
              272     387,422
              263     82,81
               67     345,250
              317     67,319
                                  8270B  -  25
                                Revision 2
                                November 1990

-------
                                   TABLE 1.
                                  (Continued)
                                   Retention     Primary   Secondary
Compound                           Time  (min.)   Ion       Ion(s)
2-Fluorobiphenyl (surr.)                --        172    171
2-Fluorophenol (surr.)                  --        112    64
Heptachlor                              --        100    272,274
Heptachlor epoxide                      --        353    355,351
Nitrobenzene-d5 (surr.)                 --         82    128,54
N-Nitrosodimethylamine                  --         42    74,44
Phenol-de (surr.)                        --         99    42,71
Terphenyl-d14  (surr.)                    --        244    122,212
2,4,6-Tribromophenol  (surr.)            --        330    332,141
Toxaphene                               --        159    231,233
I.S. = internal standard.
surr. = surrogate.
"Estimated retention times.
"Substitute for the non-specific mixture, tricresyl phosphate.
                                  8270B  -  26                       Revision  2
                                                                   November 1990

-------
                           TABLE  2.
ESTIMATED QUANTITATION LIMITS (EQLs) FOR SEMIVOLATILE ORGANICS"

                                       Estimated
                                      Quantitation
                                           Limits"
Ground water
Semivolatiles /ig/L
Acenaphthene
Acenaphthylene
Acetophenone
2-Acetyl ami nof 1 uorene
l-Acetyl-2-thiourea
2-Ami noanthraqui none
Aminoazobenzene
4-Aminobiphenyl
Anilazine
o-Anisidine
Anthracene
Aramite
Azinphos-methyl
Barban
Benz(a)anthracene
Benzo (b) f 1 uoranthene
Benzo(k)fluoranthene
Benzoic acid
Benzo (g,h,i)perylene
Benzo(a)pyrene
p-Benzoquinone
Benzyl alcohol
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
4-bromophenyl phenyl ether
Bromoxynil
Butyl benzyl phthalate
Captafol
Captan
Carbaryl
Carbofuran
Carbophenothion
Chlorfenvinphos
4-Chloroaniline
Chi orobenzi late
5-Chloro-2-methyl aniline
4-Chl oro-3-methyl phenol
3-(Chloromethyl)pyridine hydrochloride
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Coumaphos
10
10
10
20
1000
20
10
20
100
10
10
20
100
200
10
10
10
50
10
10
10
20
10
10
10
10
10
10
20
50
10
10
10
20
20
10
10
20
100
10
10
10
10
40
Low Soil /Sediment1
M9/Kg
660
660
ND
ND
ND
ND
ND
ND
ND
ND
660
ND
ND
ND
660
660
660
3300
660
660
ND
1300
660
660
660
660
ND
660
ND
ND
ND
ND
ND
ND
1300
ND
ND
1300
ND
660
660
660
660
ND
                          8270B  -  27                       Revision 2
                                                           November 1990

-------





TABLE 2.
(Continued)





Estimated
Quantisation
Limits"
Ground water Low Soil/Sediment1
Semivolatiles
p-Cresidine
Crotoxyphos
2-Cyc1ohexyl-4,6-dinitrophenol
Demeton-o
Demeton-s
Dial late (cis or trans)
Diallate (trans or cis)
2,4-Dianrinotoluene
Dibenz(a,j)acridine
Dibenz (a, h) anthracene
Dibenzofuran
Dibenzo(a,e)pyrene
Di-n-butyl phthalate
Dichlone
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos
Dicrotophos
Di ethyl phthalate
Diethylstilbestrol
Di ethyl sulfate
Dimethoate
3,3'-Dimethoxybenzidine
Dimethyl ami noazobenzene
7,12-Dimethylbenz(a)anthracene
3, 3' -Dimethyl benzi dine
a, a-Dimethyl phenethyl ami ne
2,4-Dimethylphenol
Dimethyl phthalate
1,2-Dinitrobenzene
1,3-Dinitrobenzene
1,4-Dinitrobenzene
4, 6-Dinitro-2-methyl phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap
Dinoseb
5, 5-Diphenyl hydantoi n
Di-n-octyl phthalate
M9/L
10
20
100
10
10
10
10
20
10
10
10
10
10
NA
10
10
10
20
10
10
10
10
10
20
100
20
100
10
10
10
ND
10
10
40
20
40
50
50
10
10
100
20
20
10
M9/Kg
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
660
ND
ND
ND
660
660
660
1300
660
ND
ND
ND
660
ND
ND
ND
ND
ND
ND
ND
ND
660
660
ND
ND
ND
3300
3300
660
660
ND
ND
ND
660
8270B - 28
Revision 2
November 1990

-------





TABLE 2.
(Continued)





Estimated
Quantitation
Limits"
Ground water Low Soil/Sediment1
Semi vol allies
Disulfoton
EPN
Ethion
Ethyl carbamate
Bis(2-ethylhexyl) phthalate
Ethyl methanesulfonate
Famphur
Fensulfothion
Fenthion
Fluchloralin
Fluoranthene
Fluorene
Hexachlorobenzene
Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachloroethane
Hexachl orophene
Hexachl oropropene
Hexamethyl phosphoramlde
Hydroquinone
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
Isosafrole
Kepone
Leptophos
Malathion
Maleic anhydride
Mestranol
Methapyrilene
Methoxychlor
3-Methyl chol anthrene
4,4'-Methylenebis(2-chloroanil
Methyl methanesulfonate
2-Methyl naphthal ene
Methyl parathion
2 -Methyl phenol
3-Methyl phenol
4-Methyl phenol
Mevinphos
Mexacarbate
Mi rex
Monocrotophos
Naled
M9/L
10
10
10
50
10
20
20
40
10
20
10
10
10
10
10
10
50
10
20
ND
10
20
10
10
20
10
50
NA
20
100
10
10
ine) NA
10
10
10
10
10
10
10
20
10
40
20
MQ/Kg
ND
ND
ND
ND
660
ND
ND
ND
ND
ND
660
660
660
660
660
660
ND
ND
ND
ND
660
ND
660
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
ND
660
ND
660
ND
ND
ND
ND
ND
8270B - 29                       Revision  2
                                 November 1990

-------






Senrivolatiles
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
5-Nitro-o-toluidine
4-Nitroquinol ine-1-oxide
N-Nitrosodi butyl ami ne
N-Ni trosodi ethyl ami ne
N-Nitrosodiphenylamine
N-Nitroso-di-n-propylamine
N-Nitrosopiperidine
N-Nitrosopyrrol idine
Octamethyl pyrophosphoramide
4,4'-Oxydianiline
Parathion
Pentachl orobenzene
Pentachl oron i trobenzene
Pentachl orophenol
Phenacetin
Phenanthrene
Phenobarbital
Phenol
1,4-Phenylenediamine
Phorate
Phosalone
Phosmet
Phosphamidon
Phthalic anhydride
2-Picoline
Piperonyl sulfoxide
Pronamide
Propylthiouracil
Pyrene
TABLE 2.
(Continued)
Estimated
Quantitation
Limits"
Ground water Low Soi
M9/L
10
10
10
10
20
10
50
50
20
10
10
10
20
10
50
10
40
10
20
10
10
20
40
200
20
10
10
20
50
20
10
10
10
10
10
100
40
100
100
ND
100
10
100
10





1 /Sediment1
M9/Kg
660
ND
ND
ND
ND
ND
3300
3300
ND
ND
660
ND
ND
660
3300
ND
ND
ND
ND
660
660
ND
ND
ND
ND
ND
ND
ND
3300
ND
660
ND
660
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
8270B - 30
Revision 2
November 1990

-------
                                   TABLE 2.
                                  (Continued)
                                               Estimated
                                              Quantitation
                                                 Limits"
Semivolatiles
                                      Ground waterLow Soil/Sediment1
Pyridine
Resorcinol
Safrole
Strychnine
Sul fall ate
Terbufos
1,2,4, 5-Tetrachl orobenzene
2,3,4 , 6-Tetrachl orophenol
Tetrachlorvinphos
Tetraethyl pyrophosphate
Thionazine
Thiophenol (Benzenethiol)
Toluene diisocyanate
o-Toluidine
1 , 2 , 4-Tri chl orobenzene
2, 4, 5-Trichl orophenol
2, 4, 6-Tri chl orophenol
Trifluralin
2,4,5-Trimethylaniline
Trimethyl phosphate
1,3,5-Trinitrobenzene
Tris(2,3-dibromopropyl ) phosphate
Tri-p-tolyl phosphate(h)
0,0,0-Tri ethyl phosphorothioate
ND
100
10
40
10
20
10
10
20
40
20
20
100
10
10
10
10
10
10
10
10
200
10
NT
NO
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
660
660
660
ND
ND
ND
ND
ND
ND
ND
a EQLs  listed for  soil/sediment  are based on  wet weight.   Normally data is
  reported  on a  dry weight basis, therefore,  EQLs will be higher based on the
  %  dry weight  of  each  sample.    This  is  based on  a 30  g sample  and gel
  permeation  chromatography  cleanup.
b Sample EQLs are highly matrix-dependent.  The EQLs  listed herein are provided
  for guidance and  may  not always be achievable.
ND = Not determined.
NA = Not applicable.
NT = Not tested.
Other Matrices                                       Factor1

High-concentration soil and sludges by  sonicator      7.5
Non-water miscible waste                             75

1EQL = [EQL for Low Soil/Sediment (Table 2)] X [Factor].
                                  8270B  - 31
Revision 2
November 1990

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                                   TABLE 3.
                  DFTPP KEY  IONS AND  ION ABUNDANCE CRITERIA3
       Mass
Ion Abundance Criteria
       51

       68
       70

      127

      197
      198
      199

      275

      365

      441
      442
      443
30-60% of mass 198

< 2% of mass 69
< 2% of mass 69

40-60% of mass 198

< 1% of mass 198
Base peak, 100% relative abundance
5-9% of mass 198

10-30% of mass 198

> 1% of mass 198

Present but less than mass 443
> 40% of mass 198
17-23% of mass 442
   "See  Reference 4.
                                   TABLE 4.
                          CALIBRATION CHECK COMPOUNDS
Base/Neutral Fraction
                  Acid Fraction
Acenaphthene
1,4-Di chlorobenzene
Hexachlorobutadi ene
N-Ni trosodi phenylami ne
Di-n-octyl phthalate
Fluoranthene
Benzo(a)pyrene
                  4-Chloro-3-methylphenol
                  2,4-Dichlorophenol
                  2-Nitrophenol
                  Phenol
                  Pentachlorophenol
                  2,4,6-Trichlorophenol
                                  8270B - 32
                                          Revision 2
                                          November 1990

-------
                                   TABLE 5.
          SEMIVOLATILE INTERNAL STANDARDS  WITH CORRESPONDING ANALYTES
                           ASSIGNED FOR QUANTITATION
l,4-Dich1orobenzene-d4
Naphthalene-d8
Acenaphthene-d10
Aniline
Benzyl alcohol
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
2-Chlorophenol
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
Ethyl methanesulfonate
2-Fluorophenol (surr.)
Hexachloroethane
Methyl methanesulfonate
2-Methylphenol
4-Methylphenol
N-Nitrosodimethylamine
N-Nitroso-di-n-propylamine
Phenol
Phenol-d6 (surr.)    ,
2-Picoline
Acetophenone
Benzoic acid
Bis(2-chloroethoxy)methane
4-Chloroaniline
4-Chloro-3-methylphenol
2,4-Dichlorophenol
2,6-Dichlorophenol
a,a-Dimethyl-
  phenethylamine
2,4-Dimethylphenol
Hexachlorobutadiene
Isophorone
2-Methylnaphthalene
Naphthalene
Nitrobenzene
Nitrobenzene-d8 (surr.)
2-Nitrophenol
N-Nitrosodibutyl amine
N-Nitrosopiperidine
1,2,4-Tri chlorobenzene
 Acenaphthene
 Acenaphthylene
 1-Chloronaphthalene
 2-Chloronaphthalene
 4-Chlorophenyl
   phenyl  ether
 Dibenzofuran
 Diethyl phthalate
 Dimethyl  phthalate
 2,4-Dinitrophenol
 2,4-Dinitrotoluene
 2,6-Dinitrotoluene
 Fluorene
 2-Fluorobiphenyl
   (surr.)
 Hexachlorocyclo-
   pentadiene
 1-Naphthylamine
 2-Naphthylamine
 2-Nitroaniline
 3-Nitroaniline
 4-Nitroaniline
 4-Nitrophenol
 Pentachlorobenzene
 1,2,4,5-Tetra-
   chlorobenzene
 2,3,4,6-Tetra-
   chlorophenol
 2,4,6-Tribromo-
   phenol  (surr.)
 2,4,6-Trichloro-
   phenol
 2,4,5-Trichloro-
   phenol
(surr.) = surrogate
                                  8270B - 33
                                      Revision  2
                                      November 1990

-------
                                   TABLE 5.
                                  (Continued)
Phenanthrene-d
              10
Chrysene-d12
Perylene-d12
4-Aminobiphenyl
Anthracene
4-Bromophenyl phenyl ether
Di-n-butyl phthalate
4,6-Dinitro-2-methylphenol
Diphenylamine
1,2-Diphenylhydrazi ne
Fluoranthene
Hexachlorobenzene
N-Ni trosodi phenylami ne
Pentachlorophenol
Pentachloronitrobenzene
Phenacetin
Phenanthrene
Pronamide
 Benzidine
 Benzo(a)anthracene
 Bis(2-ethylhexyl)  phthalate
 Butyl  benzyl  phthalate
 Chrysene
 3,3'-Dichlorobenzidine
 p-Dimethylaminoazobenzene
 Pyrene
 Terphenyl-d14 (surr.)
  Benzo(b)fluor-
    anthene
  Benzo(k)fluor-
      anthene
  Benzo(g,h,i)-
    perylene
  Benzo(a)pyrene
  Dibenz(a,j)acridine
  Dibenz(a,h)-
    anthracene
  7,12-Dimethylbenz-
    (a)anthracene
  Di-n-octyl  phthalate
  Indeno(l,2,3-cd)
    pyrene
  3-Methylchol-
   anthrene
(surr.) = surrogate
                                  8270B - 34
                                      Revision 2
                                      November 1990

-------
       TABLE  6.
QC ACCEPTANCE CRITERIA8
Compound
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benz(a)anthracene
Benzo(b)fl uoranthene
Benzo(k)fl uoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Benzyl butyl phthalate
0-BHC
fi-BHC
Bis(2-chloroethyl) ether
Bis(2-chloroethoxy)methane
Bis(Z-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
D1benzo(a,h) anthracene
Di-n-butyl phthalate
1 , 2-Di chl orobenzene
1,3-Dichlorobenzene
1 , 4-Di chl orobenzene
3,3'-Dichlorobenzidine
Dieldrln
Di ethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di -n-octyl phthal ate
Endosulfan sulfate
Endrin aldehyde
Fl uoranthene
Fluorene
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachlorobutadiene
Test
cone.
(M9/L)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
Limit
for s
(M9/L)
27.6
40.2
39.0
32.0
27.6
38.8
32.3
39.0
58.9
23.4
31.5
21.6
55.0
34.5
46.3
41.1
23.0
13.0
33.4
48.3
31.0
32.0
61.6
70.0
16.7
30.9
41.7
32.1
71.4
30.7
26.5
23.2
21.8
29.6
31.4
16.7
32.5
32.8
20.7
37.2
54.7
24.9
26.3
Range
for x
(M9/L)(%)
60.1-132.3
53.5-126.0
7.2-152.2
43.4-118.0
41.8-133.0
42.0-140.4
25.2-145.7
31.7-148.0
D-195.0
D-139.9
41.5-130.6
D-100.0
42.9-126.0
49.2-164.7
62.8-138.6
28.9-136.8
64.9-114.4
64.5-113.5
38.4-144.7
44.1-139.9
D-134.5
19.2-119.7
D-170.6
D-199.7
8.4-111.0
48.6-112.0
16.7-153.9
37.3-105.7
8.2-212.5
44.3-119.3
D-100.0
D-100.0
47.5-126.9
68.1-136.7
18.6-131.8
D-103.5
D-188.8
42.9-121.3
71.6-108.4
D-172.2
70.9-109.4
7.8-141.5
37.8-102.2
8270B - 35
Range
P» Ps
47-145
33-145
D-166
27.133
33-143
24-159
11-162
17-163
D-219
D-152
24-149
D-110
12-158
33-184
36-166
8-158
53-127
60-118
25-158
17-168
D-145
4-136
D-203
D-227
1-118
32-129
D-172
20-124
D-262
29-136
D-114
D-112
39-139
50-158
4-146
D-107
D-209
26-137
59-121
D-192
26.155
D-152
24-116
Revision 2
                                       November 1990

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Compound
Hexachloroethane
Indeno(l,2,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Nitrosodi-n-propylamine
PCB-1260
Phenanthrene
Pyrene
1 , 2 , 4-Tri chl orobenzene
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-Chlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl -4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
s = Standard deviation of
x = Average recovery for


Test
cone
TABLE 6.
(Continued)
Limit
for s


Range
for x
(M9/L) (M9/L) (M9/L)(%)
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
four
four
24.5
44.6
63.3
30.1
39.3
55.4
54.2
20.6
25.2
28.1
37.2
28.7
26.4
26.1
49.8
93.2
35.2
47.2
48.9
22.6
31.7
55.2-100.0
D-150.9
46.6-180.2
35.6-119.6
54.3-157.6
13.6-197.9
19.3-121.0
65.2-108.7
69.6-100.0
57.3-129.2
40.8-127.9
36.2-120.4
52.5-121.7
41.8-109.0
D-172.9
53.0-100.0
45.0-166.7
13.0-106.5
38.1-151.8
16.6-100.0
52.4-129.2
recovery measurements, in
recovery measurements, in


Range
P» Ps

40-113
D-171
21-196
21-133
35-180
D-230
D-164
54-120
52-115
44-142
22-147
23-134
39-135
32-119
D-191
D-181
29-182
D-132
14-176
5-112
37-144
M9/L.
M9/L.
p, ps = Percent recovery measured.
D = Detected; result must
a Criteria from 40 CFR
be greater than
Part
zero.
136 for Method 625. These

criteria are based
directly on the method performance data in Table 7.  Where necessary, the
limits for recovery have  been  broadened  to  assure  applicability of the
limits to concentrations below those used to develop Table 7.
                           8270B - 36
Revision 2
November 1990

-------
                                   TABLE 7.
          METHOD ACCURACY AND PRECISION AS FUNCTIONS OF CONCENTRATION8
Compound
Accuracy, as
recovery, x'
(M9/L)
Single analyst   Overall
precision, s/  precision,
              S'  (Mg/L)
Acenaphthene
Acenaphthylene
Aldrin
Anthracene
Benz(a)anthracene
Chloroethane
Benzo(b)fluoranthene
Benzo ( k) f 1 uoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Benzyl butyl phthalate
0-BHC
6-BHC
Bis(2-chloroethyl) ether
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dibenzo(a,h) anthracene
Di-n-butyl phthalate
1,2-Dichlorobenzene
1 , 3-Di chl orobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
Dieldrin
Di ethyl phthalate
Dimethyl phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Endosulfar* sulfate
Endr in "aldehyde
Fl uoranthene
Fluorene
Heptachlor
Heptachlor epoxide
0.96C+0.19
0.89C+0.74
0.78C+1.66
0.80C+0.68
0.88C-0.60
0.99C-1.53
0.93C-1.80
0.87C-1.56
0.90C-0.13
0.98C-0.86
0.66C-1.68
0.87C-0.94
0.29C-1.09
0.86C-1.54
1.12C-5.04
1.03C-2.31
0.84C-1.18
0.91C-1.34
0.89C+0.01
0.91C+0.53
0.93C-1.00
0.56C-0.40
0.70C-0.54
0.79C-3.28
0.88C+4.72
0.59C+0.71
0.80C+0.28
0.86C-0.70
0.73C-1.47
1.23C-12.65
0.82C-0.16
0.43C+1.00
0.20C+1.03
0.92C-4.81
1.06C-3.60
0.76C-0.79
0.39C+0.41
0.76C-3.86
0.81C+1.10
0.90C-0.00
0.87C-2.97
0.92C-1.87
O.lBx-0.12
0.24X-1.06
0.27X-1.28
0.21X-0.32
O.lBx+0.93
0.14x-0.13
0.22X+0.43
0.19X+1.03
0.22x+0.48
0.29X+2.40
O.lSx+0.94
0.20X-0.58
0.34X+0.86
0.35X-0.99
0.16X+1.34
0.24X+0.28
0.26X+0.73
0.13X+0.66
0.07X+0.52
0.20X-0.94
0.28X+0.13
0.29X-0.32
0.26x-1.17
0.42X+0.19
0.30X+8.51
O.lSx+1.16
0.20X+0.47
0.25X+0.68
0.24X+0.23
0.28X+7.33
fl.20x-0.16
0.28X+1.44
0.54X+0.19
0.12X+1.06
0.14X+1.26
0.21X+1.19
0.12X+2.47
O.lSx+3.91
0.22X-0.73
0.12X+0.26
0.24X-0.56
0.33X-0.46
0.21X-0.67
0.26X-0.54
0.43X+1.13
0.27X-0.64
0.26X-0.21
0.17X-0.28
0.29X+0.96
0.35X+0.40
0.32X+1.35
O.Blx-0.44
0.53X+0.92
0.30X+1.94
0.93X-0.17
0.35X+0.10
0.26X+2.01
0.25X+1.04
0.36X+0.67
0.16X+0.66
0.13X+0.34
0.30X-0.46
0.33X-0.09
0.66X-0.96
0.39X-1.04
0.65X-0.58
0.59X+0.25
0.39X+0.60
0.24X+0.39
0.41X+0.11
0.29X+0.36
0.47X+3.45
0.26x-0.07
0.52X+0.22
1.05X-0.92
0.21X+1.50
0.19X+0.35
0.37X+1.19
0.63X-1.03
0.73X-0.62
0.28X-0.60
0.13X+0.61
0.50X-0.23
0.28X+0.64
                                  8270B  - 37
                                    Revision  2
                                    November 1990

-------
                                   TABLE 7.
                                  (Continued)
Compound
Accuracy, as
recovery, x'
(M9/L)
Single analyst   Overall
precision, s/  precision,
 (M9/L)       S'  (Mg/L)
Hexachlorobenzene
Hexachlorobutadiene
Hexachloroethane
Indeno(l,2,3-cd)pyrene
Isophorone
Naphthalene
Nitrobenzene
N-Nitrosodi-n-propylamine
PCB-1260
Phenanthrene
Pyrene
1 , 2 , 4-Tri chl orobenzene
4-Chl oro-3-methyl phenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Methyl -4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
0.74C+0.66
0.71C-1.01
0.73C-0.83
0.78C-3.10
1.12C+1.41
0.76C+1.58
1.09C-3.05
1.12C-6.22
0.81C-10.86
0.87C+0.06
0.84C-0.16
0.94C-0.79
0.84C+0.35
0.78C+0.29
0.87C-0.13
0.71C+4.41
0.81C-18.04
1.04C-28.04
0.07C-1.15
0.61C-1.22
0.93C+1.99
0.43C+1.26
0.91C-0.18
0.18X-0.10
0.19X+0.92
O.Ux+0.67
0.29x+1.46
0.27X+0.77
0.21X-0.41
0.19X+0.92
0.27X+0.68
0.35X+3.61
0.12x+0.57
0.16X+0.06
O.lSx+0.85
0.23x+0.75
O.lSx+1.46
0.15X+1.25
0.16X+1.21
0.38X+2.36
O.lOx+42.29
0.16X+1.94
0.38x+2.57
0.24x+3.03
0.26X+0.73
0.16X+2.22
0.43X-0.52
0.26X+0.49
0.17X+0.80
O.BOx-0.44
0.33X+0.26
0.30X-0.68
0.27X-1-0.21
0.44X+0.47
0.43X+1.82
0.15X+0.25
O.lBx+0.31
0.21X+0.39
0.29X+1.31
0.28X+0.97
0.21X+1.28
0.22X+1.31
0.42X+26.29
0.26X+23.10
0.27X+2.60
0.44X+3.24
0.30X+4.33
0.35X+0.58
0.22X+1.81
x' =   Expected recovery for one or more measurements of a sample containing a
       concentration of C, in jug/L.

s/=    Expected single analyst standard deviation  of measurements at an average
       concentration of x, in /xg/L.

S' =   Expected interlaboratory_ standard deviation of measurements at an average
       concentration found of x, in M9/L.

C  =   True value for the concentration, in M9/L.

x" =    Average  recovery  found  for  measurements  of  samples  containing  a
       concentration of C, in
                                  8270B - 38
                                    Revision 2
                                    November 1990

-------
                                   TABLE 8.
      SURROGATE SPIKE RECOVERY LIMITS FOR WATER AND SOIL/SEDIMENT SAMPLES
                                      Low/High                Low/High
  Surrogate Compound                    Water               Soil/Sediment
Nitrobenzene-d5                        35-114                   23-120
2-Fluorobiphenyl                       43-116                   30-115
p-Terphenyl-d14                         33-141                   18-137
Phenol-d6                               10-94                    24-113
2-Fluorophenol                         21-100                   25-121
2,4,6-Tribromophenol                   10-123                   19-122
                                  8270B - 39                      Revision 2
                                                                  November 1990

-------
                                   TABLE 9.
                            METHOD PERFORMANCE  DATA
                                         PERCENT RECOVERY      PERCENT RECOVERY
COMPOUND                                    ON  DAY  0              ON  DAY  7
                                         AV6.       RSD         AVG.    RSD
3-Amino-9-ethylcarbazole                 80         8           73      3
4-Chloro-l,2-phenylenediamine            91         1          108      4
4-Chloro-l,3-phenylenediamine            84         3           70      3
l,2-Dibromo-3-chloropropane              97         2           98      5
2-sec-Butyl-4,6-dinitrophenol            99         3           97      6
Ethyl parathion                          100         2          103      4
4,4'-Methylenebis(N,N-dimethylaniline)   108         4           90      4
2-Methyl-5-nitroaniline                  99        10           93      4
2-Methylpyridine                         80         4           83      4
Tetraethyl dithiopyrophosphate           92         7           70      1
                                  8270B - 40                      Revision 2
                                                                  November 1990

-------
  00
  rv>
  ^i
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-------
                         METHOD 8270B
GAS  CHROMATOGRAPHY/MASS  SPECTROMETRY FOR SEMIVOLATILE
          ORGANICS: CAPILLARY COLUMN TECHNIQUE
    7 1 Prepare
   sample using
    Method 3540
     or 3550
 7  1 Prepare
sample using
 Method 3510
 or 3520
                           7.1 Prepare
                          sample using
                          Method 3540,
                          3550 or 3580.
                           7  2 Cleanup
                           en tract.
                          7.3 Set CC/MS
                            operating
                           condi tions.
                         Perform initial
                          calibration.
                        7 4 Perform daily
                        calibration Kith
                         SPCCs and CCCs
                        prior to analysis
                           of samples.
                          8270B  -  42
                  Revision  2
                  November 1990

-------
                     METHOD 8270B
                      (Continued)
7.S.4  Diluti
   e»tract
                        7.5 1 Screen
                      extract on  CC/FID
                        or CC/PID to
                      eliminate samples
                        that are  too
                        concentra ted.
                        7 5.3 Analyze
                      extract by  CC/HS,
                      using appripriate
                        fused - si 1ica
                      capillary column
                       7 6 1 Identify
                         analyte by
                        comparing the
                      sample and standard
                        mass spectra.
                        762 Calculate
                       concentration  of
                        each individual
                        analyte  Report
                          results.
                     c
Stop
                       8270B  -  43
                                    Revision  2
                                    November 1990

-------
                                  METHOD  8275

                 THERMAL CHROMATOGRAPHY/MASS SPECTROMETRY FOR
                   SCREENING SEMIVOLATILE ORGANIC CHEMICALS
1.0  SCOPE AND APPLICATION

      1.1  Method  8275  Is  a screening  technique that  may be  used for  the
qualitative identification of semivolatile organic compounds in extracts prepared
from nonaqueous solid wastes and soils. Direct injection of a sample may be used
in limited applications.  The following analytes  can be qualitatively determined
by this method:
     Compound Name                        CAS No."


     2-Chlorophenol                        95-57-8
     4-Methylphenol                       106-44-5
     2,4-Dichlorophenol                   120-83-2
     Naphthalene                           91-20-3
     4-Chloro-3-methylphenol               59-50-7
     1-Chloronaphthalene                   90-13-1
     2,4-Dinitrotoluene                   121-14-2
     Fluorene                              86-73-7
     Diphenylamine                        122-39-4
     Hexachlorobenzene                    118-74-1
     Dibenzothiophene                     132-65-0
     Phenanthrene                          85-01-8
     Carbazole                             86-74-8
     Aldrin                               309-00-2
     Pyrene                               129-00-0
     Benzo(k)fluoranthene                 207-08-9
     Benzo(a)pyrene                        50-32-8


     a   Chemical  Abstract Services  Registry  Number.


      1.2  Method  8275  can be  used to  qualitatively identify most  neutral,
acidic, and basic organic compounds that can be thermally desorbed from a sample,
and are capable of  being eluted without derivatization as sharp  peaks from a gas
chromatographic  fused-silica  capillary  column  coated  with  a  slightly  polar
silicone.

      1.3  This  method  is restricted  to use by or  under the  supervision  of
analysts experienced  in  the use  of gas chromatograph/mass  spectrometers  and
skilled  in  the interpretation  of mass spectra. Each  analyst must demonstrate
the ability to generate acceptable results with this method.
                                   8275 - 1                       Revision 0
                                                                  November 1990

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2.0  SUMMARY OF METHOD

      2.1  A portion  of the sample  (0.010-0.100  g)  is weighed  into  a sample
crucible.   The crucible is  placed  in a  pyrocell  and heated.   The compounds
desorbed from the sample are detected using a flame ionization detector (FID).
The FID response is used to  calculate the optimal  amount  of sample needed for
mass spectrometry.   A  second  sample  is desorbed and the compounds are condensed
on the head of a fused  silica  capillary  column.   The  column is heated using a
temperature program, and the effluent from the column is introduced into the mass
spectrometer.


3.0  INTERFERENCES

      3.1  Contamination by carryover can occur whenever low-level samples are
analyzed after high-level samples.   Whenever  an  unusually concentrated sample
is encountered,  it should  be  followed  by the analysis  of an  empty  (clean)
crucible to check for cross contamination.
4.0  APPARATUS AND MATERIALS

      4.1  Thermal Chromatograph (TC) System

            4.1.1  Thermal chromatograph™,  Ruska  Laboratories,  or  equivalent.

            4.1.2  Column  -  30 m  x  0.25 mm  ID  (or  0.32  mm  ID),  1 ^m  film
      thickness, silicone-coated,  fused-silica capillary column  (J&W Scientific
      DB-5 or equivalent).

           4.1.3  Flame Ionization detector (FID).

      4.2  Mass Spectrometer (MS)  system

            4.2.1 Mass Spectrometer  -  Capable  of  scanning  from 35  to  500 amu
      every one second or less,  using 70 volts (nominal) electron energy in the
      electron impact ionization mode.

            4.2.2  TC/MS interface - Any GC-to-MS interface producing acceptable
      calibration data in the concentration range  of interest may be used.

            4.2.3  Data  System  -  A  computer  must be  interfaced  to the  mass
      spectrometer.  The data system must allow the continuous acquisition and
      storage on machine-readable  media of all mass spectra obtained throughout
      the duration  of the  chromatographic  program.    The  computer  must  have
      software that can search any GC/MS data file for ions of a specific  mass
      (or group of masses) and  that can plot such  ion abundances versus time or
      scan  number.    This type  of  plot  is defined  as a reconstructed  ion
      chromatogram  (RIC).   Software must  also be  available  that  allows  for
      integration of the  abundances in, and RIC  between, specified time or scan-
      number limits.
                                   8275 - 2                       Revision 0
                                                                  November 1990

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      4.3  Tools and equipment
            4.3.1  Fused quartz spatula.
            4.3.2  Fused quartz incinerator ladle.
            4.3.3  Metal forceps for sample crucible.
            4.3.4  Sample crucible storage dishes.
            4.3.5  Porous fused quartz sample crucibles with lids.
            4.3.6  Sample crucible cleaning incinerator.
            4.3.7  Cooling rack.
            4.3.8  Microbalance, 1 g capacity, 0.000001 g sensitivity,
      Mettler Model M-3 or equivalent.
     4.4  Vials -  10 ml, glass with Teflon lined screw-caps or crimp tops.
     4.5  Volumetric flasks, Class A - 10 ml to 1000 ml.

5.0  REAGENTS
      5.1  Reagent grade chemicals shall be used in all  tests.  Unless otherwise
indicated, it is intended that  all  reagents shall conform to the specifications
of the Committee on Analytical  Reagents  of the American Chemical Society, where
such specifications are available.
      5.2  Solvents
            5.2.1  Methanol, CH3OH -  Pesticide  grade or equivalent.
            5.2.2  Acetone, CH3COCH3  - Pesticide grade or equivalent.
            5.2.3  Toluene, C6H5CH3 -  Pesticide grade or equivalent.
            5.2.4  Methylene chloride, CH2C12 - Pesticide grade or equivalent.
            5.2.5  Carbon disulfide,  CS2 - Pesticide grade  or  equivalent.
            5.2.6  Hexane, C6H14 -  Pesticide grade or equivalent.
            5.2.7  Other suitable solvents - Pesticide grade or equivalent.
      5.3  Stock Standard solutions  - Standard  solutions may  be prepared from
pure standard materials or purchased as certified solutions.
            5.3.1  Prepare stock standard solutions  by weighing about 0.01 g of
      pure material.   Dissolve the material  in pesticide  quality acetone, or
      other suitable solvent, and dilute to 10 ml in  a volumetric flask.  Larger
      volumes may be used at the convenience of the analyst.
                                   8275 - 3                       Revision 0
                                                                  November  1990

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            5.3.2  Transfer the stock standard solutions into glass vials with
      Teflon lined  screw-caps  or crimp tops.   Store at 4°C  and  protect from
      light.  Stock standard solutions  should  be checked frequently for signs
      of degradation or evaporation, especially prior to use in preparation of
      calibration standards.

            5.3.3  Stock standard solutions must  be  replaced  after 1 year, or
      sooner  if comparison  with quality  control check  samples  indicates  a
      problem.

      5.4  Internal Standard solutions - The internal standards recommended are
l,4-dichlorobenzene-d4,   naphthalene-da,   acenaphthene-d10,   phenanthrene-d10,
chrysene-d12, and perylene-d12.  Other compounds may be used as internal standards
as long as the requirements given in Section 7  are met.  Dissolve about 0.200 g
of each compound with a small volume of carbon disulfide.  Transfer to a 50 ml
volumetric flask and dilute to volume with methylene chloride,  so that the final
solvent is approximately 20/80  (V/V) carbon disulfide/methylene chloride.  Most
of the  compounds are  also  soluble  in small  volumes of  methanol,  acetone, or
toluene, except for perylene-d12.  Prior  to each analysis, evaporate about 10 nl
of the internal  standard onto the lid  of the crucible.  Store internal standard
solutions at 4°C or less before, and between,  use.

      5.5  Calibration  standards -  Prepare  calibration standards  within  the
working range of the TC/MS system.   Each  standard should contain each analyte
or interest (e.g.   some or all of  the  compounds  listed  in  Section 1.1  may be
included).  Each aliquot of calibration  standard  should be spiked with internal
standards prior to analysis. Stock  solutions should be stored at -10°C to -20°C
and should be freshly prepared once a year, or sooner if check standards indicate
a problem.  The  daily calibration standard should be prepared weekly, and stored
at 4°C.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See  the  introductory material  to  this Chapter,  Organic Analytes,
Section 4.1.
7.0  PROCEDURE

      7.1  Crucible Preparation

            7.1.1  Turn  on  the incinerator  and  let  it  heat for  at  least 10
      minutes.  The bore of the incinerator should be glowing red.

            7.1.2  Load the sample crucible and lid into the incinerator ladle
      and  insert  into the incinerator  bore.   Leave  in  the  incinerator for 5
      minutes, then remove and place on the cooling rack.

            7.1.3  Allow the crucibles and lids to cool for five minutes before
      placing them in the storage dishes.

CAUTION:   Do not touch the crucibles with your fingers.  This can result  in a


                                   8275 - 4                       Revision 0
                                                                  November 1990

-------
     serious burn,  as well as contamination of the crucible.  Always handle
     the sample crucibles and lids with forceps and tools specified.

      7.1.4  All sample  crucibles and lids  required  for the  number of
analyses planned should be cleaned and  placed in the storage dishes ready
for use.

7.2  Sample Preparation and Loading

      7.2.1  The analyst  should  take  care  in selecting  a sample  for
analysis, since the sample size is generally limited to 0.100 g or less.
This implies that  the  sample should be mixed  as  thoroughly as possible
before taking an aliquot.  Because the sample size  is limited, the analyst
may wish to analyze several aliquots for determination.

      7.2.2  The sample should  be mixed  or ground such  that a 0.010 to
0,100 g  aliquot  can be removed.   Remove one  sample  crucible  from the
storage dish and place  it  on the microbalance.  Establish  the tare weight.
Remove the sample crucible from the balance with the forceps and place it
on a clean surface.

      7.2.3  Load an amount of sample into the sample crucible using the
fused quartz spatula.  Place the assembly on the microbalance  and determine
the weight of the  sample.   For severely  contaminated  samples,  less than
0.010 g will  suffice, while 0.050-0.100 g is  needed for  low concentrations
of contaminants.   Place the  crucible  lid  on  the crucible;  the  sample is
now ready for analysis.

7.3  FID Analysis

      7.3.1  Load the sample into  the TC.  Hold the sample  at  30°C for 2
minutes  followed by linear  temperature  programmed heating  to 260°C at
30°C/minute.   Follow the  temperature program with an  isothermal heating
period of 10 minutes at 260°C, followed by cooling  back to 30°C.  The total
analysis cycle time is 24.2 minutes

      7.3.2  Monitor the  FID response  in  real  time during analysis, and
note the highest response  in  millivolts  (mv). Use this information to
determine  the  proper  weight  of  sample  needed  for  combined  thermal
extraction/gas chromatography/mass spectrometry.

7.4  Thermal Extraction/GC/MS

      7.4.1  Prepare a calibration curve  using a  clean crucible and lid
by  spiking  the  compounds of interest at  five concentrations  into the
crucible and applying the  internal  standards to the crucible  lid.  Analyze
these standards and establish response factors at different concentrations.

      7.4.2  Weigh  out the  amount of fresh  sample  that  will  provide
approximately 1000 to 3000 mv response.  For example, if 0.010 g of sample
gives an FID response  of  500 mv,  then  0.020  to 0.060  g (0.040 g ± 50 %)
should be used.  If 0.100 g gives  8000 mv, then 0.025 g ± 50 % should be
used.
                             8275 - 5                       Revision 0
                                                            November 1990

-------
      7.4.3  After weighing out the sample  into the crucible, deposit the
internal  standards  (10  /zL)  onto  the lid  of the crucible.    Load  the
crucible into the pyrocell,  using the  same  temperature program in Section
7.3.1.  Hold the capillary at 5°C during this time to focus the released
semi-volatiles  (the intermediate  trap  is held  at  330°C  to  pass  all
compounds onto the column).   Maintain  the splitter zone  at  310°C, and the
GC/MS transfer  line at  285°C.  After  the  isothermal  heating  period  is
complete, temperature program the column from 5°C  to  285°C  at  10°C/minute
and hold at 285°C for 5 minutes.  Acquire data during the entire  run time.

      7.4.4  If the response for any quantitation  ion exceeds the initial
calibration curve range  of the  TC/MS  system,  a  smaller  sample should be
analyzed.

7.5  Data Interpretation

      7.5.1  Qualitative Analysis

            7.5.1.1  The qualitative identification of compounds determined
      by this method is based on retention  time, and on comparison of the
      sample   mass   spectrum,    after   background   correction,   with
      characteristic ions in a reference mass spectrum. The  reference mass
      spectrum must be generated by the laboratory using the conditions
      of this method.   The characteristic ions from the reference mass
      spectrum  are  defined to  be the  three  ions of greatest  relative
      intensity, or any ions over 30% relative  intensity if less than three
      such  ions  occur  in the  reference spectrum.  Compounds  should  be
      identified as present when the criteria below are met.

                  7.5.1.1.1  The  intensities  of the  characteristic ions
            of a compound maximize in  the same scan or within one scan of
            each other.   Selection of  a  peak  by a data  system target
            compound search  routine  where the  search  is  based on  the
            presence of  a target  chromatographic peak  containing ions
            specific  for the   target  compound  at  a  compound-specific
            retention time will  be accepted as meeting this criterion.

                  7.5.1.1.2  The RRT of the sample component is within ±
            0.06 RRT units of the RRT of the  standard component.

                  7.5.1.1.3  The relative intensities of the  characteristic
            ions agree within 30% of the  relative intensities of these ions
            in  the  reference spectrum.    (Example:   For an  ion with  an
            abundance of 50% in the reference  spectrum, the corresponding
            abundance in a sample spectrum  can range between 20%  and 80%.)

                  7.5.1.1.4  Structural isomers  that produce very similar
            mass spectra should  be identified as individual isomers if they
            have sufficiently different  GC retention  times.   Sufficient
            GC resolution is achieved  if the  height of the valley between
            two isomer peaks is  less than  25% of the sum of the two peak
            heights.   Otherwise,  structural  isomers  are  identified  as
            isomeric pairs.


                             8275 - 6                       Revision 0
                                                            November 1990

-------
            7.5.1.1.5  Identification  is   hampered   when  sample
      components are not  resolved  chromatographically and produce
      mass spectra  containing  ions contributing by more  than one
      analyte.  When gas chromatographic peaks obviously represent
      more than one sample  component  (i.e.,  a broadened peak with
      shoulder(s)  or  a  valley  between  two  or  more  maxima),
      appropriate selection of analyte spectra and background spectra
      is important.  Examination of extracted ion current profiles
      of appropriate ions can aid in the selection of spectra, and
      in qualitative  identification  of compounds.  When  analytes
      coelute (i.e., only one chromatographic peak is apparent), the
      identification criteria can be met, but each analyte spectrum
      will  contain  extraneous ions  contributed by the coeluting
      compound.

      7.5.1.2  For samples containing components not associated with
the calibration  standards,  a library  search  may be  made  for the
purpose of tentative identification.  The necessity to perform this
type of  identification will be  determined  by the purpose  of the
analyses being conducted.  Computer generated library search routines
should not use normalization routines  that  would  misrepresent the
library or  unknown spectra when compared to each other.  For example,
the RCRA permit  or waste delisting  requirements may  require the
reporting of non-target analytes.  Only after visual  comparison of
sample  spectra with the  nearest library  searches  will  the  mass
spectral interpretation specialist assign a tentative identification.
Guidelines for making tentative identification are:

      (1)  Relative  intensities  of major   ions  in  the reference
spectrum (ions > 10% of the  most  abundant ion) should be present in
the sample spectrum.

      (2)  The relative intensities of the major ions  should agree
within ± 20%.   (Example:   For an ion with  an  abundance of 50% in
the standard spectrum, the corresponding sample ion  abundance must
be within 30 and 70%).

      (3)  Molecular ions present in the reference spectrum should
be present in the sample spectrum.

      (4)  Ions  present  in  the  sample  spectrum but  not  in  the
reference  spectrum should  be  reviewed for  possible  background
contamination or presence of coeluting compounds.

      (5)  Ions present in  the reference spectrum but  not  in the
sample spectrum  should be reviewed for  possible  subtraction  from
the sample  spectrum because of background contamination  or coeluting.
Data system library reduction  programs  can  sometimes  create these
discrepancies.

      Computer generated  library search routines  should  not use
normalization routines  that would  misrepresent the library or unknown
spectra when compared to each other.   Only after visual comparison
of sample with the nearest library searches will the mass spectral

                       8275 - 7                       Revision 0
                                                      November 1990

-------
            interpretation specialist assign a tentative identification.


8.0  QUALITY CONTROL

     8.1   Refer to  Chapter  One and Method 8000  for  specific quality control
procedures.


9.0  METHOD PERFORMANCE

      9.1  Table 1  presents method performance data, generated using spiked soil
samples.  Method performance data in an aqueous matrix are not available.


10.0 REFERENCES

1.   Zumberge, J.E., C. Sutton,  R.D. Worden,  T.  Junk,  T.R.  Irvin,  C.B. Henry,
     V.  Shirley,  and  E.B.  Overton,  "Determination of  Semi-Volatile Organic
     Pollutants in Soils  by  Thermal  Chromatography-Mass Spectrometry (TC/MS):
     an Assessment for Field Analysis," in preparation.
                                   8275 - 8                       Revision 0
                                                                  November  1990

-------
                                TABLE 1
                    METHOD PERFORMANCE, SOIL MATRIX
Analyte
2-Chlorophenol
4-Methyl phenol
2,4-Dichlorophenol
Naphthalene
4-Chloro-3-methyl -phenol
1 -Chi oronaphthal ene
2,4-Dinitrotoluene
Fluorene
Diphenylamine
Hexachlorobenzene
Dibenzothiophene
Phenanthrene
Carbazole
Aldrin
Pyrene
Benzo(k)fluoranthene
Benzo(a)pyrene
Averaae
Clay
30
10
23
77
9
96
7
9
5
68
20
11
4
3
7
4
4
% Recovery8
Silt
22
77
20
120
12
103
10
25
6
64
35
31
8
19
19
9
8

Subsoil
2
7
26
63
9
70
10
19
6
80
50
40
9
15
20
11
11
Mean
Recovery
18
31
23
87
10
90
9
18
6
71
35
24
7
12
15
8
8
Percent theoretical  recovery  based upon linearity of  injections  deposited
on the crucible lid  (slope and y-intercept).  Average  of  9  replicates  (-10
mg  soil  spiked with 50  ppm of  analyte); 3  different  instruments  at  3
different laboratories.
                                8275  -  9                        Revision  0
                                                               November 1990

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                        METHOD 8275
     THERMAL  CHROMATOGRAPHY/MASS SPECTROMETRY FOR
        SCREENING SEMIVOLATILE ORGANIC CHEMICALS
     Start
  7.1 Prepare
   crucible
  7.2 Prepare
  and  load
    sample
     7.2.2
   Establish
  tare  weight
  of  crucible
  7.2.3 Place
   sample in
   crucible;
   establish
    weight
   7.3.1  FID
Analysis  using
 1inear  temp.
  pr ogrammed
    heating
  7 3.2  Using
 FIO response,
   determine
 sample  weight
 for TE/CC/MS
7 4.1  Prepare
 cal ibralion
7.4  2  Prepare
  amount  of
 sample for
 appropriate
FID  response
 7.4.3  Heigh
 sample into
crucible; use
temp.  program
in Sec.  7 3.1
    7.4.4
     Is
quantitalion
ion > initial
calib. curve
  range  of
    TC/MS
7.5.1
Qualitative
Identification


    Stop
7.44  Use
 smaller
 sample
                          8275 - 10
                                       Revision 0
                                       November 1990

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                                   METHOD  8290

POLYCHLORINATED DIBENZODIOXINS (PCDDs) AND POLYCHLORINATED DIBENZOFURANS (PCDFs)
              BY  HIGH-RESOLUTION  GAS  CHROMATOGRAPHY/HIGH-RESOLUTION
                          MASS  SPECTROMETRY  (HRGC/HRMS)
 1.0   SCOPE AND APPLICATION

       1.1   This method provides procedures for the detection and quantitative
 measurement of polychlorinated dibenzo-p-dioxins (tetra- through octachlorinated
 homologues;   PCDDs),   and   polychlorinated   dibenzofurans   (tetra-   through
 octachlorinated homologues;  PCDFs) in  a  variety  of environmental  matrices and
 at part-per-trillion (ppt) to  part-per-quadrillion  (ppq)  concentrations.   The
 following compounds can be determined by this method:
                         Compound Name
             2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD)
             1,2,3,7,8-Pentachlorodibenzo-p-dioxin (PeCDD)
             1,2,3,6,7,8-Hexachlorodibenzo-p-dioxin (HxCDD)
             1,2,3,4,7,8-Hexachlorodibenzo-p-dioxin (HxCDD)
             1,2,3,7,8,9-Hexachlorodibenzo-p-dioxin (HxCDD)
             1,2,3,4,6,7,8-Heptachlorodibenzo-p-dioxin (HpCDD)
             2,3,7,8-Tetrachlorodibenzofuran (TCDF)
             1,2,3,7,8-Pentachlorodi benzofuran (PeCDF)
             2,3,4,7,8-Pentachlorodibenzofuran (PeCDF)
             1,2,3,6,7,8-Hexachlorodi benzofuran (HxCDF)
             1,2,3,7,8,9-Hexachlorodibenzofuran (HxCDF)
             1,2,3,4,7,8-Hexachlorodi benzofuran (HxCDF)
             2,3,4,6,7,8-Hexachlorodi benzofuran (HxCDF)
             1,2,3,4,6,7,8-Heptachlorodi benzofuran (HpCDF)
             1,2,3,4,7,8,9-Heptachlorodibenzofuran (HpCDF)
       1.2   The analytical  method calls  for  the  use  of  high-resolution  gas
 chromatography and  high-resolution  mass spectrometry  (HRGC/HRMS)  on purified
 sample  extracts.    Table  1  lists the  various  sample  types  covered  by  this
 analytical protocol, the  2,3,7,8-TCDD-based method calibration  limits (MCLs),
 and other pertinent information.   Samples containing concentrations of specific
 congeneric analytes (PCDDs and PCDFs) considered within the scope of this method
 that are greater than ten times the upper MCLs  must  be analyzed  by a protocol
 designed for such concentration levels, e.g.,  Method 8280.  An optional method
 for reporting the analytical results using a 2,3,7,8-TCDD toxicity equivalency
 factor (TEF) is described.

       1.3   The sensitivity  of this method is dependent  upon the level of inter-
 ferences within a given matrix.   The calibration range of the method for a 1 L
 water sample is 10  to 2000 ppq for TCDD/TCDF  and  PeCDD/PeCDF, and 1.0  to 200 ppt

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for a  10 g soil,  sediment,  fly ash, or  tissue sample for  the  same analytes
(Table 1).  Analysis of  a  one-tenth  aliquot  of the sample permits measurement
of concentrations up to 10 times the  upper MCL.  The actual limits of detection
and quantitation will  differ from the lower MCL, depending on the complexity of
the matrix.

      1.4   This method is  designed for use by analysts  who are experienced with
residue analysis and skilled in HRGC/HRMS.

      1.5   Because of  the extreme toxicity  of many of these  compounds,  the
analyst must take  the  necessary precautions  to prevent  exposure to materials
known or believed to contain PCDDs or PCDFs.   It  is the responsibility of the
laboratory  personnel  to ensure  that safe  handling procedures  are employed.
Section 11 of this method discusses safety procedures.


2.0   SUMMARY OF METHOD

      2.1   This procedure uses  matrix  specific extraction,  analyte specific
cleanup, and HRGC/HRMS analysis techniques.

      2.2   If   interferences  are  encountered,  the  method   provides  selected
cleanup  procedures  to  aid the analyst  in  their  elimination.    A  simplified
analysis flow chart is presented at the end of this method.

      2.3   A specified amount  (see Table  1) of  soil, sediment, fly ash, water,
sludge (including paper pulp),  still bottom,  fuel oil, chemical reactor residue,
fish tissue,  or human  adipose tissue  is spiked  with a solution  containing
specified amounts of each  of the nine isotopically (13C12)  labeled PCDDs/PCDFs
listed in Column  1  of Table 2.   The sample  is then extracted  according  to a
matrix specific extraction  procedure.  Aqueous  samples that are judged to contain
1 percent or more  solids,  and solid  samples  that  show an aqueous  phase,  are
filtered, the solid  phase (including the filter) and the aqueous phase extracted
separately, and the extracts combined before  extract cleanup.   The extraction
procedures are:

      a)  ToluenerSoxhlet extraction  for soil,  sediment, fly ash and paper pulp
          samples;

      b)  Methylene  chloride:!iquid-liquid extraction for water  samples;

      c)  Toluene:Dean-Stark extraction for fuel  oil and aqueous sludge samples;

      d)  Toluene extraction  for still bottom  samples;

      e)  Hexane/methylene    chloride:Soxhlet   extraction    or    methylene
          chloride:Soxhlet  extraction for  fish tissue samples; and

      f)  Methylene  chloride  extraction for  human adipose tissue  samples.

      g)  As an option,  all  solid  samples (wet or dry) can  be  extracted  with
          toluene using a Soxhlet/Dean Stark  extraction system.
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      The decision  for the selection of an  extraction  procedure for chemical
reactor residue samples is based on the appearance (consistency, viscosity) of
the samples.   Generally,  they can be handled according  to  the procedure used
for still bottom (or chemical sludge) samples.

      2.4   The extracts  are submitted  to an acid-base  washing treatment and
dried.  Following  a  solvent exchange step, the extracts are cleaned up by column
chromatography on  alumina,  silica gel, and AX-21  activated carbon on Celite 545®
(or equivalent).

            2.4.1 The  extracts  from adipose  tissue  samples are  treated with
      silica gel impregnated with  sulfuric  acid  before chromatography on acidic
      silica gel, neutral  alumina,  and  AX-21 on  Celite  545®  (or equivalent).

            2.4.2 Fish tissue and paper pulp extracts are subjected to an acid
      wash   treatment  only,   prior   to   chromatography   on  alumina   and
      AX-21/Celite 545® (or  equivalent).

      2.5   The preparation  of the  final  extract  for  HRGC/HRMS  analysis  is
accomplished by adding, to the  concentrated  AX-21/Celite 545®  (or equivalent)
column eluate, 10 to 50 nl (depending on the matrix type) of a nonane solution
containing 50 pg/jiL of each of the two recovery standards 13C12-1,2,3,4-TCDD and
13C12-l,2,3,7,8,9-HxCDD (Table 2).   The former is used to determine the percent
recoveries of tetra- and pentachlorinated PCDD/PCDF congeners, while the latter
is  used  to  determine the   percent recoveries  of  the hexa-,  hepta-  and
octachlorinated PCDD/PCDF congeners.

      2.6   One to  two pi of the concentrated  extract are injected  into an
HRGC/HRMS system  capable  of  performing  selected ion monitoring  at resolving
powers of at least 10,000  (10 percent valley definition).

      2.7   The  identification of  OCDD  and  nine  of  the  fifteen  2,3,7,8-
substituted congeners  (Table  3), for which a 13C-labeled standard is available
in the sample fortification and recovery standard  solutions (Table 2), is based
on their elution at their exact retention time (within 0.005 retention time units
measured in the routine calibration) and the simultaneous detection of the two
most  abundant  ions  in the molecular  ion  region.   The  remaining  six 2,3,7,8-
substituted congeners  (i.e.,  2,3,4,7,8-PeCDF;  1,2,3,4,7,8-HxCDD; 1,2,3,6,7,8-
HxCDF; 1,2,3,7,8,9-HxCDF;  2,3,4,6,7,8-HxCDF, and 1,2,3,4,7,8,9-HpCDF), for which
no carbon-labeled internal standards are available in the sample fortification
solution, and all  other identified PCDD/PCDF congeners are identified by their
relative retention times falling within their respective PCDD/PCDF retention time
windows, as established from the routine calibration data, and the simultaneous
detection of  the  two  most abundant ions  in the molecular  ion region.   The
identification of OCDF is  based on its retention time relative  to 13C12-OCDD and
the simultaneous detection of the  two most abundant  ions in  the molecular ion
region.  Confirmation is based on a comparison of the ratios of the integrated
ion abundance of the molecular ion species to their theoretical abundance ratios.

      2.8   Quantitation  of  the individual  congeners,  total  PCDDs  and  total
PCDFs is achieved in  conjunction with the  establishment of  a multipoint (five
points)  calibration  curve for  each  homologue,  during which each  calibration
solution is analyzed once.

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3.0   INTERFERENCES

      3.1   Solvents, reagents, glassware and other sample processing hardware
may yield  discrete artifacts or  elevated  baselines that may  cause misinter-
pretation of the chromatographic  data  (see  references  1  and  2.)   All of these
materials must be demonstrated to  be free from interferants under the conditions
of analysis by performing laboratory method blanks.  Analysts should avoid using
PVC gloves.

      3.2   The  use  of high  purity  reagents  and solvents  helps  minimize
interference problems.  Purification of  solvents  by distillation  in all-glass
systems may be necessary.

      3.3   Interferants coextracted from the sample will  vary considerably from
matrix to matrix.  PCDDs and PCDFs are often associated with  other interfering
chlorinated substances such as polychlorinated biphenyls (PCBs), polychlorinated
diphenyl ethers  (PCDPEs),   polychlorinated  naphthalenes, and  polychlorinated
alkyldibenzofurans  that may  be  found  at  concentrations several  orders  of
magnitude  higher  than the  analytes  of  interest.   Retention times  of  target
analytes must be  verified  using  reference  standards.   These  values  must
correspond to the retention  time windows  established  in Section 8.1.1.3.   While
certain cleanup techniques are provided as part of this method, unique samples
may require additional cleanup steps to achieve lower detection limits.

      3.4   A high-resolution capillary  column  (60  m DB-5, J&W Scientific,  or
equivalent) is used in this method.   However, no  single  column is  known  to
resolve all isomers.  The 60 m DB-5  GC  column is capable of 2,3,7,8-TCDD  isomer
specificity (Section  8.1.1).   In  order to determine the concentration  of the
2,3,7,8-TCDF  (if  detected  on  the DB-5  column),  the  sample  extract must  be
reanalyzed on  a column capable of 2,3,7,8-TCDF isomer specificity (e.g., DB-225,
SP-2330, SP-2331, or equivalent).  When a column becomes available that resolves
all isomers,  then  a  single  analysis  on  this  column can  be used  instead  of
analyses on more  than one  column.


4.0   APPARATUS AND MATERIALS

      4.1   High-Resolution    Gas    Chromatograph/High-Resolution    Mass
Spectrometer/Data System (HRGC/HRMS/DS) - The GC must be  equipped for temperature
programming, and  all required accessories must be available,  such  as syringes,
gases, and capillary columns.

            4.1.1 GC  Injection Port  -  The GC injection port must  be designed
      for  capillary  columns.   The  use  of  splitless injection techniques  is
      recommended.    On  column  1  juL  injections can  be used  on the 60  m DB-5
      column.   The  use  of  a moving needle injection port is  also  acceptable.
      When using  the method  described in  this protocol,  a 2 /uL injection  volume
      is used consistently (i.e.,  the injection volumes for all extracts, blanks,
      calibration solutions  and the  performance check samples  are 2  /*!_).  One  Mi-
      injections  are allowed; however,  laboratories  must  remain  consistent
      throughout  the analyses by using the same injection volume at all  times.
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            4.1.2 Gas Chromatoqraph/Mass Spectrometer  (GC/MS)  Interface - The
      GC/MS interface components should withstand 350°C.  The interface must be
      designed so that the separation of 2,3,7,8-TCDD from the other TCDD isomers
      achieved in the gas  chromatographic  column is  not appreciably degraded.
      Cold spots or  active  surfaces  (adsorption sites)  in the GC/MS interface
      can cause peak tailing  and  peak broadening.   It  is recommended that the
      GC column be fitted directly into the mass spectrometer ion source without
      being exposed to the ionizing  electron  beam.  Graphite ferrules should be
      avoided in the injection port because they may adsorb the  PCDDs and PCDFs.
      Vespel™,  or equivalent, ferrules are recommended.

            4.1.3 Mass  Spectrometer  -  The   static  resolving power  of  the
      instrument must be maintained  at a minimum of 10,000 (10 percent valley).

            4.1.4 Data System - A dedicated data system is employed to control
      the  rapid  multiple-ion monitoring  process  and  to  acquire  the  data.
      Quantitation data  (peak areas  or peak  heights) and SIM-traces (displays
      of intensities of each ion signal  being monitored including the lock-mass
      ion as  a function of time) must be acquired during  the analyses and stored.
      Quantitations may be reported  based upon  computer generated peak areas or
      upon measured  peak heights  (chart recording).   The  data system  must be
      capable of acquiring data at a minimum  of 10  ions in  a single scan. It is
      also recommended to have a data system capable of switching to different
      sets  of  ions  (descriptors)  at  specified  times  during  an  HRGC/HRMS
      acquisition.   The  data  system should be able to provide hard  copies of
      individual   ion  chromatograms  for  selected gas  chromatographic  time
      intervals.   It should also be  able  to acquire mass spectral peak profiles
      (Section 8.1.2.3)  and provide  hard  copies of  peak profiles to demonstrate
      the  required   resolving  power.    The  data  system   should  permit  the
      measurement of noise on the base line.

NOTE: The detector ADC zero  setting  must allow peak-to-peak measurement of the
     noise  on the  base  line of  every monitored  channel  and  allow for  good
     estimation of the instrument resolving power.  In  Figure 2, the effect of
     different zero  settings  on the  measured resolving power is shown.

      4.2   GC Columns

            4.2.1 In order to  have an isomer specific determination for 2,3,7,8-
      TCDD and to  allow the  detection  of  OCDD/OCDF  within a  reasonable  time
      interval in one HRGC/HRMS analysis,  use  of  the  60 m DB-5  fused  silica
      capillary column  is  recommended.  Minimum acceptance criteria must be
      demonstrated and documented  (Section  8.1.1).  At the beginning of each 12
      hour period (after mass resolution  and  GC  resolution is  demonstrated)
      during  which sample extracts or concentration calibration solutions  will
      be analyzed, column operating conditions must  be attained  for the required
      separation  on the  column  to  be used for  samples.   Operating  conditions
      known to produce acceptable results with  the recommended column are shown
      in Section  7.6.

            4.2.2 Isomer specificity  for all  2,3,7,8-substituted  PCDDs/PCDFs
      cannot  be achieved  on the 60 m DB-5 GC column alone.  In order to determine
      the proper concentrations of the individual 2,3,7,8-substituted congeners,
      the sample  extract must  be reanalyzed on  another  GC column that  resolves

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      the  isomers.    When such  a column  becomes available,  and  the  isomer
      specificity can be documented,  the  performing laboratory will be required
      to use it.

            4.2.3 30 m DB-225 fused  silica  capillary  column,  (J&W Scientific)
      or equivalent.

      4.3   Miscellaneous Equipment and Materials  - The following list of items
does not necessarily constitute an exhaustive compendium of the equipment needed
for this analytical method.

            4.3.1 Nitrogen evaporation apparatus with variable flow rate.

            4.3.2 Balances capable of accurately weighing to 0.01 g and 0.0001 g.

            4.3.3 Centrifuge.

            4.3.4 Water bath, equipped with concentric ring covers and capable
      of being temperature controlled within ± 2°C.

            4.3.5 Stainless  steel  or  glass container  large  enough  to  hold
      contents of one pint sample containers.

            4.3.6 Glove box.

            4.3.7 Drying oven.

            4.3.8 Stainless steel spoons  and spatulas.

            4.3.9 Laboratory hoods.

            4.3.10 Pipets, disposable,  Pasteur,  150 mm long  x  5 mm ID.

            4.3.11 Pipets, disposable,  serological,  10 mL,  for the preparation
      of the carbon columns specified in  Section 7.5.3.

            4.3.12 Reaction vial, 2 ml, silanized  amber glass  (Reacti-vial, or
      equivalent).

            4.3.13 Stainless  steel meat grinder with a 3 to 5 mm hole size inner
      plate.

            4.3.14 Separatory funnels,  125 ml and  2000 ml.

            4.3.15 Kuderna-Danish  concentrator,  500  ml,   fitted   with  10  ml
      concentrator tube and three ball  Snyder column.

            4.3.16 Teflon™ or carborundum (silicon carbide)  boiling chips (or
      equivalent), washed with hexane before use.

NOTE: Teflon™  boiling chips  may float in methylene chloride,  may  not  work in
      the presence of any water phase, and may be penetrated by nonpolar organic
      compounds.


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            4.3.17 Chromatographic columns, glass, 300 mm x  10.5 mm, fitted with
      Teflon™  stopcock.
            4.3.18 Adapters  for concentrator  tubes.
            4.3.19 Glass  fiber filters.
            4.3.20 Dean-Stark trap,  5 or  10  ml,  with T-joints,  condenser and
      125 ml flask.
            4.3.21 Continuous liquid-liquid extractor.
            4.3.22 All  glass Soxhlet apparatus, 500  ml  flask.
            4.3.23 Soxhlet/Dean Stark extractor (optional), all  glass,  500 ml
      flask.
            4.3.24 Glass  funnels,  sized  to hold 170  ml  of liquid.
            4.3.25 Desiccator.
            4.3.26 Solvent reservoir (125 ml_), Kontes; 12.35  cm diameter (special
      order item), compatible with gravity carbon column.
            4.3.27 Rotary evaporator with  a temperature  controlled water bath.
            4.3.28 High speed tissue homogenizer,  equipped  with  an EN-8 probe,
      or equivalent.
            4.3.29 Glass  wool,  extracted  with methylene chloride, dried  and
      stored'in a clean glass jar.
            4.3.30 Extraction jars,  glass, 250 ml, with teflon lined screw cap.
            4.3.31 Volumetric flasks,  Class A - 10 ml to 1000 mL.
            4.3.32 Glass  vials, 1  dram (or metric  equivalent).
NOTE: Reuse of glassware  should be minimized to avoid the  risk of contamination.
      All glassware  that is  reused  must  be scrupulously  cleaned as  soon as
      possible after use,  according to the  following  procedure:  Rinse glassware
      with the last  solvent used  in it.  Wash with  hot  detergent water, then
      rinse with copious amounts of tap water and several portions of organic-
      free reagent water.  Rinse with high purity acetone and  hexane and store
      it  inverted or  capped  with  solvent  rinsed  aluminum foil  in  a  clean
      environment.

5.0   REAGENTS AND STANDARD SOLUTIONS
      5.1   Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined  in Chapter  One.
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5.2   Column Chromatography Reagents

      5.2.1 Alumina,   neutral,   80/200  mesh   (Super  1,   Woelm®,   or
equivalent).   Store  in  a sealed  container at  room temperature,  in a
desiccator, over self-indicating silica gel.

      5.2.2 Alumina, acidic AG4,  (Bio Rad Laboratories catalog #132-1240,
or equivalent).  Soxhlet extract with methylene chloride for 24 hours if
blanks show contamination,  and activate by heating in a foil covered glass
container for 24 hours at  190°C.  Store in  a glass  bottle sealed with a
Teflon™ lined  screw cap.

      5.2.3 Silica gel, high purity grade,  type 60,  70-230 mesh; Soxhlet
extract with methylene chloride for 24 hours if  blanks  show contamination,
and activate by heating in  a  foil covered glass container for 24 hours at
190°C.   Store in a  glass  bottle  sealed with  a Teflon™ lined  screw cap.

      5.2.4 Silica gel impregnated with sodium hydroxide.   Add one part
(by weight)  of 1 M  NaOH  solution  to  two  parts (by  weight)  silica gel
(extracted and activated) in a screw cap bottle and mix with a glass rod
until  free of lumps.   Store in a glass bottle sealed  with a Teflon™ lined
screw cap.

      5.2.5 Silica gel impregnated with 40  percent  (by weight) sulfuric
acid.   Add two parts  (by weight)  concentrated sulfuric acid  to three parts
(by weight)  silica  gel  (extracted  and activated), mix  with  a  glass rod
until  free of lumps, and store in a screw capped glass bottle.   Store in
a glass bottle sealed with a Teflon™ lined  screw cap.

      5.2.6 Celite 545* (Supelco), or equivalent.

      5.2.7 Active carbon AX-21  (Anderson Development Co., Adrian,  MI),
or equivalent,  prewashed with methanol and dried in vacuo at 110°C.  Store
in a glass bottle sealed with a Teflon™ lined  screw cap.

5.3   Reagents

      5.3.1 Sulfuric acid, H2S04, concentrated, ACS grade, specific gravity
1.84.

      5.3.2 Potassium  hydroxide,  KOH, ACS  grade,  20 percent  (w/v)  in
organic-free reagent water.

      5.3.3 Sodium chloride,  NaCl,  analytical reagent, 5 percent (w/v) in
organic-free reagent water.

      5.3.4 Potassium carbonate, K2C03, anhydrous, analytical reagent.

5.4   Desiccating agent

      5.4.1 Sodium sulfate (powder, anhydrous), Na2S04. Purify by heating
at 400°C  for 4 hours  in  a shallow  tray,  or  by precleaning  the sodium
sulfate with methylene chloride.  If the sodium  sulfate is precleaned with


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      methylene chloride, a  method  blank must be analyzed, demonstrating that
      there is no interference from the sodium sulfate.

      5.5   Solvents

            5.5.1 Methylene  chloride, CH2C12.   High purity, distilled in glass
      or highest available purity.

            5.5.2 Hexane, C6H14.   High purity,  distilled  in glass  or highest
      available purity.

            5.5.3 Methanol,  CH3OH.  High purity, distilled in glass or highest
      available purity.

            5.5.4 Nonane, CgH^.   High purity,  distilled  in glass  or highest
      available purity.

            5.5.5 Toluene, C6H5CH3.  High purity, distilled in glass or highest
      available purity.

            5.5.6 Cyclohexane, C6H12. High purity, distilled in  glass or highest
      available purity.

            5.5.7 Acetone, CH3COCH3.  High purity, distilled in  glass or highest
      available purity.

      5.6   High-Resolution Concentration Calibration Solutions (Table 5)  - Five
nonane solutions containing unlabeled (totaling 17) and  carbon-labeled  (totaling
11) PCDDs and  PCDFs at known concentrations are used to calibrate the instrument.
The concentration ranges are  homologue dependent, with the lowest  values for the
tetrachlorinated dioxin  and  furan (1.0 pg//iL) and  the highest values for the
octachlorinated congeners (1000 pg//uL).

            5.6.1 Depending  on  the availability  of  materials, these  high-
      resolution concentration calibration  solutions may be obtained from the
      Environmental Monitoring Systems Laboratory, U.S.  EPA, Cincinnati, Ohio.
      However, additional secondary standards must be  obtained from commercial
      sources,  and  solutions  must  be prepared  in the  analyst's laboratory.
      Traceability of standards must be verified against EPA-supplied standard
      solutions.  It is the  responsibility of the laboratory to  ascertain that
      the  calibration  solutions  received  (or  prepared)  are  indeed at  the
      appropriate concentrations  before they are used  to analyze  samples.

            5.6.2 Store the concentration calibration solutions  in 1 ml minivials
      at room temperature in the  dark.

      5.7   GC Column  Performance Check  Solution - This solution contains the
first and last  eluting  isomers for  each  homologous series from tetra- through
heptachlorinated congeners.  The  solution also contains  a  series of other TCDD
isomers  for  the purpose of  documenting  the chromatographic resolution.   The
13C12-2,3,7,8-TCDD  is also present.   The laboratory  is required to  use nonane as
the solvent and  adjust the volume so  that the final concentration does not exceed
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100 pg/juL per congener.  Table 7 summarizes the qualitative composition  (minimum
requirement) of this performance evaluation solution.

      5.8   Sample Fortification Solution  -  This nonane solution contains the
nine internal  standards at the nominal  concentrations that are listed in  Table 2.
The solution contains  at least one carbon-labeled standard for each homologous
series, and it is used to measure the concentrations of the native substances.
(Note that 13C12-OCDF  is not  present  in the  solution.)

      5.9   Recovery  Standard  Solution  -  This  nonane solution  contains two
recovery standards,  13C12-1,2,3,4-TCDD and 13C12-l,2,3,7,8,9-HxCDD,  at a nominal
concentration of 50  pg/juL per compound.   10  to 50 juL of this solution will be
spiked into each sample extract before the final concentration step and HRGC/HRMS
analysis.

      5.10  Matrix Spike Fortification Solution  - Solution used to prepare the
MS and MSD  samples.   It contains all  unlabeled  analytes listed in Table 5 at con-
centrations corresponding to the HRCC 3.


6.0   SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1   See the  introductory  material  to  this chapter,  Organic Analytes,
Section 4.1.

      6.2   Sample Collection

            6.2.1 Sample collection personnel  should,  to  the extent possible,
      homogenize samples  in the field  before filling the  sample containers.
      This should minimize or eliminate the necessity for sample homogenization
      in the  laboratory.    The  analyst should make  a  judgment,  based on the
      appearance of the sample, regarding the necessity for additional mixing.
      If the sample  is clearly  not  homogeneous,  the  entire contents should be
      transferred to a glass or  stainless  steel pan for mixing with a stainless
      steel spoon or spatula before removal of a sample portion for analysis.

            6.2.2 Grab  and  composite  samples  must   be  collected  in  glass
      containers.  Conventional  sampling practices must be followed.  The bottle
      must not be prewashed with sample before collection.  Sampling equipment
      must be free of  potential  sources of contamination.

      6.3   Grinding or Blending of Fish  Samples -  If  not otherwise specified
by the U.S. EPA,  the whole fish  (frozen) should be blended or ground to provide
a homogeneous sample.  The use of a stainless steel meat grinder with  a 3 to 5
mm hole size  inner  plate is recommended.   In  some circumstances, analysis of
fillet or  specific  organs of fish  may be requested by  the U.S. EPA.   If so
requested,  the above whole fish requirement is superseded.

      6.4   Storage  and  Holding Times - All  samples,  except  fish and adipose
tissue samples,  must be stored  at  4°C  in the dark, extracted within 30 days and
completely  analyzed  within  45 days  of collection.   Fish and  adipose tissue
samples must  be stored  at  -20°C  in  the  dark,  extracted within  30  days and
completely analyzed within 45 days of collection.   Whenever samples are  analyzed


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after the holding time expiration date, the results should be considered to be
minimum concentrations and must be identified as such.

Note: The holding times listed  in  Section  6.4  are  recommendations.   PCDDs and
      PCDFs are very  stable  in  a variety of matrices,  and holding times under
      the conditions listed in Section 6.4  may  be as high  as a year for certain
      matrices.  Sample extracts, however,  should always be analyzed within 45
      days of extraction.

      6.5   Phase Separation - This is a guideline for  phase separation for very
wet  (>25 percent water)  soil,  sediment and paper pulp samples.   Place  a 50 g
portion  in  a  suitable centrifuge  bottle  and centrifuge  for 30 minutes  at
2,000 rpm.   Remove the  bottle  and mark  the  interface  level  on the  bottle.
Estimate the relative volume of each phase.  With a disposable pipet, transfer
the  liquid  layer  into a clean  bottle.   Mix the solid with  a  stainless steel
spatula and remove  a portion to be weighed and analyzed  (percent  dry  weight
determination, extraction).  Return the remaining solid portion to the original
sample bottle (empty) or to a clean sample  bottle that is properly labeled, and
store  it  as appropriate.   Analyze the  solid  phase  by  using  only  the soil,
sediment and paper pulp method.   Take  note  of,  and report, the estimated volume
of liquid before disposing of the liquid as a liquid waste.

      6.6   Soil.   Sediment,  or   Paper  Sludge   (Pulp)   Percent   Dry   Weight
Determination - The percent dry weight of soil, sediment or paper pulp samples
showing detectable levels  (see note below)  of at least one 2,3,7,8-substituted
PCDD/PCDF congener is determined according  to  the  following  procedure.   Weigh
a 10 g  portion  of  the soil or sediment sample (± 0.5 g)  to  three significant
figures.  Dry it to constant weight at 110°C in an adequately ventilated oven.
Allow  the  sample  to  cool  in a  desiccator.   Weigh the  dried  solid to three
significant figures.  Calculate and report the percent dry weight.  Do not use
this solid portion of the  sample for  extraction,  but  instead dispose of it as
hazardous waste.

NOTE: Until detection limits have been  established  (Section 1.3), the lower MCLs
      (Table 1)  may  be  used to estimate  the minimum detectable  levels.

            % dry weight = q of dry sample x 100
                              g of sample

CAUTION: Finely divided soils and sediments  contaminated  with  PCDDs/PCDFs are
         hazardous  because  of the potential  for  inhalation  or  ingestion  of
         particles containing PCDDs/PCDFs (including 2,3,7,8-TCDD).  Such samples
         should be  handled  in a  confined environment  (i.e., a closed hood or a
         glove  box).

      6.7   Lipid Content Determination

            6.7.1  Fish Tissue - To determine the lipid content  of fish  tissue,
      concentrate 125 mL of the  fish tissue extract (Section 7.2.2), in a tared
      200 mL round bottom flask,  on a  rotary evaporator until a constant weight
      (W) is achieved.
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                        100  (W)
      Percent lipid = -
                          10

      Dispose of the  lipid  residue  as  a hazardous waste if the results of the
      analysis indicate the presence of PCDDs or  PCDFs.

            6.7.2 Adipose Tissue - Details for the determination of the adipose
      tissue lipid content are provided in Section 7.3.3.

7.0   PROCEDURE

      7.1   Internal  standard addition

            7.1.1 Use a portion of 1 g  to 1000 g (± 5  percent) of the sample to
      be analyzed.   Typical  sample size requirements for different  matrices are
      given in Section  7.4  and  in Table 1.   Transfer  the  sample  portion to a
      tared flask and determine its weight.

            7.1.2 Except for adipose tissue,  add an appropriate quantity of the
      sample fortification  mixture  (Section  5.8) to the sample.   All  samples
      should be spiked with 100 /uL of  the sample  fortification mixture to give
      internal  standard concentrations  as indicated in Table  1.  As an example,
      for 13C12-2,3,7,8-TCDD, a 10 g soil sample requires the addition of 1000 pg
      of 13C12-2,3,7,8-TCDD to give the required 100 ppt fortification level.  The
      fish tissue  sample  (20 g)  must  be spiked  with  200  /il_ of  the internal
      standard solution, because half of the extract will be used  to determine
      the lipid content (Section 6.7.1).

                  7.1.2.1  For the  fortification of soil, sediment,  fly ash,
            water,  fish  tissue, paper pulp and wet  sludge samples, mix the sample
            fortification solution with 1.0 ml acetone.

                  7.1.2.2  Do not dilute  the nonane  solution  for  the  other
            matrices.

                  7.1.2.3  The fortification  of  adipose tissue  is  carried out
            at the time of homogenization (Section 7.3.2.3).

      7.2   Extraction and Purification of Fish and Paper Pulp Samples

            7.2.1 Add 60  g  anhydrous  sodium sulfate  to a 20 g portion  of a
      homogeneous fish sample (Section  6.3) and  mix thoroughly with a stainless
      steel spatula.   After breaking up any lumps, place the fish/sodium sulfate
      mixture in the Soxhlet apparatus  on top of  a glasswool  plug.   Add 250 ml
      methylene  chloride  or  hexane/methylene chloride  (1:1)  to  the  Soxhlet
      apparatus and  reflux  for 16  hours.   The  solvent must  cycle completely
      through the system five  times per hour.   Follow the same procedure for the
      partially  dewatered  paper  pulp  sample  (using  a 10 g  sample,  30  g  of
      anhydrous sodium sulfate and 200  ml of toluene).

NOTE: As an option,  a Soxhlet/Dean Stark  extractor  system may be used,  with
      toluene as  the  solvent.  No sodium sulfate  is added when  using  this option.


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            7.2.2 Transfer the  fish extract  from  Section 7.2.1  to a  250  mL
      volumetric flask and fill  to the mark with methylene chloride.  Mix well,
      then remove  125  ml  for the determination of the  lipid  content (Section
      6.7.1).   Transfer  the  remaining  125 ml  of  the extract, plus  two 15  ml
      hexane/methylene chloride  rinses of the volumetric flask, to a KD apparatus
      equipped with a Snyder column.  Quantitatively transfer all of the paper
      pulp extract to a KD apparatus equipped with a Snyder column.

NOTE: As an option, a rotary  evaporator may be used in place of the KD apparatus
      for the concentration of the extracts.

            7.2.3 Add a Teflon™,  or equivalent, boiling chip.  Concentrate the
      extract  in  a water  bath  to an apparent volume of  10  mL.   Remove the
      apparatus from the water bath and allow to cool for 5 minutes.

            7.2.4 Add  50  mL  hexane and  a new boiling  chip  to  the  KD  flask.
      Concentrate  in a water bath to  an apparent volume of 5 mL.   Remove the
      apparatus from the water bath and allow to cool for 5 minutes.

NOTE: The methylene chloride  must  have been completely removed  before proceeding
      with the next step.

            7.2.5 Remove and invert the Snyder column and rinse it into the KD
      apparatus with two  1 mL portions  of hexane.   Decant the contents  of the
      KD apparatus and  concentrator tube into a 125 mL separatory  funnel.  Rinse
      the KD apparatus with two additional 5 mL portions of hexane and add the
      rinses  to  the   funnel.    Proceed  with  the  cleanup  according   to  the
      instructions starting in Section 7.5.1.1,  but omit the procedures described
      in Sections 7.5.1.2 and 7.5.1.3.

      7.3   Extraction and Purification of Human Adipose Tissue

            7.3.1 Human adipose tissue samples must be stored at a temperature
      of -20°C or lower from  the time of collection until the  time of analysis.
      The use of chlorinated  materials during the collection of the samples must
      be avoided.  Samples are handled with stainless steel forceps, spatulas,
      or scissors.  All sample bottles (glass) are cleaned as specified in the
      note at the end of Section  4.3.   Teflon   lined caps should be used.

NOTE: The  specified  storage temperature of  -20°C  is   the  maximum  storage
      temperature  permissible  for adipose  tissue  samples.     Lower  storage
      temperatures are recommended.

            7.3.2 Adipose Tissue  Extraction

                  7.3.2.1  Weigh,  to the  nearest  0.01 g, a 10  g portion  of a
            frozen adipose tissue  sample  into a culture tube  (2.2 x 15 cm).

NOTE: The  sample  size may be  smaller,  depending  on availability.  In  such a
      situation,  the analyst  is  required  to  adjust the volume of the internal
      standard  solution  added to  the sample  to meet  the  fortification level
      stipulated  in Table 1.
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                  7.3.2.2  Allow  the adipose  tissue specimen  to  reach  room
            temperature (up to 2 hours).

                  7.3.2.3  Add 10 ml methylene chloride and 100 juL of the sample
            fortification solution.   Homogenize  the  mixture for approximately
            1 minute with a tissue homogenizer.

                  7.3.2.4  Allow  the mixture  to  separate,  then  remove  the
            methylene chloride extract from the residual solid material with a
            disposable pi pet.  Percolate  the methylene chloride through a filter
            funnel containing a clean glass wool  plug and  10 g anhydrous sodium
            sulfate.  Collect  the dried extract in a graduated  100 ml volumetric
            flask.

                  7.3.2.5  Add a second 10 ml portion of methylene chloride to
            the sample and  homogenize for 1 minute.   Decant  the solvent,  dry
            it, and  transfer it to the 100 ml volumetric flask (Section 7.3.2.4).

                  7.3.2.6  Rinse the culture tube with at least two additional
            portions of methylene chloride  (10 ml each),  and  transfer the entire
            contents  to  the  filter  funnel  containing  the  anhydrous  sodium
            sulfate.  Rinse the filter funnel and the anhydrous sodium sulfate
            contents with additional methylene chloride (20 to 40 ml) into the
            100 ml flask.   Discard the sodium sulfate.

                  7.3.2.7  Adjust the volume to the 100 ml mark with methylene
            chloride.

            7.3.3 Adipose Tissue Lipid Content Determination

                  7.3.3.1   Preweigh a clean 1 dram  (or metric equivalent) glass
            vial to  the nearest 0.0001 g on an analytical balance tared to zero.

                  7.3.3.2  Accurately transfer 1.0  ml  of  the  final  extract
            (100 ml) from  Section  7.3.2.6 to the vial. Reduce  the volume of the
            extract on a  water bath  (50-60°C)  by a  gentle  stream of purified
            nitrogen  until  an  oily  residue  remains.    Nitrogen  blowdown  is
            continued until a constant weight is achieved.

Note: When the sample size of  the  adipose  tissue  is smaller than 10 g, then the
      analyst may use a larger portion (up to 10 percent) of the extract defined
      in Section 7.3.2.7 for the lipid determination.

                  7.3.3.3  Accurately weigh  the  vial with the residue  to  the
            nearest 0.0001 g  and calculate  the weight of  the  lipid present in
            the vial based on the difference of the weights.

                  7.3.3.4  Calculate the percent lipid content of the original
            sample to the nearest 0.1 percent as shown below:

                                     U   Y  V
                                     "Ir   A  * ext
            Lipid content, LC (%)  = 	   x  100
                                     W0
                                      at
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where:

Wlr  = weight of the lipid residue to the nearest 0.0001 g calculated
      from Section 7.3.3.3,

Vext = total   volume  (100  ml)   of  the   extract  In   ml  from
      Section 7.3.2.6,

Wat  = weight of the  original  adipose  tissue sample to the nearest
      0.01 g from Section 7.3.2.1, and

Va,  = volume of the aliquot of the final  extract in ml used for the
      quantitative measure of the lipid residue  (1.0 ml).

      7.3.3.5  Record the lipid residue  measured in Section 7.3.3.3
and the percent lipid content from Section 7.3.3.4.

7.3.4 Adipose Tissue Extract Concentration

      7.3.4.1  Quantitatively   transfer  the   remaining  extract
(99.0 ml) to a 500 ml Erlenmeyer flask.   Rinse  the volumetric flask
with  20  to  30  ml  of additional  methylene  chloride   to  ensure
quantitative transfer.

      7.3.4.2  Concentrate the  extract  on  a rotary evaporator and
a water bath at 40°C until  an  oily residue  remains.

7.3.5 Adipose Tissue Extract Cleanup

      7.3.5.1  Add 200 ml hexane to the  lipid residue in the 500 ml
Erlenmeyer flask and swirl the flask to dissolve the residue.

      7.3.5.2  Slowly add, with stirring, 100 g of 40 percent (w/w)
sulfuric acid-impregnated silica* gel.  Stir  with a magnetic stirrer
for two hours at room temperature.

      7.3.5.3  Allow the solid phase to settle,  and decant the liquid
through a filter funnel containing 10  g  anhydrous sodium sulfate on
a glass wool plug, into another 500 ml Erlenmeyer flask.

      7.3.5.4  Rinse  the  solid phase with  two  50 ml  portions of
hexane.  Stir each rinse for 15 minutes, decant, and dry as described
under Section 7.3.5.3.   Combine the  hexane extracts  from Section
7.3.5.3 with the rinses.

      7.3.5.5  Rinse the sodium  sulfate  in  the filter funnel with
an  additional 25 ml  hexane  and  combine  this rinse with the hexane
extracts from Section 7.3.5.4.

      7.3.5.6  Prepare an acidic silica column  as follows:  Pack a
2  cm  x  10 cm chromatographic  column  with  a glass wool  plug,  add
approximately 20 ml hexane, add 1 g silica gel  and allow to settle,
then add 4 g  of 40 percent (w/w) sulfuric  acid-impregnated silica
gel and allow to  settle.   Elute the excess  hexane from the column

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            until  the solvent  level  reaches the  top of  the chromatographic
            packing.  Verify that the column does not have any air bubbles and
            channels.

                  7.3.5.7  Quantitatively transfer the hexane extract from the
            Erlenmeyer flask  (Sections  7.3.5.3  through  7.3.5.5)  to the silica
            gel column reservoir.  Allow the hexane extract  to  percolate through
            the column and collect the eluate in a 500 mL KD apparatus.

                  7.3.5.8  Complete  the elution by  percolating  50  ml hexane
            through the column  into  the KD  apparatus.   Concentrate the eluate
            on a  steam  bath  to approximately 5 mL.   Use  nitrogen  blowdown to
            bring the final volume to about 100 /iL.

NOTE: If the  silica gel impregnated with  40 percent sulfuric acid  is highly
      discolored  throughout  the  length of  the adsorbent  bed,  the cleaning
      procedure must be repeated beginning with Section 7.3.5.1.

                  7.3.5.9  The extract is ready for the column cleanups described
            in Sections 7.5.2 through 7.5.3.6.

      7.4   Extraction and Purification of Environmental and Waste Samples

            7.4.1 Sludge/Wet Fuel  Oil

                  7.4.1.1  Extract aqueous  sludge  or wet fuel oil  samples by
            refluxing a sample (e.g., 2  g) with  50 ml toluene  in a 125 mL flask
            fitted with a  Dean-Stark water  separator.   Continue  refluxing the
            sample until all  the water is removed.

                  7.4.1.2  Cool the sample,  filter the toluene extract through
            a glass  fiber  filter,  or equivalent,  into  a 100 mL  round bottom
            flask.

                  7.4.1.3  Rinse the filter with 10 mL toluene and combine the
            extract with the rinse.

                  7.4.1.4  Concentrate the combined  solutions to  near dryness
            on a rotary evaporator at 50°C.  Use of an inert gas to concentrate
            the extract is also permitted.   Proceed with Section  7.4.4.

NOTE: If the sludge or fuel oil  sample dissolves in toluene, treat it according
      to the instructions in  Section  7.4.2 below.  If the labeled sludge sample
      originates from pulp  (paper mills), treat it according to the instructions
      starting in Section 7.2, but without the addition of sodium sulfate.

            7.4.2 Still Bottom/Oil

                  7.4.2.1  Extract still bottom or oil samples by mixing a sample
            portion  (e.g.,  1.0 g)  with  10  mL  toluene  in  a  small beaker and
            filtering the solution  through a glass fiber filter (or equivalent)
            into a 50 mL round bottom flask.  Rinse the beaker and filter with
            10 mL toluene.


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                  7.4.2.2  Concentrate the  combined  toluene solutions to near
            dryness on a rotary evaporator at 50°C.  Proceed with Section  7.4.4.

            7.4.3 Fly Ash

Note: Because of the  tendency of fly ash to "fly",   all handling steps should
      be performed in a hood in  order to minimize contamination.

                  7.4.3.1  Weigh  about 10 g  fly  ash  to two decimal  places and
            transfer  to  an extraction jar.   Add 100  pi  sample fortification
            solution (Section 5.8), diluted  to 1 ml with acetone, to the sample.
            Add 150 ml of 1 M HC1 to the  fly ash  sample.  Seal  the jar with the
            Teflon™ lined screw  cap and  shake for 3  hours at room temperature.

                  7.4.3.2  Rinse  a glass fiber filter with toluene,  and filter
            the sample through the filter paper, placed  in a Buchner funnel, into
            all flask.   Wash  the fly ash  cake   with  approximately  500 ml
            organic-free reagent  water and dry the filter cake overnight at room
            temperature in a desiccator.

                  7.4.3.3  Add  10 g  anhydrous  powdered  sodium sulfate,  mix
            thoroughly, let sit  in a closed container for one hour,  mix again,
            let sit for another  hour, and mix again.

                  7.4.3.4  Place  the sample and  the  filter   paper  into  an
            extraction thimble,  and  extract  in a Soxhlet extraction apparatus
            charged with  200 mL  toluene  for 16 hours  using  a  five  cycle/hour
            schedule.

NOTE: As an option,  a Soxhlet/Dean  Stark extractor  system may  be  used,  with
      toluene as the solvent.  No  sodium sulfate is added when using this option.

                  7.4.3.5  Cool  and filter the toluene extract  through a glass
            fiber filter  into a  500 ml  round bottom flask.  Rinse  the  filter
            with 10 ml toluene.   Add  the rinse to the  extract  and  concentrate
            the combined toluene solutions to near dryness on a rotary evaporator
            at 50°C.   Proceed with Section 7.4.4.

            7.4.4 Transfer the concentrate to a 125  ml separatory funnel using
      15 ml hexane.   Rinse the flask with two 5  ml portions of hexane and add
      the rinses to  the funnel.   Shake the combined solutions in the separatory
      funnel for two minutes with 50 ml  of 5 percent  sodium chloride solution,
      discard the aqueous layer,  and proceed with Section 7.5.

            7.4.5 Aqueous samples

                  7.4.5.1  Allow  the sample to come to ambient temperature, then
            mark the water meniscus  on the  side  of  the 1 L  sample  bottle for
            later determination of the exact sample  volume.  Add the  required
            acetone  diluted sample fortification  solution (Section  5.8).

                  7.4.5.2  When  the  sample  is judged to contain 1  percent  or
            more solids, the sample  must be filtered through  a  0.45  urn glass


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            fiber filter that has  been  rinsed  with  toluene.   If the suspended
            solids content is too  great to  filter through  the 0.45 urn filter,
            centrifuge the sample, decant,  and then filter the aqueous phase.

                  7.4.5.3  Combine the solids from the centrifuge bottle(s) with
            the particulates  on the filter and with the filter itself and proceed
            with the Soxhlet  extraction as specified  in Sections  7.4.6.1 through
            7.4.6.4.  Remove  and  invert the Snyder column and rinse  it down into
            the KD apparatus with two 1 ml portions  of hexane.

                  7.4.5.4  Pour  the  aqueous filtrate into  a 2 L separatory
            funnel.   Add  60  ml  methylene chloride  to the  sample  bottle,  seal
            and shake for 30 seconds to rinse the inner surface.  Transfer the
            solvent to the separatory funnel and extract the sample by shaking
            the funnel for two minutes with periodic venting.

                  7.4.5.5  Allow the organic layer  to separate from the water
            phase for a minimum of 10  minutes.   If the emulsion interface between
            layers is more than one third the volume of the solvent layer, the
            analyst must  employ mechanical techniques  to complete  the phase
            separation (e.g., glass stirring rod).

                  7.4.5.6  Collect the methylene chloride  into a  KD apparatus
            (mounted  with  a  10  ml concentrator tube)  by passing  the  sample
            extracts through a filter funnel packed  with a glass wool plug and
            5 g anhydrous sodium sulfate.

NOTE: As an option,  a  rotary  evaporator may be used in place of the KD apparatus
      for the concentration of the extracts.

                  7.4.5.7  Repeat the extraction twice with fresh 60 ml portions
            of methylene chloride.  After the third extraction,  rinse the sodium
            sulfate with an additional 30 ml methylene chloride to ensure quanti-
            tative transfer.   Combine  all  extracts  and  the rinse in  the  KD
            apparatus.

NOTE: A continuous liquid-liquid extractor may  be used in place of a separatory
      funnel when experience with  a  sample  from a given source indicates that
      a serious emulsion problem will  result or an emulsion is encountered when
      using a  separatory  funnel.   Add 60 ml methylene  chloride to the sample
      bottle,  seal,   and  shake  for  30 seconds  to  rinse  the  inner  surface.
      Transfer the solvent to  the extractor.    Repeat the  rinse of the sample
      bottle with an additional 50 to 100 ml portion of methylene chloride and
      add the rinse to the extractor.  Add 200 to 500 ml methylene chloride to
      the distilling flask, add sufficient organic-free reagent water (Section
      5.1) to ensure proper operation, and extract for 24 hours.  Allow to cool,
      then  detach  the distilling flask.   Dry  and  concentrate  the extract  as
      described in Sections 7.4.5.6 and  7.4.5.8 through  7.4.5.10.  Proceed with
      Section 7.4.5.11.

                  7.4.5.8  Attach  a Snyder  column and concentrate  the extract
            on a water  bath  until  the apparent volume  of  the liquid is 5 ml.
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            Remove the KD apparatus and  allow It to drain and cool for at least
            10 minutes.

                  7.4.5.9  Remove the Snyder column,  add 50 ml hexane, add the
            concentrate obtained from the  Soxhlet extraction  of the suspended
            solids (Section  7.4.5.3), if applicable, re-attach the Snyder column,
            and concentrate to approximately  5 ml.  Add  a  new boiling chip to
            the KD  apparatus  before proceeding with  the  second concentration
            step.

                  7.4.5.10 Rinse the flask and  the  lower joint  with  two  5 ml
            portions of hexane and combine the rinses with the extract to give
            a final volume of about 15 ml.

                  7.4.5.11 Determine the original  sample volume by filling the
            sample bottle to the mark with water and transferring the water to
            a  1000  ml graduated cylinder.    Record the  sample  volume  to the
            nearest 5 ml.  Proceed with Section 7.5.

            7.4.6 Soil/Sediment

                  7.4.6.1  Add 10  g  anhydrous powdered sodium  sulfate  to the
            sample  portion  (e.g.,  10 g)  and  mix  thoroughly with  a stainless
            steel  spatula.  After breaking up any lumps, place the soil/sodium
            sulfate mixture in the  Soxhlet  apparatus on top of  a  glass wool plug
            (the use of an extraction thimble is optional).

NOTE: As an  option,  a Soxhlet/Dean  Stark  extractor  system may  be  used,  with
      toluene as the solvent.  No sodium  sulfate is added when using this option.

                  7.4.6.2  Add 200 to 250  ml  toluene  to  the Soxhlet apparatus
            and reflux for 16  hours.  The  solvent must cycle completely through
            the system five times per hour.

NOTE: If the dried sample is not of  free flowing consistency,  more sodium sulfate
      must be added.

                  7.4.6.3  Cool and  filter the extract through  a  glass fiber
            filter  into  a 500 ml  round bottom flask for  evaporation  of the
            toluene.   Rinse the filter  with  10  ml  of toluene,  and concentrate
            the combined  fractions to  near dryness on a  rotary evaporator at
            50°C.   Remove the flask  from  the  water bath  and allow to cool for
            5 minutes.

                  7.4.6.4  Transfer the residue to a 125 ml separatory funnel,
            using 15 ml of hexane.  Rinse the flask with two  additional portions
            of  hexane,  and  add  the  rinses to  the  funnel.    Proceed  with
            Section 7.5.
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7.5   Cleanup

      7.5.1 Partition

            7.5.1.1  Partition  the  hexane  extract  against  40 ml  of
      concentrated sulfuric  acid.   Shake  for  two minutes.    Remove and
      discard the sulfuric acid layer (bottom).   Repeat the  acid washing
      until no color is visible in the  acid  layer (perform  a maximum of
      four acid washings).

            7.5.1.2  Omit this step for the fish sample extract.  Partition
      the extract against 40 ml of 5 percent (w/v)  aqueous sodium chloride.
      Shake  for  two minutes.   Remove  and  discard  the  aqueous  layer
      (bottom).

            7.5.1.3  Omit this step for the fish sample extract.  Partition
      the  extract  against 40 mL of  20  percent  (w/v)  aqueous  potassium
      hydroxide  (KOH).   Shake for  two minutes.    Remove and  discard the
      aqueous layer (bottom).  Repeat the base washing until  no color is
      visible  in  the  bottom  layer   (perform  a  maximum  of four  base
      washings).    Strong  base  (KOH)   is  known  to  degrade  certain
      PCDDs/PCDFs, so contact time  must be minimized.

            7.5.1.4  Partition  the  extract against  40 mL  of  5  percent
      (w/v) aqueous sodium chloride.   Shake for two minutes.   Remove and
      discard the aqueous layer (bottom).  Dry the extract by pouring it
      through a  filter  funnel containing anhydrous  sodium sulfate  on a
      glass wool  plug,  and  collect  it  in a  50 ml  round bottom flask.
      Rinse the funnel  with the sodium sulfate with two 15 ml portions of
      hexane, add the rinses to the  50 mL flask,  and concentrate the hexane
      solution to near dryness on a rotary evaporator  (35°C  water bath),
      making  sure  all  traces of toluene (when applicable)  are removed.
      (Use of blowdown with an inert gas to concentrate the extract is also
      permitted.)

      7.5.2 Silica/Alumina Column Cleanup

            7.5.2.1  Pack a gravity column (glass, 30  cm x 10.5 mm), fitted
      with a Teflon™ stopcock, with silica gel as follows:  Insert a glass
      wool plug  into the  bottom of the  column.   Place 1 g  silica gel in
      the column and tap the column gently  to settle  the silica gel.  Add
      2g  sodium hydroxide-impregnated silica  gel,  4g sulfuric  acid-
      impregnated silica gel, and 2 g silica gel.  Tap the column gently
      after each  addition.   A small  positive pressure  (5 psi)  of clean
      nitrogen may be used if needed.  Elute with 10 mL hexane and close
      the stopcock just before exposure  of  the top layer of silica gel to
      air.   Discard  the eluate.   Check the  column  for channeling.   If
      channeling  is observed, discard the column.  Do not  tap the wetted
      column.

            7.5.2.2  Pack  a  gravity column  (glass,  300 mm  x 10.5 mm),
      fitted  with  a Teflon™  stopcock, with  alumina  as follows:   Insert
      a glass wool plug  into  the bottom  of the  column.  Add  a 4 g layer
                             8290  -  20                       Revision 0
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            of  sodium  sulfate.   Add  a 4  g  layer of  Woelm* Super  1  neutral
            alumina.  Tap the top of the column gently.  Woelm* Super 1 neutral
            alumina need not be activated or cleaned before use,  but it should
            be  stored  in  a sealed  desiccator.   Add  a 4 g  layer  of anhydrous
            sodium sulfate to cover the alumina.   Elute  with 10  ml hexane and
            close the stopcock just  before  exposure of the sodium sulfate layer
            to air.  Discard the eluate.   Check the column for channeling.  If
            channeling is  observed, discard  the  column.   Do not  tap a wetted
            column.

NOTE: Optionally, acidic alumina (Section 5.2.2) can be used in place of neutral
      alumina.

                  7.5.2.3  Dissolve the  residue  from Section 7.5.1.4  in  2 ml
            hexane and apply the hexane solution  to  the  top of  the silica gel
            column.  Rinse the  flask  with enough hexane  (3-4 ml)  to complete
            the quantitative transfer of the sample to the surface of the silica
            gel.

                  7.5.2.4  Elute the silica  gel  column with 90 ml  of  hexane,
            concentrate the eluate  on  a rotary evaporator (35°C  water bath) to
            approximately  1  ml_,  and apply the concentrate  to the top  of the
            alumina column (Section  7.5.2.2).  Rinse the rotary evaporator flask
            twice with 2  ml of hexane, and  add  the  rinses to the  top  of the
            alumina column.

                  7.5.2.5  Add  20 ml  hexane  to  the  alumina column  and elute
            until the hexane level  is just  below  the  top of the sodium sulfate.
            Do not discard the eluted hexane,  but  collect  it  in a separate flask
            and store it  for later use, as it  may  be useful in determining where
            the  labeled  analytes   are  being  lost  if  recoveries  are  not
            satisfactory.

                  7.5.2.6  Add 15 ml of 60  percent methylene chloride in hexane
            (v/v) to the  alumina column and  collect the eluate  in  a  conical
            shaped (15  ml)  concentration tube. With a carefully regulated stream
            of nitrogen, concentrate the 60  percent  methylene chloride/hexane
            fraction to about 2 ml.

            7.5.3 Carbon Column Cleanup

                  7.5.3.1  Prepare   an  AX-21/Celite  545®  column  as  follows:
            Thoroughly mix  5.40 g active  carbon  AX-21 and 62.0 g  Celite  545*
            to produce an  8 percent (w/w) mixture.   Activate the  mixture at
            130°C for 6 hours and store it  in a desiccator.

                  7.5.3.2  Cut off  both ends  of a 10 ml disposable serological
            pipet to give a 10 cm long  column.  Fire polish both ends and flare,
            if desired.   Insert a  glass wool plug  at one end,  then pack the
            column with enough Celite  545* to form a 1 cm plug,  add 1 g of the
            AX-21/Celite 545* mixture,  top with additional  Celite 545*  (enough
            for a 1 cm  plug),  and cap the packing with another glass wool plug.
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NOTE: Each new batch  of AX-21/Celite 545* must be checked as follows:  Add 50 /xL
      of  the  continuing calibration  solution to  950  nl  hexane.    Take  this
      solution through the  carbon  column cleanup step, concentrate to 50 /xL and
      analyze.  If the recovery of any of the analytes is <80 percent, discard
      this batch of AX-21/Celite 545*.

                  7.5.3.3  Rinse  the  AX-21/Celite  545* column  with  5 ml  of
            toluene,    followed   by   2 ml   of   75:20:5   (v/v)    methylene
            chloride/methanol/toluene, 1 ml of 1:1 (v/v) cyclohexane/methylene
            chloride, and  5 ml hexane.   The  flow rate  should  be  less  than
            0.5 mL/min.   Discard the rinses.  While the column is still wet with
            hexane, add the sample concentrate (Section 7.5.2.6)  to the top of
            the column.   Rinse the concentrator tube (which contained the sample
            concentrate) twice with 1  ml hexane, and add the rinses to the top
            of the column.

                  7.5.3.4  Elute the column sequentially with two 2 ml portions
            of hexane, 2 ml cyclohexane/methylene chloride (50:50,  v/v),  and 2 ml
            methylene chloride/methanol/toluene (75:20:5, v/v).  Combine these
            eluates;  this combined  fraction  may be used as  a  check  on column
            efficiency.

                  7.5.3.5  Turn the column upside down and elute  the PCDD/PCDF
            fraction  with 20 ml toluene. Verify that no carbon fines are present
            in the eluate.   If  carbon  fines  are  present in  the eluate, filter
            the eluate  through  a  glass fiber  filter  (0.45  /im) and  rinse the
            filter with 2 ml toluene.   Add the rinse to the eluate.

                  7.5.3.6  Concentrate the toluene fraction to about 1 mL on a
            rotary evaporator  by using  a water bath at 50°C.  Carefully transfer
            the  concentrate   into  a  1 ml  minivial  and,  again  at  elevated
            temperature (50°C), reduce the volume to about 100 pi using a stream
            of nitrogen  and a sand bath. Rinse the rotary evaporator flask three
            times with 300 pi of  a  solution  of 1  percent toluene in methylene
            chloride, and add  the rinses to the concentrate.   Add 10 pi of the
            nonane recovery standard solution for soil, sediment,  water,  fish,
            paper pulp  and  adipose tissue samples, or  50  pi  of the recovery
            standard  solution  for sludge, still  bottom and fly ash samples.
            Store the sample at room temperature in the dark.

      7.6   Chromatographic/Mass Spectrometric Conditions and Data  Acquisition
Parameters

            7.6.1 Gas Chromatograph

            Column coating:         DB-5
            Film thickness:         0.25 Mm
            Column dimension:        60 m x 0.32 mm
            Injector  temperature:    270°C
            Splitless valve time:    45 s
            Interface temperature:  Function of the final temperature
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            Temperature program:

            Stage     Init.    Init.        Temp.         Final        Final
                      Temp.    Hold Time    Ramp          Temp.        Hold
                      (°C)     (min)        (°C/min)      (°C)         Time (min)


             1        200      2           5             220          16
             2                             5             235           7
             3                             5             330           5

            Total time:  60 min

            7.6.2 Mass Spectrometer

                  7.6.2.1  The mass spectrometer must be operated  in  a selected
            ion monitoring  (SIM)  mode with a total  cycle  time (including the
            voltage reset time) of one second or less (Section 7.6.3.1).  At a
            minimum,  the ions  listed in  Table  6  for  each  of  the  five  SIM
            descriptors must be monitored.  Note  that with  the  exception of the
            last descriptor (OCDD/OCDF), all  descriptors contain 10  ions.   The
            selection (Table 6)  of the molecular ions M and  M+2  for 13C-HxCDF and
            13C-HpCDF  rather than M+2  and  M+4  (for consistency)  was made  to
            eliminate, even  under high-resolution mass spectrometric conditions,
            interferences occurring   in  these two  ion  channels  for  samples
            containing high  levels of  native HxCDDs and HpCDDs.  It is important
            to maintain  the  same  set  of ions for  both  calibration  and  sample
            extract analyses.  The selection of the lock-mass ion is left to the
            performing laboratory.

Note: At the option of the analyst, the tetra- and  pentachlorinated dioxins and
      furans can be combined into a single descriptor.

                  7.6.2.2  The recommended mass spectrometer tuning conditions
            are based on  the groups of monitored ions shown  in Table 6. By using
            a  PFK  molecular  leak,  tune the  instrument to  meet  the  minimum
            required  resolving  power  of  10,000  (10 percent  valley) at  m/z
            304.9824 (PFK)  or any other reference signal close to  m/z 303.9016
            (from  TCDF).     By  using  peak  matching  conditions   and   the
            aforementioned PFK reference  peak, verify that the  exact mass of m/z
            380.9760 (PFK)  is  within 5 ppm of the required value.  Note that the
            selection of the  low- and high-mass  ions must be such  that  they
            provide the largest voltage jump  performed in any of the five  mass
            descriptors (Table 6).

            7.6.3 Data Acquisition

                  7.6.3.1  The total  cycle  time for data acquisition must  be <
            1 second.  The total  cycle time includes the sum  of all  the dwell
            times and voltage reset times.

                  7.6.3.2  Acquire SIM data for all  the  ions listed in the  five
            descriptors of Table 6.


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      7.7   Calibration

            7.7.1 Initial Calibration - Initial calibration is required before
      any samples are analyzed  for PCDDs and PCDFs.  Initial calibration is also
      required  if  any routine calibration  (Section  7.7.3)  does  not  meet the
      required criteria listed in Section 9.4.

                  7.7.1.1  All  five  high-resolution  concentration calibration
            solutions listed in Table 5 must  be used for the initial calibration.

                  7.7.1.2  Tune  the  instrument  with  PFK  as  described  in
            Section 7.6.2.2.

                  7.7.1.3  Inject  2  pi  of  the GC  column  performance  check
            solution  (Section  5.7)   and  acquire  SIM  mass  spectral  data  as
            described earlier  in Section 8.1. The total cycle time must be < 1
            second.  The laboratory must not perform any further analysis until
            it  is  demonstrated  and  documented that  the  criterion listed  in
            Section 8.1.2 was met.

                  7.7.1.4  By  using  the  same  GC  (Section  7.6.1)   and  MS
            (Section 7.6.2)  conditions  that produced  acceptable  results  with
            the column  performance check  solution,  analyze  a 2 /zL  portion  of
            each of the five concentration calibration solutions once  with the
            following mass spectrometer operating parameters.

                        7.7.1.4.1   The ratio of integrated ion current for the
                  ions appearing  in Table 8 (homologous series quantitation ions)
                  must  be  within the  indicated  control  limits (set  for  each
                  homologous series).

                        7.7.1.4.2   The ratio of integrated ion current for the
                  ions  belonging to  the carbon-labeled internal  and  recovery
                  standards  must be  within  the control  limits  stipulated  in
                  Table 8.

NOTE: Sections 7.7.1.4.1 and 7.7.1.4.2 require that 17 ion ratios from Section
      7.7.1.4.1 and 11  ion ratios from Section 7.7.1.4.2 be within the specified
      control   limits  simultaneously  in  one  run.    It   is  the  laboratory's
      responsibility to take corrective action if the ion  abundance ratios are
      outside the limits.

                        7.7.1.4.3   For  each  SICP   and  for  each  GC  signal
                  corresponding to the elution  of a  target analyte  and of its
                  labeled standards,  the  signal-to-noise  ratio (S/N)  must  be
                  better than or equal to 2.5.  Measurement  of S/N is  required
                  for any GC peak  that has  an apparent S/N of  less than  5:1.
                  The result of  the calculation must  appear on  the  SICP above
                  the GC peak  in question.

                        7.7.1.4.4   Referring  to  Table  9,  calculate the  17
                  relative response factors  (RRF)  for unlabeled target analytes
                  [RRF(n); n = 1 to 17] relative to their  appropriate  internal


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standards  (Table  5)  and the  nine  RRFs for the  labeled 13C12
internal standards [RRF(m); m  = 18 to 26)] relative to the  two
recovery standards according to the following formulae:
        RRF(n)
                       X Qls
        RRF(m)  =
                    A,s x Qr
                    Q,s
where:

A,, =
            sum  of  the  integrated  ion  abundances  of  the
            quantitation  ions  (Tables 6 and 9)  for  unlabeled
            PCDDs/PCDFs,
      Ais =  sum  of  the  integrated  ion  abundances  of  the
            quantitation ions (Tables 6 and 9) for the labeled
            internal standards,

      Ars =  sum  of  the  integrated  "-ion  abundances  of  the
            quantitation ions (Tables 6 and 9) for the labeled
            recovery standards,

      QIS =  quantity of the  internal standard  injected  (pg),

      Qrs =  quantity of the  recovery standard  injected  (pg),
            and

      Qx =  quantity  of  the  unlabeled  PCDD/PCDF   analyte
            injected (pg).

The RRF(n) and RRF(m) are  dimensionless quantities;  the  units
used to express Qls, Qrs and Qx must be the same.
      7.7.1.4.5   Calculate  the  RRF  and  their  respective
percent  relative standard  deviations  (%RSD)  for  the  five
calibration solutions:
RRF(n) = 1/5  Z RRFj(n)
where n represents a particular PCDD/PCDF (2,3,7,8-substituted)
congener (n = 1  to 17; Table 9), and j is the injection number
(or calibration solution number; j = 1  to 5).

      7.7.1.4.6  The relative response factors to be used for
the determination of the concentration  of total  isomers  in  a
homologous series (Table 9) are calculated  as follows:
           8290 - 25
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                               7.7.1.4.6.1  For  congeners  that  belong   to   a
                         homologous series  containing only  one Isomer  (e.g.,
                         OCDD and OCDF) or only one 2,3,7,8-substituted  Isomer
                         (Table 4;  TCDD,  PeCDD, HpCDD, and TCDF), the mean RRF
                         used will  be  the  same as the  mean  RRF determined  In
                         Section 7.7.1.4.5.

NOTE:  The calibration solutions do not contain 13C12-OCDF as an internal standard.
       This  is because a minimum resolving power of 12,000 is required to resolve
       the [M+6]+  ion of 13C12-OCDF  from the  [M+2]+ ion of OCDD (and  [M+4]+ from
       13C12-OCDF with [M]+ of OCDD).  Therefore, the RRF for  OCDF  is calculated
       relative  to 13C12-OCDD.

                               7.7.1.4.6.2  For  congeners  that  belong   to   a
                         homologous    series   containing    more   than   one
                         2,3,7,8-substituted isomer (Table 4), the mean RRF used
                         for those  homologous series will  be the mean of the RRFs
                         calculated  for  all  individual  2,3,7,8-substituted
                         congeners  using  the equation  below:

                                         1   t
                              RRF(k) =   -   Z  RRFn
                                         t  n=l

                              where:

                              k  =  27 to 30  (Table  9),  with 27 = PeCDF;  28  =
                                    HxCDF; 29 = HxCDD; and 30 = HpCDF,

                              t  =  total number of 2,3,7,8-substituted  isomers
                                    present in the calibration solutions (Table
                                    5) for each  homologous series (e.g.,  two for
                                    PeCDF, four for HxCDF,  three for  HxCDD,  two
                                    for HpCDF).

NOTE:  Presumably,  the HRGC/HRMS response factors of different isomers  within
       a  homologous series  are  different.   However,  this  analytical protocol
       will  make the assumption that the HRGC/HRMS responses of all  isomers in
       a  homologous series  that  do not  have  the 2,3,7,8-substitution  pattern
       are the same as the responses of one or more of the 2,3,7,8-substituted
       isomer(s) in that homologous series.
                         7.7.1.4.7  Relative  response factors  [RRF(m)]  to  be
                  used for the determination of the percent recoveries for  the
                  nine internal standards are calculated as follows:

                                    Alsm  x  Qrs
                         RRF(m)
                                    Q,sm  x  Ars
                                   8290 - 26                       Revision  0
                                                                   November 1990

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                         	       1    5

                         RRF(m)   =  -    Z  RRFj(m),
                                   5   j-1
                         where:
                         m
                         Ars
18  to  26  (congener type)  and j  =  1  to  5
(injection number),

sum of the  integrated  ion abundances of  the
quantitation ions (Tables  6 and 9) for a  given
internal  standard (m = 18 to 26),

sum of the  integrated  ion abundances of  the
quantitation  ions  (Tables 6 and  9) for  the
appropriate recovery standard  (see Table  5,
footnotes),
                         Qrs,  Qlsm = quantities  of,  respectively,  the  recovery
                                  standard  (rs)   and  a  particular  internal
                                  standard (is =  m)  injected (pg),

                         RRF(m) =  relative  response  factor of  a  particular
                                  internal  standard   (m)   relative   to   an
                                  appropriate  recovery standard,  as determined
                                  from one injection,  and

                         RRF(m) =  calculated mean relative  response  factor of
                                  a particular internal  standard  (m) relative
                                  to  an  appropriate  recovery  standard,  as
                                  determined from the five  initial  calibration
                                  injections (j).

            7.7.2 Criteria for  Acceptable  Calibration  - The  criteria  listed
       below for  acceptable  calibration  must be met  before the  analysis is
       performed.

                  7.7.2.1  The percent relative standard deviations for the mean
            response factors  [RRF(n) and RRF(m)] from the 17  unlabeled standards
            must  not  exceed  ± 20  percent,  and  those  for the nine labeled
            reference compounds must not  exceed ± 30 percent.

                  7.7.2.2  The S/N  for the GC signals present in  every SICP
            (including the ones for the labeled standards) must be > 10.

                  7.7.2.3  The isotopic  ratios (Table  8)  must be  within the
            specified control limits.

NOTE: If the criterion for acceptable calibration listed in Section 7.7.2.1 is
      met, the analyte specific RRF can  then  be  considered independent of the
      analyte quantity for the calibration concentration range.  The mean RRFs
      will be used for all calculations until  the routine calibration criteria
                                   8290  -  27   .
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      (Section 7.7.4) are no  longer met.   At  such time,  new mean RRFs will be
      calculated from a new set of injections of the calibration solutions.

            7.7.3 Routine Calibration (Continuing Calibration Check) - Routine
      calibrations must be performed at  the beginning of  a  12 hour period after
      successful mass resolution and GC resolution performance checks. A routine
      calibration is also required at the end of a 12 hour shift.

                  7.7.3.1  Inject 2 pi of the concentration  calibration solution
            HRCC-3 standard (Table 5).  By using the same HRGC/HRMS conditions
            as  used  in Sections  7.6.1  and 7.6.2,  determine and  document an
            acceptable calibration as provided in Section 7.7.4.

            7.7.4 Criteria for Acceptable  Routine  Calibration  - The following
      criteria must be met before further analysis is performed.

                  7.7.4.1  The measured RRFs [RRF(n) for the unlabeled standards]
            obtained during the  routine calibration runs must  be  within  + 20
            percent of the mean values  established during the initial calibration
            (Section 7.7.1.4.5).

                  7.7.4.2  The measured  RRFs [RRF(m) for  the labeled standards]
            obtained  during  the  routine   calibration   runs  must  be  within
            + 30 percent  of the  mean values established  during  the  initial
            calibration (Section 7.7.1.4.7).

                  7.7.4.3  The ion-abundance ratios (Table 8) must be within the
            allowed control  limits.

                  7.7.4.4  If either  one  of the criteria  in  Sections  7.7.4.1
            and  1.1 A.I  is  not  satisfied, repeat  one  more  time.    If  these
            criteria are  still  not satisfied, the entire  routine  calibration
            process  (Section 7.7.1) must be reviewed.  It  is  realized  that it
            may not always be possible to achieve all RRF criteria. For example,
            it has occurred that  the  RRF  criteria for  13C12-HpCDD and 13C12-OCDD
            were not met, however, the  RRF values for the corresponding unlabeled
            compounds were  routinely  within  the  criteria established  in  the
            method.  In these cases,  24 of the  26  RRF  parameters have  met the
            QC criteria, and the data quality for the unlabeled HpCDD and OCDD
            values were not compromised as  a  result  of the calibration event.
            In these situations, the analyst must assess  the effect on overall
            data quality as  required for the data quality objectives and decide
            on appropriate  action.   Corrective  action  would be  in  order,  for
            example, if the compounds for  which the  RRF  criteria were  not met
            included both the  unlabeled  and the corresponding internal standard
            compounds.  If the ion-abundance ratio criterion (Section 7.7.4.3)
            is  not  satisfied,  refer to   the  note  in   Section  7.7.1.4.2  for
            resolution.

NOTE: An initial  calibration must  be carried out  whenever  the HRCC-3, the sample
      fortification  or  the  recovery  standard solution  is  replaced by  a  new
      solution from a different lot.
                                   8290  -  28                       Revision 0
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      7.8   Analysis

            7.8.1 Remove the sample extract (from Section 7.5.3.6)  or blank from
      storage.   With  a stream of dry,  purified nitrogen,  reduce the extract
      volume to 10 /iL to 50 /xL.

Note: A final  volume of 20 /iL or more should be used whenever possible.  A 10 juL
      final volume is difficult to handle, and  injection  of 2 nl  out  of 10 juL
      leaves  little  sample  for confirmations  and  repeat  injections,  and  for
      archiving.

            7.8.2 Inject a  2 ML  aliquot of the extract  into  the  GC,  operated
      under the  conditions  that have  been  established to  produce acceptable
      results with the performance check solution (Sections 7.6.1  and 7.6.2).

            7.8.3 Acquire SIM data according to Sections 7.6.2 and 7.6.3.  Use
      the same acquisition and mass spectrometer operating  conditions previously
      used to  determine the relative response factors (Sections 7.7.1.4.4 through
      7.7.1.4.7).  Ions characteristic for polychlorinated diphenyl ethers are
      included in the descriptors listed in Table 6.

NOTE: The  acquisition  period must  at least  encompass  the PCDD/PCDF overall
      retention time window previously  determined  (Section 8.1).  Selected ion
      current profiles (SICP) for the lock-mass ions  (one per mass descriptor)
      must also be recorded  and  included in the  data package.  These SICPs must
      be true representations of  the  evolution of the lock-mass ions amplitudes
      during  the  HRGC/HRMS run  (see Section  8.2.2  for  the  proper  level  of
      reference compound to be metered into the ion chamber.)   The analyst may
      be required to monitor a PFK ion, not as a lock mass, but  as a regular ion,
      in order to meet this requirement.  It is recommended to examine the lock-
      mass ion SICP for obvious basic sensitivity and stability changes of the
      instrument during the GC/MS run  that could affect the  measurements [Tondeur
      et al.,  1984, 1987].   Report any discrepancies  in the case narrative.

            7.8.4 Identification Criteria - For a gas  chromatographic peak to
      be  identified  as a  PCDD or  PCDF,  it  must  meet  all  of the  following
      criteria:

                  7.8.4.1  Retention Times

                        7.8.4.1.1   For  2,3,7,8-substituted congeners,  which
                  have an isotopically  labeled internal  or recovery  standard
                  present in the sample extract (this represents a total of 10
                  congeners including OCDD; Tables 2 and 3), the retention time
                  (RRT; at maximum peak  height)  of the sample components (i.e.,
                  the two ions used  for quantitation purposes  listed  in Table
                  6) must be within -1 to +3 seconds  of the  isotopically labelled
                  standard.

                        7.8.4.1.2   For 2,3,7,8-substituted compounds  that do
                  not  have an isotopically labeled internal standard present in
                  the  sample extract  (this represents a total of six congeners;
                  Table 3),  the  retention time must fall within 0.005 retention


                                  8290  - 29                       Revision  0
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                  time units  of the relative retention  times  measured in the
                  routine calibration.  Identification of OCDF is based on its
                  retention time  relative  to 13C12-OCDD  as  determined from the
                  daily routine calibration results.

                        7.8.4.1.3   For non-2,3,7,8-substituted compounds  (tetra
                  through octa; totaling 119 congeners), the retention time must
                  be within the corresponding homologous  retention time windows
                  established by analyzing the column performance  check solution
                  (Section 8.1.3).

                        7.8.4.1.4   The ion current responses for both ions used
                  for quantitative purposes (e.g., for TCDDs: m/z 319.8965 and
                  321.8936) must reach maximum simultaneously (+ 2 seconds).

                        7.8.4.1.5   The ion current responses for both ions used
                  for the labeled standards  (e.g., for  13C12-TCDD: m/z 331.9368
                  and m/z  333.9339)  must  reach  maximum simultaneously  (± 2
                  seconds).

NOTE: The  analyst  is  required  to  verify the  presence  of  1,2,8,9-TCDD  and
      1,3,4,6,8-PeCDF (Section  8.1.3) in the  SICPs  of  the  daily performance
      checks.  Should either  one  compound  be missing,  the  analyst is required
      to take corrective action as it  may indicate a potential problem with the
      ability to detect all the PCDDs/PCDFs.

                  7.8.4.2  Ion Abundance Ratios

                        7.8.4.2.1   The integrated ion  current  for the two ions
                  used for quantitation purposes must have a ratio between the
                  lower and upper limits established for the homologous series
                  to which  the peak  is  assigned.  See Sections  7.7.1.4.1  and
                  7.7.1.4.2 and Table 8 for details.

                  7.8.4.3  Signal-to-Noise Ratio

                        7.8.4.3.1   All ion current  intensities  must be  > 2.5
                  times noise level  for positive identification of a PCDD/PCDF
                  compound or a group  of coeluting isomers.  Figure 6 describes
                  the procedure to be  followed for the determination of the S/N.

                  7.8.4.4  Polychlorinated Diphenyl  Ether Interferences

                        7.8.4.4.1   In  addition  to  the  above  criteria,  the
                  identification of a GC peak as a PCDF can only be made if no
                  signal  having a S/N > 2.5 is detected, at the same retention
                  time  (+  2  seconds),  in  the corresponding  polychlorinated
                  diphenyl  ether (PCDPE,  Table 6)  channel.

      7.9   Calculations

            7.9.1 For gas  chromatographic peaks  that  have  met  the criteria
      outlined in Sections 7.8.4.1.1  through  7.8.4.3.1,  calculate the concen-
      tration of the PCDD or PCDF compounds using the formula:

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                                     AX  x  Qls
                           Cx  =  	==—
                                  Als x W x  RRF(n)
            where:
            Cx =   concentration of unlabeled PCDD/PCDF  congeners  (or group of
                  coeluting isomers within an homologous series) in pg/g,

            A,, =   sum of the integrated ion abundances of the quantitation ions
                  (Table 6) for unlabeled PCDDs/PCDFs,

            Als  =   sum of the integrated ion abundances of the quantitation ions
                  (Table 6) for the labeled internal standards,

            Qls  =   quantity, in pg,  of the internal standard added to the sample
                  before extraction,

            W =   weight, in g, of the sample (solid or liquid), and
            RRF=  calculated  mean  relative  response factor  for  the  analyte
                  [RRF(n) with n = 1 to 17; Section 7.7.1.4.5].

       If  the  analyte  is  identified as one of the 2,3,7,8-substituted PCDDs or
       PCDFs,   RRF(n)   is   the  value  calculated   using  the   equation  in
       Section_7.7.1.4.5.  However, if it is a non-2,3,7,8-substituted congener,
       the  RRF(k)   value  is  the  one   calculated   using   the  equation  in
       Section  7.7.1.4.6.2.   [RRF(k) with  k =  27  to 30].

            7.9.2 Calculate the percent recovery  of the nine internal standards
       measured in the  sample extract,  using  the  formula:


                                         Ais  x  Qrs
Internal  standard percent recovery  =  	——x  100
                                      Qis x Ars x RRF(m)

            where:

            Als =       sum of the integrated  ion  abundances of the quantitation
                       ions (Table 6)  for the labeled internal  standard,

            Ars =       sum of the integrated  ion  abundances of the quantitation
                       ions  (Table 6)  for the labeled recovery  standard; the
                       selection of the recovery  standard depends on the  type of
                       congeners (see Table 5, footnotes),

            Qls =       quantity, in pg, of the  internal  standard added to the
                       sample before extraction,

            Qrs =       quantity, in pg, of the  recovery  standard added to the
                       cleaned-up sample residue  before HRGC/HRMS analysis, and
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            RRF(m) =   calculated mean relative  response factor for the labeled
                       internal standard relative  to the appropriate (see Table
                       5, footnotes) recovery standard._This represents the mean
                       obtained in Section 7.7.1.4.7 [RRF(m) with m = 18 to 26].

NOTE:  For human  adipose  tissue, adjust  the  percent recoveries  by  adding
       1  percent  to  the calculated value  to compensate for the 1 percent of the
       extract  diverted for the lipid  determination.

            7.9.3 If the  concentration in the final extract of any of the fifteen
       2,3,7,8-substituted PCDD/PCDF compounds (Table 3) exceeds the upper method
       calibration limits (MCL) listed in Table  1  (e.g., 200 pg//iL for TCDD in
       soil),  the linear  range of  response versus concentration  may  have been
       exceeded,  and  a second analysis of the sample (using a one tenth aliquot)
       should be  undertaken.  The  volumes of the internal  and recovery standard
       solutions  should remain  the  same as described for the sample preparation
       (Sections  11.1 to  11.9.3).  For the other congeners  (including  OCDD),
       however,  report the measured concentration and  indicate  that  the value
       exceeds  the MCL.

            7.9.4 The total concentration  for each  homologous  series  of PCDD
       and PCDF is calculated by summing up the concentrations of all positively
       identified isomers of each homologous series. Therefore, the total should
       also include  the 2,3,7,8-substituted  congeners.  The total number of GC
       signals  included  in  the homologous total  concentration value must  be
       specified  in  the report.

            7.9.5 Sample  Specific Estimated Detection Limit - The sample specific
       estimated  detection limit (EDL)  is the concentration of a given analyte
       required to produce a signal with a peak height of at least  2.5 times the
       background   signal   level.      An    EDL  is   calculated  for   each
       2,3,7,8-substituted congener that is not identified, regardless of whether
       or not other non-2,3,7,8-substituted isomers are  present.  Two methods of
       calculation can be used, as follows, depending  on the  type of response
       produced during the analysis of a  particular sample.

                  7.9.5.1  Samples giving a response for both quantitation ions
            (Tables  6 and 9) that is  less than 2.5 times  the background level.

                        7.9.5.1.1   Use  the  expression   for   EDL  (specific
                  2,3,7,8-substituted PCDD/PCDF) below to  calculate an EDL for
                  each absent 2,3,7,8-substituted PCDD/PCDF (i.e., S/N < 2.5).
                  The background level is determined  by measuring the range of
                  the noise (peak to peak) for the two quantitation ions (Table
                  6)  of   a  particular  2,3,7,8-substituted  isomer  within  an
                  homologous   series,   in   the   region  of  the   SICP   trace
                  corresponding to the elution of the internal standard (if the
                  congener possesses  an internal standard)  or in the  region of
                  the SICP where the congener is  expected to elute  by comparison
                  with the routine calibration  data (for those  congeners that
                  do not  have  a 13C-labeled standard), multiplying that noise
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                  height  by 2.5,  and relating  the product  to  an  estimated
                  concentration that would produce that peak height.

                  Use the formula:


                                           2.5  x  A,   x   Qls
EDL (specific 2,3,7,8-subst. PCDD/PCDF)
                        where:
                                           A,s x W x RRF(n)
                        EDL = estimated   detection   limit   for   homologous
                              2,3,7,8-substituted PCDDs/PCDFs.
                        Ax,  Als,  W,  RRF(n), and Qls retain  the  same meanings as
                        defined in Section 7.9.1.

                  7.9.5.2  Samples  characterized  by  a  response  above  the
            background level with a S/N  of  at  least  2.5 for both quantitation
            ions (Tables 6 and 9).

                        7.9.5.2.1   When  the response  of a signal  having the
                  same retention time as  a  2,3,7,8-substituted congener has a
                  S/N  in  excess of  2.5  and does  not meet  any of  the other
                  qualitative identification criteria listed in Section 7.8.4,
                  calculate the "Estimated Maximum Possible Concentration" (EMPC)
                  according to the expression shown in Section 7.9.1,  except that
                  Ax  in Section 7.9.1 should represent the sum of the area under
                  the smaller peak and of the other peak area calculated using
                  the theoretical chlorine isotope ratio.

            7.9.6 The relative percent difference (RPD) is calculated  as follows:
                                   I  S1  -  S2  |
                         RPD  =  -  x  100
      S1  and  S2 represent sample and duplicate sample results.

            7.9.7 The 2,3,7,8-TCDD toxicity equivalents  (TE)  of PCDDs and PCDFs
      present in  the sample are  calculated,  if  requested  by the  data user,
      according to the method recommended by the Chlorinated Dioxins Workgroup
      (CDWG)  of the EPA and the Center for Disease Control (CDC).  This method
      assigns a 2,3,7,8-TCDD toxicity equivalency  factor  (TEF)  to each of the
      fifteen 2,3,7,8-substituted  PCDDs  and PCDFs  (Table 3) and to  OCDD and
      OCDF,  as shown in Table 10.   The 2,3,7,8-TCDD equivalent of the PCDDs and
      PCDFs  present in the sample is calculated by summing the TEF times their
      concentration for each of the compounds or groups of compounds listed in
      Table  10.   The exclusion of  other  homologous  series such  as mono-, di-,
      and tri- chlorinated dibenzodioxins and dibenzofurans does not mean that

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      they are non-toxic.   However,  their  toxicity,  as  known at this time, is
      much lower  than  the toxicity  of  the compounds listed  in  Table  10.  The
      above procedure for calculating the 2,3,7,8-TCDD toxicity equivalents is
      not claimed by the  CDWG to be based on a thoroughly established scientific
      foundation.  The procedure, rather, represents a "consensus recommendation
      on science  policy".   Since the procedure may  be  changed  in the future,
      reporting requirements  for PCDD  and  PCDF  data would  still  include  the
      reporting of the  analyte  concentrations of the  PCDD/PCDF  congener as
      calculated  in Sections 7.9.1 and 7.9.4.

                  7.9.7.1  Two GC Column TEF Determination

                        7.9.7.1.1   The concentration of 2,3,7,8-TCDD (see note
                  below), is calculated from the analysis of the sample extract
                  on  the  60  m  DB-5  fused  silica  capillary   column.    The
                  experimental conditions  remain  the same as  the conditions
                  described previously in Section  7.8, and  the calculations are
                  performed as outlined in Section  7.9.   The chromatographic'
                  separation  between the  2,3,7,8-TCDD  and its  close  eluters
                  (1,2,3,7/1,2,3,8-TCDD and 1,2,3,9-TCDD) must be equal or less
                  than 25 percent valley.

                        7.9.7.1.2   The  concentration of   the 2,3,7,8-TCDF is
                  obtained from the analysis of the sample extract on the 30 m
                  DB-225  fused  silica capillary  column.   However,  the  GC/MS
                  conditions must be altered so that:  (1)  only the first three
                  descriptors  (i.e.,   tetra-,  penta-,   and  hexachlorinated
                  congeners) of  Table  6 are used; and  (2) the  switching time
                  between   descriptor   2   (pentachlorinated  congeners)   and
                  descriptor 3 (hexachlorinated congeners) takes place following
                  the  elution   of  13C12-l,2,3,7,8-PeCDD.  The   concentration
                  calculations are performed as outlined in  Section  7.9.   The
                  chromatographic separation between the 2,3,7,8-TCDF  and  its
                  close eluters  (2,3,4,7-TCDF  and  1,2,3,9-TCDF)  must be  equal
                  or less than 25 percent valley.

NOTE: The confirmation and quantitation  of  2,3,7,8-TCDD (Section 7.9.7.1.1)  may
      be accomplished  on the SP-2330  GC column  instead  of  the  DB-5  column,
      provided the criteria listed in Section 8.1.2 are met  and the requirements
      described in Section 17.2.2 are followed.

                        7.9.7.1.3   For  a   gas  chromatographic  peak  to   be
                  identified as  a  2,3,7,8-substituted  PCDD/PCDF  congener,  it
                  must meet the ion abundance and signal-to-noise ratio criteria
                  listed  in  Sections 7.8.4.2  and  7.8.4.3, respectively.   In
                  addition, the retention time identification criterion described
                  in Section 7.8.4.1.1  applies here  for congeners  for  which a
                  carbon-labeled analogue  is available  in  the sample extract.
                  However,  the   relative   retention   time   (RRT)   of   the
                  2,3,7,8-substituted  congeners  for which no  carbon-labeled
                  analogues are available must fall  within 0.006 units  of  the
                  carbon-labeled  standard   RRT.     Experimentally,   this   is
                  accomplished by using the attributions described in Table 11


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                  and the results from the routine calibration run on the SP-2330
                  column.
8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control (QC) procedures.
Quality control  to  validate sample extraction is covered  in  Method  3500.   If
extract cleanup was performed,  follow the QC in Method 3600 and in the specific
cleanup method.

      8.2   System  Performance  Criteria -  System  performance  criteria  are
presented below.  The laboratory may use  the recommended GC column described in
Section 4.2.    It must be  documented  that  all  applicable system performance
criteria (specified in Sections 8.2.1 and 8.2.2)  were met before analysis of any
sample is performed.   Section  7.6  provides  recommended  GC conditions that can
be used to satisfy the required criteria.  Figure 3 provides a typical 12 hour
analysis sequence, whereby the  response factors and mass spectrometer resolving
power checks must be performed at  the beginning  and the  end of  each 12 hour
period of operation.   A GC column  performance  check is only required  at the
beginning of each 12 hour period during  which samples are  analyzed.  An HRGC/HRMS
method blank run is  required between a calibration run and  the  first sample run.
The same method blank extract may thus  be analyzed more than once if the number
of samples within a batch requires more than 12  hours of analyses.

            8.2.1 GC Column Performance

                  8.2.1.1   Inject 2 nl  (Section 4.1.1) of the column performance
            check solution  (Section 5.7) and acquire selected  ion  monitoring
            (SIM) data as described in Section 7.6.2 within a total  cycle time
            of < 1 second (Section 7.6.3.1).

                  8.2.1.2  The chromatographic separation between 2,3,7,8-TCDD
            and the peaks representing  any other unlabeled  TCDD isomers must be
            resolved with a valley of < 25 percent (Figure 4), where:


                       Valley  percent    =  (x/y)  (100)


                  x =   measured as in Figure 4  from the  2,3,7,8-closest TCDD
                        eluting isomer, and
                  y =   the peak height of 2,3,7,8-TCDD.

            It is the responsibility of the  laboratory to verify the conditions
            suitable for the appropriate resolution of 2,3,7,8-TCDD  from all
            other TCDD isomers.  The GC column performance check solution also
            contains  the known  first  and  last  PCDD/PCDF  eluters  under  the
            conditions specified in this  protocol.   Their retention  times are
            used to determine  the eight  homologue retention  time  windows that
            are used for qualitative  (Section 7.8.4.1) and quantitative purposes.
            All  peaks  (that includes  13C12-2,3,7,8-TCDD)  should be labeled  and
            identified on the chromatograms.  Furthermore,  all first eluters of


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a homologous series  should be labeled with the letter F,  and all last
eluters of a homologous series should be labeled with the letter L
(Figure 4 shows an example of peak labeling for TCDD isomers).  Any
individual selected ion current profile (SICP) (for the tetras, this
would be  the SICP for m/z  322  and  m/z 304)  or  the reconstructed
homologue ion current (for the tetras, this would correspond to m/z
320 + m/z 322  + m/z 304  + m/z 306)  constitutes  an acceptable form
of data presentation.  An SICP for the labeled compounds (e.g., m/z
334 for labeled TCDD) is also required.

      8.2.1.3  The  retention  times  for  the switching  of  SIM ions
characteristic of  one homologous  series to the next higher homologous
series must  be indicated in the SICP.   Accurate  switching  at the
appropriate  times is absolutely  necessary  for accurate monitoring
of these compounds.  Allowable tolerance on the daily verification
with the  GC performance check  solution  should  be  better than  10
seconds for  the absolute  retention  times of  all  the components  of
the  mixture.   Particular  caution  should  be exercised  for  the
switching time between the last tetrachlorinated congener  (i.e.,
1,2,8,9-TCDD)  and  the  first  pentachlorinated  congener  (i.e.,
1,3,4,6,8-PeCDF),  as these two compounds elute within 15 seconds  of
each other on the 60 m DB-5 column.  A laboratory with a GC/MS system
that is not  capable  of detecting both congeners  (1,2,8,9-TCDD and
1,3,4,6,8-PeCDF) within  one  analysis must  take  corrective action.
If the  recommended  column  is not  used, then  the  first  and  last
eluting isomer of each homologue must be determined  experimentally
on the column which  is used, and the appropriate isomers must then
be used for window definition and switching times.

8.2.2 Mass Spectrometer Performance

      8.2.2.1  The mass spectrometer must be operated in the electron
ionization mode.  A  static  resolving power of at  least 10,000 (10
percent valley  definition) must be demonstrated at appropriate masses
before any analysis  is performed (Section  7.8).   Static resolving
power checks must be performed at the beginning  and at the  end  of
each 12 hour period of operation.  However, it is recommended that
a check of the static resolution be  made and documented before and
after each analysis.  Corrective action must be implemented whenever
the resolving power does not meet the requirement.

      8.2.2.2  Chromatography time  for  PCDDs and PCDFs  exceeds the
long term mass stability of  the mass  spectrometer.   Because the
instrument is operated in the high-resolution mode,  mass drifts  of
a few ppm (e.g., 5 ppm in mass) can have serious adverse effects  on
instrument  performance.   Therefore,  a  mass   drift  correction  is
mandatory.  To  that  effect,  it is recommended to select a lock-mass
ion from the reference compound (PFK is recommended)  used for tuning
the  mass  spectrometer.   The selection  of  the  lock-mass  ion  is
dependent on the masses of the  ions monitored within each descriptor.
Table 6 offers some  suggestions  for the  lock-mass ions.   However,
an acceptable  lock-mass  ion at  any  mass between  the lightest and
heaviest ion in each descriptor  can  be  used to monitor  and correct
mass drifts. The  level of the reference  compound (PFK) metered into

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            the ion chamber during HRGC/HRMS analyses should be adjusted so that
            the amplitude  of the most  intense  selected lock-mass  ion  signal
            (regardless of the descriptor number) does not exceed 10 percent of
            the full scale deflection for  a  given  set  of detector parameters.
            Under those conditions,  sensitivity  changes that might occur during
            the analysis can be more effectively monitored.

NOTE: Excessive PFK (or any other reference substance) may cause noise problems
      and contamination of the ion source resulting in an increase in downtime
      for source cleaning.

                  8.2.2.3  Documentation of the  instrument resolving power must
            then be accomplished by  recording the peak profile of the high-mass
            reference  signal  (m/z  380.9760)  obtained during  the  above  peak
            matching experiment  by  using  the  low-mass  PFK  ion  at m/z 304.9824
            as  a  reference.   The minimum resolving power  of 10,000 must be
            demonstrated on the high-mass  ion while it is  transmitted at a lower
            accelerating  voltage than  the low-mass reference  ion, which is
            transmitted at full  sensitivity.   The format of the peak  profile
            representation (Figure  5)  must allow manual determination  of the
            resolution, i.e.,  the horizontal axis must be a calibrated mass scale
            (amu or ppm per division).  The result of the  peak width measurement
            (performed at 5 percent  of the maximum, which corresponds to the 10
            percent valley definition) must appear on the hard copy and cannot
            exceed  100  ppm at m/z  380.9760  (or 0.038 amu  at  that particular
            mass).

      8.3   Quality Control Samples

            8.3.1 Performance Evaluation  Samples  -  Included among the  samples
      in all  batches may  be samples (blind or  double  blind)  containing known
      amounts of  unlabeled  2,3,7,8-substituted  PCDDs/PCDFs  or  other PCDD/PCDF
      congeners.

            8.3.2 Performance Check Solutions

                  8.3.2.1  At the beginning of each  12 hour  period during which
            samples  are  to   be  analyzed, an  aliquot  of  the  1)  GC  column
            performance  check solution  and  2)   high-resolution  concentration
            calibration solution No. 3  (HRCC-3;  see Table 5) shall be analyzed
            to  demonstrate adequate GC resolution and  sensitivity,  response
            factor reproducibility,  and  mass range calibration,  and to establish
            the PCDD/PCDF retention  time windows.  A mass  resolution  check shall
            also be performed to demonstrate adequate mass resolution using an
            appropriate reference compound  (PFK is recommended).  If the required
            criteria  are  not  met,  remedial   action  must  be  taken  before
            any samples are analyzed.

                  8.3.2.2  To  validate  positive sample  data,  the  routine or
            continuing  calibration  (HRCC-3;  Table 5) and  the  mass resolution
            check must  be  performed also at the end of each 12 hour period during
            which samples are analyzed.   Furthermore, an  HRGC/HRMS method blank
            run must be recorded following a calibration run and  the first sample
            run.

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                  8.3.2.2.1   If the laboratory operates only during one
            period (shift) each day of 12 hours or less, the GC performance
            check solution must be analyzed  only  once (at  the beginning
            of the period) to validate the data acquired during the period.
            However, the mass resolution and continuing calibration checks
            must be performed at the  beginning  as  well as  at  the end of
            the period.

                  8.3.2.2.2   If the laboratory operates during consecutive
            12 hour periods (shifts), analysis of the GC performance check
            solution must be performed  at  the beginning  of each 12 hour
            period. The mass resolution and continuing calibration checks
            from the previous period  can be used for the beginning of the
            next period.

            8.3.2.3  Results of at least one analysis of  the  GC column
      performance check solution and of two mass  resolution and continuing
      calibration checks must be reported with the sample data collected
      during a 12 hour period.

            8.3.2.4  Deviations  from  criteria  specified   for  the  GC
      performance check  or for  the mass resolution check invalidate all
      positive sample data collected  between analyses of the performance
      check solution,  and the extracts from those  positive  samples shall
      be reanalyzed.

      If the routine calibration run  fails at the  beginning of a 12 hour
      shift, the  instructions  in  Section 7.7.4.4  must be  followed.   If
      the continuing calibration check performed at the end of a 12 hour
      period fails by no more than 25  percent RPD  for the  17  unlabelled
      compounds and 35 percent RPD for the 9 labelled reference compounds,
      use the mean  RRFs from the two daily  routine calibration runs to
      compute the analyte concentrations, instead of the RRFs obtained from
      the initial calibration.  A new  initial calibration  (new RRFs) is
      required immediately (within two  hours) following  the  analysis of
      the  samples,  whenever the  RPD   from  the  end-of-shift  routine
      calibration exceeds 25  percent or 35 percent,  respectively.  Failure
      to  perform a new initial calibration  immediately  following  the
      analysis of the samples will automatically  require reanalysis of all
      positive sample  extracts  analyzed before the failed end-of-shift
      continuing calibration check.

      8.3.3 The  GC  column  performance  check   mixture,  high-resolution
concentration calibration solutions, and the sample fortification solutions
may be obtained  from  the EMSL-CIN.   However, if not available from the
EMSL-CIN, standards can be obtained from other sources, and solutions can
be prepared in the laboratory.  Concentrations of all  solutions containing
2,3,7,8-substituted PCDDs/PCDFs, which are not obtained from the EMSL-CIN,
must be verified by comparison with  the EPA  standard solutions that are
available from the EMSL-CIN.

      8.3.4 Field Blanks - Each  batch of samples usually contains a field
blank sample  of uncontaminated soil,  sediment  or  water  that  is  to be
fortified before analysis  according to  Section  8.3.4.1.   In  addition to

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      this field blank,  a batch of samples may include  a  rinsate,  which is a
      portion of the solvent (usually trichloroethylene)  that was used to rinse
      sampling equipment.   The  rinsate  is  analyzed  to assure  that the samples
      were not contaminated by the sampling equipment.

                  8.3.4.1   Fortified Field Blank

                        8.3.4.1.1   Weigh a 10 g portion or use 1 L (for aqueous
                  samples)  of the specified field blank  sample and  add  100 ML
                  of  the  solution  containing  the   nine  internal  standards
                  (Table 2) diluted with 1.0 ml acetone (Section 7.1).

                        8.3.4.1.2   Extract by using  the procedures beginning
                  in Sections 7.4.5 or  7.4.6, as applicable,  add  10 ML  of the
                  recovery  standard  solution  (Section 7.5.3.6) and analyze a
                  2 ML aliquot of the concentrated extract.

                        8.3.4.1.3   Calculate the concentration (Section 7.9.1)
                  of 2,3,7,8-substituted PCDDs/PCDFs  and the  percent recovery
                  of the internal standards (Section 7.9.2).

                        8.3.4.1.4   Extract and analyze a ne"w simulated fortified
                  field blank whenever new lots of solvents or  reagents are used
                  for sample extraction or for column chromatographic procedures.

                  8.3.4.2   Rinsate Sample

                        8.3.4.2.1   The rinsate sample must be fortified like
                  a regular sample.

                        8.3.4.2.2   Take a  100  ml (± 0.5 ml) portion  of the
                  sampling equipment rinse  solvent (rinsate sample),  filter, if
                  necessary, and add 100 ML of the solution containing the nine
                  internal  standards (Table 2).

                        8.3.4.2.3   Using  a  KD  apparatus,   concentrate  to
                  approximately 5 ml.

NOTE: As an option,  a rotary evaporator may be used in  place of  the KD apparatus
      for the concentration of the rinsate.

                        8.3.4.2.4   Transfer the 5 ml concentrate  from  the KD
                  concentrator tube in 1 ml  portions to a 1 ml minivial, reducing
                  the volume in the minivial as  necessary with a gentle  stream
                  of dry nitrogen.

                        8.3.4.2.5   Rinse  the  KD concentrator tube with  two
                  0.5 ml portions of hexane and transfer  the rinses  to the 1 ml
                  minivial.  Blow down with dry  nitrogen as necessary.

                        8.3.4.2.6   Just before analysis,  add 10 ML recovery
                  standard solution (Table 2) and reduce the volume to its final
                                  8290  - 39                       Revision 0
                                                                  November 1990

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                  volume, as necessary (Section 7.8.1).  No column chromatography
                  is required.

                        8.3.4.2.7   Analyze  an  aliquot  following  the  same
                  procedures used to analyze samples.

                        8.3.4.2.8   Report  percent  recovery  of the  internal
                  standard and the presence of any PCDD/PCDF compounds in /xg/L
                  of rinsate solvent.

            8.3.5 Duplicate Analyses

                  8.3.5.1  In each batch of samples,  locate the sample specified
            for duplicate analysis, and analyze a second 10 g soil  or sediment
            sample portion or 1  L water sample, or an appropriate amount of the
            type of matrix under consideration.

                        8.3.5.1.1   The results  of  the  laboratory duplicates
                  (percent recovery  and concentrations  of  2,3,7,8-substituted
                  PCDD/PCDF compounds)  should agree  within  25 percent relative
                  difference (difference expressed as percentage of the mean).
                  Report all  results.

                        8.3.5.1.2   Recommended actions to help locate problems:

                              8.3.5.1.2.1  Verify    satisfactory    instrument
                       performance  (Sections 8.2 and 8.3).

                              8.3.5.1.2.2  If possible,  verify that  no error was
                       made while weighing  the sample portions.

                              8.3.5.1.2.3  Review the analytical procedures with
                       the performing laboratory personnel.

            8.3.6 Matrix Spike and Matrix  Spike Duplicate

                  8.3.6.1  Locate the sample for the MS  and MSD analyses (the
            sample may be labeled "double  volume").

                  8.3.6.2  Add  an  appropriate  volume   of  the  matrix  spike
            fortification solution (Section 5.10)  and of the sample fortification
            solution  (Section  5.8), adjusting  the  fortification  level  as
            specified in Table 1 under IS  Spiking Levels.

                  8.3.6.3  Analyze  the  MS  and  MSD  samples  as described  in
            Section 7.

                  8.3.6.4  The results  obtained  from the  MS and  MSD samples
            (concentrations of  2,3,7,8-substituted  PCDDs/PCDFs) should  agree
            within 20 percent relative difference.

      8.4   Percent Recovery  of the Internal Standards -  For  each sample, method
blank and rinsate, calculate  the  percent recovery (Section 7.9.2).  The percent


                                   8290  -  40                      Revision 0
                                                                  November 1990

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recovery should be between 40 percent and 135 percent for all 2,3,7,8-substituted
internal standards.

NOTE: A low  or high percent recovery for a  blank  does not require discarding
      the analytical data but  it  may indicate a potential problem with future
      analytical data.

      8.5    Identification Criteria

             8.5.1 If  either one  of  the identification criteria  appearing in
      Sections 7.8.4.1.1 through 7.8.4.1.4 is not met  for  an homologous series,
      it   is   reported   that   the  sample  does   not   contain   unlabeled
      2,3,7,8-substituted PCDD/PCDF  isomers  for that  homologous series at the
      calculated detection limit  (Section 7.9.5)

             8.5.2 If  the  first  initial  identification  criteria  (Sections
      7.8.4.1.1  through  7.8.4.1.4)  are met,  but   the criteria  appearing in
      Sections 7.8.4.1.5 and 7.8.4.2.1 are not met, that  sample is presumed to
      contain  interfering contaminants.   This must be noted  on the analytical
      report form,  and the sample should be rerun or the  extract reanalyzed.

      8.6    Unused  portions  of samples  and  sample  extracts must  be preserved
for six months after sample receipt to allow  further analyses.

      8.7    Reuse  of glassware  is  to  be  minimized  to  avoid  the   risk of
contamination.


9.0 METHOD PERFORMANCE

      9.1 Data are  currently not available.


10.0  REFERENCES

1.    "Control  of  Interferences in the  Analysis of Human Adipose  Tissue for
      2,3,7,8-Tetrachlorodibenzo-p-dioxin".  D. G.  Patterson, J.S. Holler, D.F.
      Grote, L.R. Alexander, C.R. Lapeza, R.C.  O'Connor and  J.A.  Liddle. Environ.
      Toxicol. Chem. 5,  355-360 (1986).

2.    "Method 8290: Analytical Procedures and Quality Assurance for Multimedia
      Analysis of Polychlorinated Dibenzo-p-Dioxins and Dibenzofurans by High-
      Resolution Gas  Chromatography/High-Resolution  Mass Spectrometry".   Y.
      Tondeur  and  W.F.  Beckert.    U.S.  Environmental   Protection  Agency,
      Environmental Monitoring Systems Laboratory,  Las Vegas,  NV.

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

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

                                  8290  -  41                       Revision 0
                                                                  November  1990

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5.    "Safety  in  Academic Chemistry Laboratories", American  Chemical  Society
      Publication, Committee on Chemical Safety (3rd Edition, 1979.)

6.    "Hybrid  HRGC/MS/MS  Method for the Characterization  of Tetrachlorinated
      Dibenzo-p-dioxins in Environmental Samples."   Y. Tondeur, W.J. Niederhut,
      S.R. Missler, and J.E. Campana, Mass Spectrom. 14, 449-456 (1987).


11.0  SAFETY

      11.1  The following  safety  practices are excerpts from  EPA  Method 613,
Section 4  (July  1982 version)  and  amended for use in conjunction  with this
method.  The 2,3,7,8-TCOD isomer has been found to be acnegenic, carcinogenic,
and teratogenic in laboratory animal  studies.  Other PCDOs and PCDFs containing
chlorine atoms in positions 2,3,7,8 are known to have toxicities comparable to
that of 2,3,7,8-TCDD.   The analyst should note that finely  divided dry soils
contaminated with  PCDDs and PCDFs  are  particularly hazardous  because  of the
potential  for inhalation and ingestion.   It is recommended that such samples be
processed in a confined environment,  such as a hood  or a glove box.  Laboratory
personnel  handling these types of samples should wear masks fitted with charcoal
filters to prevent inhalation of dust.

      11.2  The toxicity or carcinogenicity of each  reagent used in this method
is not precisely defined; however, each chemical compound should be treated as
a potential  health hazard.  From this viewpoint, exposure to these chemicals must
be kept to a minimum.  The laboratory is responsible for maintaining a current
awareness file of OSHA regulations regarding the safe handling of the chemicals
specified in this method.  A reference file of material safety data sheets should
be made available to all personnel  involved in the chemical analysis of samples
suspected to contain  PCDDs  and/or  PCDFs.   Additional references to laboratory
safety are given in references 3,  4 and 5.

      11.3  Each laboratory must develop a strict safety program for the handling
of PCDDs and PCDFs.  The laboratory practices listed below are recommended.

            11.3.1      Contamination of the  laboratory will be minimized by
      conducting most of the manipulations  in a hood.

            11.3.2      The  effluents   of  sample  splitters  for  the  gas
      chromatograph  and roughing  pumps  on the HRGC/HRMS  system  should pass
      through either a column of activated charcoal  or be bubbled through a trap
      containing oil or high boiling alcohols.

            11.3.3      Liquid waste should be dissolved in methanol or ethanol
      and irradiated with ultraviolet light at a wavelength  less  than 290 nm for
      several days (use F 40 BL lamps,  or  equivalent).   Using this analytical
      method, analyze the irradiated  liquid wastes and dispose of the solutions
      when 2,3,7,8-TCDD and -TCDF  congeners can no longer be  detected.

      11.4  The following precautions were issued by Dow  Chemical U.S.A. (revised
11/78) for safe handling of 2,3,7,8-TCDD in the laboratory and amended for use
in conjunction with this method.
                                  8290  -  42                       Revision 0
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      11.4.1      The following statements on safe handling are as complete
as possible  on  the basis  of  available toxicological  information.   The
precautions for safe  handling  and  use  are  necessarily general  in nature
since  detailed,   specific  recommendations  can  be  made only  for  the
particular exposure and circumstances of each individual use.  Assistance
in evaluating the  health  hazards of particular plant  conditions  may be
obtained from certain consulting laboratories and from State Departments
of Health or of Labor,  many of which have  an industrial  health service.
The 2,3,7,8-TCDD isomer is  extremely toxic  to certain kinds of laboratory
animals.   However,  it has  been  handled  for  years  without  injury  in
analytical and biological  laboratories.  Many techniques used in handling
radioactive and infectious materials are applicable to 2,3,7,8-TCDD.

            11.4.1.1 Protective  Equipment:   Throw away  plastic  gloves,
      apron or lab coat, safety glasses and laboratory hood adequate for
      radioactive work.  However, PVC gloves should not be used.

            11.4.1.2 Training:   Workers  must  be  trained in the  proper
      method  of  removing  contaminated  gloves  and  clothing  without
      contacting the exterior surfaces.

            11.4.1.3 Personal  Hygiene:   Thorough  washing of  hands and
      forearms after each manipulation and before breaks (coffee, lunch,
      and shift).

            11.4.1.4 Confinement:  Isolated work area,  posted with signs,
      segregated glassware and tools,  plastic  backed absorbent paper on
      benchtops.
            11.4.1.5 Waste:      Good   technique   includes   minimizing
      contaminated waste.   Plastic bag liners should be used in waste cans.

            11.4.1.6 Disposal of Hazardous  Wastes:  Refer to the November
      7, 1986 issue of the Federal Register  on Land Ban Rulings for details
      concerning the handling of dioxin containing wastes.

            11.4.1.7 Decontamination:   Personnel  -  apply  a mild soap with
      plenty  of  scrubbing action.   Glassware,  tools  and surfaces  -
      Chlorothene NU  Solvent  (Trademark of the Dow Chemical Company) is
      the least toxic  solvent shown to be effective.  Satisfactory cleaning
      may be accomplished  by rinsing with Chlorothene, then washing with
      a detergent and  water.  Dish water may be disposed to the sewer after
      percolation through a charcoal bed filter. It is prudent to minimize
      solvent  wastes  because  they require   special  disposal  through
      commercial services  that are expensive.

            11.4.1.8 Laundry:  Clothing known  to  be  contaminated should
      be  disposed with the  precautions  described  under  "Disposal  of
      Hazardous  Wastes".   Laboratory  coats  or other  clothing worn  in
      2,3,7,8-TCDD  work area  may  be  laundered.    Clothing  should  be
      collected in plastic bags.   Persons who convey  the bags and launder
      the clothing should  be advised of the hazard and trained in proper
      handling.  The clothing may be put into a washer  without contact if
      the launderer knows  the problem.   The washer should be run through
      one full cycle before being used again for other clothing.

                             8290 - 43                       Revision 0
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                  11.4.1.9 Wipe  Tests:    A  useful  method  for  determining
            cleanliness of work surfaces and tools is to wipe the surface with
            a piece of filter paper, extract  the  filter paper and analyze the
            extract.

NOTE: A  procedure  for  the  collection,  handling,  analysis,  and  reporting
      requirements of wipe tests performed  within the  laboratory is described
      in Attachment A.  The results and decision making processes are based on
      the presence of 2,3,7,8-substituted PCDDs/PCDFs.

                  11.4.1.10   Inhalation:   Any  procedure  that  may  generate
            airborne contamination must  be  carried  out  with good ventilation.
            Gross losses to a ventilation system must not be allowed.  Handling
            of the dilute solutions normally used  in analytical and animal work
            presents no  significant inhalation hazards  except  in case  of an
            accident.

                  11.4.1.11   Accidents:      Remove   contaminated   clothing
            immediately, taking precautions not  to contaminate  skin  or other
            articles.   Wash exposed skin vigorously and repeatedly until medical
            attention  is obtained.
                                  8290  - 44                       Revision 0
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                                 Attachment A

            PROCEDURES  FOR THE  COLLECTION,  HANDLING, ANALYSIS, AND
            REPORTING OF  WIPE TESTS  PERFORMED WITHIN THE  LABORATORY

This procedure is designed for the periodic evaluation of potential contamination
by  2,3,7,8-substituted PCDD/PCDF congeners  of the working  areas  inside  the
laboratory.

      A.I   Perform the wipe tests  on  surface  areas of two  inches  by one foot
with glass fiber paper saturated with  distilled  in glass acetone using a pair
of clean  stainless  steel  forceps.   Use  one  wiper for each  of  the designated
areas. Combine the wipers to one composite sample in an extraction jar containing
200 ml distilled in glass  acetone.  Place  an equal number of unused wipers in
200  ml  acetone  and   use  this  as  a  control.    Add  100 juL  of  the  sample
fortification  solution to each jar containing used or unused wipers (Section
5.8).

            A.2.1 Close the jar containing the wipers and the acetone and extract
      for 20 minutes using a wrist action shaker.  Transfer the  extract into a
      KD  apparatus  fitted with a concentration  tube  and a  three  ball  Snyder
      column.  Add two Teflon™ or Carborundum™  boiling  chips  and concentrate
      the extract to an apparent volume  of 1.0 mL on  a steam bath.   Rinse the
      Snyder column and the KD assembly  with two  1 mL  portions  of hexane into
      the concentrator tube, and concentrate its contents to near dryness with
      a gentle stream  of nitrogen.   Add  1.0 mL hexane to the concentrator tube
      and swirl the solvent on the walls.

            A.2.2 Prepare  a neutral alumina  column  as  described  in  Section
      7.5.2.2 and follow the steps outlined in Sections  7.5.2.3 through 7.5.2.5.


            A.2.3 Add  10 pi of the  recovery  standard  solution as described in
      Section 7.5.3.6.

      A.3   Concentrate the contents of the vial to a final volume of  10 (j.1
(either  in  a  minivial  or in a  capillary tube).   Inject  2 nl of each  extract
(wipe and control) onto a capillary column and analyze for 2,3,7,8-substituted
PCDDs/PCDFs  as specified  in the  analytical  method  in Section 7.8.   Perform
calculations according to Section 7.9.

      A.4   Report the presence of 2,3,7,8-substituted  PCDDs  and PCDFs  as a
quantity  (pg or ng) per wipe test experiment (WTE).  Under the conditions out-
lined in this analytical  protocol,  a lower  limit of calibration of 10 pg/WTE is
expected  for  2,3,7,8-TCDD.  A positive response  for  the blank  (control)  is
defined  as  a signal  in the  TCDD retention time  window  at any  of  the masses
monitored which is equivalent  to or above 3 pg of 2,3,7,8-TCDD  per  WTE.   For
other congeners,  use the  multiplication factors listed  in Table 1, footnote (a)
(e.g., for OCDD,  the lower MCL is 10 x 5 = 50 pg/WTE  and the positive response
for the  blank would be 3 x 5  = 15 pg).   Also,  report the  recoveries  of the
internal standards during the simplified cleanup procedure.
                                   8290  -  45                       Revision 0
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      A.5   At a minimum, wipe tests should be performed when there is evidence
of contamination in the method blanks.

      A.6   An upper limit of 25 pg per TCDD isomer and per wipe test experiment
is allowed (use multiplication factors listed in footnote (a) from Table 1 for
other congeners). This value corresponds to 2\ times the lower calibration limit
of the  analytical  method.   Steps  to correct the contamination must  be taken
whenever these levels are  exceeded.   To  that effect,  first  vacuum the working
places  (hoods,  benches,  sink)  using a  vacuum  cleaner  equipped  with  a  high
efficiency particulate absorbent (HEPA) filter and then  wash with a detergent.
A new set of wipes  should  be analyzed before anyone is  allowed  to work in the
dioxin area of the laboratory after corrective action has been taken.
                                  8290  - 46                       Revision 0
                                                                  November 1990

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                   Figure 1.
 8
       6              u             4

              Dibenzodioxin
 8
              Dibenzofuran
General  structures of d1benzo-p-d1ox1n and dlbenzofuran.

                   8290 - 47
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November 1990

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                                 Figure 2.
M/AM
                                                    5,600
                         B
                                                    5,600
                                                    8,550
                                  400 ppm
  Peak profile displays demonstrating the effect of the detector zero on the
measured resolving power.  In this example, the true resolving power is 5,600.

      A) The zero was set too high;  no  effect 1s observed  upon the measurement
      of the resolving power.

      B) The zero was adjusted  properly.

      C) The zero was set too low;  this results  1n  overestimating the actual
      resolving  power  because  the  peak-to-peak  noise   cannot  be  measured
      accurately.
                                 8290 - 48
          Revision 0
          November 1990

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                            Figure 3.
   8:00 AM
Mass Resolution
 Mass Accuracy
                    Analytical  Procedure
                       Thaw Sample Extract
                                1
                        Concentrate to 10 uL
                                I
 9:00 AM
 Initial or
 Routine
Calibration
              GC Column
              Performance
11:00 AM
        Method
         Blank
8:00 PM
                   Mass
                 Resolution
         Routine
        Calibration
               Typical 12 hour analysis sequence of events.

                             8290 - 49
                             Revision 0
                             November 1990

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           o
           o
                                    Figure 4.
                                6'8'Z'L
                          8'9'C'l
                                                                        o
                                                                        o
                                                                        n

                                                                       'lA
                                                                        (N
                                                                           0)
                                                                        M
Selected  ion current profile for m/z 322  (TCOOs) produced  by  MS  analysis of the


GC performance check solution  on  a  60 m DB-5 fused silica capillary column under


                     the conditions listed in Section 7.6.
                                    8290 - 50
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November  1990

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                                 Figure 5.
                                         Ref. mass 304.9824 Peak top
                                         Span. 200 ppm
                                         System file name
                                         Data file name
                                         Resolution
                                         Group number
                                         lonization mode
                                         Switching
                                         Ref. masses
YVES150
A 85Z567
   10000
        1
      EI +
VOLTAGE
304.9824
380.9260
                                             M/AM—10.500
                                         Channel B 380.9260 Lock mass
                                         Span 200 ppm
 Peak profiles representing two PFK reference Ions  at m/z 305 and 381.   The
resolution  of  the high-mass signal  1s  95 ppm  at 5 percent of the  peak height;
   this  corresponds to a resolving  power M/ N of 10,500 (10  percent valley
                               definition).
                                 8290  -  51
    Revision 0
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                                    Figure 6.
 20:00
22:00
24:00
26:00
28:00
30:00
                          Manual determination of S/N.

 The peak height (S) Is measured between the mean noise (lines C and 0).  These
mean signal values are obtained by tracing the line between the baseline average

 noise extremes, El and E2, and between the apex average noise extremes, E3 and
                        E4, at the apex of the signal.

 NOTE: It 1s Imperative that the Instrument Interface amplifier electronic zero
       offset  be set  high enough  so that  negative going  baseline  noise  1s
       recorded.
                                    8290 -  52
                                                     Revision  0
                                                     November 1990

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                                   Table 1.

            Types of Matrices, Sample Sizes and 2,3,7,8-TCDD-Based
                Method Calibration Limits  (Parts per Trillion)



Lower MCL(a)
Upper MCLta)
Weight (g)
IS Spiking
Levels (ppt)
Final Extr.
Vol. (AiL)(d)


Water
0.
2
1000

1

10-50
Soil
Sediment
Paper Pulp"
01 1.0
200
10

100

10-50

Fly
Ash
1.0
200
10

100

50

Fish
Tissue
1.0
200
20

100

10-50
Human
Adipose
c Tissue
1.0
200
10

100

10-50

Sludges,
Fuel Oil
5.0
1000
2

500

50

Still-
Bottom
10
2000
1

1000

50
(a) For other congeners multiply  the  values  by 1  for TCDF/PeCDD/PeCDF, by 2.5
    for HxCDD/HxCDF/HpCDD/HpCDF, and by 5 for OCDD/OCDF.

(b) Sample dewatered according to Section 6.5.

(c) One half of the extract  from  the  20  g sample  is used for determination of
    lipid content (Section 7.2.2).

(d) See Section 7.8.1, Note.


NOTE: Chemical  reactor  residues  are  treated  as  still  bottoms  if  their
      appearances so  suggest.
                                   8290  -  53                       Revision 0
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                                   Table 2.

                    Composition of the  Sample Fortification
                        and Recovery Standard Solutions3
Analyte
Sample Fortification
Solution
Concentration
(pg/juL; Solvent:
Nonane)
Recovery Standard
Solution
Concentration
(pg//iL; Solvent:
Nonane)
13C12-2,3,7,8-TCDD              10
13C12-2,3,7,8-TCDF              10
13C12-1,2,3,4-TCDD

13C12-l,2,3,7,8-PeCDD           10
13C12-l,2,3,7,8-PeCDF           10

13C12-l,2,3,6,7,8-HxCDD         25
13C12-l,2,3,4,7,8-HxCDF         25
13C12-l,2,3,7,8,9-HxCDD

13C12-l,2,3,4,6,7,8-HpCDD       25
13C12-l,2,3,4,6,7,8-HpCDF       25
13C12-OCDD                       50
                              50
                              50
(a)  These solutions should be made freshly every day because of the possibility
of adsorptive losses to glassware.   If these solutions are to be kept for more
than one day, then  the sample fortification  solution  concentrations should be
increased ten fold, and the recovery standard solution concentrations should be
doubled.  Corresponding adjustments of the spiking volumes must then be made.
                                   8290 - 54
                                          Revision  0
                                          November 1990

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                                   Table 3.

           The Fifteen 2,3,7,8-Substituted PCDD and PCDF Congeners


      PCDD                             PCDF


  2,3,7,8-TCDD(*)                   2,3,7,8-TCDF(*)

  l,2,3,7,8-PeCDD(*)                l,2,3,7,8-PeCDF(*)

  l,2,3,6,7,8-HxCDD(*)              2,3,4,7,8-PeCDF

  1,2,3,4,7,8-HxCDD                 1,2,3,6,7,8-HxCDF

  l,2,3,7,8,9-HxCDD(+)              1,2,3,7,8,9-HxCDF

  l,2,3,4,6,7,8-HpCDD(*)            l,2,3,4,7,8-HxCDF(*)

                                    2,3,4,6,7,8-HxCDF

                                    l,2,3,4,6,7,8-HpCDF(*)

                                    1,2,3,4,7,8,9-HpCDF



(*)  The 13C-labeled analogue is used as an internal  standard.

(+)  The ISC-labeled analogue is used as a recovery standard.
                                  8290  -  55                       Revision 0
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                   Table 4.

Isomers of Chlorinated Dioxins and Furans as a
   Function of the Number of Chlorine Atoms
Number of
Chlorine
Atoms
1
2
3
4
5
6
7
8
Total
Number of
Dioxin
Isomers
2
10
14
22
14
10
2
1
75
Number of
2,3,7,8
Isomers

—
—
1
1
3
1
1
7
Number of
Furan
Isomers
4
16
28
38
28
16
4
1
135
Number of
2,3,7,8
Isomers
—
—
—
1
2
4
2
1
10
                  8290  -  56
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November 1990

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                                   Table 5.

              High-Resolution Concentration Calibration Solutions
                                          Concentration (pq/uL. in Nonane)
Compound
HRCC
Unlabeled Analytes
2,3,7,8-TCDD
2,3,7,8-TCDF
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
OCDD
OCDF
Internal Standards
13C12-2,3,7,8-TCDD
13C12-2,3,7,8-TCDF
13C12-l,2,3,7,8-PeCDD
13C12-l,2,3,7,8-PeCDF
13C12-l,2,3,6,7,8-HxCDD
13C12-l,2,3,4,7,8-HxCDF
13C12-l,2,3,4,6,7,8-HpCDD
13C12-l,2,3,4,6,7,8-HpCDF
13C12-OCDD
Recovery Standards
13C12-l,2,3,4-TCDD(a)
13C12-l,2,3,7,8,9-HxCDDtb)

200
200
500
500
500
500
500
500
500
500
500
500
500
500
500
1,000
1,000

50
50
50
50
125
125
125
125
250

50
125

50
50
125
125
125
125
125
125
125
125
125
125
125
125
125
250
250

50
50
50
50
125
125
125
125
250

50
125

10
10
25
25
25
25
25
25
25
25
25
25
25
25
25
50
50

50
50
50
50
125
125
125
125
250

50
125

2.5
2.5
6.25
6.25
6.25
6.25
6.25
6.25
6.25
6.25
6.25
6.25
6.25
6.25
6.25
12.5
12.5

50
50
50
50
125
125
125
125
250

50
125

1
1
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
5
5

50
50
50
50
125
125
125
125
250

50
125
(a)   Used for  recovery  determinations of TCDD, TCDF,  PeCDD and PeCDF  internal
    standards.

(b)   Used for  recovery  determinations of  HxCDD,  HxCDF, HpCDD,  HpCDF and OCDD
    internal standards.
                                   8290 -  57
                                          Revision 0
                                          November  1990

-------
                      Table 6.

Ions Monitored for HRGC/HRMS Analysis of PCDDs/PCDFs
Descriptor
1









2









3









4









Accurate'8'
Mass
303.9016
305.8987
315.9419
317.9389
319.8965
321.8936
331.9368
333.9338
375.8364
[354.9792]
339.8597
341.8567
351.9000
353.8970
355.8546
357.8516
367.8949
369.8919
409.7974
[354.9792]
373.8208
375.8178
383.8639
385.8610
389.8156
391.8127
401.8559
403.8529
445.7555
[430.9728]
407.7818
409.7788
417.8250
419.8220
423.7767
425.7737
435.8169
437.8140
479.7165
[430.9728]
Ion
ID
M
M+2
M
M+2
M
M+2
M
M+2
M+2
LOCK
M+2
M+4
M+2
M+4
M+2
M+4
M+2
M+4
M+2
LOCK
M+2
M+4
M
M+2
M+2
M+4
M+2
M+4
M+4
LOCK
M+2
M+4
M
M+2
M+2
M+4
M+2
M+4
M+4
LOCK
Elemental
Composition
C12H435C140
C12H435C1337C10
13C12H435C140
13C12H,35C1337C10
Ci2H43Cl40,
C12H435C1337C102
13p M 35/»-| n
13M*35C1*37C102
C12H43SC1537C10
C9F13
C12H335C1437C10
C12H335C1337C120
C12H3 C14 CIO
13C12H35C137C120
C12H33SC1437C102
C12H335C1337C1202
13C12H335C1437C102
13C12H35C137C1202
Ci2H3 C1637C10
C9F13
C H35C1 37C10
C3i2H235Cl437cl20
C12H235C160
13C12H235C137C10
C12H3C13C102
C12H235C1437C1202
13C12H235C1537C102
13C12H/C1/C1202
C12H23§C1637C120
C9F17
C H35C1 37C10
C12H35C1537C120
13C12H35C170
13C12H35C1 37C10
C12H C163 C102
Ci2H35Cl537Cl202
13C12H35C1637C102
13C12H35C1 37C1202
C12H C173 C120
C9F17
Analyte
TCDF
TCDF
TCDF (S)
TCDF (S)
TCDD
TCDD
TCDD (S)
TCDD (S)
HxCDPE
PFK
PeCDF
PeCDF
PeCDF (S)
PeCDF (S)
PeCDD
PeCDD
PeCDD (S)
PeCDD (S)
HpCDPE
PFK
HxCDF
HxCDF
HxCDF (S)
HxCDF (S)
HxCDD
HxCDD
HxCDD (S)
HxCDD (S)
OCDPE
PFK
HpCDF
HpCDF
HpCDF (S)
HpCDF
HpCDD
HpCDD
HpCDD (S)
HpCDD (S)
NCDPE
PFK
                     8290  - 58
Revision 0
November 1990

-------
                                    Table  6.

                                   Continued
Descriptor
5







Accurate(a)
Mass
441.7428
443.7399
457.7377
459.7348
469.7780
471.7750
513.6775
[442.9278]
Ion
ID
M+2
M+4
M+2
M+4
M+2
M+4
M+4
LOCK
Elemental
Composition
C1235C1737C10
C1235C1637C120
C18"ClŁciQ,
C1235C1 37C1202
13C1235C1737C102
13C 35C1/C1202
C123§C1837C120
C-IO' 17
Analyte
OCDF
OCDF
OCDD
OCDD
OCDD (S)
OCDD (S)
DCDPE
PFK
(a)
    The following nuclidic masses were  used:
            H =  1.007825
            C =12.000000
          13 C =13.003355
            F =18.9984

S = internal/recovery standard
  0 = 15.994915
35C1 = 34.968853
37C1 = 36.965903
                                    8290 - 59
                                 Revision 0
                                 November 1990

-------
                                         Table  7.

                   PCDD and PCDF Congeners Present in the GC Performance
                       Evaluation Solution and Used for Defining the
                        Homologous GC  Retention Time  Windows  on  a
                                     60 m  DB-5  Column
No. of
Chlorine
Atoms
4
-------
                                    Table 8.

           Theoretical Ion Abundance  Ratios and Their Control Limits
                              for PCDDs  and PCDFs
Number of
Chlorine
Atoms
4
5
6
6(a)
y(b)
7
8
Ion
Type
JL
M+2
M±2
M+4
M+l
M+4
M
M+2
JL
M+2
M+2
M+4
M+l
M+4
Theoretical
Ratio
0.77
1.55
1.24
0.51
0.44
1.04
0.89
Control
lower
0.65
1.32
1.05
0.43
0.37
0.88
0.76
Limits
upper
0.89
1.78
1.43
0.59
0.51
1.20
1.02
(a)    Used only for 13C-HxCDF  (IS).

(b)    Used only for 13C-HpCDF  (IS).
                                   8290  -  61
Revision 0
November 1990

-------
                                Table 9.

         Relative Response  Factor [RRF (number)] Attributions


Number                         Specific Congener Name
  1                      2,3,7,8-TCDD (and total TCDDs)
  2                      2,3,7,8-TCDF (and total TCDFs)
  3                      1,2,3,7,8-PeCDD (and total PeCDDs)
  4                      1,2,3,7,8-PeCDF
  5                      2,3,4,7,8-PeCDF
  6                      1,2,3,4,7,8-HxCDD
  7                      1,2,3,6,7,8-HxCDD
  8                      1,2,3,7,8,9-HxCDD
  9                      1,2,3,4,7,8-HxCDF
  10                     1,2,3,6,7,8-HxCDF
  11                     1,2,3,7,8,9-HxCDF
  12                     2,3,4,6,7,8-HxCDF
  13                     1,2,3,4,6,7,8-HpCDD (and total HpCDDs)
  14                     1,2,3,4,6,7,8-HpCDF
  15                     1,2,3,4,7,8,9-HpCDF
  16                     OCDD
  17                     OCDF
  18                     13C12-2,3,7,8-TCDD
  19                     13C12-2,3,7,8-TCDF
  20                     13C12-l,2,3,7,8-PeCDD
  21                     13C12-l,2,3,7,8-PeCDF
  22                     13C12-l,2,3,6,7,8-HxCDD
  23                     13C12-l,2,3,4,7,8-HxCDF
  24                     13C12-l,2,3,4,6,7,8-HpCDD
  25                     13C12-l,2,3,4,6,7,8-HpCDF
  26                     13Cr,-OCDD
  27                     Total  PeCDFs
  28                     Total  HxCDFs
  29                     Total  HxCDDs
  30                     Total  HpCDFs
                               8290 - 62                       Revision 0
                                                               November 1990

-------
                                Table 10.

        2,3,7,8-TCDD Toxicity  Equivalency  Factors  (TEFs) for the
            Polychlorinated Dibenzodioxins and Dibenzofurans
Number
Compound(s)
TEF
 1
 2
 3
 4
 5
 6
 7
2,3,7,8-TCDD
1,2,3,7,8-PeCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDD
1,2,3,4,6,7,8-HpCDD
1,2,3,4,6,7,8,9-OCDD
1.00
0.50
0.10
0.10
0.10
0.01
0.001
 8
 9
10
11
12
13
14
15
16
17
2,3,7,8-TCDF
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
1,2,3,4,7,8-HxCDF
2,3,4,6,7,8-HxCDF
1,2,3,4,6,7,8-HpCDF
1,2,3,4,7,8,9-HpCDF
1,2,3,4,6,7,8,9-OCDF
0.1
0.05
0.5
  1
  1
  1
  1
  01
0.01
0.001
                                8290 - 63
                                              Revision 0
                                              November 1990

-------
                                   Table 11.
            Analyte  Relative  Retention Time Reference Attributions

Analyte                     Analyte  RRT Reference(a)

1,2,3,4,7,8-HxCDD             13C12-l,2,3,6,7,8-HxCDD
1,2,3,6,7,8-HxCDF             13C12-l,2,3,4,7,8-HxCDF
1,2,3,7,8,9-HxCDF             13C12-l,2,3,4,7,8-HxCDF
2,3,4,6,7,8-HxCDF             13C12-l,2,3,4,7,8-HxCDF
(a)  The retention time of 2,3,4,7,8-PeCDF on the DB-5 column is measured relative
   to 13C12-l,2,3,7,8-PeCDF and the retention time of 1,2,3,4,7,8,9-HpCDF relative
   to 13C12-l,2,3,4,6,7,8-HpCDF.
                                   8290 - 64                -       Revision 0
                                                                   November 1990

-------
                                                               METHOD  8290
                 POLYCHLORINATED DIBENZODIOXINS (PCDDs)  AND POLYCHLORINATED DIBENZOFURANS  (PCDFs)
                BY  HIGH-RESOLUTION  GAS CHROMATOGRAPHY/HIGH-RESOLUTION MASS  SPECTROMETRY  (HRGC/HRMS)
          ("START)
 7.1 INTERNAL STANDARD ADDITION
7.1.1 Sample size of 1 to 1000
grams, see section 7.4 & Table 1.
Determine  wt. on tared flask
7.1.2 Spike samples w/100 ul
fortification mixture yielding
internal standard cones, of
Table 1, except for adipose tissue
 7.1.2.1 For soil, sediment,  fly
 ash, water, and fish tissue, mix
 1  ml acetone with 100 ul
 mixture
7.1.2.2 Do not dilute for other
sample matrices
                                                                                          i
                           [7.2 SAMPLE EXTRACTION AND PURIFICATION!
                                                        ±
                                             [7.2 Fish and Paper Pulp]
7.2.1 Mix 60 gr sodium
sulfate and 20 gr sample;
place mix in Soxhlet; add
200 mis 1:  1  hexone/MeCI;
reflux  12 hours
7.2.2 Transfer extract to a
KD apparatus with a Snyder
column
7.2.3 Add Teflon boiling
chip; concentrate to 10
mis  in  water bath;  cool for
5 minutes
7.2.4 Add new chip, 50 mis
hexane to flask; concentrate
to 5 mis; cool for 5 mins.;
assure  MeCI out before next
step
                                              7.2.5 Rinse apparatus with
                                              hexane; transfer contents
                                              to a separatory funnel; do
                                              cleanup procedure
                                          ±
                               J7.3 Human Adipose Tissue |       I 7.4 Environmental and Waste I
7.3.1  Store samples at or
below -20 C, care taken in
handling
                                                                              7.3.2 Extraction
    .1 Weigh out sample
    .2 Let stand to room  T
    .3 Add MeCI, fortification
       soln., homogenize
    .4 Separate MeCI layer,
       filter, dry, transfer to
       vol. flask
    .5 Redo step 3, add to
       vol. flask
    .6 Rinse sample train,
       add to vol. flask
    .7 Adjust to mark w/
       MeCI
 7.3.3 Determine Lioid Content
     .1 Preweigh 1 dram
       glass vial
     .2 Transfer and reduce 1
       ml. extract to viol til
       weight constant
     .3 Calculate weight dried
       extract
     .4 Calculate %  lipid content
       from  eon.
     .5 Record lipid  extract wt.
	and % lipid  content
                                                                                           T
7.3.4 Extract Concentration
    .1 Transfer and rinse vol.
       flask contents of 7.3.2.7
       to  round bottom
    .2 Concentrate on rotovap
       at  40 C
7.3.5 Extract Cleanup
     n Dissolve SecHon 4 extract
       with hexane
     .2 Add acid impregnated
       silica, stir for 2 hours
     .3 Decant and dry liquid
       with sodium sulfaie
     .4 Rinse silica 2x w/hexone
       dry w/sodium sulfate,
       combine rinses w/step 3
     .5 Rinse sodium sulfate,
       combine rinse w/step 4
     .6 Prepare acidic silica
       column
     .7 Pass hexone extract
       through column, collect
       eluate  in 500 ml. KD
       assembly
     .8 Rinse column w/hexane,
       combine eluate w/step 7
       concentrate total eluate
       to 100 ul
Note: If  column discolored,
      repeat cleanup  (7.3.5.1)
     .9 Extract ready for column
       cleanup
                                                                 8290  -  65
                                                                         Revision  0
                                                                         November  1990

-------
                                                                      METHOD  8290
                                                                       continued
                                                            I 7.4 Environmentol ond Woste Somplesl
                      7.4.1  Sludge/Wet Fuel Oil
                           .1 Extract sample with toluene
                             using Dean-Stark water
                             separator
                           .2 Cool sample, filter through
                             glass fiber filter
                           .3 Rinse litter w/toluene,
                             combine w/extract
                           .4 Concentrate to near dryness
                             using rolovap
                      Note: Sample dissolves in toluene.
                            treat as In  Section 7.4.2;
                            sample from pulp, treat as
                            In Section 7.2	
                                     L
                                                                7.4.2 Still Bottom/On
                                                                     .1 Extract sample w/toluene
                                                                       filter through glass fiber
                                                                       filter Into round bottom
                                                                     .2 Concentrate on rotovap
                                                                       at 50 C
                          7.4.4 Transfer concentrate to sep
                               funnel using hexane; rinse
                               container, add to funnel;
                               add 5X NaCI soln., shake
                               2 minutes; discard aqueous
                               layer
7.4.5 Aqueous
     .1 Let sample stand to room T;
       mark meniscus on bottle; add
       fortification soln.
     .2 Filter sample:  centrifuge first
       if  needed
     .3 Combine filtered/centrifuged
       solids along w/filter; do Soxhlet
       extraction of Section 7.4.6.1;
       rinse assembly  ft combine
     .4 Transfer aqueous phase to sep
       funnel;  rinse sample bottles
       w/MeCI & transfer to funnel;
       shake and extract  water
     .5 Let phases separate, use
       mechanical means if needed
     .6 Pass UeCI lover through drying
       agent, collect in KD assembly
       w/concentrotor tube
     .7 Repeat step 4-6 2x, rinse
       drying agent, combine  all
       in KD assembly
Note:  Continous liquid-liquid
      extractor may be used if
      emulsion problems occur
   .8 Attach Snyder column,
      concentrate on water bath
      til 5 mis left; remove KD
      assembly, allow to  drain ft
      cool
   .9 Remove column; add hexone,
      extraction concentrate of  solids,
      ft new boiling chip; attach column,
      concentrate to 5 mis
  .10 Rinse flask ond assembly  to final
      volume 15  mis
  .11 Determine original sample volume
      by transferring meniscus volume to
      graduated cylinder
                                                                   7.4.3 Fly Ash
                   .1 Weigh sample; add
                     fortification soln. in acetone,
                     1M  HCI; shake in extraction
                     jar  for 3 hours
                   .2 Filter mix in Buchner funnel;
                     rinse filter cake  w/water;  dry
                     filter coke at room T
                   .3 Add sodium sulfote to  cake,
                     mix and let stand for  1 hr.,
                     mix again and let stand
                   .4 Place sample in  extraction
                     thimble; extract  in Soxhlet
                     for 16 hours w/toluene
                   .5 Cool and filter extract; rinse
                     containers ft combine; rotovap
                     to near dryness  at 50  C
7.4.6 Soil
     .1 Add sodium sulfate, mix; transfer mixture to
       Soxhlet assembly atop glass wool plug
     .2 Add toluene, reflux for 24 hours
Note:  Add  more sodium sulfate if sample  does not
      flow  freely
     .3 Transfer extract to round bottom
     .4 Concentrate to  10  mis on rotovap,  allow to
       cool
     .5 Transfer concentrate and hexane rinses to KD
       assembly; concentrate to tO mis, allow to
       cool
     .6 Rinse Snyder column into KD; transfer KD
       ft concentrator tube liquids to  sep  funnel;
       rinse  KD assembly w/hexane ft add to funnel
                                                                        8290  -  66
                                                                                                   Revision 0
                                                                                                   November 1990

-------
                                                            METHOD  8290
                                                              continued
            |7.5 CLEANUP)
7.5.1 Partition
    .1  Partition txlract w/concentroted
       sulturic acid:  shak*. discard
       acid layer; repeat acid vast) til
       no color present or done 4x
    .2  OMIT FOR FISH SAMPLES. Partition
       extract w/NoCI soln.; snake.
       discard aqueous layer
    .3  OMIT FOR FISH SAMPLES. Partition
       extract w/KOH  soln.; shake.
       discard base layer; repeat base
       wash til no color obtained In wash
       or  done 4x
    .4  Partition extract w/NoCI soln.;
       shake, discord  oaueous layer.
       Dry extract w/sodium sulfate
       into round bottom  flask; rinse
       sodium sulfate  w/hexone;
       concentrate hexane soln. in
       rotovap
                                                7.5.2
        eg/Alumina Column
                                                                       imn
                                                                       km
    .1 Pock a gravity column w/silica gel;
       fill w/ hexane. elute to top of bed;
       check for channeling
    .2 Pack a gravity column w/olumina;
       fill w/hexane. elute to top of bed.
       check for channeling
Note: Acidic alumina may be used Instead of
     neutral alumina.
    .3 Dissolve residue of Section 7.5.1.4
       in hexane; transfer soln. to lop of
       silica column
    .4 Elute silica column w/hexane
       directly onto alumina column
    .5 Add hexone to alumina column;
       elute to top of sodium sulfate in
       collect ana  save eluted hexane
    .6 Add MeCI/hexane  soln. to alumina
       column; collect eluate  in concentrator
       tube
                                                    7.5.3 Carbon Column
                                                        .1  Prepare AX-21
        repare AX-21/Celite 545 column;
       activate mixture at 130 C for 6
       hours;  store in dessicator
    .2 Pack a 10 ml serologicol pipet
       w/prepored  AX-2t/Celite 545 mix
Note:  Each batch of AX-21/Celite 545
      must be checked for 7. recovery
      of anatytes.
    .3 Concentrate  MeCI/hexane fraction
       of Section 7.5.2.6 to 2  mis
       w/nitrogen;  rinse  column
       w/several solns.; add sample
       concentrate and rinses  to top
       of column
    .4 Elute column sequentially
       w/: cyclohexane/MeCI;  MeCI/
       methanol/toluene; combine eluates
    .5 Turn column upside down, elute
       PCDD/PCDF fraction w/loluene;
       filter if carbon fines present
    .6 Concentrate  toluene  fraction on
       rotovap: further concentrate to
       100 ul in miniviol  using  nitrogen
       at 50  C; rinse tlosk 3x  w/1%
       toluene in MeCI; add tridecane
       recovery std.; store room temp.
       in the dark
                                                              8290  -  67
                                                                              Revision
                                                                              November
                                        0
                                        1990

-------
                                                                  METHOD 8290
                                                                   continued

7.6
1
Chromatoqraphlc. Mass Spectromttric, and
Data Acquisition Parameters
1
76
1
1 fins Chramataaranh
Select correct dimensions and parameters
of column, and set-up chromotographlc
conditions

7fi


9 Un«« ^n«-trnm«t«r
.1 Operate mass spectrometer h selected
Ion monitoring (SIM) mode; monitor Ions
of five SIM descriptors
.2 Tune mass spectrometer based on ions
of SIM descriptors
i
7fi


V IViln Ac«iiil«!Hnn
.1 Total cycle time of < or = t second
.2 Acquire SIM data for tons of 5
descriptors
                                                     771  Initial Calibration
                                                           Required before any sample analysis,
                                                           and if routine calibration does not
                                                           meet criteria
                                                          .1 All 5 calibration solns. must be
                                                            used for initial calibration
                                                          .2 Tune mass spectrometer  w/PFK as
                                                            described in Section 7.7.3
                                                          .3 Inject 2 ul of CC column performance
                                                            check soln. and acquire  SIM  data;
                                                            assure Section 8.1.2 criterion are met
                                                          .4 Analyze each of S calibration standards
                                                            using the same conditions, with the
                                                            following  MS operating parameters:
                                                           .1 Ratio of integrated ion  current for
                                                              Table 8 ions within control limits
                                                           .2 Ratio of integrated ion  current for
                                                              carbon  labeled internal and recovery
                                                              standards within control limits
                                                          Note:  Control limits must be achieved in
                                                                one run for oH Ions.
                                                           .3 Signal to noise (S/N) ratio for each
                                                              target anatyte and labeled  std. selected
                                                              ion current profiles (SICP) and
                                                              CC signals > 2.S
                                                                                 7.7.1.4
                                                                                       .4 Calcute relative response factors (RRF)
                                                                                          for unlabeled and labeled target analytes
                                                                                          relative to internal stds. (Table S)
                                                                                       .5 Calculate average and  relative standard
                                                                                          deviation for the 5 calibration solutions
                                                                                       .6 RRFs for concentration  determination of
                                                                                          total isomers  in a homologous series
                                                                                          are calculated as:
                                                                                         .1  Congeners in a homologous series w/one ,
                                                                                            isomer, mean RRF used is some as Section
                                                                                            7.7.1.4.5
                                                                                       Note:  Calibration solns. do not contain
                                                                                              labeled OCOF; therefore. RRF OCDF
                                                                                              relative to labeled OCOD
                                                                                         .2  Calculation  lor mean RRF for congeners
                                                                                            in a homologous series w/more than one
                                                                                            isomer
                                                                                       Note:  Isomers in homologous series w/o
                                                                                              2,3,7,8 substitution pattern allotted
                                                                                              same response  factor as other  2,3,
                                                                                              7,8 isomers in series
                                                                                       .7 Calculation  of  RRFs  used to determine
                                                                                          % recoveries of nine internal standards
7.7.2
itqble Cofibrotio
ist be met befoi
             listed musToe met before
     analysis
     .1 The X RSO for unlabeled stds.  must
       be within +/- 20X; for labeled.
       +/- MX
     .2 S/N ratio for CC signals > or = 2.5
     .3 Table 8  Isotopic ratios within limits
Note: When criteria for acceptable calibration
      ore met,  mean RRFs used for calculations
      until routine calibration criteria are not
      met
                                                       771 Bnnlin« Cnlihrntion
  Performed at 12 hour periods after
  successful resolution checks
.1  Inject 2 ul calibration soln. HRCC-3;
   use some HRCC/HRMS conditions of
   Sections 7.6.1 and 7.6.2; document
   an acceptable calibration
771 Triform fnr Arr^plnhl* Rnnlina (tnlihrnlipn
     .1 Measured unlabeled RRFs must be w/in
       +/- 20% of initial calibration values
     .2 Measured labeled RRFs must be w/in
       +/~ 30X of initial calibration values
     .3 Table 8 ion  abundance ratios must be
       w/in limits
     .4 Review routine calibration process if
       criteria at steps I  and 2  are not
       satisfied
      An initial calibration must be done
      when new  HRCC-3, sample fortification,
      or recovery std.  soln.  from another lot
      is used
                                                                                      Note:
                                                                  8290  -  68
                                                                                                               Revision  0
                                                                                                               November  1990

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                                                                METHOD  8290
                                                                 continued
               _L
         I  7.8 Anolvsls    I
               Anal
7.8.1 Reduce extract or blonk volume
     to 10 or SO ul
7.8.2 Into! 2 ul aliquot of the sample
     into Ih. GC
7.8.3 Acquire SIM data according to
      Sections 7.6.2 and 7.6.3
'

Note: Acquisition period must at
least encompass PCOD/PCDF
overall retention time window
                                                  7.8.4 CC Identification CriUrin
.1 Relative Retention Times
  .1 2.3.7.8 sub:  Sample components
    relative retention  time (RRT) w/ln
    -1 to 3 seconds of retention
    time of labeled internal or
    recovery std.
 .2 2.3.7.8 sub: Sample RRTs
    w/ln homologous retention
    time  windows  if w/o labeled
    internal std.
 .3 non 2,3.7.8 sub:  Retention
    time  w/in homologous
    retention time window
 .4 Ion current  responses for
    quantitotion must reach maximum
    w/in 2 seconds
 .5 Ion current  responses lor labeled
    stds. must reach maximum w/in
    2 seconds
Note:  Verify presence ol 1,2.8.9-TCUD and
      1.3.4.6.8-PeCOF in SICPs
    .2 Ion Abundance Ratios
      .1 Ratio of integrated ion current (or
        two ions used  for quantification
        w/in limits of  homologous series
    .3 Siqnol-to-Noise  Ratio
      .1 All ion current  intensities > =  2.5
    .4 Polychlorinated Diphenyl Ether
       Interferences
      .1 Corresponding  PCDPE channel clear
        of signal > =  S/N 2.5 at same
        retention time
         _L
  I 7.9 Calculation*!
J
7.9.1 Calculate concentration of PCOD
or PCOF compounds w/formulo
1
7.9.2 Calculate X recovery of nine
internal stds. using formula
Note: Add IK recovery for human
adipose tissue samples
1
7.9.3 Use smaller sample ami. if
calculated concentration exceeds
method calibration limits
1
7.9.4 Sum ol isomer concentration is
total concentration for a
homologous series
1




Lirj['»'fDl|
I
climated Detection
EDL Analyte concentration yielding
peak hi. 2.5x noise level. EOLs calculated
for non-identified 2,3.7 .8- sub congeners
Two methods of calculation:
.1 Samples w/response <2.Sx noise for
both quantification ions
.1 Use EDL expression to calculate for
absent 2,3.7.8 substituted PCDD/PCDF
.2 Samples w/response >2.Sx noise for
at least 1 quantilication ion
.1 Calculate "Estimated Maximum Possible
Concentration" (EMPC) when signal >
2.5x noise and retention time the some
1


7.9.6 Relative percent difference (RPO) formula |





*
7.9.7 Calculation ol 2.3.7 8-TCDD toxicity
eauivalenl factors (TEF) ol PCDDs and PCDFs
.1 Two CC Column TEF Determination:
Reanalyze sample extract on 60 meter
SP-2330 column
.1 Concentrations ol specified congeners
calculated from analysis done on DB-5
column
.2 Concentrations of specified congeners
calculated from analysis done on
SP-2330 column w/dilferent GC/MS
conditions
TCDD done on either column as long as
Section 8.1.2 criteria met
.3 GC peak must meet criteria of Sections
784.2 7 843 and/or 7.8.4.1.1. RRTs
of 2.3.7.8-sub congeners w/no carbon-
labeled analogues referred to w/in 0.006
RRT units of carbon-labeled std
1
fsrop^
                                                                8290  -  69
                                                                         Revision  0
                                                                         November  1990

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                                  METHOD 8315

         FORMALDEHYDE BY HIGH PERFORMANCE LIQUID CHROMATOGRAPHY  (HPLC)


1.0  SCOPE AND APPLICATION

      1.1  Method 8315 covers the determination of free formaldehyde in aqueous
samples and leachates.  The following compounds  can be determined  by this method:



     Compound Name                  CAS No.a


     Formaldehyde                   50-00-0
     Acetaldehyde                   75-07-0


     a  Chemical  Abstract Services Registry Number.


      1.2  Method 8315 is a high performance liquid chromatographic (HPLC) method
optimized  for  the determination  of formaldehyde and acetaldehyde  in  aqueous
environmental matrices and leachates of  solid samples. When this method is used
to  analyze  unfamiliar  sample  matrices,  compound  identification  should  be
supported  by  at  least  one  additional  qualitative  technique.     A  gas
chromatograph/mass  spectrometer  (GC/MS)  may   be  used  for  the  qualitative
confirmation of results  for the target analytes, using the extract produced by
this method.

      1.3  The method detection limits (MDL) are listed in  Tables 1 and 2.  The
MDL for a specific sample may differ from that listed,  depending  upon the nature
of  interferences  in the sample  matrix  and the  amount  of sample used  in the
procedure.

      1.4  The  extraction procedure  for  solid  samples  is  similar  to  that
specified in Method 1311 (1).  Thus, a single sample may be  extracted to measure
the analytes included  in the  scope  of other appropriate  methods.  The analyst
is allowed the flexibility to select chromatographic conditions appropriate for
the simultaneous measurement of combinations of these analytes.

      1.5  This method  is  restricted to use by,  or  under  the supervision of,
analysts experienced in  the use of chromatography and in the interpretation of
chromatograms.  Each analyst must demonstrate the ability to generate acceptable
results with this method, using the procedure described in Section 8.2.

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

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                                                                  November 1990

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available  to all  personnel  involved  in the  chemical  analysis.   Additional
references to laboratory safety are available.

      1.7  Formaldehyde has been tentatively classified as a known or suspected,
human or mammalian carcinogen.


2.0  SUMMARY OF METHOD

      2.1  For  wastes  comprised of  solids or  for aqueous  wastes containing
significant amounts of solid material, the aqueous phase, if any,  is separated
from the solid phase and stored for later analysis.  If necessary,  the particle
size of the solids in the waste is reduced.  The solid phase is extracted with
an amount of extraction fluid equal to 20 times the weight of the  solid phase.
The extraction fluid employed is a function of the alkalinity of the solid phase
of the waste.   A  special extractor vessel  is  used when  testing for volatiles.
Following extraction, the aqueous extract is separated from the solid phase by
filtration employing 0.6 to 0.8 /im glass fiber filter.

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

      2.3  A measured volume of aqueous sample or an appropriate amount of solids
leachate is  buffered  to pH 5  and  derivatized  with 2,4-dinitrophenylhydrazine
(DNPH),   using    either  the   solid   sorbent  or   the  methylene   chloride
derivatization/extraction option.   If the solid  sorbent option is  used,  the
derivative is extracted  using solid sorbent cartridges, followed by  elution with
ethanol.  If the methylene  chloride option  is used, the derivative  is extracted
with methylene chloride.  The methylene chloride extracts are concentrated using
the Kuderna-Danish (K-D) procedure  and solvent exchanged into methanol prior to
HPLC analysis.  Liquid chromatographic conditions are described which permit the
separation and measurement of formaldehyde in the extract by absorbance detection
at 360 nm.
3.0  INTERFERENCES

      3.1  Method  interferences  may  be  caused  by  contaminants  in  solvents,
reagents, glassware, and other sample  processing  hardware that lead to discrete
artifacts and/or elevated baselines in  the chromatograms.  All of these materials
must be routinely demonstrated to be free from interferences  under the conditions
of  the  analysis  by  analyzing  laboratory  reagent  blanks  as  described  in
Section 8.5.

            3.1.1  Glassware must be scrupulously cleaned.  Clean all  glassware
      as soon as possible after use by rinsing with the last solvent used.  This
      should be  followed by detergent washing  with  hot water,  and rinses with
      tap water  and organic-free reagent water.   It should then  be  drained,
      dried, and heated in a laboratory oven at  130°C for several  hours before
      use.  Solvent rinses with methanol may be substituted for the oven heating.


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      After drying and cooling, glassware should be stored in a clean environment
      to prevent any accumulation of dust or other contaminants.

            3.1.2  The use of high purity reagents and solvents helps to minimize
      interference problems.   Purification of solvents  by distillation in all
      glass systems may be required.

      3.2  Analysis for formaldehyde is especially complicated by its ubiquitous
occurrence in the environment.

      3.3  Matrix  interferences  may  be  caused  by  contaminants  that  are
coextracted from  the sample.   The extent of  matrix interferences  will  vary
considerably from source to source, depending upon the nature  and diversity of
the matrix being sampled.  No interferences have been observed  in the matrices
studied  as  a  result of using solid sorbent extraction as opposed  to liquid
extraction.   If  interferences  occur in  subsequent samples,   some  additional
cleanup may be necessary.

      3.4  The extent  of  interferences  that may be encountered  using liquid
chromatographic techniques has not  been fully  assessed.   Although  the  HPLC
conditions described allow for  a  resolution  of  the specific compounds covered
by this method, other matrix components may interfere.


4.0  APPARATUS AND MATERIALS

      4.1  Reaction vessel -  250 ml Florence flask.

      4.2  Separatory funnel -  250 ml, with Teflon stopcock.

      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).

      4.4  Vials -  10,  25 ml, glass with Teflon  lined screw caps or crimp tops.

      4.5  Boiling  chips  -    Solvent  extracted  with  methylene  chloride,
approximately 10/40 mesh  (silicon carbide or equivalent).
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      4.6  Balance -  Analytical,  capable of  accurately weighing to the nearest
0.0001 g.

      4.7  pH meter -  Capable of measuring to the nearest 0.01 units.

      4.8  High performance liquid chromatograph (modular)

            4.8.1 Pumping system -  Isocratic, with constant flow control capable
      of 1.00 mL/min.

            4.8.2 High pressure injection valve with 20 /*L loop.

            4.8.3 Column  -   250 mm x 4.6 mm ID,  5 /urn particle  size,  C18 (or
      equivalent).

            4.8.4 Absorbance detector -  360 rim.

            4.8.5 Strip-chart recorder compatible with detector -  Use of a data
      system for measuring peak areas and retention times is recommended.

      4.9  Glass fiber filter paper.

      4.10  Solid  sorbent cartridges  -    Packed  with  500 mg  C18 (Baker  or
equivalent).

      4.11  Vacuum manifold -   Capable of simultaneous  extraction of  up to 12
samples (Supelco or equivalent).

      4.12  Sample reservoirs -  60 ml capacity (Supelco or equivalent).

      4.13  Pipet - Capable of accurately delivering 0.10 ml solution (Pipetman
or equivalent).

      4.14  Water  bath  -   Heated,  with  concentric ring  cover, capable  of
temperature control (+)  2°C).   The bath should  be  used  under  a  hood.


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  Methylene chloride, CH2C12  - HPLC grade or equivalent.

      5.4  Methanol, CH3OH -  HPLC  grade or equivalent.
                                   8315 - 4                       Revision 0
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      5.5  Ethanol (absolute), CH3CH2OH  - HPLC grade or equivalent.

      5.6  2,4-Dinitrophenylhydrazine (DNPH) (70%  (W/W)),  [2,4-(02N)2C6H3]NHNH2,
in organic-free reagent water.

      5.7  Formalin (37.6 percent  (w/w)), formaldehyde in  organic-free reagent
water.

      5.8  Acetic acid (glacial),  CH3C02H.

      5.9  Sodium hydroxide solutions,  NaOH, 1.0 N and 5 N.

      5.10  Sodium chloride, NaCl.

      5.11  Sodium sulfite solution, Na2S03,  0.1 M.

      5.12  Hydrochloric Acid, HC1, 0.1 N.

      5.13  Extraction fluid -  Dilute 64.3 ml  of  1.0  N NaOH and  5.7 ml glacial
acetic acid to 900 ml with organic-free reagent water.  Dilute to 1 liter with
organic-free reagent water.  The pH should be 4.93 ± 0.02.

      5.14  Stock standard solutions

            5.14.1  Stock formaldehyde  (approximately 1.00 mg/mL) -  Prepare  by
      diluting 265 /zL formalin to  100 mL with organic-free reagent water.

                  5.14.1.1   Standardization of formaldehyde stock solution  -
            Transfer a 25 mL aliquot of a 0.1 M Na2S03 solution to a beaker and
            record the  pH.   Add  a 25.0 ml  aliquot of  the  formaldehyde stock
            solution (Section 5.14.1) and record the pH.   Titrate this mixture
            back  to  the original pH  using  0.1  N  HC1.    The formaldehyde
            concentration is calculated using the  following equation:

            Concentration (mg/mL)  = 30.03 x  (N HC1) x (mL  HC1) 25.0

            where:

            N HC1 = Normality of HC1 solution used
            mL HC1 = mL of standardized HC1  solution used
            30.03 = MW of formaldehyde

            5.14.2  Stock  formaldehyde  and  acetaldehyde   -  Prepare  by  adding
      265 juL formalin and  0.1  g  acetaldehyde to 90 mL of  organic-free reagent
      water and  dilute  to  100 mL.  The concentration  of  acetaldehyde in this
      solution is  1.00 mg/mL.   Calculate  the concentration  of formaldehyde  in
      this solution using the results of the  assay performed in Section  5.14.1.1.

            5.14.3  Stock standard solutions must  be replaced after six months,
      or sooner, if comparison with check standards indicates a  problem.
                                   8315  -  5                        Revision  0
                                                                   November 1990

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      5.15 Reaction Solutions

            5.15.1  DNPH (1.00 M9/L) -  Dissolve 142.9 mg of 70% (w/w) reagent
      in 100 ml absolute ethanol.  Slight heating or sonication may be necessary
      to effect dissolution.

            5.15.2  Acetate buffer  (5  N)  -   Prepare by  neutralizing glacial
      acetic acid to pH 5 with 5 N NaOH solution.  Dilute  to standard volume with
      organic-free reagent water.

            5.15.3  Sodium chloride solution  (saturated) -  Prepare by mixing an
      excess of the reagent grade solid with organic-free reagent water.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See  the  introductory material  to this Chapter,  Organic  Analytes,
Section 4.1.

      6.2  Samples must be refrigerated at 4°C,  and must be derivatized within
5 days of sample collection and analyzed within 3 days of derivatization.


7.0  PROCEDURE

      7.1  Extraction of Solid Samples

            7.1.1  All solid samples should be homogeneous.  When the sample is
      not dry, determine the dry weight  of the  sample,  using a representative
      aliquot.

                  7.1.1.1  Determination of dry weight - In certain cases, sample
            results are desired based on  a dry weight  basis.  When such data is
            desired,  or  required,  a   portion   of  sample  for  dry  weight
            determination should be weighed out  at  the same time as the portion
            used for analytical determination.

WARNING;   The drying oven  should be contained in a hood  or vented.  Significant
           laboratory contamination may result from drying a heavily contaminated
           hazardous waste sample.

                  7.1.1.2  Immediately after weighing the sample for extraction,
            weigh 5-10 g of the sample into a tared crucible.  Determine the %
            dry weight of the sample by drying overnight  at 105°C.  Allow to cool
            in a desiccator before weighing:

            % dry weight = q of dry sample x 100
                              g of sample

            7.1.2  Measure 25 g of solid into a 500 mL bottle with  a Teflon lined
      screw cap or crimp top, and add 500 mL of extraction  fluid (Section 5.13).
      Extract the solid by rotating  the  bottle  at  approximately  30  rpm for 18
                                   8315 - 6                       Revision 0
                                                                  November 1990

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      hours.  Filter the extract through glass fiber filter paper and store in
      sealed bottles at 4°C.   Each  ml of extract  represents  0.050 g  solid.

      7.2  Cleanup and Separation

            7.2.1  Cleanup procedures may not be necessary for a relatively clean
      sample matrix.  The cleanup procedures recommended in this method have been
      used for the analysis of various sample types.  If particular circumstances
      demand  the  use of  an  alternative cleanup  procedure, the  analyst  must
      determine  the  elution  profile  and  demonstrate  that the recovery  of
      formaldehyde is  no less  than  85% of  recoveries  specified in Table  3.
      Recovery may be lower for samples which form emulsions.

            7.2.2  If the sample is not clean, or the complexity is unknown, the
      entire sample should be centrifuged at  2500 rpm  for 10 minutes.   Decant
      the supernatant liquid from the  centrifuge bottle, and filter through glass
      fiber filter paper into a container which can be tightly  sealed.

      7.3  Derivatization

            7.3.1  For aqueous  samples, measure a 50 to  100 ml  aliquot of the
      sample. Quantitatively  transfer the sample aliquot  to  the reaction vessel
      (Section 4.1).

            7.3.2  For solid samples, 1 to 10 ml of leachate  (Section 7.1) will
      usually be  required.   The amount  used for a particular sample  must  be
      determined through preliminary experiments.

Note:   For all  reactions,  the  total  volume of  the  aqueous layer  should  be
        adjusted to 100 ml with  water.

            7.3.3  Derivatization  and  extraction of  the  derivative  can  be
      accomplished using  the solid sorbent (Section 7.3.4)  or methylene chloride
      option (Section 7.3.5).

            7.3.4  Solid Sorbent Option

                  7.3.4.1  Add 4 ml of acetate buffer and adjust the pH to 5.0
            ± 0.1  with glacial   acetic  acid  or 5 N NaOH.   Add  6 mL  of DNPH
            reagent,  seal the  container, and  place on a wrist-action shaker for
            30 minutes.

                  7.3.4.2  Assemble the vacuum manifold and connect to a water
            aspirator  or  vacuum pump.   Assemble solid  sorbent  cartridges
            containing a  minimum of  1.5 g   of  CIS sorbent, using  connectors
            supplied by the manufacturer, and attach the sorbent train to the
            vacuum manifold.  Condition each cartridge by passing 10 ml dilute
            acetate buffer  (10  ml  5 N  acetate  buffer  dissolved in  250  ml  of
            organic-free reagent water) through the sorbent cartridge train.

                  7.3.4.3  Remove the reaction vessel from  the  shaker  and add
            10 ml saturated NaCl solution to the vessel.
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      7.3.4.4  Add the  reaction  solution  to the sorbent train and
apply a vacuum so that the solution is drawn through the cartridges
at a rate of 3 to 5 mL/min.  Release the vacuum after the solution
has passed through the  sorbent.

      7.3.4.5  Elute  each  cartridge  train  with approximately 9 ml
of absolute ethanol,  directly into  a 10 ml volumetric flask.  Dilute
the solution to volume with absolute  ethanol, mixed thoroughly, and
place in a tightly sealed vial until analyzed.

7.3.5 Methylene Chloride Option

      7.3.5.1  Add 5 ml of acetate buffer and adjust the pH to 5.0
± 0.5  with glacial  acetic  acid  or 5 N NaOH.   Add 10  ml  of DNPH
reagent, seal the container, and  place on a  wrist-action shaker for
1 hour.

      7.3.5.2  Extract  the  solution  with three 20 ml  portions of
methylene chloride, using  a 250  ml separatory funnel,  and combine
the methylene chloride layers.  If an emulsion forms upon extraction,
remove the entire emulsion and centrifuge at  2000 rpm for  10 minutes.
Separate the layers and proceed with the next extraction.

      7.3.5.3  Assemble  a  Kuderna-Danish   (K-D)  concentrator  by
attaching a  10 mL concentrator tube  to  a  500 ml evaporator flask.
Wash the K-D apparatus with 25 ml of extraction solvent to complete
the quantitative transfer.

      7.3.5.4  Add one to  two clean boiling chips to the evaporative
flask and  attach  a three  ball Snyder  column.  Prewet  the Snyder
column by adding about  1  ml methylene chloride to  the  top.  Place
the  K-D apparatus  on  a   hot  water bath   (80-90°C)  so that  the
concentrator tube is  partially  immersed in the hot water  and the
entire lower rounded surface of the flask is bathed with hot vapor.
Adjust  the  vertical  position  of  the  apparatus  and  the  water
temperature, as required, to complete the concentration in 10-15 min.
At the  proper  rate  of  distillation  the  balls of the  column will
actively chatter, but the chambers will not  flood with condensed
solvent.  When the apparent volume of liquid reaches  10 ml, remove
the K-D apparatus and  allow it to  drain and cool for  at least 10 min.

      7.3.5.5  Prior to  liquid chromatographic analysis,  the solvent
must be exchanged to methanol.  The  analyst must ensure quantitative
transfer of the extract concentrate.   The exchange  is performed as
follows:

            7.3.5.5.1  Following  K-D  concentration of the methylene
      chloride extract  to  < 10  ml using the  macro Snyder column,
      allow the apparatus  to cool  and drain for at least  10 minutes.

            7.3.5.5.2  Momentarily remove the Snyder column,  add 5 ml
      of methanol, a  new  glass  bead, or boiling chip,  and attach
      the micro Snyder column.  Concentrate the extract using 1 ml
      of methanol  to prewet the  Snyder  column.    Place  the  K-D

                       8315 - 8                       Revision 0
                                                      November 1990

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            apparatus on the water bath so that the concentrator tube is
            partially immersed  in the hot  water.   Adjust  the  vertical
            position  of the  apparatus  and the  water temperature,  as
            required, to complete concentration.   At  the  proper rate of
            distillation the balls of  the  column  will  actively  chatter,
            but the chambers will  not flood.  When the apparent volume of
            liquid reaches < 5 ml, remove the K-D apparatus and  allow it
            to drain and cool for at least 10 minutes.

                  7.3.5.5.3  Remove the Snyder  column  and rinse the flask
            and  its  lower  joint  with  1-2 ml  of methanol  and  add  to
            concentrator tube.  A 5 ml  syringe is  recommended  for this
            operation.  Adjust the extract volume to 10 ml.  Stopper the
            concentrator tube  and store refrigerated  at  4°C  if further
            processing will not be performed immediately.   If the extract
            will be stored longer  than  two  days, it should be transferred
            to a vial  with  a Teflon lined screw cap or  crimp top.  Proceed
            with liquid  chromatographic analysis if further cleanup is not
            required.

7.4  Chromatographic Conditions (Recommended):

Column:           CIS, 250 mm x 4.6 mm ID, 5 urn particle size
Mobile Phase:     methanol/water,  75:25  (v/v),  isocratic
Flow Rate:        1.0 mL/min
UV Detector:      360 nm
Injection Volume: 20 ML

7.5  Calibration

      7.5.1  Establish  liquid  chromatographic  operating   conditions  to
produce a retention time equivalent to that indicated in Table 1 for the
solid  sorbent  option,  or  in  Table  2  for  methylene  chloride  option.
Suggested chromatographic conditions are  provided in Section 7.4.  Prepare
derivatized calibration  standards  according  to the procedure in Section
7.5.1.1.  Calibrate the chromatographic system using the  external standard
technique (Section 7.5.1.2).

            7.5.1.1  Preparation of calibration standards

                  7.5.1.1.1  Prepare calibration  standard  solutions  of
            formaldehyde and acetaldehyde  in organic-free reagent water
            from the  stock standard solution (Section 5.13.2).   Prepare
            these solutions at  the following concentrations  (in M9/mL) by
            serial dilution of the  stock standard solution: 50,  20, 10.
            Prepare  additional  calibration  standard  solutions  at  the
            following concentrations,  by dilution of the appropriate 50,
            20, or 10 /ug/mL standard:  5, 0.5,  2, 0.2, 1, 0.1.
                  7.5.1.1.2  Process each  calibration  standard solution
            through the derivatization option used for sample processing
            (Section 7.3.4 or 7.3.5).
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            7.5.1.2  External standard calibration procedure

                  7.5.1.2.1  Analyze each derivatized calibration standard
            using the chromatographic conditions listed in Tables 1 and 2,
            and tabulate peak area  against  concentration  injected.   The
            results  may  be  used   to  prepare  calibration  curves  for
            formaldehyde and acetaldehyde.

                  7.5.1.2.2  The working cal ibration curve must be veri f ied
            on  each working  day  by   the measurement  of  one  or  more
            calibration standards.   If the response for any analyte varies
            from the previously established responses by more  than 10%,
            the test must be repeated  using a fresh calibration standard
            after it is  verified that the analytical  system is in control.
            Alternatively, a  new  calibration  curve may be  prepared for
            that  compound.   If  an  autosampler   is  available,  it  is
            convenient to prepare a calibration curve daily by analyzing
            standards along with test  samples.

7.6  Analysis

      7.6.1  Analyze samples  by HPLC,  using  conditions established  in
Section 7.5.1.  Tables 1 and 2 list the retention times and MDLs that were
obtained under  these conditions.   Other HPLC columns,  chromatographic
conditions, or detectors may  be used  if  the requirements  of Section 8.2
are met, or if the data are within the  limits described in Tables 1 and 2.

      7.6.2  The  width  of  the  retention  time  window  used  to  make
identifications should be  based upon measurements of actual retention time
variations of standards  over the course of a day. Three times the standard
deviation of a retention time for a compound  can  be used  to calculate a
suggested window size; however, the experience of the analyst should weigh
heavily in the interpretation of the chromatograms.

      7.6.3  If the peak area exceeds the  linear range of the calibration
curve, a smaller sample volume should  be used.  Alternatively,  the final
solution may be diluted with ethanol and reanalyzed.

      7.6.4  If the peak area measurement is prevented by the presence of
observed interferences,  further  cleanup is required. However, none of the
3600 method series have been evaluated for this procedure.

7.7  Calculations

      7.7.1  Calculate each response factor as follows (mean value based
on 5 points):
            concentration of standard
      RF =
              area of the signal
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                               5
                              (s RFi)
                      	       1
            mean RF = RF =  	
            7.7.2  Calculate the concentration of formaldehyde and acetaldehyde
      as follows:
            /ig/ml =  (RF) (area of signal) (concentration factor)

      where:
                                          Final volume of extract
            concentration factor =
                                    Initial sample (or leachate) volume


Note:   For  solid  samples,  a dilution factor must  be  included in the equation
        to account  for  the  weight  of the  sample  used.


8.0  QUALITY CONTROL

      8.1  Refer to Chapter One for specific quality control procedures.


9.0  METHOD PERFORMANCE

      9.1  The MDLs listed in Table 1 were obtained using organic-free reagent
water and solid sorbent extraction.  Similar results were achieved using a final
effluent and sludge leachate.   The  MDLs  listed  in Table 2 were obtained using
organic-free reagent water and methylene chloride extraction.  Similar results
were achieved using representative matrices.

      9.2  This method  has been tested for linearity  of recovery  from spiked
organic-free reagent water and has been demonstrated to be applicable over the
range from 2 x MDL to 200 x MDL.

      9.3  In a single laboratory  evaluation using  several spiked matrices, the
average recoveries presented in  Tables 3 and 4 were obtained  using solid sorbent
and methylene chloride extraction, respectively.  The standard deviations of the
percent recovery are also  included in Tables 3 and 4.

      9.4  A representative chromatogram is presented in Figure 1.


10.0 REFERENCES

 1.  Federal Register,  1986, 51, 40643-40652; November 7.
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                                   TABLE 1.
               HIGH  PERFORMANCE  LIQUID  CHROMATOGRAPHY  CONDITIONS
                    AND METHOD DETECTION  LIMITS  USING  SOLID
                              SORBENT EXTRACTION
     Analyte            Retention Time                        MDL
                        (minutes)
     Formaldehyde         7.1                                 7.2
HPLC conditions:   Reverse phase CIS  column,  4.6 X 250 mm;  isocratic elution
using methanol/water (75:25, v/v); flow rate 1.0 mL/min.;  detector 360 nm.

a After correction for  laboratory blank.
                                   TABLE 2.
               HIGH PERFORMANCE  LIQUID CHROMATOGRAPHY  CONDITIONS
                  AND METHOD DETECTION LIMITS  USING METHYLENE
                              CHLORIDE EXTRACTION
     Analyte            Retention Time                        MDL
                        (minutes)
     Formaldehyde         7.1                                  7.2

     Acetaldehyde         8.6                                171a


HPLC conditions:  Reverse phase CIS column, 4.6 X 250 mm;  isocratic elution using
methanol/water  (75:25, v/v); flow rate 1.0 mL/min.; detector 360 nm.

a  These values include reagent blank concentrations of  approximately 13
   formaldehyde and 130 ng/l acetaldehyde.
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                 TABLE 3.
  SINGLE OPERATOR ACCURACY AND PRECISION
      USING SOLID SORBENT EXTRACTION
Analyte
Formaldehyde

Average
Matrix Percent
Type Recovery
Organic- free 86
Reagent Water
Final 90
Effluent
Standard
Deviation
Percent
9.4
11.0
Spike Number
Range of
(/ig/L) Analyses
15-1430 39
46.8-1430 16
Phenol
formaldehyde
Sludge
93
12.0
457-1430
15
                8315  -  13
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                                   TABLE 4.
                    SINGLE OPERATOR ACCURACY AND PRECISION
                      USING METHYLENE CHLORIDE  EXTRACTION
Analyte

Formaldehyde




Acetaldehyde






Average
Matrix Percent
Type Recovery

Organic-free
Reagent Water
Ground-
water
Liquids
Organic-free
Reagent Water
Ground-
water
Liquids
(2 types)
Solids
X
91

92.5

69.6
60.3

63.6

44.0

58.4
Standard
Deviation
Percent
P
2.5

8.2

16.3
3.2

10.9

20.2

2.7
Spike
Range
(M9/L)

50-1000

50

250
50-1000

50

250

0.10-1.08
Number
of
Analyses

9

6

12
9

12

12

12
a  Spike range in units of mg/g.
x = Average recovery expected for this method
p = Average standard deviation expected for this method.
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                             FIGURE 1
REPRESENTATIVE CHROMATOGRAM OF A 50
                              SOLUTION OF FORMALDEHYDE
3*
      FOR-D - Formaldehyde derivative
      ACET-D - Acetaldehyde derivative
                 8315 - 15
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                                                METHOD  8315
               FORMALDEHYDE BY HIGH  PERFORMANCE LIQUID  CHRQMATOGRAPHY [HPLCI
7.1.1  Ensure sample
    homogeneity:
  perform % solid
  determination,  if
    appropriate
 7.1.2 Weigh sampli
  into bottle; add
  extraction fluid;
  extract  18 hours;
       filter
   7.2.1  Perform
    cleanup, if
     necessary
  7.2.2  Centrifuge
     sample, if
     necessary
7.3 Derivatization:
measure aliquot for
liquid sample or
liquid extract of solid
sample; dilute to
total volume of 100
mis
                                                   solid
                                                   sorbent
 7.3.4.1 Add acetate
  buffer and adjust
 pH with  acetic acid
     or sodium
hydroxide; add  DNPH
    reagent; seal
 container; shake  30
      minutes
  7.3.4.2 Assemble
vacuum manifold  and
  connect to pump;
      assemble
  cartridges; attach
   sorbent train to
 manifold; condition
      cartridge
   7.3.4.3 Remove
   reaction vessels
  from shaker; add
   sodium chloride
        sol'n
 7.3.4.4 Add the
 reaction solution  to
 sorbent train; elute
 under vacuum
                                      7.3.4.5 Elute train
                                         with ethanol
                                       dilute to volume
                                       w/ethonol; mix
                                  7.3.3
                               Extraction:
                             solid sorbent or
                               methylene
                               ..chloride?,,
                                                                    •©•
methylene
  chloride
    7.3.5.1 Add acetate
     buffer and adjust
    pH with  acetic acid
        or sodium
   hydroxide; add  DNPH
       reagent; seal
    container; shake  60
         minutes
      7.3.5.2 Extract
    sol'n with 3  20-ml
        portions  of
    methylene  chloride;
    combine methylene
      chloride layers
    7.3.5.3  Assemble  a
    Kuderno-Danish
    (K-D) apparatus to
    concentrate  extract
    layers of methylene
    chloride
   7.3.5.4  Add boiling
   chips to evaporation
   flask  and  attach a
   three-ball Snyder
   column to the  K-D
   assembly; immerse
   apparatus in hot
   water bath; adjust
   positioning to finish
   concentration in  10-
   15 minutes
                                                      7.3.5.5 Exchange
                                                      solvent to methanol
                                                      using  K-D assembly
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                                             METHOD  8315
                                               continued
 7.4 Establish LC
 operating  parameters
 7.5.1.1.1 Prepare
 calibration  standards
7.5.1.1.2 Derivatize
standard solutions
7.5.1.2.1 Analyze
standards and tabulate
peak area against
concentration injected
    7.5.1.2.2 Verify
  working calibration
   curve daily  with 1
  or more standards
  7.6.1  Analyze by
     HPLC using
      specified
  conditions; other
    conditions or
  hardware may be
     used if QC
requirements are met
 7.6.2 Use retention
  times to interpret
   chromatograms
 7.6.3 If peak area
   exceeds linear
 working range,  use
  a smaller sample
 volume or the final
   solution may be
     diluted with
     ethanol and
     reanalyzed
                                         7.6.4 If peak area
                                           measurement is
                                            prevented  by
                                            interferences,
                                          further cleanup is
                                               needed
7.7.1 Calculate
response factors
for  analytes
                                                                             7.7.2 Calculate
                                                                             concentrations of
                                                                             aldehydes in sample,
                                                                             noting dilution factor
                                                                             for solid samples
                                              8315  -  17
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                                  METHOD  8316

         ACRYLAMIDE.  ACRYLONITRILE  AND ACROLEIN  BY HIGH  PERFORMANCE
                         LIQUID CHROMATOGRAPHY (HPLC)
1.0  SCOPE AND APPLICATION

      1.1  The following compounds can be determined by this method:



     Compound Name                        CAS No.a


     Acrylamide                            79-06-1
     Acrylonitrile                        107-13-1
     Acrolein (Propenal)                  107-02-8


     a  Chemical Abstract Services Registry Number.

      1.2  The method detection limits (MDLs)  for the target analytes  in organic-
free reagent water are  listed  in Table 1.  The method may be applicable to other
matrices.

      1.3  This method  is restricted to  use by  or under the  supervision  of
analysts  experienced in  the  use  of gas  chromatographs  and  skilled  in  the
interpretation of gas chromatograms.   Each analyst must demonstrate the ability
to generate acceptable results with this method.


2.0  SUMMARY OF METHOD

      2.1  Water  samples  are  analyzed by high pressure  liquid chromatography
(HPLC).   A  200 /iiL aliquot  is injected  onto a C-18 reverse-phase  column,  and
compounds in the effluent are detected with an ultraviolet (UV) detector.


3.0  INTERFERENCES

      3.1  Contamination by carryover can occur whenever high-concentration and
low-concentration samples are sequentially analyzed.  To reduce carryover,  the
sample syringe must  be  rinsed out between samples with solvent.   Whenever an
unusually concentrated  sample is  encountered,  it  should  be followed  by  the
analysis of solvent to check for cross contamination.


4.0  APPARATUS AND MATERIALS

      4.1  HPLC system

            4.1.1  One high pressure pump.


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            4.1.2  Octadecyl  Silane  (ODS,  C-18)  reverse  phase  HPLC column,
      25 cm x 4.6 mm, 10 jum,  (Zorbax, or equivalent).
            4.1.3  Variable wavelength UV detector.
            4.1.4  Data system.
      4.2  Other apparatus
            4.2.1  Water degassing unit -  1  liter  filter flask with stopper and
     pressure tubing.
            4.2.2  Analytical balance - + 0.0001 g.
            4.2.3  Magnetic stirrer and magnetic stirring bar.
            4.2.4  Sample filtration unit - syringe filter with 0.45 urn filter
      membrane, or equivalent disposable filter unit.
      4.3  Materials
            4.3.1  Syringes - 10, 25, 50 and 250 /*L and 10 ml.
            4.3.2  Volumetric pipettes, Class A, glass -1,5 and 10 ml.
            4.3.3  Volumetric flasks - 5,  10, 50 and 100 ml.
            4.3.4  Vials -  25 ml, glass with Teflon lined screw caps or crimp
      tops.

5.0  REAGENTS
      5.1  Reagent grade 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  Acrylamide, CH2:CHCONH2, 99+% purity, electrophoresis reagent grade.
      5.3  Acrylonitrile, H2C:CHCN,  99+% purity.
      5.4  Acrolein, CH2:CHCHO,  99+% purity.
      5.5  Organic-free reagent water.  All  references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
      5.6  Stock  standard  solutions  - Can be prepared  from pure  standard
materials or  can  be purchased as certified  solutions.   Commercially prepared
stock standards can be used if they are verified against EPA standards.  If EPA
standards are not  available  for  verification,  then  standards  certified by the
                                   8316 -  2                       Revision 0
                                                                  November 1990

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manufacturer  and  verified  against  a  standard  made  from  pure material  is
acceptable.

            5.6.1  Acrylamide

                  5.6.1.1  Weigh 100 mg of aery 1 amide neat standard into a 100 ml
            volumetric flask, and dilute to the mark with organic-free reagent
            water. Calculate the concentration of the standard solution from the
            actual weight used.  When compound purity  is  assayed to be 96% or
            greater, the weight can be used without  correction to calculate the
            concentration of the stock standard.

                  5.6.1.2  Transfer the  stock solution  into vials with Teflon
            lined screw caps or  crimp tops. Store at 4°C, protected from light.

                  5.6.1.3  Stock solutions must be  replaced after one year, or
            sooner if comparison with the check standards indicates a problem.

            5.6.2  Acrylonitrile and Acrolein - Prepare separate stock solutions
      for acrylonitrile and acrolein.

                  5.6.2.1  Place about 9.8 ml of organic-free reagent water into
            a 10 ml volumetric flask before weighing  the flask and  stopper. Weigh
            the flask and record the weight to  the nearest 0.1 mg.   Add  two drops
            of neat standard, using a 50 juL syringe, to the flask.  The liquid
            must fall  directly into the water, without contacting the  inside wall
            of the flask.

CAUTION;   Acrylonitrile and acrolein are toxic.   Standard preparation should
           be performed in an laboratory fume hood.

                  5.6.2.2  Stopper the flask and then reweigh. Dilute  to volume
            with organic-free reagent water.   Calculate the concentration from
            the net gain in weight.  When compound  purity is assayed to be 96%
            or greater, the weight can be used without correction to calculate
            the concentration of the stock standard.

                  5.6.2.3  Stock solutions must be  replaced after one year, or
            sooner if comparison with the check standards indicates a problem.

      5.7  Calibration standards

            5.7.1  Prepare  calibration   standards   at  a  minimum  of   five
      concentrations by diluting the stock solutions with organic-free reagent
      water.

            5.7.2  One calibration standard should be prepared at a concentration
      near, but above, the method detection limit; the remaining standards should
      correspond to the range of concentrations found in real  samples, but should
      not exceed the working range of the HPLC system (1 mg/L to  10 mg/L).
                                   8316 - 3                       Revision 0
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6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See  the  introductory material  to  this chapter,  Organic Analytes,
Section 4.1.
7.0  PROCEDURE

      7.1  HPLC Conditions

            Mobile Phase:           Degassed organic-free reagent water
            Injection Volume:       200 /xL
            Flow Rate:              2.0 mL/min
            Pressure:               38 atm
            Temperature:            25°C
            Detector UV wavelength:  195 nm

      7.2  Calibration:

            7.2.1  Prepare  standard  solutions of  acrylamide as  described  in
      Section 5.7.1.   Inject  200 ^L  aliquots of each solution,  in triplicate,
      into  the  chromatograph.   See  Method  8000  for  additional  guidance  on
      calibration by the external standard method.

      7.3  Chromatographic analysis:

            7.3.1  Analyze the samples using the same Chromatographic conditions
      used to prepare the standard curve.  Suggested Chromatographic conditions
      are given in Section 7.1.  Table 1 provides the retention times that were
      obtained under these conditions during method development.


8.0  QUALITY CONTROL

      8.1  Refer to Chapter One for specific quality control procedures.

      8.2  Before processing any samples,  the analyst must demonstrate, through
the analysis of a method blank, that all  glassware  and reagents are interference
free.


9.0  METHOD PERFORMANCE

      9.1  Method performance data are not available.


10.0 REFERENCES

1.   Hayes,  Samm "Acrylamide, Acrylonitrile,  and Acrolein Determination in Water
     by  High Pressure Liquid Chromatography," USEPA.
                                   8316 - 4                       Revision 0
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                                    TABLE 1
             ANALYTE RETENTION TIMES AND METHOD  DETECTION  LIMITS
                                  Retention             MDL
Compound                          Time (min)           (/.iQ/L)
Acrylamide                            3.5                10
Acrylonitrile                         8.9                20
Acrolein (Propenal)                  10.1                30
                                    8316 -  5                       Revision 0
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                       METHOD 8316
ACRYLAMIDE.  ACRYLONITRILE AND ACROLEIN BY HIGH PERFORMANCE
               LIQUID CHROMATOGRAPHY  (HPLC)
                         Start
                      7.1 Set  by
                         HPLC
                      Conditions
                     7 .2 Calibrate
                     Chromatograph
                           7.3
                    Chromatographic
                        analysis
                          Stop
                         8316  - 6
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November 1990

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                                  METHOD 8318

                N-METHYLCARBAMATES BY HIGH PERFORMANCE LIQUID
                             CHROMATOGRAPHY  (HPLC)
1.0  SCOPE AND APPLICATION

      1.1  Method   8318   is   used   to   determine  the   concentration   of
N-methylcarbamates in soil, water  and waste  matrices. The  following compounds
can be determined by this method:
     Compound Name                              CAS No.a


     Aldicarb (Temik)                             116-06-3
     Aldicarb Sulfone                            1646-88-4
     Carbaryl (Sevin)                              63-25-2
     Carbofuran (Furadan)                        1563-66-2
     Dioxacarb                                   6988-21-2
     3-Hydroxycarbofuran                        16655-82-6
     Methiocarb (Mesurol)                        2032-65-7
     Methomyl (Lannate)                         16752-77-5
     Promecarb                                   2631-37-0
     Propoxur (Baygon)                            114-26-1


     a   Chemical Abstract Services  Registry  Number.


      1.2  The method detection limits (MDLs) of Method 8318 for determining the
target analytes in organic-free reagent water and in soil are listed in Table 1.

      1.3  This method  is  restricted  to use by, or  under  the  supervision of,
analysts experienced in the use of high performance liquid chromatography (HPLC)
and  skilled  in  the   interpretation  of  chromatograms.    Each   analyst  must
demonstrate the ability to generate acceptable results with this method.


2.0  SUMMARY OF METHOD

      2.1  N-methylcarbamates are extracted  from aqueous samples with methylene
chloride, and  from  soils,  oily solid waste and oils with acetonitrile.   The
extract solvent is exchanged to methanol/ethylene glycol,  and then the extract
is cleaned  up  on  a  C-18 cartridge, filtered, and eluted  on  a  C-18 analytical
column.  After separation, the target  analytes  are  hydrolyzed  and derivatized
post-column, then quantified fluorometrically.

      2.2  Due  to  the  specific  nature  of  this analysis,  confirmation"  by  a
secondary method is  not essential.  However, fluorescence due  to post-column
derivatization may be  confirmed by substituting the  NaOH  and o-phthalaldehyde
solutions with organic-free  reagent  water  and reanalyzing  the  sample.    If

                                   8318 - 1                       Revision 0
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fluorescence is still  detected, then a positive interference is present and care
should be taken in the interpretation of the results.

      2.3  The  sensitivity of  the method  usually  depends on  the level  of
interferences present, rather than on the instrumental conditions.  Waste samples
with a high  level  of extractable fluorescent compounds are expected  to yield
significantly higher detection limits.


3.0  INTERFERENCES

      3.1  Fluorescent compounds,  primarily  alkyl  amines  and compounds which
yield  primary  alkyl  amines  on  base hydrolysis,  are potential   sources  of
interferences.

      3.2  Coeluting  compounds  that  are  fluorescence quenchers may result in
negative interferences.

      3.3  Impurities  in  solvents  and  reagents  are  additional   sources  of
interferences.   Before processing any samples,  the analyst must  demonstrate
daily,  through the  analysis of solvent blanks,  that  the entire analytical system
is interference free.
4.0  APPARATUS AND MATERIALS

      4.1  HPLC system

            4.1.1  An  HPLC  system  capable  of  injecting  20  n\. aliquots  and
      performing multilinear gradients at a constant flow.  The system must also
      be equipped with a data system to measure the peak areas.

            4.1.2  C-18 reverse phase HPLC column,  25 cm x 4.6 mm (5 urn).

            4.1.3  Post Column Reactor with two solvent delivery systems (Kratos
      PCRS 520  with  two Kratos  Spectroflow  400 Solvent Delivery  Systems,  or
      equivalent).

            4.1.4  Fluorescence detector (Kratos Spectroflow 980, or equivalent).

      4.2  Other apparatus

            4.2.1  Centrifuge.

            4.2.2  Analytical balance - ± 0.0001 g.

            4.2.3  Top loading balance - ± 0.01 g.

            4.2.4  Platform shaker.

            4.2.5  Heating block, or equivalent  apparatus, that can accommodate
      10 mL graduated vials (Section 4.3.11).
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      4.3  Materials
            4.3.1  HPLC injection syringe - 50 /xL.
            4.3.2  Filter paper,  (Whatman #113 or #114, or equivalent).
            4.3.3  Volumetric pipettes, Class A, glass, assorted sizes.
            4.3.4  Reverse phase cartridges,  (C-18 Sep-PakR [Waters Associates],
      or equivalent).
            4.3.5  Glass syringes - 5 ml.
            4.3.6  Volumetric flasks,  Class  A  -  5 ml, 10  ml,  25 ml,  50 mL,
      100 mL, and 1 L.
            4.3.7  Erlenmeyer flasks with teflon-lined screw caps, 250 mL.
            4.3.8  Assorted glass funnels.
            4.3.9  Separatory funnels,  with  ground glass  stoppers  and teflon
      stopcocks - 250 ml.
            4.3.10  Graduated cylinders - 100 mL.
            4.3.11  Graduated glass vials - 10 mL, 20 mL.
            4.3.12  Centrifuge tubes - 250 mL.
            4.3.13  Vials -  25  mL,  glass  with Teflon lined screw caps or crimp
      tops.
            4.3.14  Positive  displacement   micro-pipettor,   3  to   25   /xL
      displacement, (Gilson Microman [Rainin  #M-25] with tips, [Rainin #CP-25],
      or equivalent).
            4.3.15  Nylon  filter  unit,  25  mm  diameter,  0.45  pm pore  size,
      disposable (Alltech Associates, #2047,  or equivalent).

5.0  REAGENTS
      5.1  HPLC grade chemicals  shall be used in all tests.   It is intended that
all reagents shall  conform to the  specifications of the Committee on Analytical
Reagents  of the  American  Chemical  Society,  where  such  specifications  are
available.  Other grades may be  used, provided it is first ascertained that the
reagent is of sufficiently  high purity  to permit  its  use  without lowering the
accuracy of the determination.
      5.2  General
            5.2.1  Acetonitrile, CH3CN - HPLC  grade  - minimum UV cutoff at 203 nm
      (EM Omnisolv #AX0142-1, or equivalent).
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      5.2.2  Methanol, CH3OH - HPLC grade - minimum UV cutoff at 230 nm (EM
Omni sol v #MX0488-1, or equivalent).

      5.2.3  Methylene chloride, CH2C12  - HPLC grade - minimum UV cutoff
at 230 nm (EM Omni sol v #0X0831-1, or equivalent).

      5.2.4  Hexane, C6H14 - pesticide grade - (EM Omnisolv #HX0298-1, or
equivalent).

      5.2.5  Ethylene glycol,  HOCH2CH2OH - Reagent grade -  (EM Science, or
equivalent).

      5.2.6  Organic-free reagent water - All  references to water  in this
method refer to organic-free reagent water, as defined  in Chapter One.

      5.2.7  Sodium hydroxide, NaOH - reagent grade - prepare 1  L of 0.05N
NaOH solution.

      5.2.8  Phosphoric acid,  H3P04  - reagent grade.

      5.2.9  pH 10 borate buffer (J.T. Baker #5609-1, or equivalent).

      5.2.10  o-Phthalaldehyde,  o-C6H4(CHO)2  -  reagent  grade   (Fisher
#0-4241, or equivalent).

      5.2.11  2-Mercaptoethanol ,  HSCH2CH2OH   -   reagent  grade   (Fisher
#0-3446, or equivalent).

      5.2.12  N-methylcarbamate  neat   standards  (equivalence  to  EPA
standards must be demonstrated  for purchased solutions).

      5.2.13  Chloroacetic acid, C1CH2COOH,  0.1  N.

5.3  Reaction solution

      5.3.1  Dissolve 0.500 g  of o-phthal aldehyde  in 10 ml of methanol,
in a 1 L volumetric flask.  To  this solution, add 900 ml of organic-free
reagent water,  followed by 50  ml  of  the borate buffer (pH  10).   After
mixing well, add  1  ml of 2-mercaptoethanol ,  and dilute to the mark with
organic-free reagent water.  Mix the solution thoroughly.  Prepare fresh
solutions on a weekly basis, as needed.   Protect from light and store under
refrigeration.

5.4  Standard solutions

      5.4.1  Stock  standard  solutions: prepare  individual   1.0 mg/mL
solutions by adding 0.025 g of carbamate to  a  25 ml volumetric  flask, and
diluting to the  mark with methanol.  Store solutions,  under refrigeration,
in glass vials with Teflon lined screw caps  or crimp  tops.  Replace every
six months.
      5.4.2  Intermediate standard  solution:  prepare  a mixed 50.0
solution by  adding  2.5 ml of each  stock  solution  to  a 50 ml volumetric


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      flask, and  diluting  to the mark  with methanol.  Store  solutions,  under
      refrigeration, in glass vials  with Teflon lined screw caps or crimp tops.
      Replace every three months.

            5.4.3  Working standard solutions: prepare 0.5,  1.0,  2.0,  3.0 and
      5.0 /xg/mL  solutions by  adding  0.25, 0.5,  1.0,  1.5 and  2.5 mL  of the
      intermediate mixed standard to  respective  25 mL volumetric  flasks, and
      diluting  each  to the  mark  with  methanol.    Store  solutions,  under
      refrigeration, in glass vials  with Teflon lined screw caps or crimp tops.
      Replace every two months, or sooner if necessary.

            5.4.4  Mixed QC  standard  solution:  prepare  a 40.0 tig/ml  solution
      from another set of stock standard solutions, prepared similarly to those
      described in Section 5.4.1. Add 2.0 ml  of each stock solution to a 50 ml
      volumetric flask and dilute to the mark with methanol. Store the solution,
      under refrigeration,  in a glass vial  with a Teflon lined  screw cap or crimp
      top.  Replace every three months.


6.0  SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

      6.1  Due to  the extreme  instability of N-methylcarbamates  in  alkaline
media, water, waste water and  leachates should be preserved  immediately after
collection by acidifying to pH 4-5 with 0.1 N chloroacetic acid.

      6.2  Store samples at  4°C and out of direct sunlight,  from  the  time of
collection  through analysis.   N-methylcarbamates are  sensitive  to  alkaline
hydrolysis and heat.

      6.3  All samples must be  extracted  within  seven days  of collection, and
analyzed within 40 days of extraction.


7.0  PROCEDURE

      7.1  Extraction

            7.1.1  Water, domestic  wastewater, aqueous  industrial  wastes, and
      leachates

                  7.1.1.1  Measure  100  mL of sample into a  250  mL separatory
            funnel and extract  by shaking vigorously for about  2 minutes with
            30 mL of methylene chloride.  Repeat the  extraction two more times.
            Combine all three extracts  in a 100 mL volumetric flask and dilute
            to volume with methylene  chloride.   If cleanup  is required, go to
            Section 7.2. If cleanup is not required, proceed directly to Section
            7.3.1.

            7.1.2  Soils, solids, sludges, and heavy aqueous suspensions

                  7.1.2.1  Determination  of  sample % dry weight  -  In  certain
            cases, sample results are desired based on dry-weight basis.  When
            such data  is  desired,  a portion  of sample  for  this  determination


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            should be  weighed out at  the  same time  as  the portion  used  for
            analytical  determination.

WARNING:   The drying oven  should be contained in a hood or vented.  Significant
           laboratory  contamination  may result from  a  heavily  contaminated
           hazardous waste sample.

                    7.1.2.1.1 Immediately  after   weighing   the   sample   for
                  extraction, weigh 5-10 g of the sample into a tared crucible.
                  Determine the % dry weight of the sample  by drying overnight
                  at 105°C.   Allow  to cool in a  desiccator before  weighing:

                   % dry weight = q of dry  sample x 100
                                   g of sample

                  7.1.2.2  Extraction - Weigh out 20 ± 0.1  g  of sample into a
            250 ml erlenmeyer flask with a teflon-lined screw  cap.   Add 50 ml
            of acetonitrile and shake for 2  hours on a platform shaker.  Allow
            the mixture to  settle  (5-10 min),  then decant  the  extract into a
            250 ml centrifuge tube.  Repeat  the extraction  two more times with
            20 mL  of acetonitrile  and  1 hour  shaking each  time.   Decant  and
            combine  all  three  extracts.  Centrifuge  the  combined  extract  at
            200 rpm for 10 min.  Carefully decant the supernatant  into a 100 ml
            volumetric  flask and dilute to volume with acetonitrile.  (Dilution
            factor = 5)  Proceed to Section  7.3.2.

            7.1.3  Soils heavily contaminated with non-aqueous substances, such
      as oils

                  7.1.3.1  Determination of sample % dry weight -  Follow Sections
            7.1.2.1 through 7.1.2.1.1.

                  7.1.3.2  Extraction - Weigh out 20 + 0.1  g  of sample into a
            250 ml erlenmeyer flask with a teflon-lined screw  cap.   Add 60 ml
            of hexane and shake for  1  hour on a platform shaker.  Add 50 ml of
            acetonitrile and shake  for an additional 3 hours.  Allow the mixture
            to settle (5-10 min),  then decant the solvent  layers into a 250 ml
            separatory  funnel.  Drain  the acetonitrile (bottom layer)  through
            filter paper into a  100 mL volumetric flask. Add  60 mL  of hexane and
            50 mL of acetonitrile to the sample extraction  flask and shake for
            1 hour.  Allow the mixture to settle, then decant the mixture into
            the  separatory  funnel  containing  the  hexane  from  the  first
            extraction.  Shake  the separatory funnel  for 2  minutes, allow the
            phases to separate, drain the acetonitrile layer through filter paper
            into the volumetric flask, and  dilute to volume  with acetonitrile.
            (Dilution factor = 5)   Proceed  to Section 7.3.2.

            7.1.4  Non-aqueous liquids such  as  oils

                  7.1.4.1  Extraction - Weigh out 20 ± 0.1  g  of sample into a
            125  mL separatory  funnel.   Add  40  mL  of hexane and  25 mL  of
            acetonitrile and vigorously shake the sample mixture for 2 minutes.
            Allow the phases  to separate, then  drain  the  acetonitrile (bottom
            layer) into a 100 mL volumetric flask. Add 25 mL of acetonitrile to

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            the sample funnel, shake for 2 minutes, allow the phases to separate,
            drain the acetonitrile layer into the volumetric flask. Repeat the
            extraction with another 25 ml portion of acetonitrile, combining the
            extracts.    Dilute   to  volume   with   acetonitrile.     (Dilution
            factor = 5).  Proceed to Section 7.3.2.

      7.2  Cleanup  -  Pipet 20.0  ml  of  the  extract into  a 20 ml  glass vial
containing 100 /uL of ethylene glycol.    Place the vial  in  a heating block set
at 50° C,  and gently evaporate the extract under a stream of nitrogen (in  a fume
hood)  until  only the ethylene glycol  keeper remains.    Dissolve  the  ethylene
glycol residue in 2 ml of methanol, pass the extract through a pre-washed C-18
reverse phase  cartridge,  and collect the  eluate in a  5 ml volumetric  flask.
Elute the cartridge with methanol, and collect the eluate until  the final  volume
of 5.0 ml  is obtained.   (Dilution factor = 0.25)   Using a disposable  0.45 /xm
filter, filter an aliquot of the clean extract directly  into a properly labelled
autosampler  vial.   The  extract  is now  ready  for  analysis.    Proceed  to
Section 7.4.

      7.3  Solvent Exchange

            7.3.1  Water, domestic wastewater,  aqueous  industrial  wastes, and
      leachates:

            Pipet  10.0  ml  of the extract  into  a  10 ml graduated  glass vial
      containing  100 /nL of  ethylene glycol.  Place  the vial in a heating block
      set at 50° C,  and  gently evaporate  the extract under  a stream of nitrogen
       (in  a  fume hood) until  only the  ethylene glycol keeper remains.  Add
      methanol  to the ethylene glycol residue, dropwise,  until  the total  volume
      is 1.0 ml.  (Dilution factor = 0.1).   Using a disposable 0.45 jum filter,
      filter this extract directly into  a  properly labelled autosampler vial.
      The extract is now ready for analysis.  Proceed to Section 7.4.

            7.3.2  Soils, solids, sludges,  heavy aqueous suspensions,  and non-
      aqueous liquids:

            Elute 15 ml of the acetonitrile extract  through  a C-18 reverse phase
      cartridge,  prewashed with 5 ml of  acetonitrile.   Discard the first 2 ml
      of eluate and collect the remainder.   Pipet 10.0 ml of the clean extract
      into a 10 ml graduated glass vial  containing  100  pi  of ethylene glycol.
      Place the vial in a heating block  set at  50°  C, and gently evaporate the
      extract under a stream of nitrogen (in a fume hood) until  only the ethylene
      glycol keeper  remains.  Add methanol  to the ethylene  glycol  residue,
      dropwise,  until   the  total  volume  is  1.0  ml.    (Additional  dilution
      factor =0.1; overall dilution  factor =  0.5).   Using  a disposable 0.45 /xm
      filter, filter this extract  directly  into  a properly  labelled autosampler
      vial.  The extract is now ready for analysis.  Proceed to Section  7.4.

      7.4  Sample Analysis

            7.4.1  Analyze  the  samples  using the  chromatographic  conditions,
      post-column reaction parameters and instrument  parameters given in Sections
      7.4.1.1,  7.4.1.2, 7.4.1.3 and  7.4.1.4.    Table 2  provides the retention
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times that were obtained under these conditions during method development.
A chromatogram of the separation is shown in Figure 1.

            7.4.1.1  Chromatographic Conditions

      Solvent A:         Organic-free reagent water,  acidified with 0.4 ml
                        of phosphoric acid per liter of water
      Solvent B:         Methanol/acetonitrile (1:1, v/v)
      Flow rate:         1.0 mL/min
      Injection Volume: 20 /uL
      Solvent delivery system program:

      Time                                   Duration
      (min)       Function         Value      (min)        File
       0.00           FR               1.0                     0
       0.00           B%               10%                     0
       0.02           B%              80%        20           0
      20.02           B%             100%         5           0
      25.02           B%             100%         5           0
      30.02           B%               10%         3           0
      33.02           B%               10%         7           0
      36.02        ALARM                         0.01        0

            7.4.1.2  Post-column Hydrolysis Parameters

      Solution:   0.05 N aqueous sodium hydroxide
      Flow Rate:   0.7 mL/min
      Temperature:  95° C
      Residence Time:  35  seconds  (1  mL  reaction  coil)

            7.4.1.3  Post-column Derivatization Parameters

      Solution:   o-phthalaldehyde/2-mercaptoethanol (Section 5.3.1)
      Flow Rate:   0.7 mL/min
      Temperature:  40° C
      Residence time:  25  seconds  (1  mL  reaction  coil)

            7.4.1.4  Fluorometer Parameters

      Cell:                   10 ML
      Excitation wavelength:  340 nm
      Emission wavelength:    418 nm cutoff filter
      Sensitivity wavelength: 0.5 /itA
      PMT voltage:            -800 V
      Time constant:          2 sec

      7.4.2  If the peak areas of the sample signals exceed the calibration
range of  the  system,  dilute the extract as  necessary  and  reanalyze the
diluted extract.
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7.5  Calibration:

      7.5.1  Analyze a solvent blank  (20  /uL of methanol) to ensure that
the system is clean.  Analyze the calibration standards  (Section 5.4.3),
starting  with  the  0.5  jug/mL standards  and ending  with the  5.0  jug/mL
standard.  If the percent relative standard deviation (%RSD) of the mean
response factor (RF) for each analyte does not exceed 20%, the system is
calibrated and the analysis of samples may proceed.  If the %RSD for any
analyte exceeds 20%, recheck  the  system  and/or recalibrate with freshly
prepared calibration solutions.

      7.5.2  Using the established calibration mean response factors, check
the calibration of the instrument at the beginning of each day by analyzing
the 2.0 ng/ml mixed standard.   If  the  concentration of each analyte falls
within the range  of 1.70  to 2.30  Aig/mL (i.e., within + 15% of the true
value), the instrument  is  considered to be calibrated and the analysis of
samples may proceed.  If the observed value of any analyte exceeds its true
value by  more  than  ± 15%, the instrument must  be  recalibrated (Section
7.5.1).

      7.5.3  After 10 sample runs, or less,  the 2.0 jug/mL standards must
be analyzed to ensure that  the retention  times  and response factors are
still within acceptable limits.   Significant variations (i.e., observed
concentrations exceeding the true concentrations by more than + 15%) may
require a re-analysis of the samples.

7.6  Calculations

      7.6.1  Calculate each response factor as follows (mean value based
on 5 points):

            concentration of standard
              area of the signal
                       1
      mean RF = RF = —
                      A RF,)
                   [(I RF,  - RF)2]172 /  4

      %RSD of RF = 	=	X 100%
                        RF

      7.6.2  Calculate the concentration of  each N-methylcarbamate  as
fol1ows:

           or Mg/mL =  ( RF) (area of  signal)  (dilution factor)

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8.0  QUALITY CONTROL

      8.1  Before processing any samples,  the analyst must demonstrate, through
the analysis  of a method blank  for  each  matrix type, that  all  glassware and
reagents are  interference free.    Each time there is  a  change  of reagents,  a
method blank must be processed as a safeguard against laboratory contamination.

      8.2  A QC check solution must  be prepared and  analyzed with each sample
batch that is processed.  Prepare this solution,  at  a concentration of 2.0 ng/mi
of each analyte,  from the 40.0 pg/mL mixed  QC standard solution (Section 5.4.4).
The acceptable response range is 1.7 to 2.3 /ig/mL  for each analyte.

      8.3  Negative  interference  due to quenching  may be examined  by spiking
the extract with the appropriate  standard,  at an appropriate concentration, and
examining the observed response against the expected response.

      8.4  Confirm  any  detected  analytes by  substituting  the  NaOH  and  OPA
reagents in the post column  reaction  system with deionized water, and reanalyze
the suspected  extract.   Continued fluorescence response will  indicate that  a
positive interference is present (since the fluorescence  response  is not due to
the post column derivatization).   Exercise caution  in the interpretation of the
chromatogram.


9.0  METHOD PERFORMANCE

      9.1  Table 1  lists the  single  operator method  detection limit (MDL) for
each  compound  in organic-free  reagent water and  soil.   Seven/ten replicate
samples were  analyzed,  as  indicated in the table.  See reference  7  for more
details.

      9.2  Tables 2, 3  and  4 list the  single operator average  recoveries and
standard deviations  for organic-free reagent water,  wastewater  and  soil.  Ten
replicate samples were analyzed at each indicated spike concentration for each
matrix type.

      9.3  The method detection limit, accuracy and precision obtained will be
determined by the sample matrix.


10.0  REFERENCES

1.  California Department of  Health  Services,  Hazardous  Materials Laboratory,
    "N-Methylcarbamates by HPLC", Revision No.  1.0, September 14, 1989.

2.  Krause, R.T. Journal of Chromatographic Science, 1978, vol. 16, pg 281.

3.  Klotter, Kevin, and Robert Cunico,  "HPLC Post Column  Detection of Carbamate
    Pesticides", Varian Instrument Group,  Walnut Creek, CA  94598.

4.  USEPA,   "Method  531.     Measurement   of   N-Methylcarbomyloximes  and  N-
    Methylcarbamates in  Drinking Water by Direct  Aqueous  Injection HPLC with
                                   8318 -  10                      Revision 0
                                                                  November 1990

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    Post Column  Derivatization",   EPA  600/4-85-054,  Environmental Monitoring
    and Support Laboratory, Cincinnati, OH  45268.

5.  USEPA, "Method 632.  The Determination of Carbamate and Urea Pesticides in
    Industrial  and  Municipal   Wastewater",   EPA  600/4-21-014,  Environmental
    Monitoring and Support Laboratory, Cincinnati, OH  45268.

6.  Federal Register,  "Appendix B to Part 136  -  Definition  and Procedure for
    the Determination  of the Method  Detection Limit - Revision 1.11", Friday,
    October 26, 1984, 49, No. 209, 198-199.

7.  Okamoto, H.S., D. Wijekoon, C. Esperanza, J. Cheng, S. Park, J. Garcha, S.
    Gill,  K.  Perera  "Analysis for  N-Methylcarbamate  Pesticides  by  HPLC in
    Environmental Samples", Proceedings of the  Fifth Annual USEPA  Symposium on
    Waste Testing and Quality Assurance, July 24-28, 1989, Vol. II, 57-71.
                                   8318 - 11                       Revision  0
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                                TABLE 1
                  ELUTION ORDER,  RETENTION TIMES8 AND
                SINGLE OPERATOR METHOD DETECTION LIMITS
Method Detection Limits"
Compound


Aldicarb Sulfone
Methomyl (Lannate)
3-Hydroxycarbofuran
Dioxacarb
Aldicarb (Temik)
Propoxur (Baygon)
Carbofuran (Furadan)
Carbaryl (Sevin)
a-Naphthold
Methiocarb (Mesurol)
Promecarb
Retention
Time
(min)
9.59
9.59
12.70
13.50
16.05
18.06
18.28
19.13
20.30
22.56
23.02
Organic- free
Reagent Water
(M9/L)
1.9e
1.7
2.6
2.2
9.4°
2.4
2.0
1.7
-
3.1
2.5

Soil
(Mg/Kg)
44C
12
10C
>50C
12C
17
22
31
-
32
17
See Section 7.4 for chromatographic conditions

MDL for organic-free reagent water, sand,  soil  were determined by analyzing
10 low  concentration spike  replicate  for each  matrix  type  (except  where
noted).  See reference 7 for more details.

MDL determined by analyzing 7 spiked replicates.

Breakdown product of Carbaryl.
                               8318 - 12
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                                    TABLE 2
                     SINGLE OPERATOR AVERAGE RECOVERY AND
                PRECISION DATA8  FOR  ORGANIC-FREE  REAGENT WATER
Compound                      Recovered       % Recovery        SD      %RSD
Aldicarb Sulfone
Methomyl (Lannate)
3-Hydroxycarbofuran
Dioxacarb
Aldicarb (Temik)
Propoxur (Baygon)
Carbofuran (Furadan)
Carbaryl (Sevin)
Methiocarb (Mesurol)
Promecarb
225
244
210
241
224
232
239
242
231
227
75.0
81.3
70.0
80.3
74.7
77.3
79.6
80.7
77.0
75.7
7.28
8.34
7.85
8.53
13.5
10.6
9.23
8.56
8.09
9.43
3.24
3.42
3.74
3.54
6.03
4.57
3.86
3.54
3.50
4.1
    Spike Concentration = 300 ng/l of each compound, n = 10
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                                    TABLE 3
                     SINGLE OPERATOR AVERAGE  RECOVERY  AND
                        PRECISION DATA3 FOR WASTEWATER
Compound
     Recovered
% Recovery
a   Spike Concentration

b   No recovery
300 /ig/L of each compound, n =  10
SD
%RSD
Aldicarb Sulfone
Methomyl (Lannate)
3-Hydroxycarbofuran
Dioxacarb
Aldicarb (Temik)
Propoxur (Baygon)
Carbofuran (Furadan)
Carbaryl (Sevin)
Methiocarb (Mesurol)
Promecarb
235
247
251
b
258
263
262
262
254
263
78.3
82.3
83.7
-
86.0
87.7
87.3
87.3
84.7
87.7
17.6
29.9
25.4
-
16.4
16.7
15.7
17.2
19.9
15.1
7.49
12.10
10.11
-
6.36
6.47
5.99
6.56
7.83
5.74
                                   8318 - 14
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                                    TABLE 4
                     SINGLE OPERATOR AVERAGE RECOVERY AND
                           PRECISION DATA8 FOR  SOIL
Compound
Recovered
Recovery
SD
    Spike Concentration =2.00 mg/Kg of each compound, n = 10
%RSD
Aldicarb Sulfone
Methomyl (Lannate)
3-Hydroxycarbofuran
Dioxacarb
Aldicarb (Temik)
Propoxur (Baygon)
Carbofuran (Furadan)
Carbaryl (Sevin)
Methiocarb (Mesurol)
Promecarb
1.57
1.48
1.60
1.51
1.29
1.33
1.46
1.53
1.45
1.29
78.5
74.0
80.0
75.5
64.5
66.5
73.0
76.5
72.5
64.7
0.069
0.086
0.071
0.073
0.142
0.126
0.092
0.076
0.071
0.124
4.39
5.81
4.44
4.83
11.0
9.47
6.30
4.90
4.90
9.61
                                   8318 -  15
                                    Revision 0
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                            FIGURE 1
  100
R
E
S
P
0
N
S
E
90
                                                10
                              12          IS
                               TIME (HIM)
             1.00  ug/oL EACH OF:

             1.  ALDICAR3 SULFONE

             2.  METHOMYL

             3 .  3 - HYTDROXYCARBO FURAN

             
-------
                                                                               (  START
                                                                              |_7.1 Extraction
    00
    U>

    CO

    i
15
n>
to
o
           7.1.1 Water, domestic wostewoter.
                aqueous industrial wastes.
                ond leochotes
               .1 Extract 100 mis sample
                 w/30 mts MeCI 3x in sep.
                 funnel: combine extracts
                 in 100 ml. vol. flask ond
                 dilute to mark
                                 No
 7.1.2 Soils, solids, sludges.
      and heavy aqueous
	suspensions	
                     Yes
            7.2 Cleanup
               Combine 20 mis. extract
               and 100 ul ethylene glycol
               in  o gloss vial: blowdown
               mixture w/N2  in heating
               block  set at 50 C:  dissolve
               residue in 2 mis. MeOH.
               pass soln. through pre-
               woshed CIS cartridge:
               collect nluale in 5  ml. vol.
               flask: elule cartridge
               w/MeOH into vol. flask  up
               to  mark: filter MeOH  soln.
               through 0.45 um litter  into
               outosompler vial
    ^T Determine % dry  wt.:
       .1 Weigh 5-10 gr sample
         into crucible: oven dry
         overnight at 105 C; cool
         in dessicaton reweigh
     .2 Extraction:
        Weigh 20 gr. sample into
        250 Erlenmeyen add 50
        mis. acetonitrile.  shake for
        2 hrs.; decant extract into
        centrifuge tube; repeat
        extraction 2x w/ 20 mis.
        ocetonitrile. shake  1 hr.;
        combine extracts and
        centrifuge 10 mkis. 200 rpm;
        decant supernatant to 100 ml.
        vol. flask ond dilute to mark
7.1.3 Soils heavily contaminated
      with non-aqueous substances,
      such as pits	
        etermine % dry wt.:
       Follow Section 7.1.2.1
     .2 Extraction:
       Weigh 20 gr. sample into
       250 Erienmoyen odd 60 mis.
       hexone, shake 1 hr.: add  50
       mis.  ocetonrtrile. shake 3  hrs.;
       let settle, decant extract layers
       to 250 ml. sep. funnel; fitter
       bottom ocetonifrite layer into
       100 ml. vol. fbsk; repeat
       sample fbsk extraction w/some
       volumes; decant extract layers
       on top of first hexone layer;
       shake funnel: fitter bottom layer
       into vol. fbsk; dilute to mark
7.1.4 Non-aqueous liquids
      iuch os oils	
-ft!
        x (ruction:
       Weigh 20 gr. sample into
       125 ml.  sap. funnel; odd
       40  mis.  hexone ond 25 mis.
       ocelonttrite; shake,  settle, and
       drain bottom ocetonitrile layer
       into 100 ml vol. flask: repeat
       extraction 2x by adding 25 mis.
       acetonitrie to initial fbsk mix;
       combine ocetonitrile layers into
       vol. flask; dfate to  mark
                                                                                                                                                                           o
                                                                                                                                                                        o
                                                                                                                                                                        a:
                                                                                                                                                                        §
                                                                                  5
                                                                                                                                • o
                                                                                                                                ;o
                                                                                                                                 CD
                                                                                                                                • (*>
                                                               7.3 Solvent Exchange
                  7.3.1 Water, domestic wostewoter,
                        aqueous industrial wastes.
                        ond leachates:
                        Combine  10 mis extract ond
                        100 ul ethylene glycol in  a
                        glass vial; blowdown mixture
                        w/N2 in heating block at
                        50 C: odd MeOH to residue
                        to total volume of 1  ml.; filter
                        MeOH soln. through 0.45 urn
                        filter into ouloscmpler vial
                                                                           7.3 Solvent Exchange
                                  7.3.2 Soils, solids, sludges.
                                        heavy aqueous suspensions.
                                        and non-aqueous liquids:
                                        Elute 15 mis. extract through
                                        acetonilrile prewoshed CIS
                                        cartridge,  collect tatter 13 mis.:
                                        combine 10 mis. cleaned
                                        extract and 100 ul ethylene
                                        glycol in gbss viol; bbwdown
                                        mixture w/N2 in heating block
                                        at  50 C: odd  MeOH to residue
                                        to  total volume of  1  ml.: filter
                                        MeOH soln. through 0.45 urn
                                        filter into outosampler vial

-------
            I  7.4 Sample Analysis
7.4.1  Initialize Instrumentation:
   .1  Set chromatographic parameters
   .2  Set Post-column Hydrolysis parameters
   .3  Set Post-column Oerivotizotion parameters
   .4  Set Fkiorometer parameters
                     I
7.4.2 Dilute sample extract and reanalyze if
     calibration range is exceeded
  CD
  u>
  H^
  CD

   I

  t—•
  00
                                                                  -M7.5 Calibration J
                                                                          T
7.5.1 Analyze a solvent blank then the calibration
     stds.  of Section 5.4.3; ensure that %RSD of
     each  analyte response factor (RF) is < 20%;
     recheck system and recalibrate w/fresh
     solns. if %RSD > 20%
                    I
                                                       7.5.2 Check calibration doily w/2 ug/ml std.;
                                                            ensure that individual onolyte cones, fall
                                                            w/in +/- %15 of true value; recalibrate
                                                            if observed difference >  15%
r> m
o —»
3 3:
c-f O
— O

C CD
 (A)
Q. •—
                                                       7.5.3 Check calibratbn every 10  samples or less
                                                            w/2 ug/ml std.; variations > 15% may
                                                            require re-analysis of samples
                                                                                                                              7.6 Calculations
                                                                                                                                   I
                                                                                                             7.6.1 Calculate response  factors and % RSD
                                                                                                                   according to equation
                                                                                                             7.6.2 Calculate sample onolyte cones, according
                                                                                                                   to  equation
                                                                                                                           (    STOP   )

-------
                                  METHOD  8321

                SOLVENT EXTRACTABLE NON-VOLATILE COMPOUNDS BY
     HIGH- PERFORMANCE LIQUID CHROMATOGRAPHY/THERMOSPRAY/MASS SPECTROMETRY
                 (HPLC/TSP/MS) OR ULTRAVIOLET (UV) DETECTION
1.0  SCOPE AND APPLICATION

      1.1  This method covers the use  of high performance liquid chromatography
(HPLC),  coupled  with  either thermospray-mass  spectrometry  (TSP-MS),  and/or
ultraviolet/visible  (UV/VIS),  for  the determination  of  disperse azo  dyes,
organophosphoruscompounds, andTris-(2,3-dibromopropyl)phosphate, inwastewater,
ground water, sludge,  and  soil/sediment matrices.   Additionally,  it may apply
to other non-volatile  compounds  that  are  solvent  extractable,  are amenable to
HPLC, and are ionizable  under thermospray introduction  for mass spectrometric
detection.  The following compounds can be determined by this method:
      Compound Name
CAS No.Ł
          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 Dves
      Disperse Blue 3
      Disperse Blue 14
      Disperse Red 60
      Coumarin Dyes

      (Fluorescent Brighteners)
      Fluorescent Brightener 61
      Fluorescent Brightener 236

      Alkaloids
      Caffeine
      Strychnine
 2872-
 3180-
 2832-
 6439-
  730-
 5261-
17464-
 6535-
   85-
52-8
81-2
40-8
53-8
40-5
31-4
91-4
42-8
86-9
 2475-46-9
 2475-44-7
17418-58-5
 8066-05-5
63590-17-0
   58-08-2
   57-24-9
                                   8321 - 1
         Revision 0
         November 1990

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      Compound Name                                      CAS No.a


      Orqanophosphorus Compounds
      Methomyl                                           16752-77-5
      Thiofanox                                          39196-18-4
      Famphur                                               52-85-7
      Asulam                                              3337-71-1
      Dichlorvos                                            62-73-7
      Dimethoate                                            60-51-5
      Disulfoton                                           298-04-4
      Fensulfothion                                        115-90-2
      Merphos                                              150-50-5
      Methyl parathion                                     298-00-0
      Monocrotophos                                        919-44-8
      Naled                                                300-76-5
      Phorate                                              298-02-2
      Trichlorfon                                           52-68-6
      Tris-(2,3-Dibromopropyl) phosphate, (Tris-BP)        126-72-7


      a   Chemical  Abstract Services  Registry  Number.


      1.2  This method may be applicable to the analysis of other non-volatile
or semivolatile compounds.

      1.3  Tris-BP  has  been  classified  as  a  carcinogen.    Purified  standard
material and stock standard solutions should be handled in a hood.

      1.4  The compounds were chosen for analysis by HPLC/MS because they have
been designated as  problem compounds that are hard  to  analyze  by traditional
chromatographic methods  (e.g. gas  chromatography).   The  sensitivity  of this
method is dependent upon  the  level  of  interferants within  a given matrix, and
varies  with  compound  class   and  even  with  compounds  within  that  class.
Additionally,  the limit  of  detection  (LOD)  is  dependent  upon  the mode  of
operation of the  mass spectrometer.  For example,  the  LOD for caffeine in the
selected reaction monitoring  (SRM)  mode  is 45 pg of standard injected  (10  n\.
injection), while for Disperse Red  1 the LOD is  180 pg.   The LOD for caffeine
under single quadrupole scanning is 84 pg and is 600 pg for Disperse
Red 1 under similar scanning  conditions.

      1.5  The experimentally determined method detection limits (MDL) for the
target analytes are  presented in Tables 3,  10 and 13.   For further compound
identification, MS/MS (CAD  -  collision activated  dissociation)  can be used  as
an optional extension of this method.

      1.6  This method  is restricted  to use by  or under  the  supervision  of
analysts experienced in the use of high performance liquid chromatographs/mass
spectrometers and  skilled  in the interpretation of liquid  chromatograms and mass
                                   8321 - 2                       Revision 0
                                                                  November 1990

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spectra. Each analyst must demonstrate the ability to generate acceptable results
with this method.
2.0  SUMMARY OF METHOD

      2.1  This  method   provides   reverse  phase   high   performance  liquid
chromatographic  (RP/HPLC)  and  thermospray  (TSP)  mass  spectrometric  (MS)
conditions for the detection of the target analytes.  Quantitative analysis is
performed by TSP/MS, using an external standard approach.  Sample extracts can
be  analyzed  by  direct   injection  into  the  thermospray or  onto  a  liquid
chromatographic-thermospray interface.  A  gradient  elution program is used on
the chromatograph to separate the compounds.  Since this method is based on an
HPLC technique, the  use  of  ultraviolet/visible  (UV/VIS)  detection is optional
on routine samples.

      2.2  Prior to  the  use  of this  method,  appropriate sample preparation
techniques must be used.  In general, water samples are extracted at a neutral
pH  with  methylene  chloride,  using  a separatory  funnel  (Method  3510)  or  a
continuous  liquid-liquid  extractor (Method 3520).   Soxhlet  (Method  3540)  or
ultrasonic  (Method 3550)  extraction  using  methylene chloride/acetone (1:1)  is
used for  solid samples.   A  micro-extraction  technique  is  included  for the
extraction of Tris-BP from aqueous and non-aqueous matrices.


3.0  INTERFERENCES

      3.1  Refer to Methods 3500, 3600 and 8000.

      3.2  The use  of Florisil Column Cleanup (Method 3620)  has been demonstrated
to yield recoveries less than 85% for some  of the compounds in this method, and
is therefore not recommended  for all compounds.   Refer to Table 2 of Method 3620
for recoveries of organophosphorus compounds as a function of Florisil fractions.

      3.3  Compounds with high proton  affinity may mask  some  of  the target
analytes.  Therefore, an HPLC must be used as a chromatographic separator, for
quantitative analysis.

      3.4  Analytical difficulties  encountered  with specific  organophosphorus
compounds, as applied in this method, may include (but are not limited to) the
following:

            3.4.1   Methyl parathion shows  some minor degradation upon analysis.

            3.4.2  Naled can undergo debromination to form dichlorvos.

            3.4.3  Merphos often  contains  contamination  from merphos oxide.
      Oxidation  of  merphos   can   occur  during  storage,  and  possibly  upon
      introduction into the mass spectrometer.

     Refer to Method 8141 for other compound problems as related to the various
extraction methods.
                                   8321 - 3
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      3.5  Solvents, reagents, glassware, and other sample processing hardware
may  yield  discrete   artifacts   or   elevated  baselines,   or  both,  causing
misinterpretation of chromatograms or spectra.  All of these materials must be
demonstrated to be free from interferences  under the conditions of the analysis
by running reagent blanks.  Specific selection of reagents and purification of
solvents by distillation in all-glass systems may be required.

      3.6  Interferants co-extracted  from the sample will  vary considerably from
source to source.  Retention times of target analytes must be verified by using
reference standards.

      3.7  The optional use  of HPLC/MS/MS  methods  aids  in  the confirmation of
specific analytes.  These methods are less  subject  to chemical noise than other
mass spectrometric methods.


4.0  APPARATUS AND MATERIALS

      4.1  HPLC/MS

            4.1.1  High Performance Liquid  Chromatograph  (HPLC) - An analytical
      system  with  programmable   solvent  delivery system  and  all  required
      accessories including  10 /xL injection  loop,  analytical  columns, purging
      gases, etc.  The solvent delivery  system  must  be  capable,  at a minimum,
      of a binary solvent  system.  The  chromatographic  system must be capable
      of interfacing with a Mass Spectrometer (MS).

                  4.1.1.1  HPLC  Post-Column  Addition  Pump  -  A pump  for post
            column addition  should be used.   Ideally,  this pump  should be a
            syringe pump,  and does not have  to be capable of solvent programming.

                  4.1.1.2  HPLC Columns - A guard column and an analytical column
            are required.

                        4.1.1.2.1  Guard Col umn  - CIS reverse phase guard col umn,
                  10 mm x 2.6 mm  ID,  0.5 p.m frit,  or equivalent.

                        4.1.1.2.2  Analytical Column - CIS reverse phase column,
                  100  mm x 2 mm.ID, 5 pm particle  size of ODS-Hypersil; or CIS
                  reversed phase  column, 100 mm x  2 mm  ID,  3  /xm particle size
                  of MOS2-Hypersil, or equivalent.

            4.1.2  HPLC/MS interface(s)

                  4.1.2.1   Micromixer -  10 /xL,  interfaces  HPLC  column system
            with HPLC  post-column  addition solvent system.

                  4.1.2.2  Interface  -   Thermospray  ionization  interface  and
            source  that will give acceptable  calibration  response  for each
            analyte of interest at the concentration required.  The source must
            be capable of generating  both positive  and negative buffer assisted
            ions,  and  have  both  a  repeller  and  a  discharge  electrode  for
            enhancement of the ion signal in both modes,  respectively.


                                   8321  - 4                       Revision 0
                                                                  November  1990

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            4.1.3  Mass  spectrometer  system   -  A   single  quadrupole  mass
      spectrometer capable of  scanning  from 1 to 1000 amu.   The spectrometer
      must also be capable of scanning from 150 to 450 amu in 1.5 sec or less,
      using 70  volts  (nominal)  electron  energy  in  the  positive  or negative
      electron impact modes.  In addition,  the mass spectrometer must be capable
      of producing  a calibrated mass spectrum  for  PEG 400, 600,  or 800 (see
      Section 5.12).

                  4.1.3.1 Optional triple  quadrupole mass spectrometer - capable
            of generating daughter ion spectra with a collision gas in the second
            quadrupole and operation in the single quadrupole mode.

            4.1.4  Data System  - A  computer system  that  allows  the continuous
      acquisition and  storage  on machine-readable media of all  mass spectra
      obtained throughout the duration of the chromatographic program must be
      interfaced to the mass spectrometer.  The computer must have software that
      allows any MS data file to be searched for ions of a specified mass, and
      such ion abundances to be plotted versus time or scan number.  This type
      of plot is defined as an Extracted  Ion Current Profile (EICP).  Software
      must also be available that allows  integration  of  the abundances in any
      EICP between specified time or scan-number limits.  There must be computer
      software available  to operate the specific modes of  the mass spectrometer.

      4.2  HPLC  with  UV/VIS  detector  -   An  analytical   system with  solvent
programmable  pumping system for  at least  a binary  solvent system,  and all
required  accessories  including  syringes,  10  /uL  injection loop,  analytical
columns, purging gases, etc.   An automatic  injector is optional, but is useful
for multiple samples.  The columns  specified  in Section  4.1.1.2 are also used
with this system.

            4.2.1  If  the  UV/VIS detector  is  to be  used  in tandem  with the
      thermospray  interface,   then   the   detector cell  must  be  capable  of
      withstanding high pressures (at least 6000 psi).

      4.3  Purification Equipment for Azo Dye Standards

            4.3.1  Soxhlet extraction apparatus.

            4.3.2  Extraction thimbles, single thickness, 43 x 123 mm.

            4.3.3  Filter  paper,  9.0  cm  (Whatman   qualitative  No.  1  or
     equivalent).

            4.3.4  Silica-gel  column - 3  in.  x 8 in., packed with Silica gel
      (Type 60, EM reagent 70/230 mesh).

      4.4  Kuderna-Danish (K-D) apparatus  (optional).

            4.4.1  Concentrator tube -  10 ml graduated  (Kontes K-570050-1025
      or equivalent).  A  ground glass stopper  is used to prevent evaporation of
      extracts.
                                   8321 - 5                       Revision 0
                                                                  November 1990

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            4.4.2  Evaporation   flask  -   500  ml (Kontes   K-570001-500   or
      equivalent).   Attach  to  concentrator tube  with  springs,  clamps,  or
      equivalent.

            4.4.3  Snyder column  -   Two  ball  micro  (Kontes  K-569001-0219 or
      equivalent).

            4.4.4  Springs -  1/2 in. (Kontes K-662750 or equivalent).

      4.5  Disposable serological pipets - 5 ml x 1/10, 5.5 mm ID.

      4.6  Collection tube  - 15  ml conical, graduated  (Kimble No.  45165 or
equivalent).

      4.7  Vials - 5 ml conical,  glass, with Teflon  lined screw-caps or crimp
tops.

      4.8  Glass wool - Supelco No.  2-0411 or equivalent.

      4.9  Microsyringes - 100 ML, 50 ML,  10  juL  (Hamilton 701 N or equivalent),
and 50 ML (Blunted, Hamilton 705SNR or equivalent).

      4.10  Rotary evaporator - Equipped with 1,000 ml receiving flask.

      4.11  Balances - Analytical, 0.0001 g,  Top-loading, 0.01 g.

      4.12  Volumetric flasks, Class A - 10 mL to 1000 mL.

      4.13  Graduated cylinder - 100 ml.

      4.14  Separatory funnel - 250 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.

      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  Ammonium acetate, NH4OOCCH3, solution (0.1 M).   Filter through a 0.45
micron membrane filter (Millipore HA or equivalent).


                                   8321 - 6                       Revision 0
                                                                  November  1990

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      5.5  Argon gas, 99+% pure.

      5.6  Solvents

            5.6.1  Methylene chloride, CH2C12 - Pesticide quality or equivalent.

            5.6.2  Toluene, C6H5CH3 - Pesticide quality or equivalent.

            5.6.3  Acetone, CH3COCH3  -  Pesticide quality  or equivalent.

            5.6.4  Diethyl Ether,  C2H5OC2H5 -  Pesticide  quality or equivalent.
      Must  be  free  of  peroxides as  indicated by  test  strips (EM  Quant,  or
      equivalent).   Procedures  for  removal  of peroxides are provided with the
      test strips.  After cleanup, 20 ml of ethyl alcohol preservative must be
      added to each liter of ether.

            5.6.5  Methanol, CH3OH - HPLC quality or equivalent.

            5.6.6  Acetonitrile, CH3CN - HPLC quality or equivalent.

            5.6.7  Ethyl acetate CH3C02C2H5  -  Pesticide quality  or  equivalent.

      5.7  Standard Materials - pure standard materials  or certified solutions
of each analyte targeted for analysis.  Disperse azo dyes must be purified before
use according  to  Section  5.8.   Tris-(2,3-dibromopropyl) phosphate, 98+% pure,
may be  obtained  from  the U.S.EPA  Repository,  Research Triangle  Park,  North
Carolina.

      5.8  Disperse Azo Dye Purification

            5.8.1  Two procedures are  involved.  The  first step is the Soxhlet
      extraction  of  the  dye  for 24 hours with toluene  and  evaporation of the
      liquid extract to dryness, using a rotary evaporator.  The solid is then
      recrystallized from toluene, and dried in an oven  at approximately  100°C.
      If this  step does not  give the required  purity,  column chromatography
      should be employed.  Load the  solid  onto a 3 x 8   inch silica gel column
      (Section  4.3.5),  and  elute with  diethyl   ether.   Separate impurities
      chromatographically, and  collect the major dye  fraction.

      5.9  Stock  standard solutions   -  Can  be  prepared  from pure  standard
materials or can  be purchased  as certified  solutions.   Commercially prepared
stock standards can be used if they are verified  against  EPA  standards.  If EPA
standards are  not  available  for verification, then standards certified by the
manufacturer  and  verified  against  a  standard  made from  pure   material  is
acceptable.

            5.9.1  Prepare  stock  standard  solutions  by accurately  weighing
      0.0100 g of pure  material.   Dissolve the material in  methanol  or other
      suitable solvent  (e.g.  prepare  Tris-BP in  ethyl acetate), and dilute to
      known volume  in a volumetric  flask.   If compound  purity is certified at
      96% or greater,  the weight can  be used without correction  to calculate
      the concentration  of the  stock standard.    Commercially prepared stock
      standards can  be used  at  any  concentration  if they are certified by the
      manufacturer or by an independent source.

                                   8321 - 7                       Revision 0
                                                                  November 1990

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            5.9.2  Transfer the stock standard solutions into glass vials with
      Teflon lined  screw-caps or crimp-tops.   Store at 4°C  and  protect from
      light.  Stock  standard  solutions  should  be checked frequently for signs
      of  degradation  or  evaporation,   especially  just  prior  to  preparing
      calibration standards.

      5.10  Calibration standards - A minimum  of five concentrations for each
parameter of interest should be prepared through dilution of the stock standards
with methanol (or other suitable solvent).  One of these concentrations should
be near, but above,  the MDL.  The remaining concentrations should correspond to
the expected range of concentrations found in real samples, or  should define the
working range of the HPLC-UV/VIS or HPLC-TSP/MS.  Calibration  standards must be
replaced after one or two months,  or sooner if comparison with check standards
indicates a problem.

      5.11  Surrogate standards -  The  analyst should monitor the performance of
the extraction,  cleanup  (when used),  and analytical  system, along with  the
effectiveness of the method in dealing with each  sample matrix, by spiking each
sample, standard, and  blank with  one  or two  surrogates (e.g.  organophosphorus
compounds not expected to be present in the sample).

      5.12  HPLC/MS tuning  standard - Polyethylene glycol 400 (PEG-400), PEG-
600 or PEG-800.   Dilute to 10 percent (v/v) in methanol.  Dependent upon analyte
molecular weight range: m.w. < 500 amu, use PEG-400; m.w. > 500  amu, use PEG-600,
or PEG-800.
6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See the  introductory material to  this Chapter,  Organic  Analytes,
Section 4.1.
7.0  PROCEDURE

      7.1  Sample preparation -  Samples must be prepared by one of the following
methods prior to HPLC/MS analysis:

     Matrix                Methods

     Water              3510, 3520
     Soil/sediment      3540, 3550
     Waste              3540, 3550, 3580

            7.1.1  Microextraction for Tris-BP:

                  7.1.1.1  Non-Aqueous Samples

                        7.1.1.1.1  Weigh a 1 gram portion of the sample into a
                  tared beaker.   If the sample  is moist, add an equivalent amount
                  of  anhydrous  sodium sulfate and  mix well.   Add  100 /xL of
                  Tris-BP (approximate concentration  1000  mg/L)  to the sample
                                   8321 - 8                       Revision 0
                                                                  November 1990

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                  selected for spiking; the amount added should result in a final
                  concentration of 100 ng//iL  in  the  1  ml extract.

                        7.1.1.1.2  Pack  the  sample  into  a disposable pipet
                  prepared according to Section 7.1.1.1.2.1.  If packing material
                  has dried,  rinse with  methanol  first, then pack sample into
                  the pipet.

                              7.1.1.1.2.1  Remove the  glass wool plug.  Insert
                        a 1 cm  plug  of  clean  si lane  treated glass wool to the
                        bottom  (narrow end) of the pipet.  Pack 2 cm of sodium
                        sulfate (dried)  onto  the top of the glass wool.  Wash
                        pipet with 3-5 ml of methanol.

                        7.1.1.1.3  Extract  the  sample  with  3  ml  of methanol
                  followed  by 4 ml of 50%  (v/v) methanol/methylene chloride.
                  Collect extract in 15 ml graduated glass tubes.

                        7.1.1.1.4  Evaporate the extract to 1 ml using the micro
                  Snyder  column  technique  (Section  7.1.1.1.5)  or  nitrogen
                  blowdown  technique  (Section  7.1.1.1.6).   Record the volume.
                  It may not  be possible to evaporate  some sludge samples to a
                  reasonable  concentration.

                        7.1.1.1.5  Micro-Snyder Column Technique

                              7.1.1.1.5.1  Add the sample and 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 to  the  top of the
                        column.  Place the K-D apparatus in  a hot water  bath so
                        that the concentrator tube is partially immersed in the
                        hot water.  Adjust the vertical  position of the apparatus
                        and the water temperature, as required,  to complete the
                        concentration in 5-10 minutes.  At  the proper rate of
                        distillation  the balls  of  the column  will  actively
                        chatter, but  the chambers will  not flood.   When the
                        apparent volume of liquid reaches 0.5 ml, remove the K-
                        D apparatus  from the  water bath and allow it to drain
                        and cool for at least 10 minutes.   Remove  the Snyder
                        column  and  rinse the flask  and its  lower joints with
                        about  0.2  mL  of methyl ene  chloride  and  add  to  the
                        concentrator tube.  Proceed to Section 7.1.1.1.7.

                        7.1.1.1.6  Nitrogen Blowdown Technique

                              7.1.1.1.6.1  PI ace 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.


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                              7.1.1.1.6.2  The internal wall  of the tube must
                        be rinsed  down  several  times with  methylene chloride
                        during the operation.  During evaporation, the solvent
                        level in the tube must be positioned to prevent water
                        from condensing  into the sample (i.e., the solvent level
                        should be below the level of the water bath).   Under
                        normal operating conditions, the extract should not be
                        allowed to become dry.  Proceed to Section 7.1.1.1.7.

                        7.1.1.1.7  Transfer the extract to a glass vial with a
                  Teflon lined screw-cap or crimp-top and store refrigerated at
                  4°C.   Proceed  with HPLC analysis.

                  7.1.1.2  Aqueous (Water and Municipal  Waste Water) Samples

                        7.1.1.2.1  Using a 100 ml graduated cylinder,  measure
                  100 ml of sample and transfer it  to a 250 ml separatory funnel.
                  Add 200  pi  of Tris-BP (approximate  concentration 1000 mg/L)
                  to the sample  selected  for  spiking; the  amount added should
                  result in  a final concentration  of 200  ng//iL in the  1  ml
                  extract.

                        7.1.1.2.2  Add  10 ml  of  methyl ene  chloride  to  the
                  separatory funnel.  Seal and shake the separatory funnel three
                  times, approximately  30  seconds each  time,   with  periodic
                  venting to release excess pressure.  NOTE: Methylene chloride
                  creates excessive pressure rapidly; therefore,  initial venting
                  should be done immediately after the separatory funnel has been
                  sealed and  shaken  once.   Methylene chloride  is  a suspected
                  carcinogen, use necessary safety precautions.

                        7.1.1.2.3  Allow the organic layer to separate from the
                  water phase for  a minimum of  10 minutes.  If the emulsion
                  interface between layers is more  than one-third  the  size of
                  the  solvent  layer,  the  analyst  must  employ  mechanical
                  techniques to  complete  phase  separation.    See Section 7.5,
                  Method 3510.

                        7.1.1.2.4  Collect the  extract  in  a 15 ml graduated
                  glass tube. Proceed as in Section 7.1.1.1.4.

      7.2  Prior to HPLC analysis,  the extraction solvent must be exchanged to
methanol.  The exchange is  performed  during the K-D  procedures listed in all of
the extraction methods.

      7.3  HPLC Chromatographic Conditions:

            7.3.1  Analyte-specific  chromatographic conditions  are shown  in
      Table 1.   Chromatographic  conditions which  are  not  analyte-specific are
      as follows:

              Flow rate:                   0.4 mL/min
              Post-column mobile  phase:    0.1 M ammonium acetate (1% methanol)


                                   8321  -  10                       Revision 0
                                                                  November 1990

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        Post-column  flow  rate:       0.8 mL/min

      7.3.2  If there is a chromatographic problem from compound retention,
a  2% constant  flow  of  methylene chloride  may be  applied as  needed.
Methylene chloride/aqueous methanol solutions must  be  used with caution
as HPLC eluants.  Acetic  acid (1%), another mobile phase modifier, can be
used with compounds with acid functional groups.

      7.3.3  A  total  flow rate  of 1.0  to  1.5  mL/min is  necessary to
maintain thermospray  ionization.

      7.3.4  Retention  times  for  organophosphorus  compounds  on  the
specified analytical  column are presented in Table 9.

7.4  Recommended HPLC/Thermospray/MS operating conditions:

      7.4.1  Positive Ionization mode

Repeller (wire or plate):  170 to 250 v (sensitivity optimized).
Mass range: 150 to 450 amu (compound dependent,  expect  1 to  18 amu higher
            than molecular weight of the compound).
Scan time:  1.50 sec/scan.

7.4.2   Negative Ionization mode

Discharge electrode:  on
Filament:  off
Mass Range:  135 to 450 amu  (compound dependent, expect 1 amu lower than
             molecular weight of the compound).
Scan time:  1.50 sec/scan.

7.4.3  Thermospray temperatures:

Vaporizer control »   110°C to 130°C (as necessary to achieve  proper stable
                      tip and  jet temperatures without loss  of sensitivity.
                      See Manufacturer's recommendations).
Vaporizer tip -       200°C.
Jet «                 210°C to 220°C.
Source block «        240°C to 265°C.  (Some compounds may  degrade in the
                      source block at higher temperatures,  operator should
                      use  knowledge of  chemical  properties  to estimate
                      proper  source temperature).

      7.4.4  Sample  injection volume:  20  /iL  is  necessary  in  order to
overfill the 10 nl  injection  loop.

7.5  Calibration:

      7.5.1  Thermospray/MS   system   -   Must  be   hardware-tuned,   on
quadrupole 1 (and quadrupole 3 for triple  quadrupoles), for  accurate mass
assignment,  sensitivity,  and  resolution.    This is  accomplished  using
polyethylene glycol  (PEG) 400, 600, or  800  (see Section  5.12)  which has
average molecular weights of 400, 600, and 800, respectively.  A mixture


                             8321  - 11                       Revision 0
                                                            November  1990

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of these  PEGs can  be  made such that  it will approximate  the expected
working mass  range for  the analyses.   The  PEG  is introduced  via the
thermospray interface, circumventing the HPLC.

            7.5.1.1  The mass calibration parameters are as follows:

      for PEG 400 and 600           for PEG 800
      Mass range: 15 to 765 amu     Mass range: 15 to 900 amu
      Scan time: 5.00 sec/scan      Scan time: 5.00 sec/scan

            Approximately  100  scans  should  be  acquired,  with  2  to  3
      injections made.  The scan with  the  best fit to  the accurate mass
      table (see Tables 7 and 8)  should be  used as the calibration table.

            7.5.1.2  The low mass range from  15 to 100 amu is covered by
      the ions from the  ammonium acetate buffer  used in the thermospray
      process:  NH4+ (18  amu), NH4+H20 (36), CH3OHNH4+ (50) (methanol), or
      CH3CNNH4+  (59) (acetonitrile),  and CH3COOHNH4+ (78)  (acetic acid).
      The appearance  of the m/z 50  or 59  ion depends upon the  use of
      methanol or acetonitrile as the organic modifier.  The higher mass
      range is covered by the ammonium ion adducts of the various ethylene
      glycols (e.g.  H(OCH2CH2)nOH where n=4,  gives  the H(OCH2CH2)4OHNH4+ ion
      at m/z 212).

      7.5.2  Liquid Chromatograph

            7.5.2.1  Prepare calibration standards as outlined in Section
      5.10.

            7.5.2.2  Choose the proper ionization  conditions, as outlined
      in Section 7.4.1.  Inject each calibration standard onto the HPLC,
      using the  chromatographic conditions outlined in Table  1.  Calculate
      the  area   under the  curve  for  the  mass   chromatogram  of  each
      quantitation  ion.  For example,  Table 9 lists the retention times
      and  the major  ions  (>  5%)  present  in  the  positive  ionization
      thermospray  single  quadrupole  spectra of the  organophosphorus
      compounds.  In most cases the  (M+H)+ and (M+NH4)+ adduct ions are the
      only ions  of significant abundance. Plot these ions as area response
      versus the amount  injected.  The points should fall  on a straight
      line, with a correlation coefficient  of at least 0.99.

            7.5.2.3  If HPLC-UV/VIS detection is also being used, calibrate
      the instrument  by  preparing  calibration standards  as  outlined in
      Section 5.10, and injecting each calibration standard onto the HPLC
      using the  chromatographic conditions  outlined in Table 1. Integrate
      the area under the full chromatographic peak for each concentration.

            7.5.2.4  For the  methods  specified  in  Section  7.5.2.2 and
      7.5.2.3,  the  retention  time  of the  chromatographic  peak  is  an
      important variable in analyte identification.   Therefore, the ratio
      of the retention time of  the sample analyte  to  the standard analyte
      should be 1.0 ± 0.1.
                             8321  -  12                       Revision 0
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            7.5.2.5  The concentration  of  the  sample  analyte will  be
      determined by using the calibration  curves  determined in Sections
      7.5.2.2 and 7.5.2.3.  These calibration curves must be generated on
      the  same  day  as  each  sample  is  analyzed.   At least  duplicate
      determinations must be made for each sample extract.   Concentrated
      samples must be diluted by a known amount.

            7.5.2.6  Refer to  Method 8000 for  further information  on
      calculations.

            7.5.2.7  Precision can also be  calculated  from  the ratio of
      response  (area)  to the amount  injected;  this  is defined  as  the
      calibration factor (CF) for  each  standard  concentration.   If  the
      percent relative standard deviation  (%RSD)  of  the CF  is  less than
      20 percent over the working range, linearity through the origin can
      be assumed, and the average calibration factor can be used in place
      of a  calibration curve.   The CF  and %RSD can  be calculated as
      follows:

      CF = Total Area of Peak/Mass injected (ng)

      %RSD = SD/CF x 100

      where:

      SD = Standard deviation between CFs

      CF = Average CF

            7.5.2.8  The working calibration curve,  or the CF,  must be
      verified  on  each  working day  by the  injection of  one or more
      calibration standards.  If the response varies from  the  predicted
      response by more than ± 20 percent, a  new calibration curve must be
      prepared.   The % Difference is calculated  as follows:

      % Difference = (R,  - R2)/R, x 100.

      where:      R.,  = CF first  analysis.
                  R2  = CF from succeeding  analyses.

7.6  Sample Analysis

      7.6.1 Once the  LC/MS   system  has  been calibrated as outlined in
Section 7.5, then it is ready for sample analysis.

            7.6.1.1  A blank 20-/uL injection (methanol) must be analyzed
      after the standard(s)  analyses, in order to determine any residual
      contamination of the Thermospray/HPLC/MS system.

            7.6.1.2  Take a  20-jiL  aliquot of the  sample  extract from
      Section 7.1.  Start the HPLC gradient elution,  load and inject the
      sample aliquot,  and start the mass spectrometer data system analysis.
                             8321  -  13                       Revision 0
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     7.7  Calculations

            7.7.1   Using  the external standard  calibration  procedure (Method
      8000), determine the identity and quantity of each component peak in the
      sample reconstructed ion chromatogram which corresponds to the compounds
      used for calibration processes.  See Method 8000 for calculation equations.


8.0  QUALITY CONTROL

      8.1  Refer to  Chapter  One  and Method 8000 for  specific  quality control
procedures.

      8.2  Tables 4,  5,  11,  and  12 indicate the single operator accuracy and
precision for this method.  Compare the results obtained with  the  results in the
tables to determine if the data quality is acceptable.

            8.3.1  If recovery is not acceptable, check the following:

                  8.3.1.1  Check  to be  sure  that there are  no  errors  in the
            calculations, surrogate solutions  or internal standards.  If errors
            are found, recalculate the data accordingly.

                  8.3.1.2  Check  instrument  performance.     If   an  instrument
            performance problem is identified,  correct the problem and re-analyze
            the extract.

                  8.3.1.3  If no problem is found, re-extract  and  re-analyze the
            sample.

                  8.3.1.4  If, upon re-analysis, the recovery is  again not within
            limits,  flag the data as "estimated concentration".

      8.4  Instrument  performance   -   Check   the  performance  of  the  entire
analytical system daily using data  gathered from analyses of blanks, standards,
and replicate samples.

           8.4.1   See Section  7.4  for required HPLC/MS  parameters for standard
      calibration curve %RSD limits.

           8.4.2   See Section 7.5.2.4 regarding retention time window QC limits.

           8.4.3   If any  of the chromatographic QC  limits  are not  met,  the
      analyst should examine the LC system for:

            o  Leaks,
            o  Proper pressure  delivery,
            o  A dirty guard column; may need  replacing or repacking,  and
            o  Possible partial thermospray plugging.

            Any of the above items will necessitate shutting  down the  HPLC/TSP
      system,  making repairs  and/or  replacements,  and  then  restarting  the
      analyses.  The  calibration standard should be reanalyzed before any sample
      analyses, as  described in Section 7.5.

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                                                                  November 1990

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      8.4.4  The experience of the analyst performing 1 iquid chromatography
is invaluable  to  the  success of the method.   Each  day that analysis is
performed, the daily calibration  standard should be evaluated to determine
if the chromatographic system is operating properly.   If any changes are
made to the system (e.g. column change), the system must be recalibrated.

8.5  Optional Thermospray HPLC/MS/MS confirmation

      8.5.1  With respect to this method,  MS/MS shall  be defined as the
daughter ion collision activated  dissociation acquisition with quadrupole
one set on  one mass (parent  ion),  quadrupole  two pressurized with argon
and with a higher offset voltage  than normal, and  quadrupole three set to
scan desired mass range.

      8.5.2  Since  the  thermospray  process often generates  only one or
two  ions  per  compound,  the use of MS/MS  is   a  more  specific  mode of
operation yielding molecular structural information.   In this mode, fast
screening of samples can be accomplished through direct injection of the
sample into the thermospray.

      8.5.3  For MS/MS experiments,  the first quadrupole should be set to
the protonated molecule or ammoniated adduct of the analyte of interest.
The third quadrupole should be set to scan from 30 amu to just above the
mass region of the protonated molecule.

      8.5.4  The  collision gas  pressure   (Ar)  should   be  set at  about
1.0 mTorr and the collision energy at 20 eV.  If these  parameters fail to
give considerable fragmentation,  they may be raised above these settings
to create more and stronger collisions.

      8.5.5  For analytical determinations, the base peak of  the collision
spectrum shall  be taken  as the quantification ion.   For  extra specificity,
a second ion should be chosen as a backup quantification ion.

      8.5.6  Generate a calibration curve as outlined  in Section 7.5.2.
                                                                  t
      8.5.7  For  analytical  determinations,  calibration blanks  must be
run  in  the MS/MS mode to  determine  specific ion interferences.   If no
calibration  blanks  are  available,  chromatographic  separation  must be
performed  to assure  no  interferences  at  specific  masses.   For  fast
screening, the  MS/MS  Spectra of the  standard  and the  analyte  could be
compared and the ratios of the three major (most intense) ions examined.
These  ratios  should   be   approximately  the  same unless  there is  an
interference.  If an interference appears, chromatography must be utilized.

      8.5.8  For unknown concentrations, the total area of the quantitation
ion(s) is  calculated and  the  calibration  curves  generated  as  in Section
7.6 are used to attain an  injected weight number.

      8.5.9  MS/MS  techniques can also  be  used  to  perform  structural
analysis on ions represented by  unassigned m/z ratios.  The procedure for
compounds of unknown structures is to set up a CAD experiment  on the ion
of interest.  The spectrum  generated from this experiment will reflect the
structure of the  compound  by  its fragmentation pattern.  A trained mass

                             8321 - 15                      Revision 0
                                                            November  1990

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      spectroscopist  and some  history of  the sample  are usually  needed to
      interpret  the spectrum.  (CAD experiments  on  actual  standards  of the
      expected  compound  are  necessary  for confirmation  or  denial  of  that
      substance.)


9.0  METHOD PERFORMANCE

      9.1  Single operator accuracy  and  precision  studies  have been conducted
using spiked sediment, wastewater, sludge, and water samples.  The results are
presented in Tables 4, 5, 6, 11, and 12.   Tables 3, 10, and 13 list precision
and bias data that are typical with this method.

      9.2  MDLs should be calculated for the  known analytes, on each  instrument
to be used.

            9.2.1  The MDLs presented in this  method were calculated by analyzing
      three  replicates  of   four  standard   concentrations,  with  the  lowest
      concentration  being near  the  instrument detection  limit.   A  linear
      regression was  performed  on  the data  set to  calculate the  slope and
      intercept. Three times the standard deviation (3a) of the lowest standard
      amount, along with  the calculated  slope  and  intercept,  was  used to find
      the MDL.  The MDL was not calculated using the specifications  in Chapter
      One, but according to the ACS guidelines specified in Reference 4.


10.0 REFERENCES

1.  Voyksner, R.D.; Haney, C.A.   "Optimization and  Application of Thermospray
    High-Performance Liquid Chromatography/Mass Spectrometry"; Anal. Chem. 1985,
    5Z,  991-996.

2.  Blakley,  C.R.;   Vestal,   M.L.      "Thermospray   Interface  for   Liquid
    Chromatography/Mass Spectrometry"; Anal.  Chem.  1983, 55,  750-754.

3.  Taylor, V.;  Hickey, D. M., Marsden, P. J. "Single Laboratory Validation of
    EPA Method 8140";  EPA-600/4-87/009,  U.S.  Environmental  Protection Agency,
    Las Vegas, NV,  1987, 144 pp.

4.  "Guidelines for Data Acquisition and Data Quality Evaluation in Environmental
    Chemistry";  Anal. Chem.  1980, 52, 2242-2249.

5.  Betowski, L. D.; Jones, T.  L.  "The Analysis of Organophosphorus Pesticide
    Samples by HPLC/MS  and HPLC/MS/MS";  Environmental  Science and Technology.
    1988,

8.  EPA:  2nd Annual Report on Carcinogens,  NTP 81-43, Dec. 1981,  pp. 236-237.

9.  Blum, A.; Ames, B. N. Science 195. 1977,  17.

10. Zweidinger,  R.  A.; Cooper,  S.  D.;  Pellazari,  E. D., Measurements  of Organic
    Pollutants in Water and Wastewater. ASTM 686.
                                   8321  -  16                       Revision 0
                                                                  November 1990

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                                   TABLE  1.
                  RECOMMENDED HPLC CHROMATOGRAPHIC CONDITIONS
Initial
Mobile
Phase
(%)
Analytes:
Orqanoohosphorus
Initial
Time
(min)
Compounds
Gradient
(linear)
(min)

Final
Mobile
Phase
(%)

Final
Time
(min)

50/50
(water/methanol)
10        100        5
       (methanol)
Azo Dves (e.g. Disperse Red  1)

50/50                   0
(water/CH3CN)

Tris-(2.3-dibromopropv1)phosphate

50/50                   0
(water/methanol)
10
          100        5
        (CH3CN)
   100        5
(methanol)
                                   8321 - 17
                              Revision 0
                              November  1990

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                                   TABLE 2.
             COMPOUNDS AMENABLE TO THERMOSPRAY MASS SPECTROMETRY
    Disperse Azo Dyes
    Methine Dyes
    Arylmethane Dyes
    Coumarin Dyes
    Anthraquinone Dyes
    Xanthene Dyes
    Flame retardants
Alkaloids
Aromatic ureas
Amides
Amines
Ami no acids
Organophosphorus Compounds
Chlorinated Phenoxyacid Herbicides
                                   TABLE 3.
                 LIMITS OF DETECTION AND METHOD SENSITIVITIES
                        FOR DISPERSE  RED  1  AND CAFFEINE
Compound
Disperse Red 1


Caffeine


Mode
SRM
Single Quad
CAD
SRM
Single Quad
CAD
LOD
pg
180
600
2,000
45
84
240
EQL(7s)
P9
420
1400
4700
115
200
560
EQL(lOs)
pg
600
2000
6700
150
280
800
EQL = Estimated Quantitation Limit
                                  8321  -  18
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                                   TABLE 4.
            PRECISION AND ACCURACY  COMPARISONS  OF  MS  AND  MS/MS  WITH
      HPLC/UV  FOR  ORGANIC-FREE  REAGENT  WATER SPIKED  WITH DISPERSE RED  1
                  	Percent Recovery	

Sample             HPLC/UV           MS            CAD          SRM


Spike 1           82.2 ± 0.2     92.5 ± 3.7    87.6 ± 4.6    95.5 ± 17.1

Spike 2           87.4 ± 0.6     90.2 ± 4.7    90.4 ± 9.9    90.0 ± 5.9

RPD                  6.1%           2.5%          3.2%          5.9%
                                   TABLE 5.
           PRECISION AND ACCURACY COMPARISONS OF MS AND MS/MS WITH
          HPLC/UV  FOR MUNICIPAL  WASTEWATER  SPIKED  WITH  DISPERSE  RED 1
Percent Recovery
Sample
Spike 1
Spike 2
RPD
HPLC/UV
93.4 ± 0.3
96.2 ± 0.1
3.0%
MS
102.0 ± 31
79.7 ± 15
25%
CAD
82.7 ± 13
83.7 ± 5.2
1.2%
                                   8321  -  19                      Revision 0
                                                                  November 1990

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                          TABLE 6.
RESULTS FROM ANALYSES OF ACTIVATED SLUDGE PROCESS WASTEWATER
Sample
5 mg/L Spiking
Concentration
UF05A
UF05A-D
UF06A
UF16A
RPD
0 mg/L Spiking
Concentration
UH05A
UH05A-D
UH06A
UH16A
RPD
Recovery
HPLC/UV

0.721 ± 0.003
0.731 ± 0.021
0.279 ± 0.000
0.482 ± 0.001
1.3%

0.000
0.000
0.000
0.000
--
of Disperse Red 1
MS

0.664 ± 0.030
0.600 ± 0.068
0.253 ± 0.052
0.449 ± 0.016
10.1%

0.005 ± 0.0007
0.006 ± 0.001
0.002 ± 0.0003
0.003 ± 0.0004
18.2%
(mq/L)
CAD

0.796 ± 0.008
0.768 ± 0.093
0.301 ± 0.042
0.510 ± 0.091
3.6%

<0.001
<0.001
<0.001
<0.001
--
                          8321 - 20
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November 1990

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                   TABLE  7.
CALIBRATION MASSES AND % RELATIVE ABUNDANCES
                  OF  PEG  400
Mass
18.0
35.06
36.04
50.06
77.04
168.12
212.14
256.17
300.20
344.22
388.25
432.28
476.30
520.33
564.35
608.38
652.41
653.41
696.43
697.44
% Relative
Abundances8
32.3
13.5
40.5
94.6
27.0
5.4
10.3
17.6
27.0
45.9
64.9
100
94.6
81.1
67.6
32.4
16.2
4.1
8.1
2.7
   Intensity is normalized to mass 432.
                  8321 - 21                       Revision 0
                                                  November 1990

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                  TABLE 8.
CALIBRATION MASSES AND % RELATIVE ABUNDANCES
                 OF PEG 600
Mass
18.0
36.04
50.06
77.04
168.12
212.14
256.17
300.20
344.22
388.25
432.28
476.30
520.33
564.35
608.38
652.41
653.41
696.43
% Relative
Abundances9
4.7
11.4
64.9
17.5
9.3
43.9
56.1
22.8
28.1
38.6
54.4
64.9
86.0
100
63.2
17.5
5.6
1.8
         Intensity is normalized to mass 564.
                  8321 - 22                       Revision  0
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                              TABLE 9.
            RETENTION TIMES AND THERMOSPRAY MASS SPECTRA
                    OF  ORGANOPHOSPHORUS  COMPOUNDS
Compound
Monocrotophos
Trichlorfon
Dimethoate
Dichlorvos
Naled
Fensulfothion
Methyl parathion
Phorate
Disulfoton
Merphos
Retention Time
(minutes)
1:09
1:22
1:28
4:40
9:16
9:52
10:52
13:30
13:55
18:51
Mass Spectra
(% Relative Abundance)8
241 (100), 224 (14)
274 (100), 257 (19),
230 (100), 247 (20)
238 (100), 221 (40)
398 (100), 381 (23),
221 (2)
326 (10), 309 (100)
281 (100), 264 (8),
234 (48)
278 (4), 261 (100)
292 (10), 275 (100)
315 (100), 299 (15)


238 (19)


238 (5),

251 (21),



For molecules containing Cl, Br and S, only the base peak of the isotopic
cluster is listed.
                              8321  -  23
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              TABLE 10.
PRECISION AND LIMITS OF DETECTION FOR
 ORGANOPHOSPHORUS COMPOUND STANDARDS
Compound
Dichlorvos
Dimethoate
Phorate
Disulfoton
Fensulfothion
Naled
Merphos
Methyl
parathion
Ion
238
230
261
275
309
398
299
281
Standard
Quantltation
Concentration
(ng/ML)
2
12.5
25
50
2
12.5
25
50
2
12.5
25
50
2
12.5
25
50
2
12.5
25
50
2
12.5
25
50
2
12.5
25
50
2
12.5
25
50
%RSD
16
13
5.7
4.2
2.2
4.2
13
7.3
0.84
14
7.1
4.0
2.2
14
6.7
3.0
4.1
9.2
9.8
2.5
9.5
9.6
5.2
6.3
5.5
17
3.9
5.3
7.1
4.8
1.5
MDL (ng)
4
2
2
1
0.4
0.2
1
30
              8321 - 24
Revision 0
November 1990

-------
                              TABLE 11.
SINGLE OPERATOR ACCURACY AND PRECISION FOR LOW CONCENTRATION DRINKING
WATER  (A),  LOW  CONCENTRATION  SOIL  (B), MEDIUM CONCENTRATION DRINKING
             WATER (C),  MEDIUM CONCENTRATION  SEDIMENT (D)
Average
Recovery
Compound (%)
A
Dimethoate
Dichlorvos
Naled
Fensulfothion
Methyl parathion
Phorate
Disulfoton
Merphos
B
Dimethoate
Dichlorvos
Naled
Fensulfothion
Methyl parathion
Phorate
Disulfoton
Merphos
C
Dimethoate
Dichlorvos
Naled
Fensulfothion
Methyl parathion
Phorate
Disulfoton
Merphos
D
Dimethoate
Dichlorvos
Naled
Fensulfothion
Methyl parathion
Phorate
Disulfoton
Merphos

70
40
0.5
112
50
16
3.5
237

16
ND
ND
45
ND
78
36
118

52
146
4
65
85
10
2
101

74
166
ND
72
84
58
56
78
Standard
Deviation

7.7
12
1.0
3.3
28
35
8
25

4


5

15
7
19

4
29
3
7
24
15
1
13

8.5
25

8.6
9
6
5
4
Spike
Amount
ug/L
5
5
5
5
10
5
5
5
uq/Kq
50
50
50
50
100
50
50
50
uq/L
50
50
50
50
100
50
50
50
mq/Kq
2
2
2
2
3
2
2
2
Range of
Recovery
(%)

85 -
64 -
2 -
119 -
105 -
86 -
19 -
287 -

24 -


56 -

109 -
49 -
155 -

61 -
204 -
9 -
79 -
133 -
41 -
4 -
126 -

91 -
216 -

90 -
102 -
70 -
66 -
86 -

54
14
0
106
0
0
0
187

7


34

48
22
81

43
89
0
51
37
0
0
75

57
115

55
66
46
47
70
Number
of
Analyses

15
15
15
15
15
15
15
15

15
15
15
15
15
15
15
15

12
12
12
12
12
12
12
12

15
15
15
15
15
15
15
12
                              8321 - 25
Revision 0
November 1990

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                                   TABLE 12.
          SINGLE OPERATOR ACCURACY AND PRECISION FOR MUNICIPAL WASTE
           WATER (A), DRINKING WATER (B), CHEMICAL SLUDGE WASTE  (C)
Compound
Tris-BP (A)
(B)
(C)


Concentration
(ng/ML)
50
100
150
200


Average
Recovery
(%)
25
40
63

SINGLE
Average
Area
2675
5091
7674
8379
MDL
(ng/ML)
33
Standard
Deviation
8.0
5.0
11

TABLE
OPERATOR EQL
Standard
Deviation
782
558
2090
2030
Lower
EQL
(ng/ML)
113
Spike Range
Amount of % Number of
(ng/ML) Recovery Analyses
2 41 - 9.0 15
2 50-30 12
100 84-42 8

13.
TABLE FOR TRIS-BP
3*Std 7*Std 10*Std
Dev. Dev. Dev.
2347 5476 7823
Upper
EQL
(ng/ML)
172
EQL = Estimated Quantitation Limit
                                   8321  -  26
Revision 0
November 1990

-------
                     FIGURE 1.
SCHEMATIC OF THE THERMOSPRAY PROBE AND ION SOURCE
                        Flange
  i
 Source
Mounting
  Plate
              Ion Sampling
                 Cone
                       Ions
Electron  Vaporizer
 Beam  ^ Probe
\
                      Vapor
                   Temperature
                    T
                          Heater   Vaporizer
                                  Coupling
                                                                       — 1C
                     8321  -  27
                                              Revision 0
                                              November 1990

-------
                    METHOD 8321
HIGH PERFORMANCE LIQUID CHROMATOGRAPHY/THERMOSPRAY/
       MASS SPECTROMETRY OR UV-VIS DETECTION
C
                      surt
7.3 S.t HPLC
Chroutographie
condition.


7.4 S.t HPLC/
Th«rBoiprajr/MS
oonditiona


7.5
procedure


7.6 P.rforo
LC/MS
•naly»i«
                     8321  -  28
                                 Revision 0
                                 November 1990

-------
                                  METHOD 8330

                     NITROAROMATICS  AND NITRAMINES  BY  HIGH
                   PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC)
1.0  SCOPE AND APPLICATION

      1.1  Method 8330  is intended for  the analysis of  explosives  residues.
This method is limited to use  by  analysts experienced in handling and analyzing
explosive materials.  This method is used to determine the concentration of the
following compounds in a water, soil  or sediment matrix:
Compound                                            Abbrev         CAS Noa
Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine
Hexahydro-l,3,5-trinitro-l,3,5-triazine
1,3,5-Trinitrobenzene
1,3-Dinitrobenzene
Methyl-2,4,6-trinitrophenylnitramine
Nitrobenzene
2,4,6-Trinitrotoluene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
o-Nitrotoluene
m-Nitrotoluene
p-Nitrotoluene
HMX
RDX
TNB
DNB
Tetryl
NB
TNT
24DNT
26DNT
2NT
3NT
4NT
2691-41-0
121-82-4
99-35-4
99-65-0
479-45-8
98-95-3
118-96-7
121-14-2
606-20-2
88-72-2
99-08-1
99-99-0
a  Chemical Abstracts Service Registry number


      1.2  All  of  these  compounds  are  either  used  in  the  manufacture  of
explosives or are the degradation products of compounds used for that purpose.
When making stock solutions for calibration, treat each compound as if it were
extremely explosive.

      1.3  The estimated quantitation limits (EQLs) of target analytes determined
by Method 8330 in water and soil are presented in Table 1.

      1.4  This  method  is restricted  to  use by  or under  the  supervision  of
analysts  experienced in  the  use of  HPLC,  skilled  in the  interpretation  of
chromatograms, and  experienced  in handling explosive  materials.   Each analyst
must demonstrate the ability to generate acceptable results with this method.


2.0  SUMMARY OF METHOD

      2.1  Aqueous  samples  are  diluted  1/1 (v/v)  with  methanol,  filtered,
separated on a C-18 reverse phase column,  determined  at  254 nm,  and confirmed
on a CN reverse phase column.

                                   8330 -  1                       Revision 0
                                                                  November 1990

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     2.2   Soil  and  sediment samples  are  extracted using  acetonitrile  in an
ultrasonic bath, filtered, and chromatographed as in Section 2.1.


3.0  INTERFERENCES

      3.1  2,4-DNT and 2,6-DNT elute at similar retention times (retention time
difference of 0.2 minutes).   A  large concentration  of one  isomer may mask the
response of  the other isomer.   If  it  is  not apparent that both  isomers are
present (or are not detected), an isomeric mixture should be reported.

      3.2  Tetryl decomposes  rapidly in methanol/water solutions,  as well as
with heat.   All  aqueous  samples expected to  contain  tetryl  should be diluted
with acetonitrile prior to filtration.  All samples expected to contain tetryl
should not be exposed to temperatures above room temperature.

      3.3  Degradation products of tetryl  appear  as  a  shoulder on the TNT peak.
Peak heights rather  than  peak areas should be used when tetryl  is present in
concentrations that are significant  relative to the concentration of TNT.


4.0  APPARATUS AND MATERIALS

      4.1  HPLC system

            4.1.1  HPLC - equipped  with a  pump capable of  achieving 4000 psi,
      a 100 M! loop  injector  and a  254 nm UV detector  (Perkin Elmer Series 3,
      or equivalent).

            4.1.2  Columns:

                  4.1.2.1  Primary column:  C-18 Reverse phase HPLC column, 25 cm
            x 4.6 mm (5 /nm),  (Supelco  LC-18, or equivalent).
                  4.1.2.2  Secondary column:  CN Reverse phase HPLC column, 25 cm
            x 4.6 mm (5 p.m) ,  (Supelco LC-CN, or equivalent).

            4.1.3  Strip chart recorder.

            4.1.4  Digital integrator (optional).

            4.1.5  Autosampler (optional).

      4.2  Other Equipment

            4.2.1  Temperature controlled ultrasonic bath.

            4.2.2  Vortex mixer.

            4.2.3  Balance ± 0.0001 g.
                                   8330 - 2                       Revision 0
                                                                  November 1990

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      4.3  Materials
            4.3.1  Injection syringe.
            4.3.2  Filters - 0.5 pm Millex-SR, disposable, or equivalent.
            4.3.3  Pipettes, volumetric, Class A, glass  -  50  ml,  10 ml,  5 ml,
      4 ml, 2 ml, 1 ml.
            4.3.4  Vials, 20 ml, glass.
            4.3.5  Vials, 15 ml, glass, Teflon lined screw cap or crimp top.
            4.3.6  Syringes - 3 ml and 10 ml.
            4.3.7  Volumetric flasks,  Class  A  -  10  ml, 20 ml,  50  ml,  100 ml,
      200 ml, 250 ml.
            4.3.8  Mortar and pestle.
      4.4  Preparation
            4.4.1  Prepare all materials to  be used  as described  in Chapter 4
      for volatile organics.

5.0  REAGENTS
      5.1  HPLC grade chemicals  shall  be used in all  tests.  It is intended that
all reagents shall  conform to the  specifications of the Committee on Analytical
Reagents  of the  American  Chemical   Society,  where  such  specifications  are
available.  Other grades may be  used,  provided it is first ascertained that the
reagent is of sufficiently  high purity to  permit  its use without  lowering the
accuracy of the determination.
            5.1.1  Acetonitrile, CH3CN -  HPLC grade.
            5.1.2  Methanol, CH3OH -  HPLC grade.
            5.1.3  Calcium Chloride,  CaCl2  -  Reagent grade.  Prepare an aqueous
      solution of 5 g/L.
      5.2  Organic-free reagent water - All references to water in this method
refer to organic-free reagent water,  as defined in Chapter One.
      5.3  Stock Standard Solutions
            5.3.1  Analyte Standards
                  5.3.1.1  HMX - Standard Analytical Reference Material.
                  5.3.1.2  RDX - Standard Analytical Reference Material.
                                   8330 - 3                       Revision 0
                                                                  November 1990

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            5.3.1.3  DNB - Standard Analytical Reference Material.

            5.3.1.4  Tetryl - Standard Analytical Reference Material.

            5.3.1.5  TNT - Standard Analytical Reference Material.

            5.3.1.6  2,4-DNT - Standard Analytical Reference Material.

            5.3.1.7  2,6-DNT - Standard Analytical Reference Material.

            5.3.1.8  1,3,5-TNB - Standard Analytical Reference Material.

            5.3.1.9  NB - Standard Analytical Reference Material.

            5.3.1.10   2-NT - Reagent grade.

            5.3.1.11   3-NT - Reagent grade.

            5.3.1.12   4-NT - Reagent grade.

      5.3.2  Dry each  analyte  standard to  constant weight in  a vacuum
desiccator in the dark.  Place about 0.100  g (weighed  to 0.0001 g) of a
single analyte into a  100 mL volumetric  flask and dilute to volume with
acetonitrile.   Invert flask  several  times  until  dissolved.    Store in
refrigerator at 4°C  in  the dark.   Calculate the concentration of the stock
solution from the actual weight used (nominal concentration  = 1,000 mg/L).
Stock solutions may be used for up to one year.

5.4  Intermediate Standards Solutions

      5.4.1  If  both  2,4-DNT  and 2,6-DNT are to  be determined, prepare
two separate intermediate stock solutions  containing  (1) HMX, RDX, 1,3,5-
TNB, 1,3-DNB, NB, TNT, and 2,4-DNT  and  (2)  Tetryl,  2,6-DNT,  2-NT, 3-NT,
and 4-NT.   Intermediate  stock standard solutions should  be  prepared at
1,000 Mg/L, in acetonitrile when analyzing  soil samples, and in methanol
when analyzing aqueous samples.

      5.4.2  Dilute the  two  concentrated intermediate  stock  solutions,
with the appropriate solvent,  to prepare intermediate standard solutions
that cover  the range  of 2.5  -  1,000 p.g/1.  These  solutions  should be
refrigerated on preparation,  and may be used for 30 days.

5.5  Working standards

      5.5.1  Prepare working  standards by  diluting intermediate standards
solutions by 50% (v/v)  with (1)  organic-free reagent water, when analyzing
aqueous solutions,  or  (2) 5 g/L calcium chloride solution (Section 5.1.3),
when  analyzing  soil  and sediment  samples.   These  solutions  must  be
refrigerated, and may  be used for 28 days after preparation.

5.6  Eluent

      5.6.1  To prepare 1 liter of eluent,  add 500 ml of  methanol  to 500 ml


                             8330 - 4                       Revision 0
                                                            November  1990

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      of organic-free reagent water.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  Grab samples must be collected and stored in glass containers. Follow
conventional sampling procedures.

      6.2  Samples must be  kept  below 4°C  from  the time of collection through
analysis.

      6.3  Soil and sediment samples should be air dried to constant weight at
room temperature or colder  after collection.  While it is possible to analyze
wet soil samples,  it  is much more difficult to  obtain a homogeneous subsample
on  a wet  sample.    If wet soil  samples  are  to  be  analyzed,   a  moisture
determination must be made on a  separate subsample.


7.0  PROCEDURE

      7.1  Sample Preparation

            7.1.1  Aqueous Samples

                  7.1.1.1  Sample  Filtration:   Place  a  5 mL portion  of each
            water sample in  a scintillation vial,  add 5 mL of methanol,  shake
            thoroughly, and  filter through a 0.5 /xm filter.  Discard the first
            3 mL of filtrate, and retain the remainder for analysis.

            7.1.2  Soil and  Sediment Samples

                  7.1.2.1  Sample homogenization:   Dry soil  samples in air at
            room temperature or colder,  being careful  not to expose the samples
            to direct  sunlight.    Grind  sample  thoroughly in  an acetonitrile
            rinsed mortar.

                  7.1.2.2  Sample extraction

                        7.1.2.2.1  Place a 2.0 g subsample of each soil sample
                  in a 15 mL glass vial.  Add  10.0  mL  of acetonitrile, cap with
                  teflon lined cap,  vortex  swirl for  one  minute, and place in
                  ultrasonic bath for 18 hours.   If tetryl is being analyzed,
                  keep ultrasonic bath at room temperature or below.

                        7.1.2.2.2  After sonication, allow sample to settle for
                  30 minutes.  Remove 5.0  mL  of supernatant,  and combine with
                  5.0 mL of  calcium chloride solution (Section 5.1.3)  in a 20 mL
                  vial.  Shake,   and let stand for 15 minutes.

                        7.1.2.2.3  Place  supernatant   in   syringe  and  filter
                  through a 0.5 /zm filter.  Discard first  2 to 3 mL and retain
                  remainder  for  analysis.
                                   8330 - 5                       Revision 0
                                                                  November 1990

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      7.2  Chromatographic Conditions

Mobile Phase:     50/50 (v/v) methanol/organic-free reagent water
Flow rate:        1.5 mL/min
Injection volume: 100 jil
UV Detector:      254 nm

      7.3  Calibration of HPLC

            7.3.1  Analyze   working   standards   in   triplicate,   using   the
      chromatographic conditions  given in  Section  7.2.    Prepare  calibration
      curve using peak heights or  peak areas,  as appropriate.  The calibration
      curve should be linear with zero intercept.

            7.3.2  At the beginning of each  analysis day, after the midpoint of
      a  sample  run, and  after the  last  sample  of  the  day,  inject  midpoint
      calibration standards.  Compare mean peak heights obtained during the day
      with the peak  heights obtained in the morning.  If  these  values  do not
      agree within  20%,  reinject all solutions  in triplicate  and recalculate
      calibration curve.

      7.4  Sample Analysis

            7.4.1  Analyze  the samples using  the chromatographic  conditions
      given in Section 7.2.  Confirm each measurement by injecting onto the CN
      column.

            7.4.2  Table 2 presents the retention times for the  analytes on both
      the C18 and CN columns.  Figure 1 presents typical  chromatograms.


8.0  QUALITY CONTROL

      8.1  Refer to Chapter One for specific quality control procedures.

      8.2  Prior to preparation of stock solutions, acetonitrile, methanol, and
water blanks  should be run to determine possible interferences  with analyte
peaks.   If  the  acetonitrile, methanol, or  water  blanks  show contamination,  a
different batch should be used.

      8.3  Method Blanks

            8.3.1  Method blanks for the analysis of aqueous samples should be
      organic-free reagent water carried through all sample storage and handling
      procedures.

            8.3.2 Method  blanks  for  the  analysis of  soil  samples  should be
      uncontaminated soil  carried  through  all  sample storage,  extraction, and
      handling procedures.
                                   8330 - 6                       Revision 0
                                                                  November 1990

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9.0  METHOD PERFORMANCE

     9.1  Method 8330 was tested by six laboratories. The results of this testing
indicate that the results presented in Tables 3 through 5 are to be expected.


10.0  REFERENCES

1.   Bauer, C.F., S.M. Koza, and T.F. Jenkins, "Collaborative Test Results for
     a Liquid Chromatographic Method for the Determination of Explosives Residues
     in Soil," manuscript submitted to the Journal of the AOAC, April 1989.

2.   Department of the Army, "Reversed-Phase HPLC Method for the Determination
     of Explosive Residues  in  Soil," Appendix  B,  provided  by Dennis J.  Wynne,
     Chief, Technology Division, U.S. Army Toxic and Hazardous Materials Agency,
     Aberdeen Proving Ground, Maryland 21010-5401.

3.   Department of the Army, "An Improved RP-HPLC Method for the Determination
     of Nitroaromatics and Nitramines in Water" Appendix B, provided by Dennis
     J.  Wynne,  Chief,  Technology  Division,   U.S.  Army Toxic  and  Hazardous
     Materials Agency, Aberdeen Proving Ground, Maryland 21010-5401.


11.0  SAFETY

      11.1 Standard  precautionary measures  used  for  handling  other  organic
compounds  should  be  sufficient for safe handling  of the analytes  targeted by
Method 8330.
                                   8330 - 7                       Revision 0
                                                                  November 1990

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  O r-
Figure 1



 Absorbance
                                    HMX
  CJl
    -r
(0
o O
  ro
  O
                                    TNB
              DNB
                                       2-Am-DNT

                                   2,6-DNT
                                      2,4 DNT
                      8330 - 8
                    Revision 0
                    November 1990

-------
                                    TABLE 1
                         ESTIMATED QUANTITATION LIMITS
Compound
          Water   Soil
Abbrev    (M9/L)  (M9/9)
Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine
Hexahydro-l,3,5-trinitro-l,3,5-triazine
1, 3, 5-Tri nitrobenzene
1,3-Dinitrobenzene
Methy1-2,4,6-trinitrophenylnitramine
Nitrobenzene
2,4,6-Trinitrotoluene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
o-Nitrotoluene
m-Nitrotoluene
p-Nitrotoluene
HMX
RDX
TNB
DNB
Tetryl
NB
TNT
24DNT
26DNT
2NT
3NT
4NT
13.0
14.0
7.3
4.0
44.0
NA
6.9
5.7
9.4
12.0
7.9
8.5
2.2
1.0
0.25
0.25
0.65
0.26
0.25
0.25
0.26
0.25
0.25
0.25
NA  Not available
                                    TABLE 2
              RETENTION TIMES FOR ANALYTES ON C-18 AND CN COLUMNS
C-18
Analyte
HMX
RDX
TNB
DNB
Tetryl
NB
TNT
26DNT
24DNT
2NT
4NT
3NT
Retention
Time (min)
2.4
3.7
5.1
6.2
6.9
7.2
8.4
9.8
10.1
12.3
13.3
14.2
Analyte
NB
TNB
DNB
2NT
4NT
3NT
26DNT
24DNT
TNT
RDX
Tetryl
HMX
CN
Retention
Time (min)
3.8
4.1
4.2
4.4
4.4
4.5
4.6
4.9
5.0
6.2
7.4
8.4
                                   8330 - 9
              Revision 0
              November 1990

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                              TABLE 3
        INTRALABORATORY PRECISION OF  METHOD FOR SOIL  SAMPLES
              Spiked soils
          Mean
      Concentration
         (M9/9)
                    %rsd
                        Field-contaminated soils
                       Mean
                    Concentration
                    (M9/9)           SD        %rsd
HMX


RDX


TNB


DNB

tetryl

TNT


24DNT
46


60


 8.6
46

 3.5

17

40


 5.0
1.7


1.4


0.4
1.9

0.14

3.1

1.4


0.17
 3.7


 2.3


 4.6
 4.1

 4.0

17.9

 3.5


 3.4
 14
153

104
877

  2.8
 72

  1.1

  2.3

  7.0
669

  1.0
 1.8
21.6

12
29.6

 0.2
 6.0

 0.11

 0.41

 0.61
55

 0.44
12.8
14.1

11.5
 3.4

 7.1
 8.3

 9.8

18.0

 9.0
 8.2

42.3
                             8330  -  10
                                                  Revision 0
                                                  November 1990

-------
                               TABLE  4
          INTERLABORATORY ERROR OF METHOD FOR SOIL SAMPLES
Spi
ked soils
Mean
Concentration
(M/9) SD
HMX 46
RDX 60
TNB 8.6
46
DNB 3.5
tetryl 17
TNT 40
24DNT 5.0
2.6
2.6
0.61
2.97
0.24
5.22
1.88
0.22
INTERLABORATORY ERROR

HMX
RDX
TNB
TNT
Sample 1
mean
cone.
(M9/L)
nd
431
74.3
10635
Field contaminated
%rsd
5.7
4.4
7.1
6.5
6.9
30.7
4.7
4.4
Mean
Concentration
(M9/9)
14
153
104
877
2.8
72
1.1
2.3
7.0
669
1.0
SD
3.7
37.3
17.4
67.3
0.23
8.8
0.16
0.49
1.27
63.4
0.74
soils
%rsd
26.0
24.0
17.0
7.7
8.2
12.2
14.5
21.3
18.0
9.5
74.0
TABLE 5
OF METHOD FOR WATER SAMPLES8

%rsd
22.9
3.2
59.4
Samole 2
mean
cone.
(M9/L)
184"
2117
27. 6C
1746

%rsd
8.4
29.5
4.2
26.8


10 replicate determinations, except where noted
6 replicate determinations
7 replicate determinations
                             8330  -  11
Revision 0
November 1990

-------
                          Aqueous Somple
          7.1.1.1 Somole Filtration:
Sample Filtral
Place 5 mis.
                 Place 5 mis. sample in
                 scintillation vial.  Add
                 5 mis. methoncJ; shake;
                 filter through 0.5 um
                 filter.  Discard  first 3 mis.
                 retain remainder for use.
oo
OJ
o
                                7.1 Is sample in
                                 an aqueous or
                                  soil/sediment
                                    matrix?
Soil and Sediment
     Samples
                                                                           7.1.2.1  Sample Homoaenization
           Air dry sample at room T
           or below.  Avoid exposure
           to direct sunlight.  Grind
           sample in an acetonitrile
           rinsed mortar.
                                             7.3 Calibration of HPLC
                                                                                                  7.3.1 Run working stds. in triplicate.
                                                                                                        Plot [ ] vs. peak  area  or ht.
                                                                                                        Curve should be linear with
                                                                                                        zero intercept.	
                                                                         (   7.1.2.2 Sample Extraction

                                                                                           i
                                                          7.1.2.2.1 Place 2 grs. soil
                                                                   subsomple, 10 mis.
                                                                   ocetonitrile in 15 ml.
                                                                   glass vial.  Cap, vortex
                                                                   swirl, place in room T
                                                                   or below  ultrasonic bath
                                                                   for 18 hrs.
                                             7.3.2 Analyze midrange calibration
                                                  std.  at beginning, middle,
                                                  and  end of sample analyses.
                                                  Redo Section 7.3.1 if peak
                                                  areas or hts. do not agree
                                                  to w/in +/- 20X of initial
                                            	calibration values.	
                                                                                                                                   1
                                                                           7.1.2.2.2 Let sdn.  settle.  Add 5
                                                                                     mis. supernatant to 5
                                                                                     mis. calcium  chloride
                                                                                     soln. in 20 ml. vial.
                                                                          	Shake, let stand 15 mins.
                                                                                                                  |   7.4 Sample Analysis
                                                                                                    7.4.1 Analyze samples.  Confirm
                                                                                                         measurement w/injection
                                                                                                         onto CN column.
                                                                           7..1.2.2.3 Filter supernatant through
                                                                                     0.5 um filter.   Discard
                                                                                     initial 3 mis., retain
                                                                          	remainder for analysis.
                                         7.2 Set Chromatographic Conditions
                                                                                                    7.4.2 Refer to Table 2 for typical
                                                                                                   	anolyte retention times.
•30


i>
—I

r>
oo:
  IO
   o

  i 00
  I U>
JO U>
   o
                                                                                                                                                 oo
                                                                                                                                  Stop

-------
                                 METHOD 8331

                          TETRAZENE  BY  REVERSE  PHASE
                  HIGH PRESSURE LIQUID CHRQMATOGRAPHY (HPLC)
1.0  SCOPE AND APPLICATION

      1.1  This method is intended for the analysis of tetrazene, an explosive
residue,  in  soil  and water.    This method  is  limited  to  use by  analysts
experienced  in  handling  and analyzing  explosive materials.    The  following
compounds can be determined by this method:
            Compound                      CAS Noa
            Tetrazene                     31330-63-9
      a  Chemical  Abstracts  Service  Registry number


      1.2  Tetrazene degrades rapidly in water and methanol  at room temperature.
Special care must be taken to refrigerate or cool all solutions throughout the
analytical process.

      1.3  Tetrazene, in its dry form, is  extremely explosive.  Caution must be
taken during preparation of standards.

      1.4  The estimated quantitation limit  (EQL) of Method  8331 for determining
the  concentration  of   tetrazene   is approximately  7  ng/l  in  water  and
approximately 1 ing/Kg in soil.

      1.5  This method  is  restricted  to  use by  or  under the  supervision of
analysts  experienced  in the  use of HPLC,   skilled  in the  interpretation of
chromatograms, and experienced  in handling  explosive materials.   Each analyst
must demonstrate the ability to generate acceptable results with this method.


2.0  SUMMARY OF METHOD

      2.1  A 10 ml water sample is filtered, eluted on a C-18 column using ion
pairing reverse phase HPLC,  and quantitated at 280 nm.

      2.2  2  g  of  soil  are  extracted  with  55:45  v/v  methanol-water  and
1-decanesulfonic acid on a platform shaker, filtered,  and eluted on a C-18 column
using ion pairing reverse phase HPLC, and quantitated at 280 nm.
                                   8331 - 1                       Revision 0
                                                                  November  1990

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3.0  INTERFERENCES
      3.1  No interferences are known.   Tetrazene elutes early, however, and if
a computing integrator is used for peak quantification,  the baseline setting may
have to be  set to exclude baseline aberrations.  Baseline setting is particularly
important at low concentrations of analyte.

4.0  APPARATUS AND MATERIALS
      4.1  HPLC system
            4.1.1  HPLC -  Pump capable of achieving 4000 psi.
            4.1.2  100 /xL loop injector.
            4.1.3  Variable  or  fixed wavelength detector  capable of reading
      280 nm.
            4.1.4  C-18 reverse  phase  HPLC  column,  25  cm  x 4.6 mm (5  nm)
      (Supelco LC-18, or equivalent).
            4.1.5  Digital  integrator - HP 3390A (or equivalent)
            4.1.6  Strip chart recorder.
      4.2  Other apparatus
            4.2.1  Platform orbital shaker.
            4.2.2  Analytical balance - + 0.0001 g.
            4.2.3  Desiccator.
      4.3  Materials
            4.3.1  Injection syringe - 500 /xL-
            4.3.2  Filters - 0.5 p.m Millex-SR and 0.5 p.m Millex-HV, disposable,
      or equivalent.
            4.3.3  Pipets  - volumetric, glass, Class A.
            4.3.4  Scintillation vials - 20 mL, glass.
            4.3.5  Syringes - 10 mL.
            4.3.6  Volumetric flasks, Class A - 100 mL, 200 mL.
            4.3.7  Erlenmeyer flasks with ground glass stoppers - 125 mL.
                                   8331 - 2                       Revision 0
                                                                  November 1990

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      4.4  Preparation

            4.4.1  Prepare all  materials as  described  in Chapter 4 for volatile
      organics.


5.0  REAGENTS

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

      5.2  General

            5.2.1  Methanol, CH3OH -  HPLC grade.

            5.2.2  Organic-free reagent water - All references  to water in this
      method refer to organic-free reagent water,  as defined in Chapter One.

            5.2.3  1-Decanesulfonic acid, sodium salt, C10H21S03Na - HPLC grade.

            5.2.4  Acetic acid (glacial), CH3COOH  - reagent  grade.

      5.3  Standard Solutions

            5.3.1  Tetrazene - Standard Analytical Reference Material.

            5.3.2  Stock standard  solution  - Dry  tetrazene  to  constant weight
      in a vacuum desiccator in the dark.  (Tetrazene  is extremely explosive in
      the dry state.   Do not dry more reagent than  is necessary  to prepare stock
      solutions.)   Place about 0.0010  g  (weighed to  0.0001 g)  into  a 100-ml
      volumetric flask and dilute  to volume with methanol.  Invert flask several
      times until  tetrazene  is dissolved.   Store  in  freezer at  -10°C.   Stock
      solution is about 100 mg/L.  Replace stock standard solution every week.

            5.3.3  Intermediate standard solutions

                  5.3.3.1  Prepare a  4  mg/L  standard  by  diluting the  stock
            solution 1/25 v/v with methanol.

                  5.3.3.2  Pipet  0.5, 1.0,  2.0, 5.0,  10.0,  and 20.0 mL of the
            4 mg/L standard solution  into 6 separate  100 mL volumetric flasks,
            and make up  to  volume with  methanol.   Pipet 25.0 mL  of the 4 mg/L
            standard  solution  into a 50 mL  volumetric  flask,  and  make  up to
            volume with  methanol.  This results  in intermediate  standards of
            about 0.02, 0.04, 0.08, 0.2, 0.4, 0.8, 2 and 4 mg/L.

                  5.3.3.3  Cool immediately  on preparation  in  refrigerator or
            ice bath.
                                   8331 - 3                       Revision 0
                                                                  November 1990

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            5.3.4  Working standard solutions

                  5.3.4.1  Inject  4  ml of  each  of the  intermediate standard
            solutions into 6.0 mL of water.  This results in concentrations of
            about 0.008, 0.016, 0.032, 0.08, 0.16, 0.3, 0.8 and 1.6 mg/L.

                  5.3.4.2  Cool immediately on preparation  in  refrigerator or
            ice bath.

      5.5  QC spike concentrate solution

            5.5.1  Dry tetrazene to constant weight in  a vacuum desiccator in
      the dark.   (Tetrazene  is extremely explosive in the dry  state.   Do not
      dry any more than necessary to prepare standards.)  Place about 0.0011 g
      (weighed to 0.0001 g)  into a  200-ml volumetric flask and dilute to volume
      with methanol.  Invert flask several  times until tetrazene is dissolved.
      Store in freezer at -10eC. QC spike concentrate solution is about 55 mg/L.
      Replace stock standard solution every week.

            5.5.2  Prepare spiking solutions,  at concentrations appropriate to
      the concentration range of the  samples being analyzed, by diluting the QC
      spike  concentrate  solution  with  methanol.   Cool  on  preparation  in
      refrigerator or ice bath.

      5.6  Eluent

            5.6.1  To  make   about  1  liter  of   eluent,   add  2.44   g  of
      1-decanesulfonic acid,  sodium salt to 400/600 v/v methanol/water, and add
      2.0 ml of glacial acetic acid.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See the  introductory material  to  this Chapter,  Organic  Analytes,
Section 4.1.

      6.2  Samples must be collected  and stored in glass  containers.   Follow
conventional sampling procedures.

      6.3  Samples must be kept below 4°C from the  time  of collection through
analysis.


7.0  PROCEDURE

      7.1  Sample Preparation

            7.1.1  Filtration of Water Samples

                  7.1.1.1  Place a  10 mL  portion  of each  water sample  in  a
            syringe and filter through a 0.5 /urn Millex-HV filter unit.  Discard
            first 5 mL of filtrate, and retain 5 mL for analysis.
                                   8331 - 4                       Revision 0
                                                                  November 1990

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            7.1.2  Extraction and Filtration of Soil Samples

                  7.1.2.1  Determination of  sample  % dry weight  -  In certain
            cases, sample results are desired based on dry-weight basis.  When
            such data  is  desired,  a portion of sample  for  this determination
            should be  weighed out  at  the  same time  as the portion  used for
            analytical determination.

WARNING;   The drying oven should be contained in a hood  or vented.  Significant
           laboratory  contamination may result  from  a heavily  contaminated
           hazardous waste sample.

                        7.1.2.1.1  Immediately  after  weighing  the  sample for
                  extraction, weigh 5-10 g  of the  sample into a tared crucible.
                  Determine the % dry weight of the sample by drying overnight
                  at 105°C.   Allow to cool  in a  desiccator before  weighing:

                        % dry weight = q of dry sample x 100
                                           g of sample

                  7.1.2.2  Weigh 2  g soil   subsamples  into  125 ml  Erlenmeyer
            flasks with ground glass stoppers.

                  7.1.2.3  Add  50   mL   of  55/45  v/v  methanol-water  with
            1-decanesulfonic acid, sodium salt added to make a 0.1 M solution.

                  7.1.2.4  Vortex for 15 seconds.

                  7.1.2.5  Shake for 5 hr at 2000 rpm on platform shaker.

                  7.1.2.6  Place a 10 mL portion of  each soil sample extract in
            a  syringe and  filter  through  a 0.5 /urn  Millex-SR  filter unit.
            Discard first 5 ml of filtrate, and retain 5 ml  for analysis.

      7.2  Sample Analysis

            7.2.1  Analyze  the  samples  using  the  chromatographic  conditions
      given in Section 7.2.1.1.  Under these conditions, the retention time of
      tetrazene is 2.8 min.   A  sample chromatogram, including  other compounds
      likely to be present in samples containing tetrazene,  is shown in Figure 1.

                  7.2.1.1  Chromatographic  Conditions

            Solvent:            0.01   M   1-decanesulfonic   acid,    in   acidic
                               methanol/water (Section 5.5)
            Flow rate:         1.5 mL/min
            Injection volume:  100 nl
            UV Detector:        280 nm

      7.3  Calibration of HPLC

            7.3.1  Initial Calibration -  Analyze the working standards (Section
      5.3.4),  starting with  the 0.008  mg/L  standards and  ending with  the


                                   8331 - 5                       Revision 0
                                                                  November 1990

-------
      0.30 mg/L standard.  If the percent relative standard deviation (%RSD) of
      the mean response  factor  (RF)  for each  analyte  does  not exceed 20%, the
      system is calibrated and the analysis of samples  may proceed.   If the %RSD
      for any analyte exceeds 20%,  recheck  the  system and/or recalibrate with
      freshly prepared calibration solutions.

            7.3.2  Continuing Calibration -  On a daily basis, inject 250 /uL of
      stock standard  into 20 ml water.   Keep solution  in  refrigerator until
      analysis.  Analyze  in  triplicate  (by  overfilling loop) at the beginning
      of the  day,  singly after  each  five  samples,  and  singly  after the' last
      sample of the day.   Compare response  factors  from the mean peak area or
      peak height  obtained over the  day with the response  factor  at  initial
      calibration.  If these values do not agree within 10%, recalibrate.


8.0  QUALITY CONTROL

      8.1  Refer to Chapter One for specific quality control procedures.

      8.2  Prior to preparation  of stock solutions, methanol  should be analyzed
to determine possible interferences  with the  tetrazene peak.  If the methanol
shows contamination, a different batch of methanol should be used.

      8.3  Method Blanks

            8.3.1  Method  blanks  for the  analysis of  water  samples should be
      organic-free reagent water carried through all  sample  storage and handling
      procedures.

            8.3.2  Method  blanks  for the analysis  of soil  samples  should be
      uncontaminated soil  carried through all  sample  storage, extraction, and
      handling procedures.


9.0  METHOD PERFORMANCE

      9.1  Method 8331 was tested in a  laboratory over a period of four days.
Spiked organic-free reagent water and standard soil were analyzed in duplicate
each  day for  four days.    The H.PLC was  calibrated   daily  according  to the
procedures given in  Section 7.1.  Method performance data are presented in Tables
1 and 2.
10.0  REFERENCES

1.  Walsh, M.E., and T.F. Jenkins,  "Analytical  Method  for Determining Tetrazene
    in Water," U.S. Army Corps of Engineers, Cold Regions Research & Engineering
    Laboratory, Special  Report 87-25, 1987.

2.  Walsh, M.E., and T.F. Jenkins,  "Analytical  Method  for Determining Tetrazene
    in Soil," U.S. Army Corps of Engineers,  Cold  Regions Research & Engineering
    Laboratory, Special  Report 88-15, 1988.
                                   8331 - 6                       Revision 0
                                                                  November 1990

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11.0  SAFETY

      11.1   Standard precautionary  measures  used for  handling  other organic
compounds should  be  sufficient for  safe handling  of the analytes targeted by
Method 8331.
                                   8331  - 7                        Revision  0
                                                                   November 1990

-------
   I6f
   12
6
8
                   FIGURE 1
                          TNT
                    0.064
               Absorbonct Units
                   8331  - 8
Revision 0
November 1990

-------
            TABLE 1.
METHOD PERFORMANCE, WATER MATRIX
Spike
Cone.
(M9/L)
0.00



7.25



14.5



29



72.5



145



290



725



OVERALL
Ava % Recovery
Replicate
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery

Day 1
0.0
NA
0.0
NA
8.9
122
6.6
91
14.6
101
14.8
102
31.8
110
29.5
102
71.1
98
71.2
98
140.6
97
138.5
96
289.4
100
282.0
97
737.6
102
700.2
97

Day 2
0.0
NA
0.0
NA
7.8
108
9.9
137
14.6
101
14.1
97
30.0
103
29.7
102
73.6
102
71.3
98
143.8
99
140.8
97
288.5
99
284.2
98
707.2
98
695.8
96

Day 3
0.0
NA
0.0
NA
7.4
102
8.5
117
13.8
95
14.1
98
30.8
106
30.4
105
75.7
104
70.7
98
144.7
100
140.9
97
291.0
100
281.9
97
714.3
99
714.2
99

Day 4
0.0
NA
0.0
NA
9.4
130
6.7
92
14.6
101
15.2
105
28.7
99
30.7
106
73.9
102
71.6
99
142.1
98
136.9
94
289.8
100
282.5
97
722.0
100
716.3
99

Average
% Recovery

NA

. NA

116

109

99

100

105

104

101

98

98

96

100

97

99

97
102
            8331 - 9
Revision 0
November  1990

-------
            TABLE 2
METHOD PERFORMANCE, SOIL MATRIX
Spike
Cone.
(M9/L)
0.00



1.28



2.56



5.12



12.8



25.6



OVERALL
Ava % Recovery
Replicate
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery
Replicate 1
% Recovery
Replicate 2
% Recovery

Day 1
0.0
NA
0.0
NA
0.6
49
1.2
92
1.4
56
1.5
59
2.9
57
3.0
58
7.8
61
8.0
62
17.2
67
16.7
65

Day 2
0.0
NA
0.0
NA
0.9
73
0.7
56
1.5
58
2.0
79
3.0
58
3.0
59
7.6
59
8.4
66
16.7
65
16.8
66

Day 3
0.0
NA
0.0
NA
0.6
48
0.8
63
1.6
61
1.4
56
2.9
56
3.5
69
7.8
61
7.7
60
17.4
68
17.6
69

Day 4
0.0
NA
0.0
NA
1.0
74
0.7
56
1.6
61
1.3
50
2.9
56
3.1
60
8.1
63
8.2
64
17.3
68
17.2
67

Average
% Recovery

NA

NA

61

67

59

61

57

61

61

63

67

67
62
           8331  -  10
Revision 0
November  1990

-------
                     METHOD 8331
            TETRAZENE BY REVERSE PHASE
   HIGH PRESSURE LIQUID CHROMATOGRAPHY  (HPLC1
     Start
7.1.1 Filter  10
   ml water
sample;  discard
  first  5  ml;
analyze  last  5
    7.1.2.1
  Determine  X
  dry weight
7.1.2.2-7.1.2.5
Extract 2g soil
  with 50 ml
    solvent
 7.1.2.6 Filter
 10 ml extract;
 discard 5 ml;
 analyze last 5
      ml
  7 . 2  Analyze
 samples  using
chromatographic
 conditions  in
Section 7.2.1.1
 7.3.1 Initial
 Calibration:
Analyze working
   standards
(Section 5.3.3)
 7.3.1 Is XRSD
  of mean RF
     >20%?
 7.3.1  Recheck
    system/
  recalibrate
with new  cali-
 bration  solu.

No
7.3.2
Continuing
Calibration
                             Stop
                      8331  - 11
                                  Revision 0
                                  November 1990

-------
                                  METHOD 8410

                 GAS  CHROMATOGRAPHY/FOURIER TRANSFORM  INFRARED
              (GC/FT-IR) SPECTROMETRY FOR SEMIVOLATILE ORGANICS:
                               CAPILLARY COLUMN
1.0  SCOPE AND APPLICATION

      1.1  This method covers the  automated  Identification,  or compound class
assignment of  unidentifiable compounds,  of  solvent  extractable  semivolatile
organic compounds which are amenable  to gas chromatography, by GC/FT-IR. GC/FT-
IR  can  be  a  useful   complement  to  GC/MS  analysis  (Method  8270).   It  is
particularly well  suited  for the identification of specific  isomers that are
not differentiated using  GC/MS.   Compound  class  assignments are  made using
infrared group absorption frequencies.  The presence of an infrared band in the
appropriate group  frequency region may be taken  as evidence  of  the possible
presence of a particular compound class,  while its absence may be construed as
evidence that the compound class in question is not present.  This evidence will
be further strengthened by the presence of confirmatory group frequency bands.
Identification limits of the following compounds have been demonstrated by this
method.
      Compound Name
                                   8410 - 1
CAS No.'
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)pyrene
Benzoic 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-Chl oronaphthal ene
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
Dimethyl phthalate
83-32-9
208-96-8
120-12-7
56-55-3
50-32-8
65-85-0
111-91-1
111-44-4
39638-32-9
117-81-7
101-55-3
85-68-7
106-47-8
59-50-7
91-58-7
95-57-8
106-48-9
7005-72-3
218-01-9
132-64-9
84-74-2
95-50-1
541-73-1
106-46-7
120-83-2
131-11-3
                  Revision 0
                  November 1990

-------
      Compound Name                             CAS No.8


      Diethyl phthalate                            84-66-2
      4,6-Dinitro-2-methylphenol                  534-52-1
      2,4-Dinitrophenol                            51-28-5
      2,4-Dinitrotoluene                          121-14-2
      2,6-Dinitrotoluene                          606-20-2
      Di-n-octyl phthalate                        117-84-0
      Di-n-propyl phthalate                       131-16-8
      Fluoranthene                                206-44-0
      Fluorene                                     86-73-7
      Hexachlorobenzene                           118-74-1
      1,3-Hexachlorobutadiene                      87-68-3
      Hexachlorocyclopentadi ene                    77-47-4
      Hexachloroethane                             67-72-1
      Isophorone                                   78-59-1
      2-Methylnaphthalene                          91-57-6
      2-Methylphenol                               95-48-7
      4-Methylphenol                              106-44-5
      Naphthalene                                  91-20-3
      2-Nitroaniline                               88-74-4
      3-Nitroaniline                               99-09-2
      4-Nitroaniline                              100-01-6
      Nitrobenzene                                 98-95-3
      2-Nitrophenol                                88-75-5
      4-Nitrophenol                               100-02-7
      N-Nitrosodimethylamine                       62-75-9
      N-Nitrosodiphenylamine                       86-30-9
      N-Nitroso-di-n-propylamine                  621-64-7
      Pentachlorophenol                            87-86-5
      Phenanthrene                                 85-01-8
      Phenol                                      108-95-2
      Pyrene                                      129-00-0
      1,2,4-Trichlorobenzene                      120-82-1
      2,4,5-Trichlorophenol                        95-95-4
      2,4,6-Trichlorophenol                        88-06-2


      a   Chemical  Abstract Services  Registry  Number.


      1.2  This method is applicable to the determination of most extractable,
semivolatile-organic compounds  in  wastewater,  soils and  sediments,  and solid
wastes.   Benzidine can be subject to losses during solvent concentration and GC
analysis;  o-BHC,  6-BHC,  endosulfan I  and   II,  and  endrin  are  subject  to
decomposition under the  alkaline conditions  of  the  extraction step;  endrin is
subject to decomposition during GC analysis;  and hexachlorocyclopentadiene and
N-nitrosodiphenylamine may decompose during extraction and GC analysis.  Other
extraction and/or instrumentation procedures  should be considered for unstable
analytes.


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      1.3  The identification limit of this method may depend strongly upon the
level and  type  of gas  chromatographable  (GC)  semi volatile extractants.   The
values listed in Tables  1 and 2 represent the minimum quantities of semivolatile
organic compounds which have been identified by the specified GC/FT-IR system,
using this  method and under routine environmental analysis conditions.  Capillary
GC/FT-IR wastewater identification limits of 25 /ug/L may be achieved for weak
infrared absorbers  with this  method,  while  the corresponding  identification
limits for  strong  infrared absorbers is 2 p.g/1.   Identification limits for other
sample matrices  can  be calculated from the  wastewater values  after choice of the
proper sample workup procedure (see Section 7.1).


2.0  SUMMARY OF METHOD

      2.1  Prior  to using  this  method,  the  samples  should  be prepared  for
chromatography  using the  appropriate sample preparation  and  cleanup methods.
This  method describes  chromatographic conditions  that  will  allow for  the
separation of the compounds in the  extract  and uses  FT-IR for detection  and
quantitation of the target analytes.


3.0  INTERFERENCES

      3.1  Glassware and  other sample processing hardware  must be thoroughly
cleaned to prevent contamination  and misinterpretation.  All of these materials
must be demonstrated to be free from interferences  under the conditions of the
analysis  by  running  method  blanks.     Specific  selection  of  reagents  or
purification of solvents by distillation in all-glass  systems may  be required.

      3.2  Matrix interference will  vary  considerably from source  to source,
depending upon the diversity of the residual  waste being  sampled.  While general
cleanup  techniques  are provided as  part  of this  method,  unique  samples  may
require additional cleanup to isolate the analytes of interest from interferences
in order to achieve maximum sensitivity.

      3.3  4-Chlorophenol  and  2-nitrophenol  are subject  to interference from
co-eluting compounds.

      3.4  Clean  all glassware as  soon as possible after use  by  rinsing with
the last solvent used.   Glassware should be sealed/stored in  a clean environment
immediately  after  drying  to  prevent any  accumulation   of  dust  or  other
contaminants.
4.0  APPARATUS AND MATERIALS

      4.1  Gas Chromatographic/Fourier Transform Infrared Spectrometric Equipment

            4.1.1  Fourier  Transform-Infrared  Spectrometer  - A  spectrometer
      capable of collecting at least one scan set per second at 8 cm"1 resolution
      is  required.    In  general,  a  spectrometer  purchased  after 1985,  or
      retrofitted to meet post-1985 FT-IR improvements, will be necessary to meet
      the detection limits of this protocol.  A state-of-the-art A/D converter


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      is required, since  it  has  been shown that the  signal-to-noise  ratio of
      single beam GC/FT-IR systems is A/D converter limited.

            4.1.2  GC/FT-IR Interface - The interface should be lightpipe volume-
      optimized for the selected  chromatographic conditions  (lightpipe volume
      of  100-200  juL  for   capillary  columns).   The  shortest  possible  inert
      transfer line (preferably fused silica) should  be  used to  interface the
      end of  the  chromatographic column  to  the lightpipe.   If  fused  silica
      capillary columns are employed, the  end  of the GC column can serve as the
      transfer line if it  is adequately heated.   It has been  demonstrated that
      the optimum lightpipe volume is equal to the full width at half height of
      the GC eluate peak.

            4.1.3  Capillary Column  -  A  fused  silica DB-5 30  m  x  0.32  mm
      capillary column with 1.0 /xm film thickness (or equivalent).

            4.1.4  Data Acquisition - A  computer system dedicated to the GC/FT-
      IR system to  allow  the continuous  acquisition  of  scan  sets for  a full
      chromatographic run.  Peripheral data storage systems should be available
      (magnetic tape and/or disk) for the storage of all acquired data.  Software
      should be available  to allow the acquisition and  storage of every scan set
      to locate the file numbers and transform  high S/N scan sets, and to provide
      a real time reconstructed chromatogram.

            4.1.5  Detector - A cryoscopic, medium-band  HgCdTe  (MCT)  detector
      with the smallest practical focal  area.   Typical  narrow-band MCT detectors
      operate from 3800-800 cm"1 but medium-band MCT detectors can reach 650 cm"1.
      A 750 cm'1 cutoff (or lower)  is  desirable since it allows the detection of
      typical carbon-chlorine stretch and  aromatic out-of-plane  carbon-hydrogen
      vibrations of environmentally  important organo-chlorine  and polynuclear
      aromatic compounds.   The MCT detector sensitivity (D)" should be > 1 x 1010
      cm.

            4.1.6  Lightpipe -  Constructed of  inert materials, gold coated, and
      volume-optimized for the  desired chromatographic conditions (see Section
      7.3).

            4.1.7  Gas  Chromatograph  -  The  FT-IR  spectrometer  should  be
      interfaced to a temperature programmable gas  Chromatograph  equipped with
      a Grob-type  (or  equivalent) purged splitless injection system suitable for
      capillary glass columns or an on-column injector system.

            A short,  inert transfer line should interface the gas Chromatograph
      to the  FT-IR  lightpipe and, if applicable,  to  the GC detector.   Fused
      silica GC columns may be directly interfaced  to the lightpipe  inlet and
      outlet.

      4.2  Dry Purge  Gas  - If  the spectrometer is  the purge-type,  provisions
should be made to provide  a suitable continuous  source of dry purge-gas to the
FT-IR spectrometer.

      4.3  Dry  Carrier Gas  -  The  carrier gas  should be  passed through  an
efficient cartridge-type drier.


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      4.4  Syringes - 1-juL, 10-^L.
5.0  REAGENTS

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

      5.2  Organic-free reagent water.  All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.

      5.3  Solvents

            5.3.1  Acetone, CH3COCH3 - Pesticide quality, or equivalent.

            5.3.2  Methylene chloride, CH2C12 - Pesticide quality, or equivalent.

      5.4  Stock Standard  Solutions (1000  mg/L)  -  Standard  solutions  can be
prepared from pure standard materials or purchased as a certified solution.

            5.4.1  Prepare stock standard solutions by accurately weighing 0.1000
      ± 0.0010 g of pure material.  Dissolve the material in pesticide quality
      acetone  or other  suitable solvent  and  dilute  to  volume  in  a  100 ml
      volumetric flask.  Larger  volumes  can be  used  at the convenience of the
      analyst.  When compound  purity is assayed to be  96 percent or greater, the
      weight may be  used without correction to  calculate the concentration of
      the stock standard.  Commercially  prepared  stock standards may be used at
      any concentration if they  are  certified by the manufacturer or  by an
      independent source.

            5.4.2  Transfer the stock standard solutions into bottles with Teflon
      lined screw-caps.  Store  at  4°C and  protect  from light.  Stock standard
      solutions  should  be  checked  frequently  for  signs  of degradation or
      evaporation, especially just  prior to preparing  calibration standards  from
      them.

            5.4.3  Stock standard solutions must be replaced after 6 months or
      sooner if  comparison with  quality  control  reference samples indicates a
      problem.

      5.5  Calibration Standards and Internal Standards -  For  use in situations
where GC/FT-IR will  be  used for primary quantitation  of  analytes  rather  than
confirmation of GC/MS identification.

            5.5.1  Prepare calibration standards that contain the compounds of
      interest,  either  singly  or  mixed together.    The  standards  should be
      prepared at concentrations that will  completely  bracket  the working range
      of  the  chromatographic system  (at   least one  order  of  magnitude is
      suggested).


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            5.5.2  Prepare  Internal  standard  solutions.    Suggested  Internal
      standards  are  1-fluoronaphthalene,  terphenyl,  2-chlorophenol,  phenol,
      bis(2-chloroethoxy)methane, 2,4-dichlorophenol, phenanthrene, anthracene,
      and butyl benzyl phthalate.  Determine the internal standard concentration
      levels from the minimum identifiable quantities.


6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1  See  the  introductory material  to this  chapter,  Organic Analytes,
Section 4.1.
7.0  PROCEDURE

      7.1  Sample Preparation - Samples must be prepared by one of the following
methods prior to GC/FT-IR analysis.

                          Matrix                Methods

                          Water                 3510, 3520
                          Soil/sediment         3540, 3550
                          Waste                 3540, 3550, 3580

      7.2  Extracts may be cleaned up  by Method 3640, Gel-Permeation Cleanup.

      7.3  Initial Calibration - Recommended GC/FT-IR conditions:

           Scan time:  At least 2 scan/sec.
           Initial column temperature  and hold time:  40°C for 1 minute.
           Column temperature program:  40-280°C at 10°C/min.
           Final column temperature hold:  280°C.
           Injector temperature:  280-300°C.
           Transfer line temperature:  270°C.
           Lightpipe:  280°C.
           Injector:  Grob-type, splitless or on-column.
           Sample volume:  2-3 pi.
           Carrier gas:  Dry helium at about 1 mL/min.

      7.4  With an oscilloscope, check  the detector centerburst intensity versus
the manufacturer's specifications.  Increase the source voltage,  if necessary,
to meet  these  specifications.   For  reference  purposes,  laboratories  should
prepare a plot of time versus detector voltage over at least a 5 day period.

      7.5  Capillary Column  Interface Sensitivity Test -  Install a 30 m x 0.32 mm
fused silica capillary column coated with 1.0 jum of DB-5 (or equivalent).  Set
the lightpipe  and transfer lines at  280°C,  the injector at  225°C  and  the GC
detector at 280°C (if used).  Under splitless Grob-type or on-column injection
conditions,  inject 25  ng  of  nitrobenzene,  dissolved  in 1  juL  of methylene
chloride.  The nitrobenzene  should be identified by the on-line  library software
search within the first five hits (nitrobenzene should be contained within the
search library).
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      7.6  Interferometer -  If the  interferometer  is air-driven,  adjust  the
interferometer drive air pressure to manufacturer's specifications.

      7.7  MCT Detector Check  -  If  the  centerburst  intensity  is  75  percent or
less of  the  mean intensity of the  plot maximum obtained by  the  procedure of
Section  7.4,  install  a new  source  and  check  the MCT  centerburst with  an
oscilloscope versus the manufacturer's specifications  (if available).  Allow at
least five hours of new source operation before data acquisition.

      7.8  Frequency Calibration  -  At  the  present  time,  no  consensus  exists
within the spectroscopic community  on a suitable frequency  reference standard
for vapor-phase FT-IR.   One reviewer has suggested the use of indene as an on-
the-fly standard.

      7.9  Minimum  Identifiable   Quantities  -  Using   the  GC/FT-IR  operating
parameters  specified  in  Section  7.3,  determine  the  minimum  identifiable
quantities for the compounds of interest.

            7.9.1  Prepare a plot of lightpipe temperature versus MCT centerburst
      intensity (in volts or other vertical height units).  This plot should span
      the temperature range between ambient and the lightpipe thermal limit in
      increments of about 20°C. Use  this plot for daily QA/QC (see Section 8.4).
      Note that modern  GC/FT-IR interfaces  (1985  and later) may have eliminated
      most of this temperature effect.

      7.10 GC/FT-IR Extract Analysis

            7.10.1  Analysis - Analyze the dried methylene chloride extract using
      the chromatographic  conditions specified  in  Section  7.3 for capillary
      column interfaces.

            7.10.2  GC/FT-IR  Identification -  Visually  compare  the  analyte
      infrared  (IR)  spectrum versus  the search  library spectrum of the  most
      promising  on-line library   search  hits.    Report,  as  identified,  those
      analytes with  IR  frequencies  for  the  five  (maximum  number)  most intense
      IR bands (S/N > 5) which are within ± 5.0 cm"1 of the corresponding bands
      in  the library  spectrum.   Choose  IR bands  which are sharp  and  well
      resolved.  The software  used  to locate  spectral  peaks  should  employ the
      peak "center of gravity" technique.   In  addition,  the  IR frequencies of
      the analyte and library spectra should  be determined with the same computer
      software.

            7.10.3  Retention Time Confirmation - After visual  comparison of the
      analyte and library spectrum as described  in Section 7.10.2, compare the
      relative retention times (RRT)  of the analyte and an  authentic standard
      of the most  promising  library search  hit.   The  standard and analyte RRT
      should agree within + 0.01  RRT units when both are determined at the same
      chromatographic conditions.

            7.10.4  Compound Class or Functionality  Assignment - If the analyte
      cannot  be  unequivocally   identified,  report  its  compound  class  or
      functionality.  See Table 3 for gas-phase group  frequencies to  be used as
      an aid for compound class assignment.   It should  be noted that  FT-IR gas-


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      phase group stretching frequencies are 0-30 cm"1 higher in frequency than
      those of the condensed phase.

            7.10.5  Quantitation -  Although this protocol can be used to confirm
      GC/MS identifications, with  subsequent  quantisation,  FT-IR quantitation
      guidelines are also provided.

            7.10.6  Integrated   Absorbance   Technique    -    After   analyte
      identification, construct a  standard calibration  curve of concentration
      versus  integrated  infrared  absorbance.   For  this  purpose,  choose  for
      integration only those FT-IR scans which are  at or  above the peak half-
      height.   The calibration curve should span at least one order of magnitude
      and the working range should bracket the analyte concentration.

            7.10.7  Maximum  Absorbance  Infrared  Band  Technique  -  Following
      analyte  identification,  construct  a  standard  calibration  curve  of
      concentration versus maximum infrared band intensity.  For this  purpose,
      choose an intense,  symmetrical  and well  resolved IR absorbance band.

            (Note that IR transmission  is  not proportional  to concentration).
      Select  the FT-IR  scan  with the  highest  absorbance  to  plot  against
      concentration.  The calibration curve should  span at  least one  order of
      magnitude and the working  range should bracket the analyte concentration.
      This method is most practical for  repetitive,  target compound analyses.
      It is more sensitive than the integrated absorbance technique.

            7.10.8  Supplemental GC Detector Technique -  If a GC detector  is used
      in tandem with the  FT-IR  detector,  the  following  technique may  be used:
      following analyte identification,  construct a standard calibration curve
      of concentration  versus integrated peak area.  The calibration curve should
      span at  least one order of magnitude and the working range should bracket
      the analyte concentration. This method  is most practical for repetitive,
      target compound analyses.


8.0  QUALITY CONTROL

      8.1  Refer to  Chapter One for  specific quality control  procedures.  Quality
control  to  validate sample extraction  is covered  in Method 3500 and  in  the
extraction method utilized.   If  extract cleanup was performed,  follow the QC in
Method 3600 and in the specific cleanup method.

      8.2  One Hundred  Percent Line Test - Set  the  GC/FT-IR operating conditions
to those employed for the Sensitivity Test  (see Section 7.5).  Collect 16 scans
over the entire detector  spectral  range.   Plot  the  test and measure the peak-
to-peak noise between 1800 and 2000 cm'1.  This noise should be < 0.15%.   Store
this plot for future reference.

      8.3  Single Beam Test -  With  the GC/FT-IR at analysis conditions, collect
16 scans in the  single beam mode.   Plot the  co-added file  and compare  with a
subsequent file acquired  in  the  same fashion several  minutes later.  Note if the
spectrometer  is   at  purge  equilibrium.   Also  check the  plot  for  signs  of
deterioration of the lightpipe potassium bromide windows.   Store this  plot for
future reference.

                                   8410 - 8                       Revision 0
                                                                  November 1990

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deterioration of the lightpipe potassium bromide windows.  Store this plot for
future reference.

      8.4  Align  Test  -  With  the  lightpipe  and  MCT detector  at  thermal
equilibrium, check the intensity of the centerburst versus the signal temperature
calibration curve.  Signal  intensity  deviation  from the predicted intensity may
mean thermal equilibrium has not  yet been  achieved,  loss of  detector coolant,
decrease  in source  output,  or  a loss  in signal  throughput  resulting  from
lightpipe deterioration.

      8.5  Mirror Alignment - Adjust the  interferometer mirrors to attain the
most  intense signal.   Data  collection  should  not be  initiated  until  the
interferogram is stable.  If necessary, align the mirrors prior to each GC/FT-
IR run.

      8.6  Lightpipe - The lightpipe and lightpipe windows should be protected
from moisture and  other corrosive substances  at all  times.   For this purpose,
maintain the lightpipe temperature above the maximum  GC program temperature but
below its thermal  degradation limit.   When not in use,  maintain the lightpipe
temperature slightly above  ambient.  At all times maintain a flow of dry, inert,
carrier gas through the lightpipe.

      8.7  Beamsplitter -  If the spectrometer is thermostated,  maintain the
beamsplitter at  a temperature  slightly  above  ambient  at  all times.   If the
spectrometer  is  not  thermostated, minimize exposure  of the  beamsplitter to
atmospheric water vapor.


9.0  METHOD PERFORMANCE

      9.1  Method  8410  has been  in  use at the U.S.  Environmental   Protection
Agency  Environmental  Monitoring  Systems  Laboratory  for more  than  two years.
Portions  of it  have been reviewed by key members of  the  FT-IR spectroscopic
community (9).   Side by side comparisons  with  GC/MS sample  analyses indicate
similar  demands  upon analytical  personnel  for the  two  techniques.   Extracts
previously  subjected to GC/MS analysis are generally compatible with GC/FT-IR.
However,  it  should  be  kept  in mind that lightpipe windows are typically water
soluble.  Thus, extracts must be  vigorously dried  prior to analysis.


10.0 REFERENCES

1.   Handbook  for  Analytical   Quality  Control  in   Water   and   Wastewater
     Laboratories;   U.S.   Environmental   Protection   Agency.     Environmental
     Monitoring and Support Laboratory.  ORD Publication Offices of  Center for
     Environmental Research Information: Cincinnati,  OH,  March 1979;  Section 4,
     EPA-600/4-79-019.

2.   Freeman, R.R.   Hewlett Packard Application  Note:   Quantitative Analysis
     Using  a Purged Solitless In.iection Technique; ANGC 7-76.

3.   Cole,  R.H.     Tables  of  Wavenumbers  for  the   Calibration  of Infrared
     Spectrometers; Pergamon:  New York, 1977.


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                                                                  November 1990

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4.   Grasselli, J.G.; Griffiths,  P.R.;  Hannah,  R.W.  "Criteria for Presentation
     of Spectra from Computerized  IR  Instruments";  ADD!.  Spectrosc.  1982, 36>
     87.

5.   Nyquist, R.A.  The Interpretation of Vaoor-Phase Infrared Spectra.  Group
     Frequency Data; Volume I. Sadtler Laboratories:  Philadelphia, PA, 1984.

6.   Socrates, G.   Infrared Characteristic Group Frequencies;  John  Wiley and
     Sons:  New York, NY, 1980.

7.   Bellamy, L.J.  The Infrared  Spectra  of Complex Organic Molecules; 2nd ed.;
     John Wiley and Sons:  New York, NY,  1958.

8.   Szymanski, H.A.   Infrared Band Handbook. Volumes I and  II;  Plenum:   New
     York, NY, 1965.

9.   Gurka, D.F.  "Interim Protocol for the Automated Analysis of Semivolatile
     Organic  Compounds  by  Gas  Chromatography/Fourier  Transform-  Infrared
     Spectrometry"; APP!. Spectrosc. 1985, 39, 826.

10.  Griffiths, P.R.;  de  Haseth,  J.A.; Azarraga, L.V.   "Capillary GC/FT-IR";
     Anal. Chem. 1983,  55, 1361A.

11.  Griffiths, P.R.; de Haseth,  J.A.   Fourier Transform-Infrared Spectrometrv;
     Wiley-Interscience:  New York, NY, 1986.

12.  Gurka, D. F.; Farnham, I.; Potter, B. B.; Pyle, S.; Titus, R. and Duncan,
     W. "Quantitation Capability of a Directly Linked Gas Chromatography/Fourier
     Transform Infrared/Mass Spectrometry System"; Anal. Chem..  1989, 61, 1584.
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                              TABLE  1.
FUSED SILICA CAPILLARY COLUMN GAS CHROMATOGRAPHIC/FOURIER TRANSFORM
    INFRARED  IDENTIFICATION  LIMITS FOR  BASE/NEUTRAL  EXTRACTABLES
Compound
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Bis(2-chloroethyl) ether
Bi s (2-chl oroethoxy)methane
Bis (2-chl oroisopropyl) ether
Butyl benzyl phthalate
4-Bromophenyl phenyl ether
2-Chl oronaphthal ene
4-Chloroaniline
4-Chlorophenyl phenyl ether
Chrysene
Di-n-butyl phthalate
Dibenzofuran
Diethyl phthalate
Dimethyl phthalate
Di-n-octyl phthalate
Di-n-propyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Bis-(2-ethylhexyl) phthalate
Fluoranthene
Fluorene
Hexachlorobenzene
Hexachlorocyclopentadiene
Hexachloroethane
1 , 3-Hexachl orobutadi ene
Isophorone
2-Methyl naphthal ene
Naphthalene
Nitrobenzene
N-Nitrosodimethylamine
N-Nitrosodi-n-propylamine
N-Nitrosodiphenylaminee
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
Identification
ng injected8
40(25)
50(50)
40(50)
(50)
(100)
70(10)
50(10)
50(10)
25(10)
40(5)
110
40
20(5)
(100)
20(5)
40
20(5)
20(5)d
25(10)
25(5)
50
50
50
20
20
25(10)
100(50)
40(50)
40
120
50
120
40
110
40(25)
25
20(5)
50(5)
40
40
40
40
50(50)
100(50)
50(25)
Limit
M9/Lb
20(12.5)
25(25)
20(25)
(25)
(50)
35(5)
25(5)
25(5)
12.5(5)
20(2.5)
55
20
10(2.5)
(50)
10(2.5)
20
10(2.5)
10(2.5)
12.5(5)
12.5(2.5)
25
25
25
10
10
12.5(5)
50(25)
20(25)
20
60
25
60
20
55
20(12.5)
12.5
10(2.5)
25(2.5)
20
20
20
20
25(25)
50(25)
25(12.5)
i/max, cm"1
799
799
874
745
756
1115
1084
1088
1748
1238
851
1543
1242
757
1748
1192
1748
1751
1748
1748
1458
779
1474
1547
1551
1748
773
737
1346
814
783
853
1690
3069
779
1539
1483
1485
1501
1564
1583
1362
729
820
750
                             8410 - 11
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November 1990

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                                 TABLE 1.
                               (Continued)


Determined using  on-column  injection and the conditions  of Section 7.3.  A
medium band  HgCdTe  detector [3800-700cm~1; D'value (Apeak 1000  Hz,  1)  4.5 x
1010 cm Hz1/2W"1]  type  with a 0.25 mm2 focal chip was used.  The GC/FT-IR system
is a 1976 retrofitted model.

Based on a 2 /xL injection of a one  liter  sample that has been extracted and
concentrated to a volume  of  1.0  ml_.

Most intense IR peak and  suggested  quantitation peak.

Values in parentheses were  determined with a new  (1986)  GC/FT-IR system. A
narrow band HgCdTe detector  [3800-750cm'1; D'value (Apeak 1000 Hz, 1) 4 x 1010
cm Hz1/2W"1] was  used.   Chromatographic conditions are those  of Section 7.3.

Detected as diphenylamine.
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                                   TABLE 2.
      FUSED SILICA CAPILLARY COLUMN GAS CHROMATOGRAPHIC/FOURIER TRANSFORM
   INFRARED ON-LINE AUTOMATED IDENTIFICATION LIMITS FOR ACIDIC  EXTRACTABLES
                                    Identification
Compound
ng injected8
»/niax, cm
                                                                            .-1 c
Benzoic acid
2-Chlorophenol
4-Chlorophenold
4-Chl oro-3-methyl phenol
2-Methyl phenol
4-Methyl phenol
2,4-Dichlorophenol
2,4-Dinitrophenol
4, 6-Dinitro-2-methyl phenol
2-Nitrophenold
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
2,4,5-Trichlorophenol
70
50
100
25
50
50
50
60
60
40
50
50
70
120
120
35
25
50
12.5
25
25
25
30
30
20
25
25
35
60
60
1751
1485
1500
1177
748
1177
1481
1346
1346
1335
1350
1381
1184
1470
1458
a  Operating conditions are the same as those cited  in Section 7.3.
b  Based on a 2 /iL  injection of a one  liter  sample that  has  been  extracted  and
   concentrated to a volume of 1.0 mL.
0  Most intense IR peak and suggested  quantitation peak.
d  Subject to interference from co-eluting compounds.
                                   8410 - 13
                                    Revision  0
                                    November 1990

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          TABLE  3.
GAS-PHASE GROUP FREQUENCIES
Number of
Functionality Class Compounds
Ether
Ester
Nitro
Nitrile
Ketone
Amide
Al kyne
Acid
Phenol
Aryl, Alkyl
Benzyl, Alkyl
Diaryl
Dialkyl
Alkyl, Vinyl
Unsubstituted Aliphatic
Aromatic
Monosubstituted Acetate
Aliphatic
Aromatic
Aliphatic
Aromatic
Aliphatic (acyclic)
(a, 6 unsaturated)
Aromatic
Substituted Acetamides
Aliphatic
Aliphatic
Dimerized-Aliphatic
Aromatic
1,4-Disubstituted
1,3-Disubstituted
14
3
5
12
3
29
11
34
5
18
9
9
13
2
16
8
8
24
22
2
10
10
15
15
15
10
10
10
Frequency
Range, i/cm"1
1215-1275
1103-1117
1238-1250
1084-1130
1204-1207
1128-1142
1748-1761
1703-1759
1753-1788
1566-1594
1548-1589
1377-1408
1327-1381
1535-1566
1335-1358
2240-2265
2234-2245
1726-1732
1638-1699
1701-1722
1710-1724
3323-3329
3574-3580
1770-1782
3586-3595
3574-3586
1757-1774
3645-3657
1233-1269
1171-1190
3643-3655
1256-1315
1157-1198
         8410 - 14
Revision 0
November 1990

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TABLE 3.
(Continued)
Functionality
Phenol (continued)


Alcohol






Amine


Al kane



Aldehyde





Benzene





Class

1,2-Disubstituted

Primary Aliphatic


Secondary Aliphatic

Tertiary Aliphatic

Primary Aromatic
Secondary Aromatic
Aliphatic




Aromatic


Aliphatic


Monosubstituted





Number of
Compounds

6

20
11
16
17
10
10
6
15
5
10
14



12
12
12
6
6
6
7
24
24
11
23
25
Frequency
Range, i/cm"1

3582-3595
1255-1274
3630-3680
1206-1270
1026-1094
3604-3665
1231-1270
3640-3670
1213-1245
3480-3532
3387-3480
760- 785
2930-2970
2851-2884
1450-1475
1355-1389
1703-1749
2820-2866
2720-2760
1742-1744
2802-2877
2698-2712
1707-1737
1582-1630
1470-1510
831- 893
735- 790
675- 698
8410 - 15
Revision 0
November 1990

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    TABLE  4.   FUSED SILICA CAPILLARY COLUMN GC/FT-IR QUANTITATION RESULTS
Compound
Concentration
  Range, and
Identification
  Limit, nga
 Maximum
Absorbance"
Correlation
Coefficient11
 Integrated
Absorbancec
 Correlation
Coefficient*
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzoic acid
Benzo(a)pyrene
Bi s (2-chl oroethoxyjmethane
Bis(2-chloroethyl) ether
Bis (2-chl oroisopropyl) ether
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
4-Chloroaniline
4-Chl oro-3-methyl phenol
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenole
4-Chlorophenyl phenyl ether
Chrysene
Dibenzofuran
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
2,4-Dichlorophenol
Dimethyl phthalate
Dimethyl phthalate
Dinitro-2-methyl phenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl phthalate
Bis(2-ethylhexyl) phthalate
Fluoranthene
Fluorene
Hexachlorobenzene
1,3-Hexachlorobutadiene
Hexachl orocycl opentadi ene
Hexachloroethane
Isophorone
2-Methyl naphthalene
25-250
25-250
50-250
50-250
50-250
100-250
25-250
25-250
50-250
25-250
25-250
25-250
25-250
100-250
25-250

25-250
100-250
25-250
25-250
25-250
25-250
25-250
25-250
25-250
25-250
50-250
50-250
25-250
25-250
25-250
25-250
25-250
25-250
50-250
50-250
100-250
25-250
25-250
50-250
0.9995
0.9959
0.9969
0.9918
0.9864
0.9966
0.9992
0.9955
0.9981
0.9995
0.9999
0.9991
0.9975
0.9897
0.9976

0.9999
0.9985
0.9697
0.9998
0.9937
0.9985
0.9994
0.9964
0.9998
0.9998
0.9936
0.9920
0.9966
0.9947
0.9983
0.9991
0.9983
0.9987
0.9981
0.9960
0.9862
0.9986
0.9984
0.9981
0.9985
0.9985
0.9971
0.9921
0.9892
0.9074
0.9991
0.9992
0.9998
0.9996
0.9994
0.9965
0.9946
0.9988
0.9965

0.9997
0.9984
0.8579
0.9996
0.9947
0.9950
0.9994
0.9969
0.9996
0.9997
0.9967
0.9916
0.9928
0.9966
0.9991
0.9993
0.9966
0.9989
0.9995
0.9979
0.9845
0.9992
0.9990
0.9950
                                                                    (continued)
                                   8410 - 16
                                  Revision 0
                                  November 1990

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                             TABLE 4.   (Continued)
Compound
Concentration
  Range, and
Identification
  Limit, nga
 Maximum
Absorbance"
Correlation
Coefficient11
 Integrated
Absorbance0
 Correlation
Coefficient"
2-Methyl phenol
4-Methyl phenol
Naphthalene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
2-Nitrophenole
4-Nitrophenol
N-Ni trosodimethyl ami ne
N-Ni trosodi phenyl ami ne
N-Ni trosodi -n-propyl amine
Pentachlorophenol
Phenanthrene
Phenol
Pyrene
1,2,4-Trichlorobenzene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
25-250
25-250
25-250
25-250
25-250
25-250
25-250

50-250
25-250
25-250
25-250
50-250
25-250
25-250
50-250
50-250
25-250
25-250
0.9972
0.9972
0.9956
0.9996
0.9985
0.9936
0.9997

0.9951
0.9982
0.9994
0.9991
0.9859
0.9941
0.9978
0.9971
0.9969
0.9952
0.9969
0.9964
0.9959
0.9954
0.9994
0.9990
0.9992
0.9979

0.9953
0.9993
0.9971
0.9995
0.9883
0.9989
0.9966
0.9977
0.991
0.9966
0.9965
   Lower end of range is at or near the identification limit.

   FT-IR scan with highest absorbance plotted against concentration.

   Integrated absorbance of  combined  FT-IR scans which occur  at  or above the
   chromatogram peak half-height.

   Regression analysis  carried  out  at four concentration  levels.   Each level
   analyzed in duplicate chromatographic conditions are stated in Section 7.3.

   Subject to interference from co-eluting compounds.
                                   8410  -  17
                                  Revision 0
                                  November 1990

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                        METHOD 8410
 GAS CHROMATOGRAPHY/FOURIER TRANSFORM INFRARED (GC/FT-IR)
 SPECTROMETRY FOR SEMIVOLATILE ORGANICS:  CAPILLARY  COLUMN
Start


7 7 Replace
Source

7 . 8 Frequency

No
7.10.7 Standard
calibration
curve of cone .
v* . max . IR
band int«n*i ty
                         8410  -  18
Revision 0
November 1990

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                                  METHOD  1312

                  SYNTHETIC PRECIPITATION LEACHING PROCEDURE
1.0 SCOPE AND APPLICATION

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

      1.2    If a total analysis of the  soil, waste, or wastewater demonstrates
that individual analytes are not present, or that they are present but at such
low concentrations that the appropriate  regulatory  levels could not possibly be
exceeded, Method 1312 need not be run.

      1.3    If  an  analysis of  any one of the  liquid fractions of  the 1312
extract  indicates  that   a  regulated   compound   is   present  at  such  high
concentrations that,  even after accounting for dilution from the other fractions
of the extract, the concentration would be above the regulatory level  for that
compound, then the waste  is  hazardous and it is not  necessary  to analyze the
remaining fractions of the extract.

      1.4    If an analysis of extract obtained using a bottle extractor shows
that the concentration of  any regulated  volatile analyte exceeds the regulatory
level for that  compound, then the waste is hazardous and extraction using the ZHE
is not necessary.  However, extract from a  bottle  extractor  cannot  be used to
demonstrate that the concentration of volatile compounds is  below the regulatory
level.

2.0   SUMMARY OF METHOD

      2.1    For liquid samples  (i.e..  those  containing  less than 0.5 percent
dry solid material),  the sample,  after filtration through a 0.6 to 0.8 p.m glass
fiber filter, is defined as the 1312 extract.

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

      2.3    If compatible (i.e., multiple phases will  not form on combination),
the initial liquid phase of the waste is  added to the liquid extract, and these
are analyzed together.   If incompatible,  the  liquids are analyzed separately and
the  results are mathematically  combined to  yield a  volume-weighted  average
concentration.
                                   1312 - 1                       Revision 0
                                                                  November 1990

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3.0   INTERFERENCES

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

4.0   APPARATUS AND MATERIALS

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

      4.2    Extraction Vessels

             4.2.1    Zero  Headspace Extraction Vessel  (ZHE).  This device is for
      use only  when  the  sample is  being  tested for the mobility of volatile
      analytes (i.e., those listed in Table 1).  The ZHE (depicted in Figure 2)
      allows for liquid/solid  separation  within the  device and effectively
      precludes headspace.   This type of vessel allows for initial liquid/solid
      separation, extraction, and final  extract filtration without opening the
      vessel (see Step 4.3.1).  These vessels shall  have an  internal  volume of
      500-600 ml and  be equipped to accommodate a 90-110  mm filter.  The devices
      contain VITON*1 0-rings which should  be  replaced  frequently.  Suitable ZHE
      devices known to EPA are identified  in  Table 3.

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

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

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

             4.2.2    Bottle  Extraction Vessel.    When  the  sample  is  being
      evaluated using the nonvolatile extraction, a jar with sufficient capacity
      to hold  the  sample   and  the  extraction fluid is  needed.   Headspace is
      allowed in this vessel.
      VlTON® is  a trademark of  Du Pont.
                                   1312 - 2                       Revision 0
                                                                  November 1990

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

      4.3    Filtration  Devices:   It  is  recommended that  all  filtrations  be
performed in a hood.
  i

             4.3.1    Zero-Headspace  Extraction Vessel  (ZHE):   When the sample
      is evaluated for volatiles, the zero-headspace extraction vessel described
      in Step  4.2.1  is  used  for  filtration.   The device shall  be capable  of
      supporting and  keeping  in place the glass  fiber filter and  be able  to
      withstand the pressure  needed to accomplish separation (50 psi).

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

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

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

      4.4    Filters:  Filters shall  be made  of borosilicate glass fiber, shall
contain no binder materials,  and  shall have an effective pore  size of 0.6  to
0.8-/xm or equivalent.  Filters known to EPA which meet these specifications are
identified in  Table 5.    Pre-filters  must not  be  used.   When  evaluating the
mobility of metals,  filters shall be acid-washed prior to  use by rinsing with IN

                                   1312 - 3                       Revision 0
                                                                  November 1990

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nitric acid followed by three consecutive rinses with deionized distilled water
(a minimum of 1-L per rinse is recommended).  Glass fiber filters are fragile and
should be handled with care.

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

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

             4.6.1    If a  waste contains an aqueous liquid phase or if a waste
      does not  contain a  significant  amount of  nonaqueous  liquid  (i.e..  <1
      percent of total waste), the TEDLAR* bag or a 600 ml syringe should be used
      to collect and combine the initial  liquid and solid extract.

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

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

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

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

      4.9    Beaker or Erlenmeyer flask, glass, 500 mL.

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

      4.11   Magnetic stirrer.

5.0   REAGENTS

      5.1    Reagent  grade chemicals  shall be  used  in  all tests.    Unless
otherwise  indicated,  it is  intended  that  all reagents  shall  conform to  the
specifications of the Committee on  Analytical Reagents of the American Chemical
Society, where  such  specifications are available.   Other grades may  be  used,
       TEDLAR* is a  registered trademark of Du Pont.
                                   1312 -  4                       Revision  0
                                                                  November 1990

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provided it is first  ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.

      5.2     Reagent  water.   All references  to reagent water  in  this method
refer to one of the following, as appropriate.

              5.2.1    Inorganic Analytes:  Water which is generated by any method
      which would achieve the performance standards for ASTM Type II water.  The
      analyte(s) of concern must  be no higher than the highest of either (1.) the
      detection  limit,  or (2) five  percent  of the regulatory  level  for that
      analyte, or (3) five percent of the measured  concentration  in the sample.

              5.2.2    Volatile Analytes:   Water in which an interferant is not
      observed  at  the method  detection  limit  of  the compounds  of  interest.
      Organic-free water can be generated  by  passing tap water through a carbon
      filter  bed  containing  about  1  Ib.  of  activated  carbon.    A  water
      purification system may be  used to generate organic-free deionized water.
      Organic-free water may also be prepared by boiling water for 15 minutes.
      Subsequently,  while  maintaining  the   temperature  at  90°C,  bubble  a
      contaminant-free inert gas through the water for 1 hour.  The analyte(s)
      of concern must be no higher than the highest of either  (1) the detection
      limit, or  (2)  five  percent  of  the regulatory level  for that analyte, or
      (3) five percent of the measured concentration in the sample.

              5.2.3    Semivolatile Analytes:   Water in which an interferant is
      not observed at the method detection limit of the compounds of interest.
      Organic-free water can be generated  by  passing tap water through a carbon
      filter  bed  containing  about  1  Ib.  of  activated  carbon.    A  water
      purification system may be  used to generate organic-free deionized water.
      The analyte(s)  of concern must  be no higher than the  highest of either (1)
      the detection limit, or (2)  five percent of the regulatory  level for that
      analyte, or (3) five percent of the measured  concentration  in the sample.

      5.3     Sulfuric acid/nitric acid (60/40 weight percent mixture) H2S04/HN03.
Cautiously mix  60  g  of concentrated sulfuric acid with 40  g  of concentrated
nitric acid.

      5.4     Extraction fluids.

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

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

              5.4.2    Extraction  fluid  #2:   This  fluid  is made  by  adding the
      60/40 weight percent mixture of sulfuric and nitric acids to reagent water
      (Step 5.2) until the pH  is  5.00 ± 0.05.   The fluid  is used to determine
      the Teachability  of soil from a  site  that  is  west of  the  Mississippi
      River.
                                   1312 - 5                       Revision 0
                                                                  November 1990

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

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

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

6.0   SAMPLE  COLLECTION, PRESERVATION, AND HANDLING

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

      6.2     There may be requirements on the minimal size of the field sample
depending upon the  physical  state or states of the waste  and the analytes of
concern.  An  aliquot  is  needed for the  preliminary  evaluations of the percent
solids  and   the  particle size.    An  aliquot  may  be   needed  to conduct the
nonvolatile analyte extraction procedure (see Step 1.4 concerning the use of this
extract for  volatile  organics).   If volatile  organics are of concern,  another
aliquot may  be needed.  Quality control measures may require additional aliquots.
Further, it  is always wise to collect more  sample just  in case something goes
wrong with the initial attempt to conduct the test.

      6.3     Preservatives shall not be added to  samples before extraction.

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

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

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

7.0   PROCEDURE

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

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

                      7.1.1.1     If the sample  will obviously  yield no  free
             liquid  when  subjected  to  pressure  filtration  (i.e.,  is  100%
             solids), weigh out a representative subsample (100 g minimum) and
             proceed to Step 7.1.3.

                      7.1.1.2     If  the   sample  is  liquid  or  multiphasic,
             liquid/solid  separation to make  a preliminary  determination of
             percent solids is  required.   This  involves the filtration  device
             discussed in Step 4.3.2, and is outlined in Steps 7.1.1.3 through
             7.1.1.9.

                      7.1.1.3   Pre-weigh the  filter  and the container that will
             receive the filtrate.

                      7.1.1.4     Assemble filter holder and filter following the
             manufacturer's  instructions.    Place  the  filter on the  support
             screen and secure.

                      7.1.1.5   Weigh  out  a  subsample  of the waste  (100  gram
             minimum) and record the  weight.

                      7.1.1.6  Allow slurries to stand to permit the solid phase
             to settle.  Samples that settle  slowly  may be centrifuged prior to
             filtration.   Centri.fugation  is to  be used  only  as  an  aid to
             filtration.   If  used,  the  liquid  should be decanted and filtered
             followed by filtration  of  the  solid  portion of the waste through
             the same filtration system.

                      7.1.1.7   Quantitatively transfer the sample to the filter
             holder (liquid and  solid phases).   Spread the  sample evenly over
             the  surface  of the filter.   If filtration  of the waste  at 4°C
             reduces the amount of  expressed liquid over what would be expressed
             at room  temperature,  then allow  the  sample to warm up to  room
             temperature in the device before filtering.

NOTE: If sample material (>1  percent  of original  sample weight)  has obviously
      adhered to the  container  used to transfer the sample  to  the  filtration
      apparatus, determine the weight of this residue and subtract it from the
      sample weight determined in  Step 7.1.1.5  to  determine the  weight  of the
      sample that will be filtered.


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             Gradually apply vacuum or gentle  pressure  of  1-10  psi,  until  air
      or pressurizing  gas moves  through  the  filter.   If  this point  is  not
      reached under 10 psi, and if no additional  liquid has passed through the
      filter in any 2-minute interval, slowly  increase  the  pressure  in 10 psi
      increments to a maximum of 50 psi.  After each incremental  increase of 10
      psi,  if the pressurizing  gas has not moved  through the filter,  and if no
      additional liquid has passed through the  filter in any 2-minute interval,
      proceed to the next  10-psi increment.  When  the pressurizing gas begins to
      move through the filter,  or when liquid flow has ceased at 50 psi (i.e.,
      filtration does not  result in any additional filtrate within any 2-minute
      period), stop the filtration.

NOTE: Instantaneous application of high  pressure can degrade the  glass fiber
      filter and may cause premature  plugging.

                      7.1.1.8   The material in the filter holder is defined as
             the solid phase of the sample,  and the filtrate is  defined as the
             liquid phase.

NOTE: Some samples, such  as  oily  wastes and  some paint  wastes,  will  obviously
      contain some material  that appears to be a liquid,  but even after applying
      vacuum or pressure filtration, as outlined  in Step 7.1.1.7, this material
      may not filter.  If this  is the case,  the material within  the filtration
      device is defined as a solid.   Do not  replace the original filter with a
      fresh filter under any circumstances.   Use  only one filter.

                      7.1.1.9   Determine the  weight of  the liquid  phase  by
             subtracting the weight of the filtrate container (see Step 7.1.1.3)
             from the total weight of the filtrate-filled container.  Determine
             the weight of the solid phase  of the  sample  by subtracting  the
             weight of the liquid phase from  the  weight  of the total sample,  as
             determined in Step 7.1.1.5 or 7.1.1.7.

                      Record the  weight  of  the  liquid  and  solid  phases.
             Calculate the percent solids as follows:

                                Weight of  solid (Step 7.1.1.9)
      Percent solids =  	   x 100

                       Total weight of waste  (Step 7.1.1.5  or 7.1.1.7)

             7.1.2    If the  percent solids determined in Step 7.1.1.9 is equal
      to or greater than  0.5%,  then proceed  either to  Step  7.1.3  to  determine
      whether the  solid material  requires  particle size reduction or to Step
      7.1.2.1 if it is noticed  that a small amount of the filtrate is entrained
      in wetting  of the  filter.   If  the percent solids  determined  in  Step
      7.1.1.9 is less than 0.5%, then proceed to  Step 7.2.9 if the nonvolatile
      1312 analysis is to  be performed, and to Section 7.3 with a fresh portion
      of the waste if the  volatile 1312 analysis  is  to be performed.

                      7.1.2.1    Remove the  solid  phase and  filter  from  the
             filtration apparatus.
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                      7.1.2.2    Dry  the  filter and solid phase at 100 ± 20°C
             until  two  successive weighings yield  the  same value within  + 1
             percent.  Record the final weight.

Note: Caution should be taken to  ensure  that the  subject solid will  not  flash
      upon heating.  It  is recommended  that  the drying oven be vented to a hood
      or other appropriate device.

                      7.1.2.3    Calculate the percent dry solids as follows:


Percent        (Weight of dry sample + filter) - tared weight of filter
dry solids  =  	   x 100

                   Initial weight of sample (Step 7.1.1.5 or 7.1.1.7)


                      7.1.2.4    If  the percent dry solids  is  less  than  0.5%,
             then  proceed to Step 7.2.9  if the nonvolatile 1312 analysis  is to
             be performed, and to Step 7.3 if the volatile 1312 analysis  is to
             be performed.  If the percent dry solids is greater than or  equal
             to 0.5%, and if the nonvolatile 1312 analysis is to be performed,
             return  to  the  beginning of this Section (7.1)  and, with  a  fresh
             portion  of sample,  determine whether  particle  size  reduction is
             necessary  (Step 7.1.3).

             7.1.3    Determination of whether the sample  requires particle-size
      reduction (particle-size is reduced during  this step):   Using  the  solid
      portion of the  sample, evaluate  the solid  for particle size.   Particle-
      size reduction is required,  unless the solid has a surface area per gram
      of material  equal  to or greater than 3.1 cm , or is smaller than 1  cm in
      its narrowest  dimension  (i.e., is capable  of passing through a 9.5 mm
      (0.375 inch)  standard sieve).   If the  surface area  is  smaller or the
      particle size  larger than described above,  prepare the solid portion of
      the sample for extraction by crushing, cutting, or grinding the waste to
      a surface area  or particle  size as described above.   If the  solids are
      prepared for organic  volatiles extraction,  special precautions  must be
      taken (see Step 7.3.6).

Note: Surface area criteria are meant for filamentous (e.g., paper, cloth, and
      similar) waste materials.   Actual measurement of surface area is not
      required, nor is it recommended.  For materials that do not obviously meet
      the criteria,  sample-specific methods  would need  to be  developed and
      employed to  measure the surface  area.  Such  methodology is currently not
      available.

             7.1.4    Determination  of appropriate extraction fluid:

                      7.1.4.1    For  soils, if the sample is  from a site that is
             east  of the Mississippi  River,  extraction fluid  #1  should be used.
             If the sample is from a  site that is west of  the Mississippi River,
             extraction fluid #2  should  be used.
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                      7.1.4.2    For wastes and wastewater, extraction fluid #1
             should be used.

                      7.1.4.3    For  cyanide-containing  wastes and/or  soils,
             extraction fluid #3 (reagent water) must be used because leaching
             of cyanide- containing samples under acidic conditions may result
             in the formation of hydrogen cyanide gas.

             7.1.5    If  the aliquot  of the  sample  used for  the preliminary
      evaluation (Steps 7.1.1 - 7.1.4) was determined to be 100% solid at Step
      7.1.1.1,  then it can be used for the Section 7.2 extraction (assuming at
      least 100 grams  remain), and the Section 7.3 extraction  (assuming at least
      25 grams remain).  If the aliquot was subjected to the procedure in Step
      7.1.1.7,  then another  aliquot shall  be  used for the volatile extraction
      procedure in  Section 7.3.   The aliquot of  the waste subjected  to the
      procedure in Step 7.1.1.7 might be appropriate for use for the Section 7.2
      extraction if an adequate amount of  solid (as determined by Step 7.1.1.9)
      was obtained.  The amount of solid necessary is dependent upon whether a
      sufficient amount of extract will be produced to support the  analyses.  If
      an  adequate  amount  of solid  remains,  proceed  to Step  7.2.10  of the
      nonvolatile 1312 extraction.

      7.2    Procedure when Volatiles are not Involved

      A  minimum  sample   size  of  100  grams  (solid  and  liquid  phases)  is
recommended.  In some  cases,  a  larger  sample size may be appropriate, depending
on the  solids  content of  the waste  sample (percent solids, See  Step 7.1.1),
whether the initial  liquid phase of the waste  will be miscible with the aqueous
extract of the  solid, and whether inorganics, semivolatile organics, pesticides,
and herbicides are all analytes of concern.  Enough solids should be generated
for extraction  such that the volume  of  1312 extract will be sufficient to support
all of the  analyses required.   If  the  amount  of  extract generated by a single
1312 extraction will not be sufficient to perform all  of the analyses, more than
one extraction  may be performed and  the extracts from each combined  and aliquoted
for analysis.

             7.2.1    If the sample will obviously yield no liquid when subjected
      to pressure  filtration  (i.e., is 100 percent solid, see  Step 7.1.1), weigh
      out  a subsample of  the  sample  (100 gram  minimum)  and  proceed  to  Step
      7.2.9.

             7.2.2    If  the  sample   is  liquid  or  multiphasic,  liquid/solid
      separation is required.  This involves the filtration device described in
      Step 4.3.2 and is outlined in Steps 7.2.3 to 7.2.8.

             7.2.3  Pre-weigh the container that will receive the filtrate.

             7.2.4    Assemble   the  filter  holder  and  filter following  the
      manufacturer's instructions.   Place the filter on the support screen and
      secure.  Acid wash the filter if evaluating the mobility of metals (see
      Step 4.4).

Note: Acid washed  filters  may be used  for  all  nonvolatile extractions even when
      metals are not of concern.

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             7.2.5  Weigh out a subsample of the sample (100 gram minimum) and
      record the weight.  If the waste  contains  <0.5  percent dry solids (Step
      7.1.2), the liquid portion of the waste, after filtration, is defined as
      the 1312 extract. Therefore, enough of  the sample  should be filtered so
      that  the  amount  of  filtered liquid  will  support  all  of  the  analyses
      required of  the  1312  extract.  For wastes  containing >0.5  percent  dry
      solids (Steps 7.1.1 or 7.1.2), use the  percent  solids information obtained
      in Step 7.1.1 to determine the optimum sample  size (100 gram minimum) for
      filtration.   Enough solids should  be  generated  by  filtration to support
      the analyses to be performed on the 1312 extract.

             7.2.6  Allow slurries  to stand to permit the  solid  phase to settle.
      Samples that  settle slowly may be  centrifuged prior to filtration.   Use
      centrifugation  only  as   an   aid   to  filtration.     If  the  sample  is
      centrifuged,  the liquid  should  be decanted  and  filtered  followed  by
      filtration of the solid portion of the waste through the same filtration
      system.

             7.2.7  Quantitatively  transfer the sample (liquid and solid phases)
      to the filter holder  (see Step  4.3.2).   Spread  the  waste sample evenly
      over the surface of the filter.  If filtration  of the waste at 4°C reduces
      the amount  of  expressed  liquid  over what would  be  expressed  at  room
      temperature, then allow the sample to  warm up  to room temperature in the
      device before filtering.

NOTE: If waste material  (>1 percent of the original sample weight) has obviously
      adhered to the  container  used  to transfer the  sample  to the filtration
      apparatus,  determine the weight of this  residue and subtract it from the
      sample weight determined  in  Step  7.2.5, to determine  the  weight of the
      waste sample that will  be filtered.

             Gradually  apply vacuum or gentle pressure of 1-10 psi,  until  air
      or pressurizing gas  moves through the  filter.   If  this point  if  not
      reached under 10 psi,  and if no additional  liquid has passed through the
      filter in any 2-minute interval, slowly increase the  pressure  in 10-psi
      increments to maximum of  50  psi.   After each  incremental increase of 10
      psi,  if the pressurizing gas  has  not moved through  the filter,  and if no
      additional  liquid has passed  through the filter  in any 2-minute interval,
      proceed to  the next 10-psi increment.  When  the pressurizing gas begins to
      move through  the  filter,  or  when  the liquid  flow  has ceased at  50  psi
      (i.e.. filtration does  not result  in any  additional  filtrate  within  a
      2-minute period), stop  the filtration.

NOTE: Instantaneous application of  high  pressure can  degrade  the  glass fiber
      filter and may cause premature plugging.

             7.2.8  The material in the  filter holder is  defined as  the solid
      phase of the  sample,  and the filtrate  is  defined  as  the  liquid phase.
      Weigh the  filtrate.   The liquid phase  may now  be either  analyzed  (see
      Steps 7.2.12) or stored at 4°C until time of analysis.
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NOTE: Some wastes,  such  as oily wastes and some  paint  wastes,  will obviously
      contain some material which appears to be a liquid.  Even after applying
      vacuum or pressure  filtration,  as  outlined  in  Step 7.2.7, this material
      may not filter.  If this is the case, the material within the filtration
      device is defined as a solid, and is carried through the extraction as a
      solid.  Do not replace the original filter with a fresh filter under any
      circumstances.  Use only one filter.

             7.2.9    If the  sample contains <0.5% dry solids (see Step 7.1.2),
      proceed to Step 7.2.13.   If  the sample  contains  >0.5 percent dry solids
      (see Step 7.1.1 or  7.1.2), and if particle-size reduction of the solid was
      needed in Step 7.1.3, proceed to Step 7.2.10.   If the sample as received
      passes a 9.5 mm sieve, quantitatively transfer the solid material into the
      extractor bottle along  with the  filter used to  separate the initial liquid
      from the solid phase, and proceed to Step 7.2.11.

             7.2.10   Prepare the solid portion of the sample for extraction by
      crushing, cutting,  or grinding  the  waste  to a  surface area or particle-
      size as described in Step 7.1.3.  When the surface area or particle-size
      has been appropriately altered, quantitatively transfer the solid material
      into an extractor  bottle.  Include the filter used  to  separate the initial
      liquid from the solid phase.

NOTE: Sieving of the waste is not normally required.  Surface area requirements
      are  meant  for  filamentous   (e.g., paper,  cloth)  and  similar  waste
      materials.  Actual  measurement  of  surface area is not recommended.   If
      sieving  is  necessary,   a  Teflon-coated sieve  should be  used to  avoid
      contamination of the sample.

             7.2.11   Determine  the amount of extraction fluid to  add  to  the
      extractor vessel as follows:

                        20 x  % solids  (Step 7.1.1) x  weight of waste
                              filtered   (Step 7.2.5  or  7.2.7)
Weight of         =  	
extraction fluid
                                            100

             Slowly  add  this  amount of appropriate  extraction  fluid (see Step
      7.1.4) to the  extractor  vessel.  Close the  extractor bottle tightly (it is
      recommended that Teflon tape be used to ensure a  tight  seal), secure in
      rotary extractor  device,  and rotate  at  30 ±  2  rpm  for  18 + 2  hours.
      Ambient temperature (i.e.. temperature of room in which extraction takes
      place) shall  be maintained at 23 + 2°C during the extraction period.

NOTE: As agitation  continues,  pressure may build up within the extractor bottle
      for some  types of  sample  (e.g..  limed or  calcium carbonate-containing
      sample may  evolve  gases  such   as  carbon  dioxide).   To  relieve  excess
      pressure, the extractor bottle may be periodically opened (e.g.. after 15
      minutes, 30 minutes, and 1 hour) and vented into  a hood.

             7.2.12   Following the 18 + 2  hour extraction, separate the material
      in the  extractor  vessel into its  component liquid and solid  phases by
      filtering through  a  new glass  fiber filter, as outlined  in  Step  7.2.7.

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For final filtration of the  1312  extract,  the  glass  fiber filter may be
changed,  if  necessary,  to  facilitate filtration.   Filter(s)  shall  be
acid-washed (see Step 4.4) if evaluating the mobility of metals.

        7.2.13   Prepare  the  1312  extract  as follows:

                7.2.13.1   If the sample contained no initial liquid phase,
        the filtered liquid material obtained from Step 7.2.12 is defined
        as the 1312 extract.   Proceed  to Step 7.2.14.

                7.2.13.2   If compatible  (e.g.. multiple  phases  will  not
        result on combination),  combine the  filtered liquid resulting from
        Step 7.2.12 with the  initial  liquid phase  of the sample obtained
        in  Step  7.2.7.    This  combined  liquid  is defined  as  the  1312
        extract.  Proceed  to  Step  7.2.14.

                7.2.13.3   If the  initial  liquid  phase of  the  waste,  as
        obtained from Step 7.2.7,  is not or  may  not be compatible with the
        filtered liquid resulting  from Step 7.2.12,  do  not combine these
        liquids.  Analyze  these liquids, collectively defined as the 1312
        extract, and combine  the  results  mathematically,  as described in
        Step 7.2.14.

        7.2.14   Following  collection  of the 1312 extract,  the  pH of the
extract should be  recorded.   Immediately  aliquot and preserve the extract
for analysis.   Metals  aliquots  must be acidified with nitric acid to pH <
2.  If precipitation is observed upon addition of nitric acid to a small
aliquot  of  the  extract,   then  the  remaining portion of  the  extract  for
metals analyses shall  not be acidified and the extract shall  be analyzed
as  soon  as  possible.     All   other  aliquots  must  be  stored  under
refrigeration (4°C) until analyzed.   The 1312  extract  shall  be prepared
and analyzed according to appropriate analytical  methods.  1312 extracts
to be analyzed for metals  shall  be acid digested except  in those instances
where digestion causes loss  of metallic analytes.   If an analysis of the
undigested extract shows that the concentration of any regulated metallic
analyte  exceeds the  regulatory  level,  then the  waste  is  hazardous  and
digestion of the extract  is  not  necessary.   However,  data on undigested
extracts  alone  cannot  be used  to demonstrate  that  the  waste  is  not
hazardous.   If the  individual  phases  are  to  be  analyzed  separately,
determine the volume of  the  individual  phases (to + 0.5 percent), conduct
the appropriate  analyses,  and combine  the results mathematically by using
a simple volume-weighted  average:

                                   (V,) (C,)  +  (V2) (C2)
Final Analyte Concentration   =  	
                                        V,   +   V2
where:

V,  = The volume of the first phase (L).
C,  = The concentration of the analyte of concern in the  first phase (mg/L).
V2  = The volume of the second phase (L).
C2  = The concentration of the analyte  of  concern  in the second phase
     (mg/L).

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             7.2.15   Compare the analyte concentrations in the 1312 extract with
      the levels identified in the  appropriate  regulations.   Refer  to Section
      8.0 for quality assurance requirements.

      7.3    Procedure when Volatiles are Involved

      Use the  ZHE  device  to  obtain  1312  extract  for  analysis of  volatile
compounds only.   Extract resulting from  the  use  of the ZHE shall not be used to
evaluate the mobility of non-volatile analytes (e.g.,  metals,  pesticides, etc.).

      The ZHE device has approximately a 500 ml  internal capacity.  The ZHE can
thus accommodate a maximum of 25 grams of solid (defined  as  that fraction of a
sample from which no additional  liquid may be forced out by an applied pressure
of 50 psi), due  to  the  need  to add an  amount of  extraction  fluid equal  to 20
times the weight of the solid phase.

      Charge the ZHE with sample  only  once and do not open the device until the
final extract (of the  solid) has been collected.   Repeated  filling of the ZHE to
obtain 25 grams of solid is not permitted.

      Do not allow the  sample, the  initial  liquid phase,  or the extract  to be
exposed to the atmosphere for any more time  than is  absolutely necessary.  Any
manipulation of these materials should be done when cold (4°C) to minimize loss
of volatiles.

             7.3.1    Pre-weigh the (evacuated) filtrate  collection  container
      (see Step 4.6) and set  aside.   If  using a  TEDLAR* bag,  express all  liquid
      from  the  ZHE device  into  the  bag,   whether  for the  initial   or  final
      liquid/solid separation, and  take  an  aliquot  from the liquid  in the bag
      for analysis.   The containers listed  in Step 4.6 are recommended for use
      under the conditions stated in Steps  4.6.1-4.6.3.

             7.3.2    Place the ZHE  piston within the body  of the ZHE (it may be
      helpful first  to  moisten  the  piston  0-rings slightly  with  extraction
      fluid).   Adjust the piston within the ZHE body to a height  that will
      minimize the distance the piston will  have to move once the ZHE is charged
      with sample (based upon sample size requirements  determined  from Step 7.3,
      Step  7.1.1  and/or 7.1.2).   Secure the gas inlet/outlet  flange (bottom
      flange)  onto  the  ZHE  body  in   accordance   with   the  manufacturer's
      instructions.   Secure the glass fiber  filter between the support screens
      and set aside.  Set liquid inlet/outlet flange (top  flange) aside.

             7.3.3    If the  sample  is 100%   solid (see  Step 7.1.1),  weigh out
      a subsample (25 gram maximum)  of the waste, record weight, and proceed to
      Step 7.3.5.

             7.3.4    If the sample  contains <0.5% dry solids (Step 7.1.2), the
      liquid portion of  waste, after filtration, is defined as the 1312 extract.
      Filter enough of  the  sample so  that  the  amount of  filtered  liquid will
      support all of  the volatile analyses  required.  For  samples  containing
      >0.5%  dry  solids  (Steps  7.1.1  and/or  7.1.2),  use the  percent  solids
      information obtained in Step 7.1.1 to determine the optimum  sample size to
      charge into the ZHE.  The recommended  sample size is as follows:


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                      7.3.4.1     For  samples containing  <5% solids  (see  Step
             7.1.1),  weigh  out a 500 gram  subsample  of waste and  record the
             weight.

                      7.3.4.2     For  wastes  containing  >5%  solids  (see  Step
             7.1.1),  determine  the  amount of waste to charge  into  the  ZHE as
             fol1ows:

                                             25
Weight of waste to charge ZHE =  	   x 100

                                  percent solids (Step 7.1.1)

             Weigh  out  a subsample of  the  waste of the appropriate size and
      record the weight.

             7.3.5    If particle-size  reduction of  the solid portion  of the
      sample was required in Step 7.1.3,  proceed to  Step 7.3.6.   If particle-
      size reduction was not required in Step 7.1.3,  proceed to Step 7.3.7.

             7.3.6    Prepare the sample for extraction by crushing, cutting, or
      grinding the solid portion of the waste to a surface area or particle size
      as described in Step 7.1.3.1.  Wastes  and appropriate reduction equipment
      should  be refrigerated,  if  possible,  to  4°C prior to  particle-size
      reduction.   The means used to  effect particle-size  reduction must not
      generate heat  in  and  of  itself.   If reduction  of  the solid phase  of the
      waste is  necessary,  exposure  of  the  waste to  the atmosphere  should be
      avoided to the extent possible.

NOTE: Sieving of  the waste is  not  recommended  due  to  the possibility  that
      volatiles may  be  lost.   The use  of an appropriately graduated ruler is
      recommended as an acceptable alternative.  Surface area requirements are
      meant for filamentous (e.g..  paper,  cloth) and  similar waste materials.
      Actual measurement of surface area is not recommended.

             When  the  surface  area or  particle-size  has  been  appropriately
      altered, proceed to Step 7.3.7.

             7.3.7    Waste  slurries  need  not be  allowed to stand to permit the
      solid phase to settle.  Do not centrifuge samples  prior to filtration.

             7.3.8    Quantitatively transfer the  entire sample (liquid and solid
      phases) quickly to the ZHE.   Secure the  filter  and support screens into
      the top flange of the  device and secure the top flange to the ZHE body in
      accordance with the manufacturer's instructions. Tighten  all ZHE fittings
      and place the device in the vertical position (gas inlet/outlet flange on
      the bottom).   Do  not  attach the extraction collection device to the top
      plate.

Note: If sample material (>1% of original sample weight) has obviously adhered
      to the container  used to transfer the sample to the ZHE,  determine the
      weight of this residue and subtract it from the sample weight determined
      in Step 7.3.4  to  determine the weight of the waste  sample  that will be
      filtered.

                                  1312  -  15                      Revision 0
                                                                  November  1990

-------
             Attach  a  gas  line to the gas  inlet/outlet  valve  (bottom flange)
      and, with the liquid  inlet/outlet valve  (top flange) open, begin applying
      gentle pressure of 1-10 psi  (or  more  if  necessary) to force all headspace
      slowly out  of  the ZHE device into a hood.   At the  first  appearance of
      liquid from  the  liquid inlet/outlet  valve,  quickly close  the valve and
      discontinue  pressure.   If  filtration  of the waste  at  4°C  reduces the
      amount  of  expressed  liquid over   what  would  be  expressed  at  room
      temperature, then allow the sample  to warm up to room temperature in the
      device before  filtering.   If the waste is  100 percent  solid (see  Step
      7.1.1), slowly increase the pressure  to  a maximum of 50 psi to force most
      of the headspace out of the device  and proceed to Step 7.3.12.

             7.3.9    Attach   the   evacuated   pre-weighed  filtrate  collection
      container to  the liquid inlet/outlet valve  and  open the  valve.   Begin
      applying gentle  pressure  of 1-10 psi to  force  the liquid phase  of the
      sample into  the  filtrate collection  container.   If no additional  liquid
      has passed through the  filter in any 2-minute interval,  slowly increase
      the pressure  in  10-psi increments  to a maximum  of 50 psi.   After  each
      incremental  increase of 10 psi,  if no  additional liquid has passed through
      the filter in any 2-minute interval,  proceed  to the next 10-psi increment.
      When liquid flow has  ceased  such that continued pressure filtration at 50
      psi does not result in any additional filtrate within a 2-minute period,
      stop the  filtration.   Close the liquid  inlet/outlet  valve,  discontinue
      pressure to the piston, and disconnect and weigh the filtrate collection
      container.

NOTE: Instantaneous  application of high  pressure  can degrade  the  glass fiber
      filter and may cause premature plugging.

             7.3.10   The  material  in  the ZHE  is defined  as the solid phase of
      the sample and the filtrate is defined as the liquid phase.

NOTE: Some samples,  such as  oily  wastes and  some  paint wastes,  will obviously
      contain some material which appears  to be a  liquid.  Even after applying
      pressure filtration,  this material will  not  filter.  If this is the case,
      the material within the  filtration device is  defined  as  a  solid,  and is
      carried through the 1312 extraction  as a solid.

             If the  original waste contained <0.5  percent dry solids (see  Step
      7.1.2), this  filtrate  is defined  as the 1312  extract  and  is  analyzed
      directly.  Proceed to Step 7.3.15.

             7.3.11   The  liquid  phase may now be  either  analyzed  immediately
      (see Steps 7.3.13 through 7.3.15) or  stored at  4°C under minimal headspace
      conditions until  time  of analysis.   Determine the  weight  of extraction
      fluid #3 to add to the ZHE as follows:
                                 20 x % solids (Step 7.1.1)  x weight
                               of waste filtered (Step 7.3.4 or 7.3.8)
Weight of extraction fluid =  	

                                                 100
                                   1312  -  16                       Revision 0
                                                                  November 1990

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       7.3.12   The  following  steps detail  how  to add  the  appropriate
amount of  extraction fluid  to the  solid  material within  the  ZHE  and
agitation of the  ZHE vessel.   Extraction fluid #3 is  used  in  all  cases
(see Step 5.7).

                7.3.12.1   With  the ZHE in the vertical  position, attach a
       line from the extraction fluid reservoir to the liquid inlet/outlet
       valve.   The  line  used  shall  contain fresh extraction  fluid  and
       should be preflushed with fluid to eliminate any  air pockets in the
       line.    Release  gas pressure  on the  ZHE   piston  (from  the  gas
       inlet/outlet  valve), open the liquid  inlet/outlet valve, and begin
       transferring  extraction fluid  (by pumping  or  similar means)  into
       the ZHE.  Continue pumping  extraction fluid  into the ZHE until  the
       appropriate  amount  of fluid has been introduced into the device.

                7.3.12.2    After  the  extraction  fluid  has  been  added,
       immediately close the liquid  inlet/outlet valve and disconnect the
       extraction fluid line.   Check the ZHE to ensure that all valves are
       in  their closed  positions.    Manually  rotate  the  device in  an
       end-over-end  fashion  2 or 3  times.    Reposition  the ZHE  in  the
       vertical  position  with  the   liquid  inlet/outlet  valve  on  top.
       Pressurize the ZHE  to 5-10 psi (if necessary)  and slowly open  the
       liquid inlet/outlet valve  to  bleed out any headspace (into a hood)
       that may have been introduced due to the  addition  of extraction
       fluid.   This  bleeding  shall  be done  quickly and shall  be stopped
       at the  first  appearance of liquid from  the  valve.   Re-pressurize
       the ZHE  with 5-10 psi  and  check all ZHE fittings  to  ensure  that
       they are closed.

                7.3.12.3    Place the ZHE in  the  rotary extractor apparatus
       (if it  is  not already  there)  and rotate at  30 ± 2 rpm for 18+2
       hours.   Ambient  temperature  (i .e..  temperature of room in  which
       extraction  occurs)  shall  be maintained   at  23  ±  2°C  during
       agitation.

       7.3.13   Following the  18+2 hour  agitation  period,  check  the
pressure behind  the ZHE piston by  quickly  opening and closing  the  gas
inlet/outlet valve and noting  the  escape of  gas.  If the pressure has  not
been maintained (i.e.,   no  gas  release observed), the ZHE  is leaking.
Check the ZHE  for leaking as  specified  in  Step  4.2.1,  and  perform  the
extraction again with a new sample of waste.  If  the  pressure within  the
device has been maintained, the material  in the extractor vessel  is  once
again separated into its  component liquid and solid phases.  If the waste
contained an initial  liquid  phase,  the liquid may be  filtered directly
into the  same filtrate collection container (i.e.,  TEDLAR* bag) holding the
initial   liquid phase  of  the  waste.   A  separate filtrate  collection
container must  be  used if combining would create multiple phases, or there
is  not  enough  volume left  within  the  filtrate   collection  container.
Filter through the glass fiber filter, using the  ZHE  device as discussed
in Step 7.3.9.  All extracts shall be filtered and  collected if the TEDLAR*
bag is used,  if the extract is multiphasic,  or if the  waste  contained an
initial  liquid phase  (see Steps 4.6  and  7.3.1).
                             1312  -  17                       Revision 0
                                                            November 1990

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NOTE: An in-line glass  fiber  filter  may be used to filter the material within
      the ZHE if it is  suspected that the glass fiber filter has been ruptured

             7.3.14   If the original  sample contained no  initial liquid phase,
      the filtered liquid material obtained  from Step 7.3.13 is defined as the
      1312  extract.    If the  sample  contained an  initial  liquid  phase,  the
      filtered liquid material obtained from Step  7.3.13 and the initial liquid
      phase (Step 7.3.9) are collectively defined as the  1312 extract.

             7.3.15   Following collection  of  the  1312  extract,  immediately
      prepare the extract for analysis and store with minimal  headspace at 4°C
      until analyzed.   Analyze the 1312 extract  according  to the appropriate
      analytical  methods.     If the  individual  phases  are   to  be  analyzed
      separately  (i.e..  are  not  miscible),   determine  the  volume  of  the
      individual phases (to  0.5%), conduct the appropriate  analyses, and combine
      the results mathematically by using a  simple volume- weighted average:

                              (V,) (C,)  + (V2)  (C2)
      Final Analyte     =   	
      Concentration
                                          V2
      where:
      V1 = The volume of the first phases (L).
      C1 = The concentration of the analyte of concern in the first phase (mg/L).
      V2 = The volume of the second phase (L).
      C2 = The concentration of the analyte  of concern in the second phase
           (mg/L).

             7.3.16  Compare the analyte concentrations in the 1312 extract with
      the levels identified  in  the appropriate  regulations.  Refer to Section
      8.0 for quality assurance requirements.

8.0   QUALITY CONTROL

      8.1    A minimum of one blank (using the same extraction fluid  as used for
the samples) for every 20 extractions that have  been conducted in an extraction
vessel.

      8.2    A  matrix spike  shall  be  performed  for  each waste type  (e.g..
wastewater treatment sludge, contaminated soil,  etc.)  unless the result exceeds
the regulatory level and the data  is being used solely to demonstrate that the
waste property exceeds the regulatory level.  A minimum of one matrix spike must
be analyzed for each analytical batch. The bias determined from the matrix spike
determination shall  be used to correct the measured values.  (See  Steps 8.2.4 and
8.2.5)  As a minimum,  follow the matrix spike addition  guidance provided in each
analytical method.

             8.2.1  Matrix spikes  are to be added after filtration of the 1312
      extract and before preservation.   Matrix spikes  should not be added prior
      to  1312 extraction of the sample.
                                   1312  -  18                       Revision 0
                                                                  November  1990

-------
             8.2.2   In most cases, matrix  spike  levels should be  added  at a
      concentration equivalent to the  corresponding  regulatory  level.   If the
      analyte concentration  is  less than one  half the regulatory  level,  the
      spike  concentration  may  be  as   low   as   one  half  of  the  analyte
      concentration, but may not be less  than  five times  the method detection
      limit.  In order  to avoid differences in matrix effects,  the matrix spikes
      must be added to  the same nominal  volume of 1312 extract  as that which was
      analyzed for the unspiked sample.

             8.2.3   The  purpose  of  the  matrix  spike   is  to  monitor  the
      performance  of  the analytical methods  used,  and to determine  whether
      matrix interferences exist.  Use of other internal  calibration methods,
      modification of  the  analytical  methods,  or  use  of  alternate  analytical
      methods may be needed to accurately measure the analyte concentration in
      the  1312  extract when  the recovery  of  the matrix  spike is  below  the
      expected analytical method performance.

             8.2.4   Matrix  spike  recoveries are  calculated  by the following
      formula:

             %R  (% Recovery) = 100 (Xs - Xu) /  K

      where:
             Xs = measured value for the spiked sample
             Xu = measured value for the unspiked sample,  and
             K  = known value of the spike in  the sample.

             8.2.5   Measured values are corrected for analytical bias using the
      following formula:

             Xc = 100  (Xu /  %R)

      where:
             Xc = corrected value,  and
             Xu = measured value of the unspiked sample.

      8.3  All  quality  control measures described  in the appropriate analytical
methods shall be followed.

      8.4   Samples must  undergo  1312 extraction within  the  following  time
periods:
                                   1312  -  19                       Revision 0
                                                                  November 1990

-------
                      SAMPLE  MAXIMUM  HOLDING TIMES  (davs)








Volatiles
Semi -
volatiles
Mercury
Metals,
except
mercury
From: Field
Collec-
tion

To: 1312
extrac-
tion

14

14
28

180

From: 1312
extrac-
tion

To: Prepara-
tive
extrac-
tion
NA

7
NA

NA

From: Prepara-
tive
extrac-
tion

To: determi-
native
analysis
14

40
28

180

Total
Elapsed
Time





28

61
56

360

NA = Not Applicable
If sample holding  times  are exceeded, the values  obtained  will  be considered
minimal  concentrations.    Exceeding  the  holding  time  is  not  acceptable  in
establishing that a waste does not exceed the regulatory level.  Exceeding the
holding  time  will  not  invalidate characterization  if  the  waste  exceeds  the
regulatory level.

9.0   METHOD PERFORMANCE

      9.1    Precision results for semi-volatiles and metals:  An eastern soil
with high organic content and a western soil with low organic content were used
for the semi-volatile and metal leaching experiments.  Both  types of soil were
analyzed prior to contaminant spiking.  The results are shown in Table 6.  The
concentrations  of  contaminants   leached   from  the  soils  were  consistently
reproducible, as shown  by the low relative standard deviations  (RSDs)  of the
recoveries (generally less than 10 % for most of the compounds).

      9.2    Precision results for volatiles:  Four different soils were spiked
and tested for the  extraction  of volatiles.  Soils One and Two were from western
and eastern Superfund sites.   Soils Three  and Four were mixtures of a western
soil with low organic content and  two  different municipal sludges.  The results
are shown  in  Table 7.   Extract  concentrations  of volatile  organics  from the
eastern soil were lower than from the western soil.  Replicate Teachings of Soils
Three and  Four  showed lower  precision than  the leachates  from  the Superfund
soils.
                                   1312  -  20
Revision 0
November 1990

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10.0  REFERENCES

1.0   Environmental Monitoring Systems Laboratory, "QA Support for RCRA Testing:
      Annual Report".  EPA Contract 68-03-3249, January 1989.

2.0   Research Triangle Institute,  "Interlaboratory  Comparison of Methods 1310,
      1311, and 1312 for Lead in Soil".   U.S. EPA Contract 68-01-7075, November
      1988.
                                   1312  -  21                       Revision 0
                                                                  November 1990

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                         Table 1.  Volatile Analytes1
Compound                                                      CAS No.
Acetone                                                      67-64-1
Benzene                                                      71-43-2
n-Butyl alcohol                                              71-36-3
Carbon disulfide                                             75-15-0
Carbon tetrachloride                                         56-23-5
Chlorobenzene                                                108-90-7
Chloroform                                                   67-66-3
1,2-Dichloroethane                                           107-06-2
1,1-Dichloroethylene                                         75-35-4
Ethyl acetate                                                141-78-6
Ethyl benzene                                                100-41-4
Ethyl ether                                                  60-29-7
Isobutanol                                                   78-83-1
Methanol                                                     67-56-1
Methylene chloride                                           75-09-2
Methyl ethyl ketone                                          78-93-3
Methyl isobutyl ketone                                       108-10-1
Tetrachloroethylene                                          127-18-4
Toluene                                                      108-88-3
1,1,1,-Trichloroethane                                       71-55-6
Trichloroethylene                                            79-01-6
Trichlorofluoromethane                                       75-69-4
l,l,2-Trichloro-l,2,2-trifluoroethane                        76-13-1
Vinyl chloride                                               75-01-4
Xylene                                                      1330-20-7
  When testing for any or all  of these analytes,  the zero-headspace extractor
  vessel  shall be used instead of the bottle extractor.
                                   1312  -  22                       Revision 0
                                                                  November 1990

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                Table  2.  Suitable  Rotary Agitation Apparatus1
Company
Location
 Model  No.
Analytical Testing and
  Consulting Services,
  Inc.

Associated Design and
  Manufacturing Company
Environmental Machine and
  Design, Inc.

IRA Machine Shop and
  Laboratory

Lars Lande Manufacturing
Millipore Corp.
Warrington, PA
 (215) 343-4490
Alexandria, VA
(703) 549-5999
Lynchburg, VA
(804) 845-6424

Santurce, PR
(809) 752-4004
 4-vessel  extractor (DC20S);
 8-vessel  extractor (DC20);
12-vessel  extractor (DC20B)
 2-vessel
 4-vessel
 6-vessel
 8-vessel
12-vessel
24-vessel
(3740-2);
(3740-4);
(3740-6);
(3740-8);
(3740-12);
(3740-24)
 8-vessel (08-00-00)
 4-vessel (04-00-00)

 8-vessel (011001)
Whitmore Lake, MI 10-vessel (10VRE)
(313) 449-4116     5-vessel (5VRE)
Bedford, MA
(800) 225-3384
 4-ZHE or
 4 l-liter
 bottle extractor
 (YT300RAHW)
1  Any device that  rotates the extraction vessel in an end-over-end fashion at 30
±2 rpm is acceptable.
                                   1312 - 23
                                  Revision 0
                                  November  1990

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             Table 3.  Suitable Zero-Headspace  Extractor Vessels1
Company
Location
Model No.
Analytical Testing &
  Consulting Services, Inc.

Associated Design and
  Manufacturing Company

Lars Lande Manufacturing2
Millipore Corporation


Environmental Machine
and Design, Inc.
Warrington, PA
(215) 343-4490

Alexandria, VA
(703) 549-5999

Whitmore Lake, MI
(313) 449-4116

Bedford, MA
(800) 225-3384

Lynchburg, VA
(804) 845-6424
C102, Mechanical
Pressure Device

3745-ZHE, Gas
Pressure Device

ZHE-11,  Gas
Pressure Device

YT30090HW, Gas
Pressure Device

VOLA-TOX1, Gas
Pressure Device
1  Any device that meets the specifications listed in Step 4.2.1  of the method is
suitable.

2  This  device  uses  a 110 mm filter.
                                   1312  -  24
                                  Revision 0
                                  November  1990

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                      Table 4.  Suitable Filter Holders1
Company
Nucleopore Corporation
Micro Filtration
Systems
Millipore Corporation
Location
Pleasanton, CA
(800) 882-7711
Dublin, CA
(800) 334-7132
(415) 828-6010
Bedford, MA
(800) 225-3384
Model/
Catalogue #
425910
410400
302400
311400
YT30142HW
XX1004700
Size
142 mm
47 mm
142 mm
47 mm
142 mm
47 mm
1  Any device  capable  of separating the liquid from the solid phase of the waste
is suitable,  providing that it is chemically compatible with the waste and the
constituents to be analyzed.  Plastic devices (not listed above) may be used when
only  inorganic  analytes are  of  concern.   The 142 mm  size  filter  holder is
recommended.
                       Table 5.  Suitable Filter Media1
Company
Millipore Corporation
Nucleopore Corporation
Whatman Laboratory
Products, Inc.
Micro Filtration
Systems
Location Model
Bedford, MA AP40
(800) 225-3384
Pleasanton, CA 211625
(415) 463-2530
Clifton, NJ GFF
(201) 773-5800
Dublin, CA GF75
(800) 334-7132
(415) 828-6010
Pore
Size
(Mm)
0.7
0.7
0.7
0.7
1  Any filter that meets the specifications  in Step 4.4 of the Method is suitable.
                                   1312  -  25                       Revision 0
                                                                  November 1990

-------
  TABLE 6 - METHOD 1312 PRECISION RESULTS FOR SEMI-VOLATILES AND METALS
Eastern Soil (t>H 4.



FORTIFIED ANALYTES
bis(2-chloroethyl) -
ether
2-Chlorophenol
1,4-Dichlorobenzene
1 , 2 -Dichlorobenzene
2 -Methylphenol
Nitrobenzene
2 , 4 - D ime thy Ipheno 1
Hexachlorobutadiene
Acenaphthene
2,4-Dinitrophenol
2 , 4-Dinitrotoluene
Hexachlorobenzene
gamma BHC (Lindane)
beta BHC
METALS
Lead
Cadmium
Amount
Spiked
(Mg)

1040
1620
2000
8920
3940
1010
1460
6300
3640
1300
1900
1840
7440
640

5000
1000
* •= Triplicate analyses.
** = Duplicate analyses: one v
Amount
Recovered*
(Mg)

834
1010
344
1010
1860
812
200
95
210
896**
1150
3.7
230
35

70
387
alue was rejc

% RSD


12.5
6.8
12.3
8.0
7.7
10.0
18.4
12.9
8.1
6.1
5.4
12.0
16.3
13.3

4.3
2.3
jcted as
,2) Western Soil (vti 5.0)
Amount
Recovered*
(Mg)

616
525
272
1520
1130
457
18
280
310**
23**
585
10
1240
65.3

10
91
an outlier at the

% RSD


14.2
54.9
34.6
28.4
32.6
21.3
87.6
22.8
7.7
15.7
54.4
173.2
55.2
51.7

51.7
71.3
90%
confidence level using the Dixon Q test.
                               1312 -  26
Revision 0
November 1990

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                    TABLE 7 - METHOD 1312 PRECISION RESULTS FOR VOLATILES


Soil

No. 1

(Western)

ound Name
:one
•lonitrile
ene
ityl Alcohol
-Butanol)
ion disulfide
ion tetrachloride
irobenzene
iroform
Dichloroe thane
Dichloroethane
•1 acetate
'Ibenzene
•1 ether
iutanol (4 -Methyl
.-propanol)
tylene chloride
iyl ethyl ketone
:-Butanone)
iyl isobutyl
:tone
1,2-Tetrachloro-
:hane
2,2-Tetrachloro-
:hane
•achloroethene
tene
1-Trichloro-
:hane
2-Trichloro-
:hane
ihloroethene
i_ i _ ~_
inloro-
.uororae thane
2-Trichloro-
•ifluoroe thane
rl chloride
Avg.
%Rec.
44.0
52.5
47.8

55.5
21.4
40.6
64.4
61.3
73.4
31.4
76.4
56.2
48.0

0.0
47.5

56.7

81.1

69.0

85.3
45.1
59.2

47.2

76.2
54.5
20.7

18.1
10.2

* %RSD
12.4
68.4
8.29

2.91
16.4
18.6
6.76
8.04
4.59
14.5
9.65
9.22
16.4

ND
30.3

5.94

10.3

6.73

7.04
12.7
8.06

16.0

5.72
11.1
24.5

26.7
20.3
Soil

No. 2

(Eastern)
Avg.
%Rec.
43.8
50.5
34.8

49.2
12.9
22.3
41.5
54.8
68.7
22.9
75.4
23.2
55.1

0.0
42.2

61.9

88.9

41.1

58.9
15.2
49.3

33.8

67.3
39.4
12.6

6.95
7.17

* %RSD
2.25
70.0
16.3

14.6
49.5
29.1
13.1
16.4
11.3
39.3
4.02
11.5
9.72

ND
42.9

3.94

2.99

11.3

4.15
17.4
10.5

22.8

8.43
19.5
60.1

58.0
72.8
Soil No
(Western
Sludge)
Avg.
%Rec . **
116.0
49.3
49.8

65.5
36.5
36.2
44.2
61.8
58.3
32.0
23.0
37.5
37.3

61.8
52.0

73.7

58.3

50.8

64.0
26.2
45.7

40.7

61.7
38.8
28.5

21.5
25.0
. 3
and


%RSD
11.5
44.9
36.7

37.2
51.5
41.4
32.0
29.1
33.3
54.4
119.8
36.1
31.2

37.7
37.4

31.3

32.6

31.5

25.7
44.0
35.2

40.6

28.0
40.9
34.0

67.8
61.0
Soil No. 4
(Western and
Sludge)
Avg.
%Rec.*** %RSD
21.3 71.4
51.8 4.6
33.4 41.1

73.0 13.9
21.3 31.5
24.0 34.0
33.0 24.9
45.8 38.6
41.2 37.8
16.8 26.4
11.0 115.5
27.2 28.6
42.0 17.6

76.0 12.2
37.3 16.6

40.6 39.0

39.8 40.3

36.8 23.8

53.6 15.8
18.6 24.2
31.4 37.2

26.2 38.8

46.4 25.4
25.6 34.1
19.8 33.9

15.3 24.8
11.8 25.4
  * Triplicate analyses
 ** Six replicate analyses
*** Five replicate analyses
                                         1312 - 27
Revision 0
November 1990

-------
  Motor
(30 ± 2 rpm
Extraction Vessel Holder
                                 UUU
            Figure 1.   Rotary Agitation Apparatus
                          1312 - 28
                          Revision 0
                          November 1990

-------
                               Liquid Inlet/Outlet Valve
   Top Flange
                  ^•^MMM
      Support Screen S*

                Filter//

       Support Screen
       Viton O-Rings
Bottom Flange
 Pressurized Gas
 Inlet/Outlet Valve
Pressure
 Gauge
                Figure 2.  Zero-Headspace Extractor (ZHE)
                                1312 - 29
                 Revision 0
                 November 1990

-------
                            METHOD 1312

        SYNTHETIC  PRECIPITATION  LEACHING PROCEDURE
   Separate
 liquids from
solids with 0.6
-  0.8 urn glass
 fiber filter
    Discard
    solids
   Separate
 liquids from
solids with 0.6
-  0.8 urn glass
 fiber filter
                                                      Solid
                                      Yes
                         Extract »/
                      appropriate fluid
                      1) Bottle extractor
                      for non-volatile!
                      2) ZHE device for
                          volatile!
    Reduce
 particle size
  to <9.5 mm
                             1312 -  30
                       Revision  0
                       November 1990

-------
                                 METHOD 1312

      SYNTHETIC  PRECIPITATION  LEACHING  PROCEDURE (continued)
Discard
solids
            Solid
Store
at
1 iquid
4 C
   Separate
 extract from
iclida u/ 0.6  -
 0.8 urn glass
 fiber filter
    I
  liquid
compatible \ No
 with the
 extract?
 Measure amount of
liquid and analyze
  (mathematically
 combine result w/
 result of extract
    analysis)
                                             Combine
                                           extract «/
                                           liquid phase
                                            of waste
                                             Analyze
                                             liquid
                                              STOP
                                  1312  - 31
                                                       Revision  0
                                                       November 1990

-------
                                 METHOD 9040A

                         pH ELECTROMETRIC MEASUREMENT
1.0  SCOPE AND APPLICATION

      1.1    Method 9040 is used to measure the pH of aqueous wastes and those
multiphase wastes where the aqueous  phase constitutes at least 20% of the total
volume of the waste.

      1.2    The corrosivity of concentrated acids and bases, or of concentrated
acids and  bases  mixed with  inert  substances, cannot  be measured.   The  pH
measurement requires some water content.

2.0   SUMMARY

      2.1    The pH of the sample is determined electrometrically using either
a glass  electrode  in  combination with a reference potential  or  a combination
electrode.   The measuring  device  is  calibrated  using a series of  standard
solutions of known pH.

3.0   INTERFERENCES
                                                 i
      3.1    The  glass  electrode,  in  general,  is  not  subject to  solution
interferences from color, turbidity, colloidal matter, oxidants, reductants, or
high salinity.

      3.2    Sodium error at pH levels >10 can be reduced or eliminated by using
a low-sodium-error electrode.

      3.3    Coatings  of  oily  material   or   particulate matter  can  impair
electrode response.  These coatings can usually be removed by gentle wiping or
detergent washing,  followed by rinsing with  distilled water.   An  additional
treatment with hydrochloric acid  (1:10) may be necessary to remove any remaining
film.

      3.4    Temperature effects on the  electrometric determination of pH arise
from two  sources.   The first  is  caused  by the change in electrode  output at
various  temperatures.   This  interference  can be controlled  with instruments
having temperature compensation or by calibrating the electrode-instrument system
at the temperature of the samples.   The second source of temperature effects is
the change of pH due to changes in the sample  as the temperature changes.  This
error is sample-dependent and  cannot be controlled.  It should,  therefore, be
noted by reporting both the pH and temperature at the time of analysis.

4.0   APPARATUS AND MATERIALS

      4.1    pH meter:  Laboratory or field model.  Many instruments are commer-
cially available with various specifications and optional  equipment.

      4.2    Glass electrode.
                                   9040A  -  1                       Revision 1
                                                                  November 1990

-------
      4.3    Reference electrode:  A silver-silver chloride or other reference
electrode of constant potential may be used.

NOTE: Combination  electrodes  incorporating  both  measuring  and  referenced
      functions are  convenient  to  use and are available  with  solid,  gel-type
      filling materials that require minimal maintenance.

      4.4    Magnetic stirrer and Teflon-coated stirring bar.

      4.5    Thermometer or temperature sensor for automatic compensation.

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    Primary  standard  buffer  salts  are  available  from  the  National
Institute of Standards and Technology  (Special Publication  260)  and  should be
used in  situations where extreme accuracy is necessary. Preparation of reference
solutions from these salts  requires  some special precautions and handling, such
as low-conductivity dilution  water,  drying ovens, and carbon-dioxide-free purge
gas.  These solutions should be replaced at least once each month.

      5.3    Secondary  standard buffers  may be  prepared  from  NBS  salts  or
purchased as solutions from commercial  vendors.   These  commercially available
solutions  have been  validated  by comparison  with  NIST  standards  and  are
recommended for routine use.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1    All samples must be collected using a sampling plan that addresses
the considerations discussed in Chapter Nine of this manual.

      6.2    Samples should be analyzed as soon as possible.

7.0   PROCEDURE

      7.1    Calibration:

             7.1.1    Because of the wide variety of pH meters and accessories,
      detailed  operating procedures  cannot be incorporated  into  this method.
      Each analyst must  be acquainted  with  the  operation of each  system and
      familiar with all  instrument  functions.  Special attention to care of the
      electrodes is recommended.

             7.1.2    Each  instrument/electrode system  must  be  calibrated at a
      minimum of two points that  bracket the  expected pH of the samples and are
      approximately three pH  units  or more apart.  (For corrosivity characteri-
      zation, the calibration of the pH meter should include a  buffer of pH 2
      for acidic  wastes and  a pH  12  buffer  for caustic  wastes.)    Various

                                  9040A -  2                       Revision 1
                                                                  November 1990

-------
      instrument  designs  may  involve  use   of   a   dial   (to  "balance"  or
      "standardize") or a slope adjustment, as outlined  in the manufacturer's
      instructions.  Repeat adjustments on successive portions of the two buffer
      solutions until readings are within 0.05 pH units of the buffer solution
      value.

      7.2    Place the sample or buffer solution in a clean glass beaker using
a sufficient volume to cover  the sensing elements of the electrodes and to give
adequate clearance for the magnetic stirring  bar.    If field measurements are
being made, the electrodes may be immersed directly  into the sample stream to an
adequate depth and moved in a manner to ensure  sufficient sample movement across
the electrode-sensing element as indicated by  drift-free  readings  (<0.1 pH).

      7.3    If the sample temperature differs by more than 2°C from the buffer
solution, the measured pH values must be corrected.   Instruments are equipped
with automatic or  manual compensators that electronically adjust for temperature
differences.  Refer to manufacturer's instructions.

      7.4    Thoroughly rinse and gently wipe  the electrodes  prior to measuring
pH of samples.  Immerse the electrodes into the sample beaker or sample stream
and gently  stir at a constant rate to provide homogeneity  and  suspension of
solids.   Note and record  sample  pH  and  temperature.  Repeat  measurement on
successive volumes of sample  until values differ by  <0.1 pH units.  Two or three
volume changes are usually sufficient.

8.0   QUALITY CONTROL

      8.1    Refer to Chapter One for specific quality control procedures.

      8.2    Electrodes must be thoroughly rinsed between  samples.

9.0   METHOD PERFORMANCE

      9.1    Forty-four analysts in twenty laboratories analyzed six synthetic
water samples  containing exact  increments  of  hydrogen-hydroxyl  ions,  with the
following results:
                                                            Accuracy as
pH Units

   3.5
   3.5
   7.1
   7.2
   8.0
   8.0
Standard Deviation
     oH  Units

       0.10
       0.11
       0.20
       0.18
       0.13
       0.12
                                                       Bias
-0.29
-0.00
+1.01
-0.03
-0.12
+0.16
  Bias
oH Units

  -0.01

  +0.07
  -0.002
  -0.01
  +0.01
10.0 REFERENCES

1.    National  Institute  of  Standards  and  Technology,
      Material Catalog 1986-87, Special Publication 260.
                                     Standard  Reference
                                   9040A -  3
                                            Revision 1
                                            November 1990

-------
          METHOD  9040A

pH  ELECTROMETRIC MEASUREMENT
             Start
        7.1 Calibrate pH
             meter
       7.2 Place sample or
       buffer solution in
         glass beaker
           7.3 Does
          temperature
         differ by mor
          than 2C from
            buffer?
    7.3 Correct
measured pH values
          7.4 Immerse
        electrodes and
         measure  pH of
            sample
       7.4 Note and  record
       pH and temperature;
       repeat 2 or 3 times
        with different
            volumes
             Stop
           9040A -  4
                     Revision  1
                     November  1990

-------
                                 METHOD 9045A

                               SOIL AND HASTE oH
1.0   SCOPE AND APPLICATION
      1.1    Method 9045  is an electrometric procedure which has been approved
for measuring pH in calcareous and non-calcareous soils and waste samples.

2.0   SUMMARY OF METHOD

      2.1    The  soil  sample  is  mixed  either  with reagent  water or  with a
calcium chloride solution  (see Section  5.0), depending  on whether the soil is
calcareous or non-calcareous,  and  the pH of the resulting  solution is measured.
The waste  sample  is mixed with  reagent  water,  and the  pH of  the resulting
solution is measured.

3.0   INTERFERENCES

      3.1    Samples with  very low or very high pH may give incorrect readings
on  the  meter.    For  samples with  a  true pH  of >10, the measured pH  may be
incorrectly  low.   This  error can  be minimized  by using  a  low-sodium-error
electrode.  Strong acid solutions, with  a true  pH of <1,  may give incorrectly
high pH measurements.

      3.2    Temperature  fluctuations will cause measurement errors.

      3.3    Errors  will   occur  when the electrodes become  coated.    If an
electrode becomes  coated  with  an  oily material  that will  not  rinse free, the
electrode can either (1)  be cleaned  with  an  ultrasonic  bath,  or (2) be washed
with detergent, rinsed  several  times  with water, placed  in 1:10 HC1 so that the
lower third of the electrode is submerged,  and then thoroughly rinsed with water.

4.0   APPARATUS AND MATERIALS

      4.1    pH Meter with means for temperature compensation.

      4.2    Electrodes:

             4.2.1   Calomel  electrode.

             4.2.2   Glass electrode.

             4.2.3   A combination electrode can be employed instead of calomel
      or glass.

      4.3    Beaker:   50-mL.

      4.4    Class A volumetric flasks:    1 L and 2 L.

      4.5    Analytical  balance:   capable of weighing 0.1 g.

      4.6    Aluminum foil.

                                  9045A  - 1                       Revision 1
                                                                  November 1990

-------
5.0  REAGENTS

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

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

      5.3    Primary  standard buffer  salts  are available  from  the National
Institute of Standards  and Technology  (NIST)  and should  be  used  in situations
where extreme accuracy  is  necessary.   Preparation  of reference solutions from
these  salts requires  some  special  precautions and  handling,  such as  low-
conductivity dilution water,  drying ovens,  and carbon-dioxide-free purge gas.
These solutions should be replaced at least once each month.

      5.4    Secondary  standard  buffers  may  be  prepared from NIST  salts  or
purchased as solutions  from  commercial  vendors.  These  commercially available
solutions,   which  have been  validated  by comparison  with NIST standards,  are
recommended for routine use.

      5.5    Stock calcium chloride solution  (CaCl2),  3.6 M:   Dissolve 1059 g of
CaCl? • 2H20 in  reagent  water in  a  2-liter Class  A  volumetric flask.   Cool the
solution, dilute it to volume with  reagent water,  and  mix  it  well.  Dilute 20 ml
of this solution to 1  liter with reagent water in  a Class A volumetric flask and
standardize it  by titrating a 25-mL  aliquot of the diluted solution with standard
0.1 N AgN03, using 1  ml  of 5% K2Cr04 as the indicator.

      5.6    Calcium chloride (CaCl,),  0.01 M:  Dilute 5 ml of stock 3.6  M CaCl,
to 1.8 liters with reagent water.  If the pH of this  solution is  not between 5
and 6.5, adjust  the  pH  by adding a little Ca(OH)2  or HC1.    As a  check  on the
preparation of  this solution, measure its electrical conductivity.  The specific
conductivity should be 2.32 ± 0.08 umho per cm at 25°C.

      5.7    Hydrochloric acid (HC1):  1:3 mixture with reagent water.

      5.8    Silver nitrate  (AgN03), 0.1N:  volumetric standard.

      5.9    Potassium  chromate  (K2Cr04), 5%.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1    All samples must be collected using  a sampling  plan that addresses
the considerations discussed in Chapter Nine of this  manual.

      6.2    Samples  should  be analyzed  as soon as possible.

7.0   PROCEDURE

      7.1  Calibration:
                                   9045A  -  2                       Revision 1
                                                                  November 1990

-------
       7.1.1    Because  of the wide variety of pH meters and accessories,
detailed operating  procedures  cannot be incorporated  into  this method.
Each analyst  must  be acquainted with  the  operation of each  system and
familiar with all  instrument functions.  Special attention to care of the
electrodes is recommended.

       7.1.2    Each instrument/electrode  system must be calibrated at a
minimum of two points that bracket the expected  pH of the samples and are
approximately  three pH  units   or  more apart.    Repeat adjustments  on
successive portions of the two  buffer solutions  until readings are within
0.05 pH units of the buffer solution value.

7.2    Determination of calcareous vs. non-calcareous soils:

       7.2.1    Place approximately 0.5 g of sample (less than 60 mesh) on
a piece of aluminum foil.

       7.2.2    Add one  or two drops  of   1:3  HC1  to  the  sample.   The
presence of CaC03  is indicated  by  a  bubbling  or audible fizz.

       7.2.3    If   the  sample   produces  bubbling   or fizzing,  it  is  a
calcareous soil.  If no bubbling or fizzing occurs, the sample is a non-
calcareous soil.

7.3    Sample preparation  and pH measurement of non-calcareous soils:

       7.3.1    To  20 g of soil in a 50-mL beaker,  add 20  mL of reagent
water and stir the  suspension several times during the next 30 min.

       7.3.2    Let the  soil suspension stand for about  1 hr to allow most
of the suspended clay to settle out from the suspension.

       7.3.3    Adjust the electrodes in the clamps of the electrode holder
so that,  upon  lowering the electrodes into  the beaker, the glass electrode
will be immersed just deep enough into the clear supernatant solution to
establish a good electrical contact through the  ground-glass joint or the
fiber-capillary hole.  Insert the electrodes into  the sample solution in
this  manner.    For  combination  electrodes,   immerse  just  below  the
suspension.

       7.3.4    If  the sample temperature differs by more than 2°C from the
buffer solution, the measured pH values must be corrected.

       7.3.5    Report the results as "soil pH  measured in  water."

7.4    Sample preparation  and pH measurement of calcareous soils:

       7.4.1    To  10 g of  soil in  a 50-mL beaker, add 20 mL  of  0.01 M
CaCl2 (Step 5.6) solution and stir the suspension several times during the
next 30 min.

       7.4.2    Let the soil suspension stand for  about 30  min to allow
most of the suspended clay to settle out from the  suspension.
                             9045A  -  3                       Revision 1
                                                            November 1990

-------
             7.4.3    Adjust the electrodes in the clamps of the electrode holder
      so that,  upon  lowering the electrodes into the beaker, the glass electrode
      will be immersed well into the partly settled suspension and the calomel
      electrode will  be  immersed  just deep enough  into  the  clear supernatant
      solution to establish a good electrical contact through the ground-glass
      joint or the fiber-capillary hole.  Insert the electrode into the sample
      solution in this manner.

             7.4.4    If  the sample temperature  differs by more than 2°C from the
      buffer solution, the measured pH values must be corrected.

             7.4.5    Report the results  as  "soil pH measured in 0.01 M CaCl2".

      7.5    Sample preparation and pH measurement of waste materials:

             7.5.1    To  20  g of waste sample in a 50-mL beaker add  20 ml reagent
      water and stir the suspension several  times during the next 30 min.

             7.5.2    Let the  waste suspension  stand for about 15 min to allow
      most of the suspended waste to settle out from the suspension.

NOTE:        If  the  waste  is hydroscopic and  absorbs all the reagent  water,
             begin the experiment  again using 20 g of waste and 40  ml of reagent
             water.

NOTE:        If  the  supernatant  is multiphasic,  decant  the  oily  phase  and
             measure the pH of the aqueous phase.   The electrode may need to be
             cleaned  (Step  3.3) if it becomes coated with an oily material.

             7.5.3    Adjust the electrodes in the clamps of the electrode holder
      so that,  upon  lowering the electrodes into the beaker, the glass electrode
      will be immersed just deep enough  into the clear supernatant to establish
      a good electrical  contact through the ground-glass joint or  the  fiber-
      capillary hole.  Insert the  electrodes into  the  sample solution  in  this
      manner.  For combination electrodes,  immerse just below the suspension.

             7.5.4    If  the sample temperature  differs by more than 2°C from the
      buffer solution, the measured pH values must be corrected.

             7.5.5    Report the results  as  "waste  pH measured in  water."

8.0   QUALITY CONTROL

      8.1    Refer to Chapter One for specific quality control procedures.

      8.2    Electrodes must be thoroughly rinsed between samples.

9.0  METHOD PERFORMANCE

      9.1  No data provided.

10.0  REFERENCES

1.0   Black, Charles  Allen;  Methods  of Soil  Analysis;  American Society  of
      Agronomy:  Madison, WI,  1973.


                                   9045A  - 4                       Revision 1
                                                                  November 1990

-------
                           METHOD  9045A
                        SOIL AND WASTE pH
                             START
                          7 1 Calibrate
                             each
                          ins t rument/
                           elect rode
                            ays tern
  7.2.1  Place
 0 5 g sample
  on aluminum
     foil
                         7.S.I Add
                        water to 20 g
                        was te;  stir
                                                    7  5  2 Let
                                                      was te
                                                   suspension
                                                  stand  for 15
                                                    minu tea
   7  4.1 Add
   calcium
   chloride
solution to lOg
  soil; stir
   7  4  2 Let
     soi 1
  suspension
-stand  for 30
   minu tes
                           7.3.1 Add
                         water to 20 g
                          soil;  stir
 7 3 2  Let
   soil
suspension
stand for 1
   hour
    Is
supernatan t
u 1 tiphasic?
                                                 Repeat
                                               experiment
                                                with  20 g
                                              waste and 40
                                                mL water
 Decant  oily
   phase.
measure  pH  of
aqueous  phase
                             9045A  -  5
                                            Revision  1
                                            November  1990

-------
   METHOD  9045A
SOIL  AND WASTE pH
    (CONTINUED)
      Insert
    eleclrodej
    into sample
     solution
                          Correct
                         measured pH
                          values
    9045A - 6
Revision 1
November  1990

-------
                                  METHOD 9056

                          AN ION CHROMATOGRAPHY METHOD
1.0   SCOPE AND APPLICATION

      1.1   This  method  addresses the sequential determination  of the anions
chloride,  fluoride,  bromide,  nitrate, nitrite, phosphate,  and  sulfate in the
collection solutions from the  bomb combustion of solid waste samples,  as well as
all water  samples.

      1.2   The minimum  detection limit  (MDL),  the  minimum concentration of a
substance  that can be measured and reported with 99% confidence that the value
is  above  zero,   varies  for  anions   as  a  function of  sample  size  and  the
conductivity scale used.  Generally, minimum detectable concentrations are in the
range of 0.05 mg/L for F- and 0.1 mg/L for Br", Cl", N03",  N02",  P04 , and SO,
with a 100-/zL sample loop and a  10-umho full-scale  setting on the conductivity
detector.  Similar values may  be  achieved by using a  higher scale  setting and an
electronic integrator.  Idealized detection limits of an order of magnitude lower
have been determined  in reagent water by using a 1 umho full-scale  setting (Table
1).

      The upper limit of  the method is dependent on total  anion concentration and
may be determined experimentally.  These limits may be extended by appropriate
dilution.

2.0   SUMMARY OF METHOD

      A small volume of  combustate collection  solution  or other water sample,
typically  2 to 3 ml, is  injected  into an ion chromatograph to flush and fill a
constant  volume  sample  loop.    The  sample is  then  injected into  a  stream of
carbonate-bicarbonate eluent of the  same  strength as the collection solution or
water sample.

      The sample is pumped through three different ion exchange columns  and into
a conductivity detector.   The  first two columns, a precolumn or guard column and
a separator column, are packed  with low-capacity, strongly basic anion exchanger.
Ions are separated into discrete bands based on their affinity for the exchange
sites of  the  resin.   The last column is a suppressor column that reduces the
background conductivity of the eluent to  a  low or negligible  level and converts
the anions in the sample  to  their corresponding acids.  The separated anions in
their acid form are measured using an electrical-conductivity cell.  Anions are
identified  based  on  their  retention   times  compared  to  known  standards.
Quantitation is accomplished by measuring the peak height or  area and comparing
it to a calibration curve generated from known standards.

3.0   INTERFERENCES

      3.1   Any species with a retention time similar to  that of the desired ion
will interfere.  Large quantities of ions eluting close to the ion of interest
will also result  in an interference.   Separation can be improved by adjusting the
eluent concentration and/or flow rate.


                                   9056 - 1                       Revision 0
                                                                  November 1990

-------
      Sample dilution and/or the use of the method of standard additions can also
be used.

      For example,  high  levels  of organic acids may  be  present in industrial
wastes, which may interfere with inorganic anion analysis.  Two common species,
formate and acetate, elute between fluoride and chloride.

      3.2   Because  bromide  and nitrate elute  very close together,  they are
potential  interferents  for  each  other.  It is advisable not to have Br"/N03"
ratios higher than 1:10 or 10:1  if both anions are  to be quantified.  If nitrate
is observed to  be an interference with bromide, use  of  an  alternate detector
(e.g.. electrochemical detector) is recommended.

      3.3   Method  interferences may  be caused  by  contaminants  in the reagent
water, reagents, glassware, and other sample processing apparatus that lead to
discrete artifacts or elevated baseline in ion chromatograms.

      3.4   Samples  that  contain particles  larger than  0.45  urn  and  reagent
solutions that  contain particles  larger  than 0.20 jum  require  filtration to
prevent damage to instrument columns and flow systems.

      3.5   If a packed bed suppressor column  is used, it will  be  slowly consumed
during analysis and, therefore, will  need to be regenerated.  Use of either an
anion fiber suppressor or  an anion micromembrane suppressor eliminates the time-
consuming regeneration step through the use of a continuous flow of regenerant.

4.0   APPARATUS AND MATERIALS

      4.1   Ion chromatograph,  capable  of  delivering  2 to 5 ml of eluent per
minute at a  pressure of 200 to 700 psi  (1.3 to 4.8 MPa). The chromatograph shall
be equipped with an injection valve,  a 100-juL sample loop, and set up with the
following components, as  schematically illustrated in  Figure 1.

            4.1.1    Precolumn, a guard column  placed before the separator column
      to  protect  the separator  column from  being  fouled by particulates or
      certain organic constituents (4 x 50 mm, Dionex  P/N 030825 [normal  run],
      or P/N 030830  [fast run], or equivalent).

            4.1.2    Separator   column,   a  column   packed  with  low-capacity
      pellicular anion exchange resin that is styrene  divinylbenzene-based has
      been found to be suitable  for resolving  F", CT,  N02", P04   , Br",  N03", and
      SO/2  (see  Figure 2) (4 x 250 mm, Dionex  P/N  03827 [normal  run],  or P/N
      030831 [fast run],   or equivalent).

            4.1.3    Suppressor  column,  a column that  is  capable of converting
      the eluent  and separated  anions to their respective  acid forms (fiber,
      Dionex P/N 35350, micromembrane, Dionex P/N  38019 or equivalent).

            4.1.4    Detector,    a    low-volume,   flowthrough,    temperature-
      compensated,  electrical  conductivity cell  (approximately 6  pi  volume,
      Dionex, or equivalent) equipped with  a meter  capable of reading from 0 to
      1,000 iuseconds/cm on a linear scale.
                                   9056 - 2                       Revision 0
                                                                  November  1990

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            4.1.5    Pump, capable of delivering a constant flow of approximately
      2 to 5 mL/min throughout the test  and tolerating a pressure of 200 to 700
      psi (1.3 to 4.8 MPa).

      4.2   Recorder,  compatible  with the detector  output with  a  full-scale
response time in 2 seconds or less.

      4.3   Syringe, minimum capacity of 2 ml  and equipped with a male pressure
fitting.

      4.4   Eluent and regenerant  reservoirs,  suitable  containers for storing
eluents and regenerant.  For example, 4 L collapsible bags can be used.

      4.5   Integrator, to integrate the area under the chromatogram.  Different
integrators can perform this  task when  compatible  with  the electronics of the
detector  meter  or  recorder.    If  an integrator  is used,  the  maximum  area
measurement must be within the linear range of the integrator.

      4.6   Analytical balance, capable of weighing to the nearest 0.0001 g.

      4.7   Pipets, Class A volumetric flasks, beakers:   assorted sizes.

5.0   REAGENTS

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

      5.2   Reagent water.   All  references to water in this method  refer to
reagent water, as  defined in Chapter One.  Column life may be extended by passing
reagent water through a 0.22-/am filter prior to use.

      5.3   Eluent, 0.003M NaHC03/0.0024M Na2C03.   Dissolve 1.0080 g of sodium
bicarbonate (0.003M NaHC03) and 1.0176 g of sodium carbonate (0.0024M Na2C03) in
reagent water and dilute to 4 L with reagent water.

      5.4   Suppressor regenerant  solution.   Add  100 ml of IN H?S04  to 3 L of
reagent water in a collapsible bag and dilute to 4 L with reagent water.

      5.5   Stock solutions (1,000 mg/L).

            5.5.1    Bromide  stock  solution   (1.00  ml  =  1.00  mg Br").   Dry
      approximately 2 g of sodium bromide (NaBr) for  6 hours at 150°C, and cool
      in a desiccator.  Dissolve  1.2877  g of  the  dried  salt  in reagent water,
      and dilute to 1 L with reagent water.

            5.5.2    Chloride  stock solution (1.00  ml  = 1.00 mg CT).  Dry sodium
      chloride (NaCl) for 1 hour at 600°C, and cool in a desiccator.  Dissolve
      1.6484 g of the dry  salt in  reagent water, and dilute to 1 L with reagent
      water.

                                   9056 - 3                       Revision 0
                                                                  November  1990

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            5.5.3    Fluoride  stock solution  (1.00 ml = 1.00 mg F").  Dissolve
      2.2100 g of sodium fluoride  (NaF) in reagent water, and dilute to 1  L with
      reagent water.  Store in chemical-resistant glass or polyethylene.

            5.5.4    Nitrate  stock  solution  (1.00  ml  =  1.00  mg  NO,").   Dry
      approximately  2 g  of sodium  nitrate   (NaNO,)  at  105°C  for  24  hours.
      Dissolve exactly 1.3707 g of the dried salt in reagent water, and  dilute
      to 1 L with reagent water.

            5.5.5    Nitrite  stock solution  (1.00  ml = 1.00 mg N02").   Place
      approximately 2 g of sodium nitrate (NaN02)  in a  125 ml beaker and  dry to
      constant weight (about 24 hours) in a desiccator containing concentrated
      H2SO,.   Dissolve 1.4998  g  of the dried  salt in reagent water, and  dilute
      to  1  L with  reagent  water.   Store  in  a  sterilized  glass bottle.
      Refrigerate and prepare monthly.

NOTE:       Nitrite is easily oxidized, especially in the  presence of  moisture,
            and only fresh reagents are to be used.

NOTE:       Prepare sterile bottles for storing nitrite solutions by heating for
            1 hour at 170°C in an  air  oven.

            5.5.6    Phosphate stock solution  (1.00 ml = 1.00 mg P043").  Dissolve
      1.4330 g of potassium dihydrogen phosphate (KH2P04)  in reagent water, and
      dilute to 1 L with reagent water.  Dry  sodium sulfate (Na2S04) for  1 hour
      at 105°C and cool  in a desiccator.

            5.5.7    Sulfate stock solution (1.00 ml  = 1.00 mg S042").  Dissolve
      1.4790  g  of the  dried  salt  in  reagent  water, and  dilute  to  1  L with
      reagent water.

      5.6   Anion  working solutions.    Prepare  a  blank  and  at   least  three
different working solutions containing the following  combinations of anions.  The
combination anion solutions must be prepared  in  Class A  volumetric flasks.  See
Table 2.

            5.6.1    Prepare  a high-range  standard  solution  by diluting  the
      volumes of each anion specified  in  Table  2  together to 1  L  with reagent
      water.

            5.6.2    Prepare the intermediate-range standard solution by diluting
      10.0 ml of the high-range standard solution (see Table 2)  to 100 mL with
      reagent water.

            5.6.3    Prepare the low-range standard solution by diluting 20.0 ml
      of the intermediate-range standard solution (see Table 2)  to 100 ml with
      reagent water.

      5.7   Stability of standards.  Stock standards are stable for at least 1
month when stored at 4°C.  Dilute working standards  should be prepared weekly,
except those that contain nitrite  and  phosphate, which should be prepared fresh
daily.
                                   9056 - 4                       Revision 0
                                                                  November 1990

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6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

      6.2   Analyze the samples as soon as possible after collection.  Preserve
by refrigeration at 4°C.

7.0   PROCEDURE

      7.1   Calibration

            7.1.1    Establish   ion   chromatographic   operating   parameters
      equivalent to those indicated in Table 1.

            7.1.2    For each analyte of interest, prepare calibration standards
      at  a minimum  of  three  concentration  levels  and  a   blank  by  adding
      accurately measured volumes of  one or more stock standards  to a  Class A
      volumetric flask and diluting  to  volume  with  reagent water.    If  the
      working range exceeds the linear range of the system, a sufficient number
      of standards  must be  analyzed to allow an accurate calibration curve to be
      established.   One of the standards  should  be  representative of a  concen-
      tration  near,  but above, the  method  detection limit  if the  system  is
      operated on an applicable attenuator range.  The other standards should
      correspond to the range of concentrations expected in the sample or should
      define the working range of the detector.   Unless  the attenuator range
      settings  are  proven  to  be  linear,  each  setting  must  be  calibrated
      individually.

            7.1.3    Using  injections  of 0.1 to 1.0 mL (determined by injection
      loop volume)  of  each  calibration standard, tabulate peak  height  or area
      responses against the concentration.  The  results  are  used  to prepare a
      calibration curve  for each analyte.   During this  procedure,  retention
      times must be recorded.   The retention time is  inversely proportional  to
      the concentration.

            7.1.4    The  working  calibration  curve  must  be  verified  on  each
      working day,  or whenever the anion eluent is changed, and for every batch
      of samples.   If the response or retention time for any analyte varies from
      the expected  values by more than ± 10%,  the test must be repeated, using
      fresh calibration standards.  If the results are still more than ± 10%,  an
      entirely new  calibration curve must be prepared for that analyte.

            7.1.5    Nonlinear  response  can result when  the  separator column
      capacity is exceeded (overloading).   Maximum  column loading (all  anions)
      should not exceed about 400 ppm.

      7.2   Analyses

            7.2.1    Sample preparation.  When  aqueous  samples are injected,  the
      water passes  rapidly through the columns,  and  a negative  "water  dip"  is
      observed  that may   interfere  with the early-eluting  fluoride  and/or
      chloride ions.   The  water dip should  not  be observed  in  the  combustate
      samples; the  collecting  solution is a concentrated  eluent  solution  that

                                   9056 -  5                        Revision  0
                                                                  November 1990

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will "match" the eluent strength when diluted to 100-mL with reagent water
according to  the bomb combustion procedure.   Any  dilutions  required in
analyzing other  water samples  should be made  with  the  eluent solution.
The water dip, if present, may be removed by  adding concentrated eluent to
all samples and standards.   When  a manual system is used, it is necessary
to  micropipet concentrated buffer  into each  sample.    The  recommended
procedures follow:

(1)   Prepare a  100-mL stock of eluent 100 times normal  concentration by
      dissolving  2.5202  g  NaHCO, and 2.5438 g Na2C03 in  100-mL  reagent
      water.  Protect the volumetric flask from air.

(2)   Pipet 5 mL of each sample into a  clean  polystyrene micro-beaker.
      Micropipet 50 nl of the concentrated buffer into the beaker and stir
      well.

Dilute the samples with eluent, if necessary, to concentrations within the
linear range of the calibration.

      7.2.2   Sample  analysis.

              7.2.2.1    Start   the   flow   of   regenerant   through  the
      supressor column.

              7.2.2.2    Set up the recorder range for maximum sensitivity
      and any additional  ranges needed.

              7.2.2.3    Begin to pump  the  eluent through  the  columns.
      After a stable baseline is obtained, inject a midrange standard.  If
      the peak height  deviates  by more than  10% from that of the previous
      run, prepare fresh  standards.

              7.2.2.4    Begin  to  inject  standards starting with  the
      highest concentration standard and decreasing  in concentration.  The
      first sample should be a quality control  reference sample to check
      the calibration.

              7.2.2.5    Using the  procedures  described in Step  7.2.1,
      calculate the regression  parameters for the initial standard curve.
      Compare these  values with those  obtained in  the  past.   If they
      exceed  the control  limits,  stop   the analysis and  look for  the
      problem.

              7.2.2.6    Inject  a quality  control  reference  sample.   A
      spiked  sample or a sample  of  known content must  be  analyzed with
      each  batch  of  samples.    Calculate  the concentration  from  the
      calibration  curve  and compare  the  known value.   If the  control
      limits are exceeded,  stop the  analysis until  the  problem is found.
      Recalibration is necessary.

              7.2.2.7    When an acceptable value  has been  obtained for
      the quality control sample, begin  to inject the samples.
                             9056 - 6                       Revision 0
                                                            November 1990

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                     7.2.2.8    Load  and Inject  a fixed  amount  of well-mixed
            sample.   Flush injection loop thoroughly,  using  each new sample.
            Use  the same  size loop  for  standards  and  samples.   Record the
            resulting  peak size in  area or  peak height  units.   An automated
            constant volume injection system may  also be  used.

                     7.2.2.9    The width of  the retention time window used to
            make  identifications  should be  based  on measurements  of actual
            retention  time variations of standards  over  the  course of a day.
            Three times the standard deviation of a  retention time can be used
            to calculate a suggested window size  for a compound.  However, the
            experience of the  analyst should weigh heavily in the  interpretation
            of chromatograms.

                     7.2.2.10    If the response for the peak exceeds the working
            range of the system, dilute the sample with an appropriate amount of
            reagent water  and  reanalyze.

                     7.2.2.11    If the resulting chromatogram  fails to produce
            adequate  resolution,  or  if  identification of specific  anions is
            questionable,  spike  the  sample  with  an  appropriate amount  of
            standard and reanalyze.

NOTE:       Retention time is  inversely proportional  to concentration.  Nitrate
            and  sulfate  exhibit the  greatest  amount of  change,  although all
            anions  are affected  to  some degree.    In  some  cases,  this  peak
            migration can produce poor resolution or misidentification.

      7.3   Calculation

            7.3.1    Prepare  separate  calibration  curves for  each anion  of
      interest by plotting peak size  in area, or peak height units of standards
      against concentration values.  Compute sample concentration by comparing
      sample peak response with the standard curve.

            7.3.2    Enter  the  calibration  standard  concentrations and  peak
      heights from  the integrator or  recorder  into a calculator  with linear
      least squares capabilities.

            7.3.3    Calculate  the  following  parameters:   slope (s), intercept
      (I), and correlation coefficient  (r).  The slope and intercept define a
      relationship  between the concentration and instrument  response  of the
      form:

                              y, = s,  x, + I  (1)


where:       y,  = predicted instrument response

             s,-  = response  slope

             xf  = concentration of standard  i

             I = intercept

                                   9056 - 7                       Revision 0
                                                                  November 1990

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      Rearrangement of the above equation yields the concentration corresponding
      to an instrumental measurement:
                            Xj = (Yj - D/SJ    (2)
      where:
             Xj = calculated concentration  for  a  sample
             yj = actual  instrument  response  for  a  sample
             Sj and  I are calculated slope and intercept from calibration above.
            7.3.4   Enter  the sample  peak  height into  the  calculator,  and
      calculate the sample concentration in milligrams per liter.
8.0   QUALITY CONTROL
      8.1   Refer to Chapter One  for specific quality control  procedures.
      8.2   After every 10  injections, analyze a midrange calibration standard.
If the instrument response  has changed  by  more than  5%,  recalibrate.   Verify
continuing calibration  by analyzing a midrange standard with every sample batch.
      8.3   Analyze all samples in duplicate. Take  the duplicate sample through
the entire sample preparation and analytical  process.
9.0   METHOD PERFORMANCE
      9.1   Single-operator accuracy  and precision for reagent, drinking  and
surface water,  and mixed domestic and  industrial wastewater are listed in Table
3.
      9.2   Combustate samples.   These data are based on 41 data points obtained
by six laboratories who each analyzed four used crankcase oils and three fuel  oil
blends with crankcase in duplicate.  The  oil  samples were combusted using Method
5050.  A  data  point  represents one  duplicate analysis of a sample.   One data
point was judged to be an  outlier and was not included in  the  results.
            9.2.1   Precision. The  precision of the method as determined by  the
      statistical examination of  interlaboratory  test results  is as follows:
            Repeatability - The difference  between  successive  results obtained
      by the sample operator with the same  apparatus  under constant operating
      conditions on identical test material  would  exceed, in  the long run,  in
      the normal and correct operation of the test method,  the  following values
      only in 1 case in 20 (see Table 4):
                         Repeatability = 20.9 /x*

      *where x is the average of  two results in M9/9-
                                   9056  - 8                       Revision  0
                                                                  November 1990

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            Reproducibilitv -  The difference between two single and independent
      results obtained by different operators working in different laboratories
      on identical test material would exceed, in the  long  run,  the  following
      values only in 1 case in 20:
                        Reproducibility = 42.1
      *where x is the average value of two results in M9/9-

            9.2.2    Bias.  The  bias  of this  method  varies  with concentration,
      as shown in Table 5:
                     Bias  = Amount  found  - Amount expected

10.0  REFERENCES

1.    Environmental  Protection Agency.   Test Method for the  Determination  of
Inorganic Anions in Water  by  Ion  Chromatography.  EPA Method 300.0.  EPA-600/4-
84-017.  1984.

2.    Annual Book  of ASTM Standards,  Volume 11.01 Water D4327,  Standard  Test
Method for Anions in Water by Ion Chromatography,  pp.  696-703.  1988.

3.    Standard Methods for the Examination of Water and Wastewater, Method 429,
"Determination of Anions by Ion Chromatography with Conductivity Measurement,"
16th Edition of Standard Methods.

4.    Dionex, 1C 16  Operation  and  Maintenance  Manual,  PN 30579,  Dionex Corp.,
Sunnyvale, CA  94086.

5.    Method  detection  limit  (MDL)   as described  in  "Trace  Analyses  for
Wastewater," J.  Glaser, D. Foerst,  G.  McKee, S. Quave,  W.  Budde,  Environmental
Science and Technology, Vol.  15,  Number 12,  p.  1426,  December 1981.

6.    Gaskill, A.; Estes,  E.  D.;  Hardison,  D. L.;  and Myers,  L. E.  Validation
of Methods for Determining Chlorine in Used  Oils and Oil Fuels.   Prepared for
U.S. Environmental  Protection Agency Office of Solid Waste.   EPA Contract No. 68-
01-7075, WA 80.   July 1988.
                                   9056 - 9                       Revision 0
                                                                  November 1990

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                                   TABLE 1.
                CHROMATOGRAPHIC  CONDITIONS  AND METHOD DETECTION
                            LIMITS  IN  REAGENT WATER
Analyte
Fluoride
Chlorine
Nitrite-N
0-Phosphate-P
Nitrate-N
Sulfate
Retention8
time
min
1.2
3.4
4.5
9.0
11.3
21.4
Relative
retention
time
1.0
2.8
3.8
7.5
9.4
17.8
Method6
detection limit,
mg/L
0.005
0.015
0.004
0.061
0.013
0.206
Standard conditions:

Columns - As specified in 4.1.4
            Detector - As specified in 4.1.4
            Eluent - As specified in 5.3

Concentrations of mixed standard (mg/L):
            Fluoride 3.0
            Chloride 4.0
            Nitrite-N 10.0
Sample loop - 100 ;uL
Pump volume - 2.30 mL/min
0-Phosphate-P 9.0
Nitrate-N 30.0
Sulfate 50.0
     calculated from data obtained using an attentuator setting of 1 umho full
scale.  Other settings would produce an MDL proportional to their value.
                                   9056  -  10
            Revision 0
            November 1990

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                          TABLE 2.
PREPARATION OF STANDARD SOLUTIONS FOR INSTRUMENT CALIBRATION
Hiqh-ranae standard (see 5.6.1)







Fluoride (F")
Chloride (CV)
Nitrite (N02~)
Phosphate (P043~)
Bromide (Br~)
Nitrate (N03")
Sulfate (S042')
Milliliters
of each
stock solution
(1.00 mL =
1.00 mg)
diluted to
1,000 ml
10
10
20
50
10
30
100




An ion
concentration
mg/L
10
10
20
50
10
30
100



Intermediate-
range standard,
mg/L
(see 5.6.2)
1.0
1.0
2.0
5.0
1.0
3.0
10.0



Low-range
standard,
mg/L (see
5.6.3)
0.2
0.2
0.4
1.0
0.2
0.6
2.0
                          9056  -  11
Revision 0
November 1990

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                                   TABLE 3.
                    SINGLE-OPERATOR ACCURACY AND  PRECISION
Sampl e
Analyte type
Chloride



Fluoride



Nitrate-N



Nitrite-N



0-Phosphate-P



Sulfate



RW
DM
SW
WW
RW
DW
SW
WW
RW
DW
SW
WW
RW
DW
SW
WW
RW
DE
SW
WW
RW
DW
SW
WW
Spike
mg/L
0.050
10.0
1.0
7.5
0.24
9.3
0.50
1.0
0.10
31.0
0.50
4.0
0.10
19.6
0.51
0.52
0.50
45.7
0.51
4.0
1.02
98.5
10.0
12.5
Number
of
replicates
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Mean
recovery,
%
97.7
98.2
105.0
82.7
103.1
87.7
74.0
92.0
100.9
100.7
100.0
94.3
97.7
103.3
88.2
100.0
100.4
102.5
94.1
97.3
102.1
104.3
111.6
134.9
Standard
deviation,
mg/L
0.0047
0.289
0.139
0.445
0.0009
0.075
0.0038
0.011
0.0041
0.356
0.0058
0.058
0.0014
0.150
0.0053
0.018
0.019
0.386
0.020
0.04
0.066
1.475
0.709
0.466
RW = Reagent water.
DW = Drinking water.
SW = Surface water.
WW = Wastewater.
                                   9056 - 12
                                        Revision 0
                                        November 1990

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                                   TABLE 4.
               REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN
              USED OILS BY BOMB OXIDATION AND ION CHROMATOGRAPHY
Average value,             Repeatability,          Reproducibility,
500
1,000
1,500
2,000
2,500
3,000
467
661
809
935
1,045
1,145
941
1,331
1,631
1,883
2,105
2,306
                                   TABLE 5.
              RECOVERY AND BIAS DATA FOR CHLORINE IN USED OILS BY
                     BOMB OXIDATION AND ION CHROMATOGRAPHY
Amount
Expected
Mg/g
320
480
920
1,498
1,527
3,029
3,045
Amount
found
Mg/g
567
773
1,050
1,694
1,772
3,026
2,745

Bias,
Mg/g
247
293
130
196
245
-3
-300

Percent,
bias
+77
+61
+14
+13
+16
0
-10
                                   9056  -  13                       Revision 0
                                                                  November  1990

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           FIGURE 1
SCHEMATIC OF ION CHROMATOGRAPH
                                                          WASTE
      (1)  Eluent reservoir
      (2)  Pump
      (3)  Precolumn
      (4)  Separator column
      (5)  Suppressor column
      (6)  Detector
      (7)  Recorder or integrator,  or both
          9056 - 14
Revision 0
November 1990

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       FIGURE 2
TYPICAL ANION  PROFILE
        •     12
         MINUTIS
 I
20
      9056  -  15
             Revision 0
             November 1990

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                                 METHOD 9056
                         AN ION CHROMATOGRAPHY METHOD
START


chroma tographic
operating
parameters

7.1.2 Prepare
cal ibration
minimum of three
concent ration
levels and a blank
1
7.1.3 Prepare
calibration curves
1
7.1.4 Verify the
cal ibration curves
each working day or
whenever the anion
eluent is changed,
and for every batch
of samples
-

/ X. 7.2.1 If a dilution
S 7.2.1 Are X. Yes is necessary the
( samples ) » dilution should be
>w aqueous? / made with eluent
N. / solution
No
7.2.2 Analyze
s tandards beginning
with the highest
concentration and
decreasing in
concentration

7.2.1 Add
concentrated eluent
<— to all sarnies and
standards to remove
water dip
1
•+

7.2.2.5 Compare
results to
cal ibration curve;
if results exceed
control 1 imi ts ,
identify problem
before proceeding
1
7.2.2.6 Inject a
spiked sample of
known cone . ;
calculate the cone..
from the cal ibration
curve ; if resul t
exceeds cont rol
limits, find problem
before proceeding
1
722.7 Begin
sample analysis
1
7 2.2.8 Analyze all
samples in same
manner
1


/I 2 .2 .10 >v
/ Doe« response N. Yes 7 2.2.10 Dilute
( for peak exceed J > sample with reagent
N. norking / water
N. range? /
No
7.3 1 Prepare
sample calibration
curves for each
anion of interest
and compute sample
concentration





concentrations from
•* instrumental
response

{ STOP )

                                  9056 - 16
Revision 0
November 1990

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                                 METHOD 9070A

                       TOTAL  RECOVERABLE OIL AND GREASE
                  (GRAVIMETRIC.  SEPARATORY  FUNNEL  EXTRACTION)
1.0   SCOPE AND APPLICATION

      1.1    This method measures the fluorocarbon-113 extractable matter from
surface and saline waters and industrial, domestic, and aqueous wastes.  It is
applicable to the determination of relatively nonvolatile hydrocarbons, vegetable
oils, animal fats, waxes, soaps, greases, and related matter.

      1.2    The method is not applicable to measurement of light hydrocarbons
that volatilize  at  temperatures below  70°C.   Petroleum fuels,  from gasoline
through No. 2  fuel oils, are completely or partially lost  in the solvent removal
operation.

      1.3    Some  crude  oils  and  heavy  fuel  oils  contain  a  significant
percentage of residue-type materials that are not soluble in fluorocarbon-113.
Accordingly, recoveries of these materials will be low.

      1.4    The method  covers  the range from 5 to  1,000  mg/L of extractable
material.

      1.5    When determining the  level of oil and  grease  in  sludge samples,
Method 9071 is to be employed.

2.0   SUMMARY OF METHOD

      2.1    The  1-liter sample is  acidified to  a low pH  (2)  and serially
extracted  with fluorocarbon-113   in a  separatory  funnel.    The solvent  is
evaporated from the extract and the residue is weighed.

3.0   INTERFERENCES

      3.1    Matrix interferences  will  likely  be  coextracted from the sample.
The extent of these interferences will vary from waste to waste,  depending on the
nature and diversity of the waste being analyzed.

4.0   APPARATUS AND MATERIALS

      4.1    Separatory funnel:  2,000-mL, with Teflon stopcock.

      4.2    Vacuum pump, or other source of vacuum.

      4.3    Flask:  Boiling, 125-mL  (Corning  No. 4100 or equivalent).

      4.4    Distilling head:  Claisen or equivalent.

      4.5    Filter paper:  Whatman No. 40, 11 cm.
     Replacement solvent will  be specified in  a forthcoming  regulation.
                                   9070A  -  1                       Revision 1
                                                                  November 1990

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5.0   REAGENTS

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

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

      5.3    Hydrochloric acid, 1:1:  Mix equal volumes of concentrated HC1 and
reagent water.

      5.4    Fluorocarbon-1132(l,l,2-trichloro-l,2,2-trifluoroethane): Boiling
point, 48eC.

      5.5    Sodium  sulfate:  Anhydrous crystal.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1    A  representative  sample should  be  collected  in  a  1-liter glass
bottle.  If analysis  is  to be delayed for more than a few hours, the sample must
be preserved by the addition of 5 mL HC1 (Step 5.3) at the  time  of collection and
refrigerated at 4°C.

      6.2    Collect  a  representative sample in a wide-mouth glass bottle that
has been rinsed with  the solvent to remove any detergent film and acidify in the
sample bottle.

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

      6.4    Because  losses  of grease will  occur  on  sampling equipment,  the
collection of a composite sample is impractical.  Individual  portions collected
at prescribed time intervals must be analyzed separately to  obtain the average
concentration over an extended period.

7.0   PROCEDURE

      7.1    Mark the sample bottle at the water meniscus for later determina-
tion of sample volume.  If the sample was not acidified at  time of collection,
add 5 mL HC1  (Step 5.3) to the sample bottle.  After mixing the  sample, check the
pH by touching  pH-sensitive paper to the cap to ensure that the pH  is 2 or lower.
Add more acid if necessary.

      7.2    Pour the sample into  a separatory funnel.

      7.3    Tare a boiling flask  (pre-dried in an oven  at 103°C and stored in
a desiccator).   Use gloves  when handling  flask to avoid adding fingerprints.
     Replacement solvent will  be specified  in  a  forthcoming  regulation.

                                   9070A  - 2                       Revision 1
                                                                  November 1990

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      7.4     Add  30 ml fluorocarbon-113  (Step  5.3) to the  sample bottle and
rotate the bottle to rinse the sides.   Transfer  the solvent into the separatory
funnel.  Extract by shaking vigorously for 2 min.   Allow the  layers to separate
and filter the solvent layer through a funnel containing solvent-moistened filter
paper.

NOTE:         An emulsion that fails to dissipate can be broken  by pouring about
              1 g sodium sulfate (Step  5.4)  into the filter paper cone and slowly
              draining  the  emulsion through the  salt.  Additional  1-g portions
              can  be added  to  the  cone  as required.

      7.5     Repeat Step  7.4  twice more,  with  additional   portions  of fresh
solvent, combining  all solvent  in  the  boiling flask.

      7.6     Rinse  the tip of the separatory funnel, the filter paper, and then
the  funnel  with  a  total of  10-20 ml  solvent and  collect the  rinsings  in the
flask.

      7.7     Connect the boiling flask to the distilling head and evaporate the
solvent by immersing the lower half of the  flask  in water at  70°C.  Collect the
solvent for reuse.  A solvent blank should  accompany each set of samples.

      7.8     When  the  temperature in  the distilling head reaches  50°C  or the
flask appears dry,  remove the distilling head.  To  remove solvent vapor, sweep
out the flask for  15 sec with  air by inserting a  glass tube that is connected to
a vacuum  source.   Immediately remove the flask from heat  source  and wipe the
outside to remove excess moisture  and  fingerprints.

      7.9     Cool the boiling flask in a desiccator for 30 min. and weigh.

      7.10    Calculation:
                      mg/L total oil and grease
                                                    R - B
             where:

                      R =        residue, gross weight of extraction flask minus
                                 the  tare weight  (mg);

                      B =        blank  determination,  residue  of  equivalent
                                 volume of  extraction  solvent, mg; and

                      V =        volume  of  sample  in  liters,  determined  by
                                 refilling sample bottle to calibration line and
                                 correcting  for acid addition, if necessary.

8.0   QUALITY CONTROL

      8.1    Refer to  Chapter One for specific quality control procedures.

      8.2    Comprehensive  quality  control  procedures are  specified  for  each
target compound in the referring analytical method.
                                   9070A  -  3
Revision 1
November 1990

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      8.3    The matrix duplicate and matrix spike samples are brought through
the whole sample preparation and analytical process.

      8.4    The use of corn oil  is  recommended  as a reference sample solution.

9.0   METHOD PERFORMANCE

      9.1    Two oil and grease methods (Methods 9070 and 9071) were tested on
sewage by a single laboratory.  This method determined the oil and grease level
in the sewage to be 12.6 mg/L.  When 1-liter portions of the sewage were dosed
with 14.0 mg of a mixture of No. 2 fuel oil and Wesson oil,  the recovery was 93%,
with a standard deviation of + 0.9 mg/L.

10.0  REFERENCES

1.    Blum, K.A.,  and M.J. Taras,  "Determination  of Emulsifying Oil in Industrial
Wastewater," JWPCF Research Suppl.,  40, R404 (1968).

2.    Standard Methods for the Examination of Water and Wastewater,  14th ed.,
p. 515.
                                   9070A - 4                      Revision  1
                                                                  November 1990

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                                     METHOD 9070A
TOTAL RECOVERABLE OIL  AND GREASE  (GRAVIMETRIC,  SEPARATORY FUNNEL  EXTRACTION)
                             7.2 Pour
                            sample into
                            separatory
                              funnal
7.3 Tare
boiling flask


7.4 Add
f luorocarbon-
113; extract;
filtar
solvent layer


7.S Repeat
twice adding
froth solvent


7 . 5 Combine
solvent in —
boiling flask
                                                                7.7 Cvaporate
                                                                  solvent;
                                                                  collect for
                                                                    reuse
                                                                 7 . 8 Remove
                                                                 solvent vapor
                                                                  7.9 Cool
                                                                  flask and
                                                                    weigh
   7.10
  Calculate
total amount
 of oil and
  grease
                                                                    Stop
                                       9070A - 5
           Revision 1
           November 1990

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                                  METHOD 9075

                TEST METHOD FOR TOTAL CHLORINE IN NEW AND USED
          PETROLEUM PRODUCTS  BY  X-RAY  FLUORESCENCE SPECTROMETRY  (XRR
1.0   SCOPE AND APPLICATION

      1.1   This test method covers the determination of total  chlorine in new
and used  oils,  fuels,  and related materials,  including  crankcase,  hydraulic,
diesel,  lubricating  and  fuel  oils,  and  kerosene.    The chlorine content  of
petroleum products is often required prior to their use as a fuel.

      1.2   The applicable  range  of this method  is  from 200 ng/g to percent
levels.

2.0   SUMMARY OF METHOD

      2.1   A well-mixed sample, contained in a disposable plastic sample cup,
is loaded into an X-ray fluorescence (XRF) spectrometer.   The intensities of the
chlorine K alpha and sulfur K alpha lines are measured,  as are the intensities
of appropriate background lines.   After  background  correction,  the  net inten-
sities are used with a calibration equation to determine the chlorine content.
The sulfur intensity is used to correct for absorption by sulfur.

3.0   INTERFERENCES

      3.1   Possible interferents  include metals, water, and sediment in the oil.
Results of spike recovery measurements and measurements on diluted samples can
be used to check for interferences.

      Each sample,  or one  sample from a group of closely related samples, should
be spiked  to confirm that  matrix effects are  not  significant.  Dilution  of
samples that  may contain  water or sediment can product  incorrect results,  so
dilution  should  be undertaken with  caution and  checked by spiking.   Sulfur
interferes with the chlorine determination, but a  correction is made.

      Spike recovery measurements  of used crankcase oil  showed that diluting
samples five  to one  allowed accurate measurements on  approximately 80% of the
samples.  The other 20% of the samples were not accurately analyzed  by XRF.

      3.2   Water  in samples absorbs X-rays due to  chlorine.   For this inter-
ference, using as short  an X-ray counting  time  as  possible is beneficial.  This
appears to be related to stratification of samples into aqueous and  nonaqueous
layers while  in the analyzer.

      Although  a   correction  for   water  may be  possible,  none  is  currently
available.  In general,  the  presence  of any free water as a separate  phase or a
water content greater than 25% will reduce the chlorine signal  by  50  to 90%.
                                   9075 - 1                      Revision  0
                                                                 November  1990

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4.0   APPARATUS AND MATERIALS

      4.1   XRF spectrometer,  either energy dispersive or wavelength dispersive.
The instrument must be able to accurately resolve and measure the intensity of
the chlorine and sulfur lines with acceptable precision.

      4.2   Disposable sample cups with suitable plastic film such as Mylar*.

5.0   REAGENTS

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

      5.2   Mineral oil, mineral  spirits or  paraffin oil,  sulfur and chlorine
free, for preparing standards and dilutions.

      5.3   1-Chlorodecane (Aldrich Chemical Co.), 20.1%  chlorine,  or similar
chlorine compound.

      5.4   Di-n-butyl sulfide (Aldrich Chemical Co.), 21.9% sulfur by weight.

      5.5   Quality control standards such as the standard reference materials
NBS 1620, 1621,  1622,  1623,  and  1624, sulfur in oil  standards,  and NBS 1818,
chlorine in oil standards.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All samples must be collected using a sampling plan that addresses
the considerations discussed in Chapter Nine.

      6.2   The collected sample  should be kept headspace free prior to prepara-
tion and analysis to minimize volatilization losses of organic  halogens.  Because
waste oils may contain toxic and/or carcinogenic substances,  appropriate field
and laboratory safety procedures should be followed.

      6.3   Laboratory sampling of the sample  should be performed on a well-mixed
sample of oil.   The mixing should be kept to a minimum and carried out as nearly
headspace free as possible to minimize volatilization losses of organic halogens.

      6.4   Free water,  as  a  separate phase, should  be removed  and cannot be
analyzed by this method.

7.0   PROCEDURE

      7.1   Calibration and standardization.

            7.1.1     Prepare  primary  calibration  standards  by diluting  the
      chlorodecane and n-butyl  sulfide with mineral  spirits  or similar material.


                                   9075 - 2                      Revision 0
                                                                 November 1990

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      7.1.2     Prepare working calibration standards that contain sulfur,
chlorine, or both according to the following table:
Cl:
 S:

1.
2.
3.
4.
500, 1,000, 2,000, 4,000, and 6,000 M9/9
0.5, 1.0, and 1.5% sulfur
0.5% S, 1,000 M9/9 Cl
0.5% S, 4,000 M9/9 Cl
1.0% S,   500 M9/9 Cl
1.0% S, 2,000 M9/9 Cl
5.   1.0% S,  6,000 M9/9 Cl
6.   1.5% S,  1,000 M9/9 Cl
7.   1.5% S,  4,000 M9/9 Cl
8.   1.5% S,  6,000 M9/9 Cl
Once  the  correction  factor for  sulfur interference  with chlorine  is
determined, fewer standards may be required.

      7.1.3     Measure the  intensity of the chlorine K  alpha line and the
sulfur  K  alpha  line  as  well   as  the  intensity of  a suitably  chosen
background.  Based on counting statistics, the relative  standard deviation
of each peak measurement should be 1% or less.

      7.1.4     Determine  the  net chlorine  and  sulfur intensities  by
correcting each peak for background.   Do this for all of the calibration
standards as well as for a paraffin blank.

      7.1.5     Obtain  a linear calibration  curve for sulfur by performing
a least squares fit of  the net sulfur  intensity to the standard concentra-
tions,  including the  blank.   The chlorine  content  of  a standard  should
have little effect on the net sulfur  intensity.

      7.1.6     The  calibration  equation   for  chlorine must  include  a
correction  term for  the  sulfur concentration.    A  suitable  equation
follows:
where:
                      Cl  =  (ml  +  b)  (1  +  k*S)
                                                      (1)
      I = net chlorine intensity
      m, b, k* = adjustable parameters.
                                           f
Using  a  least  squares  procedure,   the  above  equation  or  a  suitable
substitute  should  be  fitted  to  the data.   Many  XRF  instruments  are
equipped  with  suitable computer programs to  perform  this fit.   In  any
case, the resulting equation should be shown to be accurate by analysis of
suitable standard materials.

7.2   Analysis.

      7.2.1     Prepare a calibration curve as described in Step 7.1.   By
periodically measuring  a very stable sample containing  both  sulfur  and
chlorine,  it may be  possible  to use the calibration  equations  for more
than 1 day.  During  each  day, the suitability of the calibration curve
should be checked by analyzing standards.
                             9075 - 3
                                                     Revision  0
                                                     November  1990

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            7.2.2     Determine the net chlorine  and  sulfur  intensities for a
      sample in the same manner as was done for the standards.

            7.2.3     Determine the chlorine and  sulfur  concentrations  of the
      samples from the calibration equations.  If the sample concentration for
      either element is beyond the range of the standards, the sample should be
      diluted with mineral oil and reanalyzed.

8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control procedures.

      8.2   One sample in ten should  be analyzed in triplicate and the relative
standard deviation reported.  For each triplicate,  a separate preparation should
be made, starting from the original sample.

      8.3   Each sample, or one sample in ten from a group of similar samples,
should  be  spiked  with the elements  of interest  by  adding  a known  amount  of
chlorine or sulfur to the sample.  The spiked amount should  be between 50% and
200% of the sample concentration,  but the  minimum addition  should  be at least
five times the limit  of detection.  The percent recovery should be reported and
should be between 80% and 120%.  Any sample suspected of containing >25% water
should also be spiked with organic chlorine.

      8.4   Quality control  standard  check  samples should be analyzed every day
and should agree within 10% of the expected value  of the standard.

9.0   METHOD PERFORMANCE

      These data are  based on 47 data points obtained by seven laboratories who
each analyzed four used crankcase  oils and  three fuel oil blends with crankcase
in duplicate.   A data point represents one  duplicate analysis of a sample.  Two
data points were determined to be outliers and are not  included  in these results.

      9.1   Precision.   The  precision  of the method  as determined  by  the
statistical examination of interlaboratory  test results  is as follows:

      Repeatability - The difference between successive results obtained by the
same operator with the same  apparatus under constant operating  conditions  on
identical test material would exceed, in the long run,  in the normal  and correct
operation of the test  method,  the following values  only in  1 case  in 20 (see
Table 1):


                         Repeatability =5.72
      *where x is the average of two results in

            Reoroducibilitv - The difference between two single and independent
      results obtained by different operators working in different laboratories
      on identical test material would exceed, in the  long run,  the  following
      values only in 1 case in 20:
                                   9075 -  4                     Revision 0
                                                                November 1990

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                        Reproducibility = 9.83
      *where x is the average value  of  two results in /xg/g.

      9.2   Bias.  The bias of this test method varies with concentration, as
shown in Table 2:

                    Bias  = Amount  found - Amount expected.

10.0  REFERENCE

1.    Gaskill, A.; Estes,  E.D.;  Hardison, D.L.; and Myers, I.E.  Validation of
      Methods for Determining Chlorine in Used Oils and Oil Fuels.   Prepared for
      U.S. Environmental Protection Agency, Office of Solid Waste.   EPA Contract
      No. 68-01-7075, WA  80.   July 1988.
                                   9075 -  5                      Revision 0
                                                                November 1990

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                  TABLE  1.   REPEATABILITY AND REPRODUCIBILITY
                         FOR CHLORINE IN USED OILS BY
                        X-RAY  FLUORESCENCE SPECTROMETRY
Average value,              Repeatability,            Reproducibility,
    M9/9                         M9/9                      M9/9
     500                          128                        220
   1,000                          181                        311
   1,500                          222                        381
   2,000                          256                        440
   2,500                          286                        492
   3,000                          313                        538
               TABLE 2.  RECOVERY AND BIAS DATA FOR CHLORINE IN
                 USED OILS BY X-RAY FLUORESCENCE SPECTROMETRY
Amount
expected,
M9/9
320
480
920
1,498
1,527
3,029
3,045
Amount
found,
M9/9
278
461
879
1,414
1,299
2,806
2,811

Bias,
M9/9
-42
-19
-41
-84
-228
-223
-234

Percent
bias
-13
-4
-4
-6
-15
-7
-8
                                   9075 - 6                      Revision  0
                                                                 November  1990

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                              METHOD  9075
        TEST METHOD FOR TOTAL CHLORINE  IN NEW AND USED
PETROLEUM  PRODUCTS  BY X-RAY  FLUORESCENCE SPECTROMETRY  (XRF)
         START
      7.1.1 - 7.1.2
   Prepare calibration
        3 tandards
      71.3 Measure
      intensity of
      3 tandards and
       background
   7,1.4  Determine net
      intensity for
     standards and a
     paraffin blank
      7.1.5 - 7.1.6
        Construct
   calibration curves
     for sulfur and
        chl o r me
       7.2.1 Check
   calibration curves
      perlodica11y
   throughout the day
7.2.2 Determine net
chlorine and  sulfur
    intensi ties
  7.2.3 Determine
chlorine and  sulfur
concentrations from
calibration curves
      7.2.3
     Is sample
   concentration
  beyond range of
    standards?
7.2.3 Dilute  sample
 with mineral  oil
                                9075  - 7
                                          Revision  0
                                          November  1990

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                                  METHOD  9076

           TEST METHOD FOR TOTAL CHLORINE IN NEW AND USED PETROLEUM
             PRODUCTS BY OXIDATIVE COMBUSTION AND MICROCOULOMETRY
1.0   SCOPE AND APPLICATION

      1.1   This test method covers the determination of total chlorine in new
and  used  oils,  fuels  and  related materials, including  crankcase,  hydraulic,
diesel, lubricating  and fuel oils,  and  kerosene by oxidative  combustion and
microcoulometry.  The chlorine content of petroleum products is often required
prior to their use as a fuel.

      1.2   The  applicable  range of  this method  is  from  10  to 10,000  ng/g
chlorine.

2.0   SUMMARY OF METHOD

      2.1   The  sample  is  placed  in  a quartz  boat  at  the  inlet of  a  high-
temperature quartz combustion tube.   An inert carrier gas such as argon, carbon
dioxide, or nitrogen sweeps across^the inlet while oxygen flows into the center
of the combustion tube.  The boat and sample  are advanced  into a vaporization
zone of approximately  300°C to volatilize the  light  ends.   Then the  boat is
advanced to the center of the combustion tube, which is at 1,000°C.  The oxygen
is diverted to pass directly  over the sample to oxidize any remaining refractory
material.   All during this  complete  combustion cycle, the chlorine is converted
to chloride and oxychlorides, which  then  flow into an  attached titration cell
where they quantitatively react with silver ions.  The silver ions thus consumed
are coulometrically replaced.  The total current  required to replace the silver
ions is a measure of the chlorine present in  the injected samples.

      2.2   The reaction occurring in the  titration cell as chloride enters is:

                           Cl" + Ag+	> AgCl                 (1)

      The silver ion  consumed in the above  reaction is generated coulometrically
thus:

                             Ag°	>  Ag+ + e" y             (2)

      2.3   These microequivalents of silver  are equal  to the number of micro-
equivalents of titratable sample ion entering the titration cell.

3.0   INTERFERENCES

      3.1   Other titratable halides will  also give a positive response.  These
titratable halides include HBr and  HI  (HOBr + HOI  do  not precipitate silver).
Because these oxyhalides do not react in  the  titration cell,  approximately 50%
microequivalent response is detected from bromine and iodine.

      3.2   Fluorine as fluoride does not precipitate silver,  so it  is not an
interferant nor is it detected.
                                   9076 - 1                     Revision 0
                                                                November 1990

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      3.3   This  test method  is  applicable in  the  presence of  total  sulfur
concentrations of up  to 10,000 times the chlorine level.

4.0   APPARATUS AND MATERIALS1

      4.1   Combustion furnace.   The  sample should  be oxidized  in an electric
furnace capable of maintaining a temperature of 1,000'C to oxidize the organic
matrix.

      4.2   Combustion tube,  fabricated  from quartz  and constructed so that a
sample, which is vaporized  completely  in the inlet  section,  is  swept into the
oxidation zone by an  inert  gas where  it  mixes  with  oxygen and is burned.   The
inlet end of the tube connects to a boat insertion device where the sample can
be  placed  on  a  quartz   boat by  syringe,   micropipet,  or  by  being  weighed
externally.  Two gas  ports are provided,  one for an inert gas  to flow across the
boat and one for oxygen to enter the combustion tube.

      4.3   Microcoulometer,  Stroehlein  Coulomat  702  CL or equivalent, having
variable gain and bias control, and capable of measuring the potential  of the
sensing-reference electrode pair, and  comparing this  potential  with  a  bias
potential,  and  applying  the  amplified  difference  to  the  working-auxiliary
electrode pair so as  to generate a titrant.   The microcoulometer output signal
shall be proportional to the generating current.  The microcoulometer may have
a digital  meter and circuitry to convert this output signal directly to nanograms
or micrograms of chlorine or micrograms per gram chlorine.

      4.4   Titration cell.   Two different configurations have been applied to
coulometrically titrate chlorine for this method.

            4.4.1     Type I uses a sensor-reference pair of electrodes to detect
      changes in silver ion  concentration and a generator anode-cathode pair of
      electrodes to  maintain constant  silver ion concentration and an inlet for
      a gaseous  sample  from the  pyrolysis  tube.   The  sensor,  reference,  and
      anode  electrodes  are  silver electrodes.   The  cathode  electrode  is  a
      platinum wire.   The reference  electrode  resides in a  saturated  silver
      acetate half-cell.   The electrolyte contains 70% acetic acid in water.

            4.4.2     Type II uses  a  sensor-reference  pair  of electrodes  to
      detect changes  in silver ion concentration and a generator anode-cathode
      pair of electrodes to maintain constant silver  ion concentration, an inlet
      for a gaseous  sample that passes through  a 95% sulfuric acid dehydrating
      tube from the  pyrolysis tube, and a sealed two-piece titration cell  with
      an exhaust tube to  vent fumes to an external exhaust.  All  electrodes can
      be  removed  and replaced independently without reconstructing the  cell
      assembly.   The  anode  electrode  is  constructed  of silver.   The  cathode
      electrode is constructed of platinum.  The anode  is separated  from the
      cathode by a 10% KNO, agar bridge, and  continuity  is maintained through an
      aqueous 10% KN03 salt bridge.   The sensor electrode  is  constructed  of
     1Three commercial  analyzers  fulfill  the  requirements  for  apparatus  Steps
4.1 through 4.4 and have been found satisfactory for this  method.   They are
the two Dohrmann Models DX-20B and MCTS-20 and Mitsubishi  Model  TSX-10
available from Cosa Instrument.

                                   9076 - 2                     Revision 0
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      silver.  The reference electrode is a silver/silver chloride ground glass
      sleeve, double-junction electrode with aqueous 1M KN03 in the outer chamber
      and aqueous 1M KC1  in the inner  chamber.

      4.5   Sampling syringe, a microliter syringe of 10 /iL capacity capable of
accurately delivering 2 to 5 /LiL of  a  viscous  sample  into the  sample boat.

      4.6   Micropipet, a positive displacement micropipet capable of accurately
delivering 2 to 5 nl of a viscous sample into the  sample boat.

      4.7   Analytical balance.   When  used  to weigh  a  sample of 2 to 5 mg onto
the boat, the balance shall be accurate to + 0.01 mg.  When used to determine the
density of the sample,  typically 8 g per  10 ml, the balance shall  be accurate to
± 0.1 g.

      4.8   Class A volumetric flasks:   100 ml.

5.0   REAGENTS

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

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

      5.3   Acetic acid,  CH3C02H.  Glacial.

      5.4   Isooctane, (CH3)2CHCH2C(CH3)3 (2,2,4-Trimethylpentane).

      5.5   Chlorobenzene, C6H5C1.

      5.6   Chlorine,   standard   stock  solution  -  10,000   ng  Cl//iL,  weigh
accurately 3.174 g of chlorobenzene into 100-mL Class A volumetric flask.  Dilute
to the mark with isooctane.

      5.7   Chlorine,  standard  solution.   1,000  ng  Cl/^L,  pipet  10.0  mL of
chlorine stock solution (Step 5.6) into a 100-mL volumetric flask and dilute to
volume with isooctane.

      5.8   Argon, helium, nitrogen, or carbon dioxide, high-purity grade (HP)
used as the carrier gas.   High-purity grade gas has a  minimum purity of 99.995%.

      5.9   Oxygen,  high-purity grade  (HP), used as the reactant gas.

      5.10  Gas regulators.  Two-stage regulator must  be used on the reactant and
carrier gas.

      5.11  Cell Type  1.
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            5.11.1    Cell  electrolyte solution.   70% acetic acid: combine 300
      ml reagent water with 700 mL acetic acid (Step 5.3) and mix well.

            5.11.2    Silver acetate,  CH3C02Ag.   Powder purified for saturated
      reference electrode.

      5.12  Cell Type 2.

            5.12.1    Sodium acetate,  CH3C02Na.

            5.12.2    Potassium nitrate,  KN03.

            5.12.3    Potassium chloride,  KC1.

            5.12.4    Sulfuric acid (concentrated),  H2S04.

            5.12.5    Agar,  (jelly strength  450 to 600  g/cm2).

            5.12.6    Cell  electrolyte solution -  85% acetic acid:  combine 150
      ml reagent water with  1.35  g sodium acetate (Step 5.12.1) and mix well;
      add 850 ml acetic acid  (Step 5.3) and mix well.

            5.12.7    Dehydrating  solution - Combine 95 mL sulfuric acid (Step
      5.12.4) with 5 mL reagent water and mix well.

CAUTION:    This is an exothermic reaction and may proceed with bumping unless
            controlled by the  addition of sulfuric  acid.   Slowly add sulfuric
            acid to reagent water.  Do not add water to sulfuric acid.

            5.12.8    Potassium nitrate (10%),  KN03.   Add 10 g potassium nitrate
      (Step 5.12.2) to 100 mL reagent water and mix well.

            5.12.9    Potassium nitrate  (1M),  KN03.    Add  10.11  g  potassium
      nitrate (Step 5.12.2) to 100 mL reagent water and mix well.

            5.12.10   Potassium chloride  (1M),  KC1.    Add  7.46  g  potassium
      chloride (Step 5.12.3) to 100 mL reagent water and mix well.

            5.12.11   Agar bridge  solution - Mix 0.7 g agar (Step 5.12.5), 2.5g
      potassium nitrate  (Step 5.12.2),  and  25 mL  reagent  water  and  heat to
      boiling.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      6.1   All  samples must be collected using a sampling plan that addresses
the considerations discussed in Chapter Nine.

      6.2   Because the collected  sample will be analyzed for total  halogens, it
should be kept headspace free and refrigerated prior to preparation  and analysis
to minimize volatilization losses of organic halogens.   Because waste oils may
contain toxic and/or carcinogenic substances,  appropriate field and laboratory
safety procedures should be followed.
                                   9076 - 4                      Revision  0
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      6.3   Laboratory subsampling of the sample  should be performed on a well-
mixed sample of oil.

7.0   PROCEDURES

      7.1   Preparation of apparatus.

            7.1.1     Set  up the analyzer as  per the  equipment manufacturer's
      instructions.

            7.1.2     Typical  operating  conditions:  Type  1.

                      Furnace  temperature	   1,OOO'C
                      Carrier  gas  flow	      43 cm /min
                      Oxygen gas  flow	     160 cm /min
                      Coulometer
                        Bias	     250 mV
                        Gain	      25%

            7.1.3     Typical  operating  conditions:  Type  2.

                      Furnace  temperature	   H-l 850°C
                                                          H-2 1,QOO°C
                      Carrier  gas  flow	   250 cm /min
                      Oxygen gas  flow	   250 cm /min
                      Coulometer
                        End  point  potential  (bias)	   300 mV
                      Gain G-l	     1.5 coulombs/A mV
                          G-2	     3.0 coulombs/A mV
                          G-3	     3.0 coulombs/A mV
                      ES-1 (range  1)	    25 mV
                      ES-2 (range  2)	    30 mV

NOTE: Other conditions may be  appropriate.  Refer  to the instrumentation manual.

      7.2   Sample introduction.

            7.2.1     Carefully fill  a 10-jiL syringe with 2  to 5  juL of sample
      depending on the  expected  concentration of total chlorine.   Inject the
      sample through the septum onto the cool  boat,  being certain to touch the
      boat with the needle tip to displace the last droplet.

            7.2.2     For  viscous  samples that cannot be drawn  into the syringe
      barrel, a positive displacement micropipet  may be used.  Here,  the 2-5 juL
      of sample is  placed on  the boat from the  micropipet  through  the opened
      hatch port.  The  same technique as with the  syringe is used to displace
      the last droplet into  the boat.  A tuft of quartz  wool  in  the boat can aid
      in completely transferring the sample from the micropipet into the boat.

NOTE: Dilution  of samples  to  reduce  viscosity is  not  recommended  due  to
      uncertainty  about  the  solubility  of the  sample  and  its  chlorinated
      constituents.   If a positive displacement micropipet  is not  available,
      dilution may be attempted to enable injection of viscous samples.


                                   9076 - 5                     Revision  0
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            7.2.3     Alternatively,  the sample  boat  may be  removed  from the
      instrument and  tared  on an analytical balance.   A sample of 2-5 mg is
      accurately weighed directly into the boat and the boat and sample returned
      to the inlet of the instrument.

                               2-5 /iL = 2-5 mg

NOTE: Sample dilution may be required to ensure that the titration system is not
      overloaded with  chlorine.   This  will  be  somewhat system  dependent and
      should be determined before analysis is attempted.  For example, the MCTS-
      20 can titrate up to  10,000 ng chlorine in a single injection or weighed
      sample, while the DX-20B has an upper  limit  of 50,000 ng chlorine.  For 2
      to 5 juL  sample  sizes, these correspond to nominal concentrations in the
      sample of 800 to 2,000 jzg/g and 4,000 to  10,000 M9/g»  respectively.  If
      the system  is  overloaded,  especially with  inorganic  chloride,  residual
      chloride  may persist in  the  system  and  affect results  of subsequent
      samples.  In general,  the analyst  should ensure  that the baseline returns
      to normal before running the next sample.   To speed baseline recovery, the
      electrolyte  can  be  drained  from  the  cell and replaced  with  fresh
      electrolyte.

NOTE: To determine total  chlorine, do not extract the sample either with reagent
      water or with an organic solvent such as toluene or isooctane.   This may
      lower  the inorganic  chlorine  content as  well   as result  in losses  of
      volatile solvents.

            7.2.4     Follow the manufacturer's recommended procedure for moving
      the sample and boat into the combustion tube.

      7.3   Calibration and standardization.

            7.3.1     System recovery -  The  fraction of chlorine  in a standard
      that  is  titrated  should   be  verified every  4   hours  by  analyzing  the
      standard solution (Step  5.7).  System recovery is typically 85% or better.
      The pyrolysis tube should be replaced whenever system recovery drops below
      75%.

NOTE: The 1,000 /xg/g system recovery sample is suitable for all systems except
      the MCTS-20 for which a  100 jug/g  sample should  be used.

            7.3.2     Repeat the   measurement of this   standard at  least three
      times.

            7.3.3     System blank -  The blank  should be  checked daily  with
      isooctane.  It is typically less than 1 /xg/g chlorine.   The system blank
      should be subtracted  from both samples and standards.

      7.4   Calculations.

            7.4.1     For systems that read  directly in mass units of chloride,
      the following equations  apply:

                Chlorine,  /*g/g (wt/wt)  =    Disp1ays      -  B                (3)
                                         (V.) (D8) (RF)

                                   9076 - 6                      Revision  0
                                                                 November  1990

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or
                Chlorine,  M9/9 (wt/wt) =    Disp1ays      - B                (4)
                                            (M)  (RF)
where:
Display     =   Integrated value in nanograms  (when  the  integrated values are
                displayed in micrograms,  they must  be multiplied by 10 )
                DisplayB  = blank measurement    Displays = sample measurement

      V     =   Volume of sample injected in  microliters
                VB  =  blank volume               Vs = sample volume

      D     =   Density of sample,  grams  per  cubic  centimeters
                DB  =  blank density              Ds = sample density

     RF     =   Recovery factor =  ratio of chlorine       =    Found -  Blank
                determined in standard minus  the  system           Known
                blank, divided by  known standard  content

      B     =   System blank, jug/g chlorine               =       Display.
                                                                 (VB)  (DB)

      M     =   Mass of sample,  mg

            7.4.2     Other systems internally compensate for recovery factor,
      volume, density, or  mass  and  blank,  and thus  read out directly in parts
      per million chlorine units.  Refer to instrumentation manual.

8.0   QUALITY CONTROL

      8.1   Refer to Chapter One for specific quality control procedures.

      8.2   Each sample should be analyzed twice.  If the results do not agree
to within  10%,  expressed  as the  relative percent difference  of the results,
repeat the analysis.

      8.3   Analyze matrix spike and matrix spike duplicates - spike samples with
a chlorinated organic at a level  of total  chlorine commensurate with the levels
being determined.  The spike recovery should be reported and should be between
80 and 120% of the expected value.  Any sample suspected of containing >25% water
should also be spiked with organic chlorine.

9.0   METHOD PERFORMANCE

      These data are based on 66 data points obtained by 10 laboratories who each
analyzed four used  crankcase oils  and three  fuel  oil  blends with crankcase in
duplicate.  A data  point  represents one duplicate analysis  of  a sample.   One
laboratory and four  additional data points  were determined to be  outliers and are
not included in these results.
                                   9076 - 7                     Revision 0
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      9.1   Precision.   The  precision  of  the method  as determined  by  the
statistical examination of interlaboratory test results  is as  follows:

      Repeatability - The difference between successive results obtained by the
same operator with  the  same apparatus under constant operating conditions  on
identical test material would exceed, in the long run, in the normal  and  correct
operation of the test method the following values only in  1  case in 20 (see Table
                         Repeatability = 0.137
      *where x is the average of two results  in  M9/g«

            Reproducibilitv - The difference between two single and  independent
      results obtained by different operators working in different laboratories
      on identical test material would exceed, in the  long run, the  following
      values only in 1 case in 20:


                       Repioducibility = 0.455 
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                                   TABLE 1.
               REPEATABILITY  AND  REPRODUCIBILITY  FOR CHLORINE  IN
                    USED OILS BY  MICROCOULOMETRIC TITRATION
Average value               Repeatability,                 Reproducibility,
    M9/9                         M9/9                          M9/9
     500                           69                              228
   1,000                          137                              455
   1,500                          206                              683
   2,000                          274                              910
   2,500                          343                            1,138
   3,000                          411                            1,365
                                   TABLE 2.
               RECOVERY AND BIAS DATA FOR CHLORINE IN USED OILS
                         BY MICROCOULOMETRIC TITRATION
Amount
expected,
M9/9
320
480
920
1,498
1,527
3,029
3,045
Amount
found
M9/9
312
443
841
1,483
1,446
3,016
2,916

Bias,
M9/9
-8
-37
-79
-15
-81
-13
-129

Percent
bias
-3
-8
-9
-1
-5
0
-4
                                   9076 -  9                     Revision 0
                                                                November 1990

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                                METHOD 9076
     TEST METHOD FOR TOTAL CHLORINE  IN NEW AND USED PETROLEUM
       PRODUCTS BY  OXIDATIVE  COMBUSTION  AND MICROCOULOMETRY
7.2.2 Inject
 sample into
  cool boat
   Kith
 micropipet
                      7.2.4 Move
                      sample and
                       boat into
                      combus tion
                         tube
                      7.3.1 Verify
                        ays tern .
                       recovery
                      every 4 hours
7.2.1 Inject
 sample into
  cool boat
with syringe
                                                             7.32 Repeat
                                                               s tandard
                                                              measurement
                                                               at least
                                                              three times
 73.3 Check
system blank
 daily with
  is ooctane
                   7.4 Calculate
                     chlo rine
                   concent ration
                      STOP
                                 9076  - 10
                          Revision 0
                          November 1990

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                                  METHOD 9077

           TEST METHODS FOR TOTAL CHLORINE IN  NEW AND USED  PETROLEUM
                       PRODUCTS (FIELD TEST KIT METHODS)
1.0   SCOPE AND APPLICATION

      1.1    The  method  may be used  to  determine if a new  or used petroleum
product meets or  exceeds  requirements for total  halogen measured as chloride.
An analysis of the chlorine content of petroleum products is often  required prior
to their  use as a  fuel.   The method is specifically designed  for used oils
permitting onsite testing at remote locations by nontechnical  personnel to avoid
the delays for laboratory testing.

      1.2    In  these field  test  methods,  the  entire  analytical  sequence,
including  sampling,  sample  pretreatment, chemical  reactions,  extraction,  and
quantification, are combined in a single kit using  predispensed  and encapsulated
reagents.  The overall objective  is to provide  a simple, easy to  use procedure,
permitting nontechnical  personnel  to perform a test  with analytical  accuracy
outside of a laboratory  environment in under 10 minutes.  One of the kits is
preset at  1,000  ^9/9 total  chlorine  to  meet regulatory requirements  for used
oils.  The other kits provide  quantitative results  over  a  range of 750 to 7,000
/ng/g and 300 to 4,000 jug/g.

2.0   SUMMARY OF METHOD

      2.1    The oil  sample (around 0.4 g by volume) is dispersed in a solvent
and reacted  with  a mixture  of metallic  sodium catalyzed  with  naphthalene and
diglyme at ambient temperature.  This process converts all organic halogens to
their respective sodium halides.   All  halides in the treated mixture, including
those present prior to the reaction,  are  then extracted  into an aqueous buffer,
which is then  titrated  with mercuric nitrate using diphenyl carbazone  as the
indicator.  The end point of the titration is the formation of the blue-violet
mercury diphenylcarbazone complex.  Bromide and iodide are  titrated and reported
as chloride.

      2.2    Reagent  quantities are  preset  in  the fixed end  point kit (Method
A) so  that the color of the  solution at  the  end of the titration indicates
whether the  sample  is above  1,000 p,g/g chlorine  (yellow)  or below  1,000 ng/g
chlorine (blue).

      2.3    The first quantitative kit (Method B)  involves a reverse titration
of a  fixed  volume of mercuric nitrate with the extracted sample such that the end
point is denoted  by a change from blue to yellow in the titration vessel over the
range of the kit  (750 to 7,000 p.g/g).   The final  calculation  is based  on the
assumption that the oil  has a specific gravity of 0.9.

      2.4    The second quantitative kit (Method C)  involves  a  titration of the
extracted sample with mercuric nitrate by means of a 1-mL microburette such that
the end point  is  denoted by a change from pale yellow  to red-violet  over the
range of the kit (300 to 4,000 ng/g).   The concentration of  chlorine  in the
original oil  is then read from a  scale on the microburette.


                                   9077 - 1                       Revision 0
                                                                  November 1990

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NOTE:        Warning--All  reagents  are  encapsulated  or  contained  within
             ampoules.  Strict  adherence to the operational  procedures  included
             with the kits as well as accepted safety procedures (safety glasses
             and gloves) should be observed.

NOTE:        Warning—When crushing  the  glass ampoules, press  firmly in  the
             center of the ampoule once.  Never attempt to recrush  broken glass
             because the glass may come through the plastic and  cut  fingers.

NOTE:        Warning—In case of accidental breakage onto skin or clothing, wash
             with large amounts of water.  All the  ampoules are poisonous  and
             should not be taken internally.

NOTE:        Warning—The gray ampoules  contain  metallic  sodium.    Metallic
             sodium is a flammable water-reactive  solid.

NOTE:        Warning—Do not ship kits on passenger aircraft.  Dispose of used
             kits properly.

NOTE:        Caution—When the sodium  ampoule  in  either kit is crushed, oils
             that contain more than 25% water will  cause  the sample to turn
             clear to light gray.   Under these circumstances, the results  may
             be biased excessively low and should  be disregarded.

3.0   INTERFERENCES

      3.1    Free water, as a  second phase, should  be removed.  However, this
second phase can be analyzed separately for chloride content if  desired.
                                   9077 -  2                       Revision  0
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                                   METHOD A

                        FIXED  END  POINT TEST  KIT METHOD
4.0A  APPARATUS AND MATERIALS

      4.1A   The  CLOR-D-TECT  10001  is  a  complete  self-contained  kit.    It
includes:  a sampling  tube to withdraw a fixed sample  volume  for analysis; a
polyethylene test tube #1 into which the sample is introduced for dilution and
reaction with metallic sodium; and a  polyethylene tube #2 containing a buffered
aqueous  extractant,   the mercuric  nitrate  titrant,  and  diphenyl  carbazone
indicator.  Included are instructions to conduct the test and a color chart to
aid in determining the end point.

5.0A  REAGENTS

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

      5.2A   All  necessary reagents are contained within the kit.

      5.3A   The  kit  should  be examined upon  opening  to see that  all  of the
components are  present  and  that all the  ampoules  (4)   are  in place  and not
leaking.  The  liquid  in  Tube #2  (yellow cap)  should be approximately 1/2 in.
above the 5-mL line and  the  tube  should  not  be leaking. The ampoules are not
supposed to be  completely full.

6.0A  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1A   All  samples must be collected  using a sampling plan that addresses
the considerations discussed  in Chapter Nine.

      6.2A   Because the collected sample will be analyzed for total halogens,
it should be kept headspace  free and refrigerated  prior   to  preparation and
analysis to minimize  volatilization losses of organic halogens.  Because waste
oils may  contain  toxic and/or carcinogenic  substances,  appropriate field and
laboratory safety procedures  should be followed.

7.0A  PROCEDURE

      7.1A   Preparation.  Open analysis carton, remove  contents, mount plastic
test tubes in the provided holder. Remove syringe and glass sampling capillary
from foil pouch.
     Available from Dexsil Corporation, One Hamden Park Drive,  Hamden, CT 06517.
                                   9077 - 3                       Revision 0
                                                                  November 1990

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NOTE:         Perform the test in a warm, dry area with  adequate light.  In cold
              weather,  a truck  cab  is  sufficient.    If  a warm  area  is  not
              available, Step  7.3  should be performed while warming Tube #1 in
              palm  of hand.

      7.2A    Sample  introduction.   Remove white cap from  Tube #1.   Using the
plastic syringe, slowly draw the oil  up  the capillary tube  until it reaches the
flexible adapter tube.   Wipe excess oil  from the  tube with  the provided tissue,
keeping capillary  vertical.   Position capillary  tube into  Tube #1, and detach
adapter tubing, allowing capillary to drop to the bottom of the tube.  Replace
white cap on tube.  Crush the capillary by squeezing the  test tube several times,
being careful not  to break the glass reagent ampoules.

      7.3A    Reaction.  Break the  lower  (colorless) capsule  containing the clear
diluent solvent  by squeezing the  sides  of the  test tube.   Mix  thoroughly by
shaking the tube  vigorously  for 30 seconds.    Crush  the  upper  grey  ampoule
containing metallic sodium,  again by squeezing the sides of the test tube.  Shake
vigorously  for 20  seconds.   Allow reaction to proceed  for  60 seconds,  shaking
intermittently several  times while timing with a watch.

NOTE:         Caution—Always  crush  the clear  ampoule  in each  tube  first.
              Otherwise, stop the test and start over using another complete kit.
              False (low) results  may occur and  allow a contaminated sample to
              pass  without detection if  clear ampoule is not crushed first.

      7.4A    Extraction.  Remove caps from both tubes.  Pour the clear buffered
extraction solution from Tube #2 into Tube #1.  Replace the white cap on Tube #1,
and  shake  vigorously  for  10 seconds.   Vent tube by partially unscrewing  the
dispenser cap. Close cap securely, and shake for an additional  10 seconds.  Vent
again, tighten cap, and stand tube  upside  down on white  cap.   Allow phases to
separate for 2 minutes.

      7.5A   Analysis.  Put  filtration  funnel into  Tube  #2.   Position  Tube #1
over funnel and open nozzle on dispenser cap.  Squeeze  the  sides  of Tube #1 to
dispense the clear  aqueous lower phase through the filter  into  Tube #2 to the 5-
ml_ line on Tube #2.  Remove the filter  funnel.  Replace the yellow cap on Tube
#2 and close the nozzle on the dispenser cap.  Break  the colorless lower capsule
containing  mercuric nitrate  solution by squeezing the  sides  of the  tube,  and
shake for  10 seconds.   Then break the  upper colored  ampoule containing  the
diphenylcarbazone  indicator,  and  shake  for  10  seconds.   Observe  color
immediately.

      7.6A    Interpretation of results

              7.6.1A Because all reagent levels are preset,  calculations are not
      required.  A  blue solution  in Tube #2  indicates a chlorine content in the
      original oil  of  less than 1,000 /xg/g,  and  a yellow color indicates that
      the chlorine  concentration is greater than  1,000 ng/g. Refer to the color
      chart enclosed with  the kit in interpreting the titration end point.

             7.6.2A Report the results  as < or >  1,000 ng/g chlorine in the oil
      sample.
                                   9077 - 4                       Revision 0
                                                                  November 1990

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8.0A  QUALITY CONTROL

      8.1A   Refer to Chapter One for specific quality control procedures.

      8.2A   Each  sample  should be tested two  times.   If the results  do not
agree, then a third test must be performed.   Report the results of the two that
agree.

9.0A  METHOD PERFORMANCE

      9.1A   No formal  statement is made about either the precision or bias of
the overall test  kit  method for determining chlorine in  used  oil  because the
result merely states whether  there  is conformance  to the  criteria for success
specified in the procedure,  (i.e.. a blue or yellow color in the final solution).
In a collaborative study, eight laboratories analyzed four used crankcase oils
and three fuel oil blends with crankcase  in duplicate  using the test kit.  Of the
resulting 56 data points, 3 resulted  in incorrect  classification  of the oil's
chlorine content (Table 1).   A data point represents one duplicate analysis of
a sample.   There  were  no disagreements within  a laboratory on  any duplicate
determinations.
                                   9077 - 5                       Revision 0
                                                                  November 1990

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                                   TABLE 1.
                 PRECISION AND BIAS INFORMATION FOR METHOD A-
                        FIXED END POINT TEST KIT METHOD
  Expected
concentration,
                              Percent agreement*3
Expected results,    Percent
                    correct8  Within     Between
320
480
920
1,498
1,527
3,029
3,045
< 1,000
< 1,000
< 1,000
> 1,000
> 1,000
> 1,000
> 1,000
100
100
100
87
75
100
100
100
100
100
100
100
100
100
100
100
100
87
75
100
100
aPercent correct—percent correctly identified as above or below
   1,000
bPercent agreement --percent agreement within or between laboratories,
                                   9077 - 6
                                                Revision 0
                                                November 1990

-------
       START
                                           METHOD 9077  A
                               FIXED END POINT TEST  KIT  METHOD
7 1A Open  test kit
7 . 2A Draw  oil into
  capillary  tuba;
remove  excess oil;
drop capillary tube
 into Tube tl and
cap Tube /I: crush
  capillary  tube
    7.3A  Break
colorless  capsule;
  mix;  crush grey
capsule;  mix; allow
reaction  to proceed
    for 60 sec.
 7.1A Pour Tube t2
solution  into Tube
  t\;  mix; vent;
  allow phases  to
     separate
7 5A Filter aqueous
lower phase in Tube
 fi into  Tube #2;
   remove filter
   funnel; break
colorless capsule;
 mix;  break upper
 colored  capsule;
mix; observe color
 7 6.1  Chlorine
content  is > 1000
     ug/g
 7.6.1  Chlorine
content is < 1000
     ug/g
                               7.6.2 Report
                                  results
                                   STOP
                                              9077  -  7
                                                             Revision 0
                                                             November 1990

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                                   METHOD B

           REVERSE TITRATION QUANTITATIVE END POINT TEST KIT METHOD

4.OB APPARATUS AND MATERIALS

      4.IB    QuantiClor2 kit components (see Figure 1).

              4.1.IB   Plastic reaction  bottle:  1 oz, with  flip-top dropper cap
      and a crushable glass ampoule containing sodium.

              4.1.2B   Plastic buffer bottle:  contains  9.5  ml of aqueous buffer
      solution.

              4.1.3B   Titration vial:   contains  buffer  bottle and indicator-
      impregnated paper.

              4.1.4B   Glass vial:   contains 2.0 ml of  solvents.

              4.1.5B   Micropipet and  plunger,  0.25 ml_.

              4.1.6B   Activated carbon  filtering column.

              4.1.7B   Titret and valve  assembly.

      4.2B    The  reagents  needed  for the test  are  packaged in  disposable
containers.

      4.3B    The  procedure  utilizes  a  Titret.   Titrets*  are  hand-held,
disposable cells  for  titrimetric analysis.   A Titret  is  an  evacuated  glass
ampoule (13 mm diameter) that contains an exact amount of a standardized liquid
titrant^   A  flexible valve  assembly  is attached  to the tip  of  the  ampoule.
Titrets* employ the principle of reverse  titration; that  is, small  doses of
sample are added to the titrant to the appearance of the end point color.  The
color change indicates that  the equivalency point has been reached.  The flow of
the sample  into  the  Titret may  be  controlled  by using  an  accessory  called a
Titrettor™.

5.OB  REAGENTS

      5.IB    The crushable glass ampoule,  which is inside the reaction bottle,
contains 85 mg of metallic sodium in a light oil dispersion.

      5.2B    The buffer bottle contains 0.44 g of NaH2P04 • 2H20 and 0.32 ml of
HN03 in distilled  water.

      5.3B    The glass vial contains  770 mg Stoddard Solvent (CAS No.  8052-41-
3), 260 mg toluene,  260 mg  butyl  ether,  260  mg diglyme,  130 mg naphthalene, and
70 mg demulsifier.
     2Quanti-Chlor Kit, Titrets*, and Titrettor™ are manufactured by Chemetrics,
Inc., Calverton, VA  22016.  U.S. Patent No. 4,332,769.

                                   9077 - 8                       Revision 0
                                                                  November 1990

-------
      5.4B    The Titret contains 1.12 mg mercuric nitrate in distilled water.

      5.5B    The indicator-impregnated paper contains approximately 0.3 mg of
diphenylcarbazone and 0.2 mg of brilliant yellow.

6.OB  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

      See Section 6.0A of Method A.

7.OB PROCEDURE

      7.IB    Shake  the glass  vial  and pour  its  contents into  the  reaction
bottle.

      7.2B    Fill the micropipet with a well-shaken oil sample by pulling the
plunger until  its top edge is even with the top edge of the micropipet.  Wipe off
the excess oil and transfer the sample  into the reaction bottle  (see Figure 2.1).

      7.3B    Gently  squeeze  most of the air out of  the  reaction bottle (see
Figure 2.2).  Cap the bottle securely, and shake vigorously for 30 seconds.

      7.4B    Crush the sodium  ampoule by pressing against the outside wall of
the reaction bottle (see Figure 2.3).

NOTE:         Caution—Samples  containing  a high  percentage  of water  will
              generate  heat  and  gas,  causing  the reaction  bottle walls  to
              expand.  To release the  gas,  briefly loosen  the cap.

      7.5B    Shake the reaction  bottle vigorously for 30  seconds.

      7.6B    Wait 1 minute.  Shake the reaction bottle occasionally during this
time.

      7.7B    Remove the buffer bottle from the  titration vial, and slowly pour
its contents into the reaction bottle (see Figure 2.4).

      7.8B    Cap the reaction  bottle  and  shake gently for a  few seconds.   As
soon as the foam subsides,  release the  gas  by  loosening the cap.   Tighten the
cap, and shake vigorously for 30 seconds.   As before,  release any gas that has
formed, then turn the reaction bottle upside down (see Figure 2.5).

      7.9B    Wait 1 minute.

      7.10B   While holding the filtering column in a vertical position, remove
the plug.  Gently tap the column to settle the carbon  particles.

      7.11B   Keeping the reaction bottle upside down,  insert the flip top into
the end of the filtering column  and position  the column over the titration vial
(see Figure 2.6).  Slowly squeeze the  lower aqueous layer  out  of the reaction
bottle and into the filtering column.   Keep squeezing until  the  first drop of oil
is squeezed out.
                                   9077 - 9                       Revision 0
                                                                  November 1990

-------
NOTE:          Caution--The  aqueous layer  should flow  through the  filtering
               column  into the titration vial  in about  1 minute.  In rare cases,
               it  may  be  necessary  to  gently  tap the column  to begin  the flow.
               The indicator paper  should remain  in the titration vial.

      7.12B    Cap the titration vial  and shake  it vigorously  for 10 seconds.

      7.13B    Slide the flexible end of the valve assembly over the tapered tip
of the Titret so that it fits snugly (see Figure 3.1).

      7.14B    Lift  (see  Figure  3.2) the control bar  and  insert the  assembled
Titret into the Titrettor™.

      7.15B    Hold the Titrettor™ with the  sample pipe in the sample,  and press
the control bar to snap the pre-scored tip  of the Titret (see Figure  3.3).

NOTE:          Caution—Because  the Titret  is  sealed  under  vacuum, the  fluid
               inside  may be agitated when  the tip snaps.

      7.16B    With the tip of the sample pipe in the  sample, briefly  press  the
control  bar to pull  in a  SMALL amount  of sample  (see Figure 3.3).   The  contents
of the Titret will turn purple.

NOTE:          Caution—During the  titration, there will  be  some  undissolved
               powder  inside  the Titret.   This does  not  interfere  with  the
               accuracy of the test.

      7.17B    Wait 30 seconds.

      7.18B    Gently  press the control bar again to allow another  SMALL amount
of the sample to be drawn into the  Titret.

NOTE:          Caution--Do not press the control  bar unless  the sample  pipe is
               immersed in the sample.  This prevents  air from being drawn into
               the Titret.

      7.19B    After each addition,  rock the entire assembly to mix  the  contents
of the Titret.  Watch for a color change from purple to  very pale yellow.

      7.20B    Repeat  Steps 13.18 and  13.19 until the color change  occurs.

NOTE:          Caution—The end point color change (from  purple to  pale  yellow)
               actually goes through an intermediate  gray color.    During this
               intermediate stage,  extra caution should  be  taken  to bring  in
               SMALL amounts of sample and  to mix the Titret contents well.

      7.21B    When the color of the liquid in  the Titret changes to  PALE YELLOW,
remove the Titret from the Titrettor™.  Hold  the Titret  in a vertical  position
and carefully read the test  result  on  the scale opposite the liquid level.
                                  9077 - 10                       Revision  0
                                                                  November 1990

-------
      7.22B    Calculation

                       7.22.IB  To obtain results in micrograms per gram total
               chlorine,  multiply scale  units  on the Titret  by 1.3 and  then
               subtract  200.

8.OB  QUALITY CONTROL

      8.IB     Refer  to  Chapter One for specific quality control procedures.

      8.2B     Each  sample  should be  tested two times.  If the  results  do  not
agree to within 10%, expressed as  the relative percent difference  of the results,
a third test must be performed.   Report the results of the two that agree.

9.OB  METHOD PERFORMANCE

      9.IB     These  data  are  based  on  49  data  points  obtained  by  seven
laboratories who each analyzed four used crankcase oils and  three  fuel oil  blends
with crankcase in duplicate.  A data point represents one duplicate analysis of
a sample.   There were no outlier data points or laboratories.

      9.2B     Precision.   The precision  of the method as  determined  by  the
statistical examination of interlaboratory test results  is as  follows:

      Repeatability - The difference between successive results obtained  by the
same operator  with  the  same apparatus under constant operating conditions  on
identical  test material  would exceed, in the long run,  in the normal and correct
operation  of the  test method, the following values only in 1 case  in 20  (see
Table 2):


                         Repea tabi lity = 0.31 
-------
                                   TABLE 2.
            REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN USED
              OILS BY THE QUANTITATIVE END POINT TEST KIT METHOD
Average value,                Repeatability,        Reproducibility,
1,000
1,500
2,000
2,500
3,000
310
465
620
775
930
600
900
1,200
1,500
1,800
                                   TABLE 3.
            RECOVERY  AND BIAS DATA FOR CHLORINE  IN USED OILS BY THE
                    QUANTITATIVE END POINT TEST KIT METHOD
Amount
expected,
M9/9
320 (< 750)a
480 (< 750)a
920
1,498
1,527
3,029
3,045
Amount
found,
M9/g
776
782
1,020
1,129
1,434
1,853
2,380

Bias,
Mg/g
+16
+32
+100
-369
-93
-1,176
-665

Percent
bias
+3
+4
+11
-25
-6
-39
-22
  The lower limit of the kit is 750 p.g/g.
                                   9077 -  12                      Revision 0
                                                                  November 1990

-------
                                                      Reaction bottle
Titration via
                                              Filtering
                                              Column
                                   assembly
                                      6
  *—'r
Buffer
bottle
                             Micro pipet
 Figure 1.  Components of CHEMetrics Total Chlorine in Waste Oil Test Kit
          (Cat. No. K2610).
                              9077 -  13
                                                 Revision 0
                                                 November 1990

-------
Push plunger
down to
transfer
sample
            Figure 2.1
                                                             Figure 2.2
                       * Crush
          Figure 2.3
                                          Buffer Bottle
                 Figure 2.4
              Reaction bottle
              upsidedown in
              component tray
          Figure 2.5
Aqueous
Layer
                                                        Filtering Column
                                                                        Figure 2.6
                                                         Titration Vial
            Figure 2.   Reaction-Extraction  Procedure.
                               9077  -  14
                         Revision  0
                         November 1990

-------
  Attaching
  the Valve
  Assembly
    Figure 3.1
Valve
Assembly
                      Titret
                                   \
                                       /\
  Snapping
  the Tip
    Figure 3.2
                       Lift control bar
 Performing the
 Analysis
    Figure 3.3

  Watch for
  color change
  here

Press control bar

  Sample pipe


  Sample
         Reading
         the Result
           Figure 3.4


         Read
         scale units
         when color
         changes
         permanently
          Figure 3.  Titration Procedure
                    9077 - 15
                           Revision 0
                           November 1990

-------
                           METHOD 9077 B
REVERSE  TITRATION QUANTITATIVE END POINT TEST  KIT  METHOD
       START
...
7. IB Shake glass
vial, pour into
reaction bottle
1
7-2B Fill
micropipet with
oil; remove excess
oil; t rans f er oil
to reaction bottle

7 . 3B Squeeze air
from reaction
bottle; cap ; mix
i
7.4B Crush sodium
ampoule
.
7 5B - 7 .68 Shake
reaction bottle for
30 seconds ; wai t
one minute

7 . 7B Pour buffer
into reaction
bottle

•»

7 SB - 7.9B Shake
gent 1 y ; rel ease
gas; shake; release
gas; turn bottle
upside down; wait
one minute

7 .10B Prepare
filtering column
1
7 .118 Filter lower
aqueous layer
through filtering
column into
ti t ra t i on vial
.
7.12B Shake vial
1
7.13B Assemble
valve assembly over
Titret
..
7.14B Insert Titret
into Titrettor
                                                7.158 Snap tip  of
                                                    Titret
                                               7.16B - 7.20B Pull
                                                 3ma 11 amount of
                                               sample into Titret;
                                                  mix; wai t 30
                                                 seconds;  repea t
                                               process until color
                                               changes from purple
                                                 to  pale yellow
                                                7.21B When color
                                                 changes to pale
                                                 yel1ow, remove
                                               Titret;  record  test
                                               result from Titret
                                                 7.22B Calculate
                                                concent ration  of
                                                chlorine in ug/g
                                                     STOP
                             9077  - 16
Revision 0
November 1990

-------
                                   METHOD C

             DIRECT TITRATION QUANTITAVE END POINT TEST KIT METHOD

4.0C  APPARATUS AND MATERIALS

      4.1C    The  CHLOR-D-TECT Q40003  is  a  complete  self-contained kit.   It
includes:  a sampling syringe to  withdraw a  fixed  sample volume for  analysis; a
polyethylene test tube #1 into which the sample is introduced for dilution and
reaction  with  metallic sodium;  a  polyethylene tube #2 containing  a buffered
aqueous extractant and the diphenylcarbazone  indicator; a microburette containing
the mercuric nitrate titrant; and a plastic filtration funnel.  Also included are
instructions to conduct the test.

5.0C  REAGENTS

      5.1C   All  necessary reagents are contained within the kit.  The diluent
solvent containing the catalyst,  the metallic sodium, and the diphenylcarbazone
are separately glass-encapsulated in the precise quantity required for analysis.
A predispensed volume  of  buffer  is contained in the second polyethylene tube.
Mercuric nitrate titrant  is also supplied in a sealed titration burette.

      5.2C   The  kit  should be  examined  upon  opening  to   see that  all  of the
components are present and that  all ampoules (3) are in place and not leaking.
The liquid in Tube #2  (clear cap) should be approximately 1/2 in.  above the 5-mL
line and the tube  should  not  be  leaking.   The ampoules are not supposed to be
completely full.

6.0C  SAMPLE COLLECTION,  PRESERVATION, AND HANDLING

      6.1C   See  Section  6.0A of Method A.

7.0C  PROCEDURE

      7.1C   Preparation.  Open analysis carton, remove contents, mount plastic
test tubes in the provided holder.

NOTE:        Perform the  test in a warm, dry area  with  adequate light.  In cold
             weather,  a  truck  cab is  sufficient.    If  a warm  area  is  not
             available, Step 19.3  should be performed while warming Tube #1 in
             palm of hand.

      7.2C   Sample introduction.  Unscrew the white dispenser cap from Tube #1.
Slide the plunger  in the empty syringe  a few times to make certain  that it slides
easily.  Place the top of the syringe in the oil sample to be tested, and pull
back on the  plunger until it reaches  the stop and cannot  be  pulled further.
Remove the syringe from the sample container, and wipe any excess oil from the
outside of the syringe with the enclosed tissue.  Place the tip of the syringe
in Tube #1, and dispense the oil  sample by depressing the  plunger. Replace the
white cap on the tube.
     Available from Dexsil Corporation, One Hamden Park Drive,  Hamden, CT 06517.

                                   9077 -  17                       Revision 0
                                                                  November 1990

-------
      7.3C   Reaction.  Break the lower (colorless) capsule containing the clear
diluent solvent  by  squeezing the sides of  the  test tube.  Mix  thoroughly by
shaking the  tube vigorously  for 30  seconds.   Crush  the upper  grey  ampoule
containing metallic  sodium, again by squeezing the  sides of the  test tube.  Shake
vigorously for 20 seconds.  Allow reaction  to proceed  for 60  seconds,  shaking
intermittently several times while timing with  a watch.

NOTE:        Caution--Always  crush  the  clear  ampoule  in  each  tube  first.
             Otherwise, stop the test  and start  over using  another complete kit.
             False  (low)  results may  occur  and  allow a contaminated sample to
             pass without detection if clear ampoule is not crushed first.

      7.4C   Extraction.  Remove caps from both  tubes.  Pour the clear buffered
extraction solution  from Tube #2 into Tube #1.  Replace the white cap  on Tube #1,
and  shake  vigorously  for  10 seconds.   Vent tube by partially unscrewing the
dispenser cap.  Close cap securely,  and shake for an additional  10 seconds.  Vent
again, tighten cap,  and stand tube  upside down  on white  cap.   Allow phases to
separate for 2 minutes.

NOTE:        Tip Tube #2 to an angle of only about 45°.  This  will prevent the
             holder from sliding out.

      7.5C   Analysis.  Put  filtration funnel into  Tube  #2.   Position  Tube #1
over funnel and open nozzle on dispenser cap.  Squeeze the sides  of Tube #1 to
dispense the clear aqueous lower phase through the filter into  Tube #2 to the 5-
mL line on Tube #2.   Remove  the filter funnel,  and close the nozzle  on the
dispenser cap.  Place the plunger rod in the titration burette and press until
it clicks  into  place.   Break off (do not  pull  off) the  tip  on  the titration
burette.   Insert the burette into  Tube  #2, and  tighten  the  cap.   Break the
colored ampoule,  and shake gently for  10 seconds.  Dispense titrant dropwise by
pushing down on burette rod in small increments.  Shake the tube  gently to mix
titrant with solution in Tube #2  after each  increment.  Continue adding titrant
until solution turns from  yellow to  red-violet.  An intermediate pink color may
develop in the solution, but  should  be disregarded.  Continue titrating until a
true red-violet color is realized.   The chlorine concentration of the original
oil sample is read directly off the titrating burette  at  the  tip  of the black
plunger.  Record this result  immediatley  as  the  red-violet color will fade with
time.

8.0C QUALITY CONTROL

      8.1C   Refer to Chapter One for specific quality control procedures.

      8.2C   Each sample  should be tested  two  times.   If the results  do not
agree to within 10%,  expressed as the relative percent difference of the results,
a third test must be performed.   Report the results of the two that agree.

9.0C METHOD PERFORMANCE

      9.1C   These data are based on 96 data points obtained by 12 laboratories
who each analyzed six  used crankcase oils and two fuel oil  blends with crankcase
in duplicate.  A data point represents one duplicate analysis  of a sample.
                                   9077  -  18                       Revision 0
                                                                  November 1990

-------
      9.2C   Precision.   The precision  of the  method  as determined  by the
statistical  examination of interlaboratory  test  results  is as follows:

      Repeatability -  The  difference between successive results  obtained by the
same operator with  the  same  apparatus  under constant operating conditions on
identical test material would exceed, in the long  run, in the  normal  and correct
operation of the test method, the  following  values  only in  1  case in 20 (see
Table 4):
                         Repeatability = 0.175
      *where x is the average of two results  in

      Reproducibilitv - The difference between two single and independent results
obtained by different operators working  in  different laboratories on identical
test material  would exceed, in the long run, the following values only in  1 case
in 20:
                       Reproducibility = 0.331
      *where x is the average value of two  results  in pg/g.

      9.3C   Bias.  The bias of this test method  varies with concentration, as
shown in Table 5:

                     Bias = Amount  found - Amount expected

10.0 REFERENCE

1.    Gaskill, A.; Estes,  E.D.;  Hardison, D.L.; and Myers, L.E.  Validation of
      Methods for Determining Chlorine in Used Oils and Oil Fuels.   Prepared for
      U.S. Environmental Protection Agency,  Office of Solid Waste.   EPA Contract
      No. 68-01-7075, wA 80.   July 1988.
                                  9077 - 19                      Revision 0
                                                                 November 1990

-------
                                   TABLE 4.
            REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN USED
              OILS BY THE QUANTITATIVE END POINT TEST KIT METHOD
Average value,                Repeatability,        Reproducibility,
    M9/9                          M9/9                   M9/9
500
1,000
1,500
2,000
2,500
3,000
4,000
88
175
263
350
438
525
700
166
331
497
662
828
993
1,324
                                   TABLE 5.
            RECOVERY  AND BIAS  DATA  FOR  CHLORINE  IN  USED  OILS  BY  THE
                    QUANTITATIVE END POINT TEST KIT METHOD
Amount
expected,
M9/9
664
964
1,230
1,445
2,014
2,913
3,812
4,190
Amount
found,
M9/9
695
906
1,116
1,255
1,618
2,119
2,776
3,211

Bias,
M9/9
31
-58
-114
-190
-396
-794
-1,036
-979

Percent
bias
+5
-6
-9
-13
-20
-27
-27
-23
                                   9077  -  20                       Revision 0
                                                                  November  1990

-------
                          METHOD 9077  C
DIRECT TITRATION QUANTITAVE  END  POINT TEST  KIT METHOD
                  START
            7.1C Open test  kit
            7.2C Draw oil  into
             syringe;  remove
               excess  oil;
            dispense oil  into
                 Tube  ti
               7.3C Break
           colorless capsule;
             mix;  crush grey
           capsule; mix; allow
           reaction to proceed
             for 60 seconds
             7.4C Pour Tube H
            solution into  Tube
             #1;  mix;  vent;
             allow phases  to
                separate
            7.SC Filter  aqueous
            lower phase  in Tube
            fl into Tube t2,
              remove filter
                 funnel
7.SC  Place plunger
   in  titraton
  burette; press;
 break  off burette
tip;  insert burette
 in Tube #2;  break
 colored ampoule;
       shake
   7.SC Dispense
  titrant; shake;
  repeat process
  until solution
 turns from yellow
   to red*violet
 7.SC Record level
  from titrating
     buret te
      STOP
                            9077  -  21
                                 Revision 0
                                 November 1990

-------
                                 METHOD 9200A

                                    NITRATE
1.0  SCOPE AND APPLICATION

      1.1    This method is applicable to the analysis of groundwater, drinking,
surface, and saline waters, and domestic and industrial wastes.  Modifications
can be made to remove  or  correct  for  turbidity,  color, salinity,  or dissolved
organic compounds in the sample.

      1.2    The applicable range  of concentration is 0.1 to 2 mg N03-N per liter
of sample.

2.0   SUMMARY OF METHOD

      2.1    This method  is based upon  the  reaction  of the  nitrate  ion with
brucine sulfate in a 13 N  H2S04 solution at a temperature  of 100°C.   The color
of the resulting complex is measured at 410  nm.  Temperature control of the color
reaction is extremely critical.

3.0   INTERFERENCES

      3.1    Dissolved organic matter will  cause an off color in 13  N  H2S04 and
must  be compensated  for   by  additions   of  all   reagents  except the  brucine-
sulfanilic  acid  reagent.    This  also  applies to  natural color,  not  due  to
dissolved organics,  that is present.

      3.2    If the  sample is colored or  if the conditions  of the  test cause
extraneous  coloration,  this  interference  should  be   corrected  by  running  a
concurrent sample under the same conditions but in the absence of the brucine-
sulfanilic acid reagent.

      3.3    Strong  oxidizing  or reducing  agents  cause  interference.   The
presence of  oxidizing  agents may  be  determined  by a  residual  chlorine test;
reducing agents may be detected with potassium permanganate.

             3.3.1    Oxidizing agents'  interference  is  eliminated  by  the
      addition of sodium arsenite.

             3.3.2    Reducing agents  may be  oxidized  by addition of H202.

      3.4    Ferrous  and   ferric  ion  and  quadrivalent manganese give  slight
positive  interferences,  but  in  concentrations  less  than  1  mg/L  these  are
negligible.

      3.5    Uneven  heating  of the samples and  standards during  the  reaction
time will  result  in erratic  values.    The  necessity  for  absolute  control  of
temperature during the critical  color development period cannot be too strongly
emphasized.
                                   9200A  -  1                       Revision 1
                                                                  November 1990

-------
4.0   APPARATUS AND MATERIALS

      4.1     Spectrophotometer  or  filter photometer  suitable  for measuring
absorbance at 410 nm.

      4.2     Sufficient  number  of 40-  to 50-mL glass sample tubes for reagent
blanks, standards, and samples.

      4.3     Neoprene-coated wire racks  to hold  sample tubes.

      4.4     Water bath  suitable  for use  at 100°C.  This bath should contain a
stirring mechanism so that all tubes are  at the  same temperature and should be
of  sufficient capacity  to  accept the  required  number of  tubes  without  a
significant drop in temperature when the  tubes are immersed.

      4.5     Water bath  suitable  for use  at 10-15°C.

      4.6     Analytical  balance:   capable of weighing to 0.0001  g.

      4.7     Class A volumetric flasks:   1 L.

      4.8     pH  Indicator paper.

5.0  REAGENTS

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

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

      5.3     Sodium  chloride  solution  (30%):   Dissolve 300 g  NaCl in reagent
water and dilute to 1 liter with  reagent water.

      5.4     Sulfuric acid solution: Carefully add 500 ml concentrated H2S04 to
125 ml reagent water.  Cool  and  keep tightly stoppered to prevent absorption of
atmospheric moisture.

      5.5     Brucine-sulfanilic acid reagent:  Dissolve 1 g brucine sulfate --
(C23H26N204)2 . H2S04 . 7H20 --  and  0.1 g  sulfanilic acid  (NH2C6H4S03H • H20)  in
70 ml not reagent water.  Add 3 ml  concentrated HC1,  cool,  mix,  and dilute to 100
ml with reagent water.   Store  in a dark bottle  at 5°C.  This solution is stable
for  several  months;  the pink color that  develops  slowly does not affect its
usefulness.  Mark bottle with warning.  "CAUTION:  Brucine Sulfate is toxic; do
not ingest."

      5.6     Potassium nitrate stock solution  (1.0 ml = 0.1  mg  N03-N):  Dissolve
0.7218 g anhydrous potassium  nitrate  (KN03)  in  reagent water and  dilute  to 1
liter in a Class A volumetric flask.  Preserve with 2 ml chloroform per liter.
This solution is stable for at least 6 months.

                                   9200A  - 2                       Revision 1
                                                                  November 1990

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      5.7    Potassium  nitrate  standard solution  (1.0  mi =  0.001  mg N03-N):
Dilute  10.0  mL  of  the  stock  solution  (Step  5.6) to  1  liter  in  a  Class  A
volumetric flask.  This standard solution should be prepared fresh weekly.

      5.8    Acetic acid  (1+3):  Dilute  1 volume glacial acetic acid  (CH3COOH)
with 3 volumes of reagent water.

      5.9    Sodium hydroxide  (1 N):   Dissolve 40  g of NaOH in reagent water.
Cool and dilute to 1 liter with reagent water.

6.0  SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

      6.2    Analysis should be performed within 48 hours.  If analysis can be
done within 24 hours, the sample should  be  preserved by refrigeration at 4°C.
When samples must be stored for more than  24 hours, they should  be preserved with
sulfuric acid (2 mL/L concentrated H2S04) and  refrigerated.

7.0  PROCEDURE

      7.1    Adjust the  pH  of  the  samples  to  approximately  7  with acetic acid
(Step 5.8)  or sodium hydroxide  (Step 5.9).   If necessary,  filter  to remove
turbidity.  Sulfuric acid can be used in place of acetic acid, if preferred.

      7.2    Set  up the  required number  of  sample  tubes in  the rack to handle
the reagent blank, standards,  and  samples.   Space  tubes evenly throughout the
rack to allow for even flow  of bath water between the tubes.  This should assist
in achieving uniform heating of all tubes.

      7.3     If  it is necessary to  correct for color or dissolved organic matter
which will cause  color on  heating, run a set of duplicate samples with all of the
reagents, except the brucine-sulfanilic acid.

      7.4    Pipet 10.0 mL of standards and samples or an aliquot of the samples
diluted to 10.0 mL into the sample tubes.

      7.5     If  the  samples are saline, add  2 mL of the 30% sodium chloride
solution (Step 5.3) to the reagent blank,  standards, and samples. For freshwater
samples,  sodium  chloride solution  may be omitted.   Mix contents of tubes by
swirling; place rack in cold-water bath  (0-10°C).

      7.6    Pipet 10.0 mL  of sulfuric acid solution  (Step 5.4) into each tube
and mix  by  swirling.   Allow tubes  to come to  thermal  equilibrium in the cold
bath.    Be  sure  that  temperatures  have  equilibrated  in  all  tubes  before
continuing.

             7.6.1    Add 0.5 mL brucine-sulfanilic acid reagent (Step 5.5) to
      each tube  (except  the interference control  tubes)  and  carefully mix by
      swirling; place the rack of tubes  in the 100°C water bath for exactly 25
      minutes.
                                   9200A -  3                       Revision 1
                                                                  November  1990

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CAUTION:     Immersion of the tube rack  into  the  bath  should  not decrease the
             temperature of the bath  by more than  1-2°C.  In order to keep this
             temperature decrease to  an  absolute minimum,  flow  of  bath water
             between the tubes  should not be restricted by crowding  too many
             tubes into the  rack.  If color development  in the standards reveals
             discrepancies  in  the procedure, the operator should  repeat the
             procedure after reviewing the temperature control steps.

      7.7    Remove rack of tubes from the hot-water bath,  immerse in the cold-
water bath, and allow to reach thermal equilibrium (20-25°C).

      7.8    Read absorbance against  the  reagent  blank at  410 nm using a 1-cm
or longer cell.

      7.9    Calculation:

             7.9.1   Obtain a  standard  curve by  plotting the  absorbance  of
      standards run  by the  above  procedure  against mg/L  N03-N.   (The color
      reaction does not always follow Beer's law.)

             7.9.2   Subtract the absorbance of the sample  without the brucine-
      sulfanilic reagent from the absorbance of the sample  containing brucine-
      sulfanilic acid  and  determine  mg/L  N03-N.   Multiply by  an  appropriate
      dilution factor if less than 10 ml of sample is taken.

8.0  QUALITY CONTROL

      8.1    Refer to Chapter One for specific quality control procedures.

      8.2    Linear calibration curves must be composed of  a minimum of  a blank
and five  standards.   A set  of  standards  must be included with  each  batch  of
samples.

      8.3    Dilute  samples if  they  are  more  concentrated  than the  highest
standard or if they fall on the plateau of a calibration curve.

      8.4    After  calibrating,  verify   calibration  with  an  independently
prepared check standard.

      8.5    Matrix spikes  and matrix spike duplicates are brought through the
whole sample preparation and analytical process.

9.0  METHOD PERFORMANCE

      9.1    Twenty-seven analysts  in fifteen  laboratories  analyzed natural-
water  samples  containing  exact  increments   of   inorganic nitrate,  with  the
following results:
                                   9200A -  4                      Revision 1
                                                                  November 1990

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         Increment as            Precision as           Accuracy as
      Nitrogen, Nitrate       Standard Deviation      Bias        Bias
          (mg/L N)                 (mg/L N)            (%)      (mg/L N)
0.16
0.19
1.08
1.24
0.092
0.083
0.245
0.214
-6.79
+8.30
+4.12
+2.82
-0.01
+0.02
+0.04
+0.04
10.0  REFERENCES

1.    Annual Book of ASTM Standards,  Part 31,  "Water," Standard D992-71, p. 363
(1976).

2.    Jenkins, D.  and  L.  Medsken,  "A Brucine Method  for  the Determination of
Nitrate in Ocean, Estuarine, and Fresh Water," Anal.Chem., 36, p. 610 (1964).

3.    Standard Methods for the Examination of Water and Wastewater,  14th ed., p.
427, Method 419D (1975).
                                   9200A -  5                       Revision 1
                                                                  November 1990

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                          METHOD  9200A

                              NITRATE
                              START
    7.3  Run
duplicates with
 all  reagenti
except brucine
sulfanilic acid
  7.5  Add  30S
sodium chloride
solution;  mm;
 place in  cold
  water bath

-
7.1 Adjust pH
of samples to
7; filter if
necessary
                           7.2  Set up
                          sample  tubes
                             in rack
                           7  4  Pipette
                          standards and
                          samples  into
                          sample tubes
                           7.6  Pipette
                          sulfuric acid
                          solution into
                           each tube;
                               mix
                                                   761 Add
                                                    brucine
                                                  sulfanilie
                                                 acid reagent
                                                 to  each tube
  7.6 1  Bathe
 rack of tubes
 in 100C water
  for 25 min
  7 . 7  Immerse
 tubes in  cold
water;  allow to
 reach thermal
  equilibr ium
   78  Read
  absorbance
    against
 reagent  blank
   at  410  nm
791  Obtain a
std absorbance
   curve  and
calculate mg/L
    nitrate
     STOP
                            9200A -  6
                      Revision 1
                      November 1990

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                                  METHOD  9252

                   CHLORIDE (TITRIMETRIC. MERCURIC NITRATE)
1.0   SCOPE AND APPLICATION

      1.1    This method is applicable to ground water, drinking, surface, and
saline waters, and domestic and industrial wastes.

      1.2    The method  is suitable for all concentration  ranges  of chloride
content; however,  in  order to avoid large titration volume,  a  sample aliquot
containing not more than 10 to 20 mg Cl"  per 50 ml is used.

      1.3    Automated titration may be used.

2.0   SUMMARY OF METHOD

      2.1    An  acidified sample  is titrated  with mercuric  nitrate  in the
presence of mixed diphenylcarbazone-bromophenol blue indicator.   The end point
of the titration is the formation of the blue-violet mercury diphenylcarbazone
complex.

3.0   INTERFERENCES

      3.1    Anions  and  cations at  concentrations  normally found  in surface
waters do not interfere.   However,  at the  higher concentration  often found in
certain wastes,  problems may occur.

      3.2    Sulfite  interference  can be eliminated by oxidizing the 50 ml of
sample solution with 0.5-1 ml of H202.

4.0   APPARATUS AND MATERIALS

      4.1    Standard laboratory titrimetric equipment, including 1 mL or 5 mL
microburet with 0.01 mL gradations.

      4.2    Class A volumetric flasks:   1 L and  100 mL.

      4.3    pH Indicator  paper.

      4.4    Analytical balance:  capable of weighing to 0.0001 g.

5.0   REAGENTS

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

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

                                   9252 -  1                        Revision 1
                                                                  November 1990

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      5.3     Standard  sodium chloride  solution,  0.025 N:   Dissolve 1.4613 g ±
0.0002 g of sodium chloride (dried at 600°C for 1  hr)  in chloride-free water in
a 1 liter Class A volumetric  flask and dilute to the mark with reagent water.

      5.4     Nitric  acid  (HNO,) solution:  Add 3.0 ml concentrated nitric acid
to 997 ml of  reagent water ("3 + 997" solution).

      5.5     Sodium  hydroxide (NaOH) solution (10 g/L):  Dissolve approximately
10 g of NaOH  in reagent water and dilute to 1 L with reagent water.

      5.6     Hydrogen  peroxide  (H202):   30%.

      5.7     Hydroquinone  solution  (10  g/L):    Dissolve   1  g  of  purified
hydroquinone  in reagent water in a 100 ml Class A volumetric  flask and dilute to
the mark.

      5.8     Mercuric  nitrate titrant (0.141 N):   Dissolve 24.2 g Hg(N03)2 • H20
in 900 mL of reagent water acidified with 5.0 ml  concentrated HN03 in a 1 liter
volumetric  flask and  dilute to  the  mark with  reagent  water.   Filter,  if
necessary.   Standardize against standard  sodium  chloride solution  (Step 5.3)
using the procedures outlined in  Section 7.0.  Adjust to exactly  0.141  N and
check.  Store in a dark bottle.  A 1.00 mL aliquot is equivalent to 5.00 mg of
chloride.

      5.9     Mercuric  nitrate titrant  (0.025  N):   Dissolve  4.2830 g Hg(N03)2 •
H20 in 50 mL  of   reagent   water  acidified  with   0.05 mL  of  concentrated
HN03 (sp. gr. 1.42)  in  a 1 liter  volumetric  flask and dilute to the  mark with
reagent  water.   Filter,  if  necessary.   Standardize against  standard  sodium
chloride  solution  (Step 5.3)  using the  procedures  outlined in Section 7.0.
Adjust to exactly 0.025 N and check.  Store in a dark bottle.

      5.10    Mercuric  nitrate titrant (0.0141 N):  Dissolve  2.4200  g Hg(N03)2 •
H20 in 25 mL of reagent water acidified with 0.25 mL of concentrated HN03 (sp.
gr. 1.42) in  a  1 liter Class A  volumetric flask and dilute to the mark with
reagent  water.   Filter,  if  necessary.   Standardize against  standard  sodium
chloride  solution  (Step 5.3)  using the  procedures  outlined in Section 7.0.
Adjust to exactly 0.0141 N and check.  Store in a dark bottle.   A 1 mL aliquot
is equivalent to 500 jug of chloride.

      5.11    Mixed indicator reagent:  Dissolve 0.5 g crystalline diphenylcar-
bazone and 0.05  g bromophenol  blue powder in 75 mL 95% ethanol in a 100 mL Class
A volumetric  flask  and dilute to the mark with  95% ethanol.   Store  in  brown
bottle and discard after 6 mo.

      5.12    Alphazurine indicator  solution:   Dissolve 0.005 g of  alphazurine
blue-green dye in 95% ethanol  or  isopropanol  in 100 mL Class A volumetric flask
and dilute to the mark with 95% ethanol  orv isopropanol.

6.0   SAMPLE COLLECTION, PRESERVATION,  AND HANDLING

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

      6.2     There are  no special requirements for preservation.

                                  9252  -  2                       Revision 1
                                                                  November 1990

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7.0   PROCEDURE

      7.1    Place 50 ml of sample  in a vessel for titration.  If the concentra-
tion is greater than 20 mg/L chloride, use 0.141 N mercuric nitrate titrant (Step
5.8) in  Step 7.6,  or dilute sample  with reagent water.  If the concentration is
less than 2.5 mg/L of chloride, use  0.0141 N mercuric nitrate titrant (Step 5.10)
in Step 7.6.  Using a 1 mL or 5 ml microburet, determine an indicator blank on
50 ml chloride-free water using Step 7.6.  If the concentration  is less than 0.1
mg/L of chloride,  concentrate an appropriate volume to 50 ml.

      7.2    Add 5 to 10 drops of mixed  indicator reagent (Step 5.11); shake or
swirl solution.

      7.3    If a blue-violet or red color appears, add HN03 solution (Step 5.4)
dropwise until  the color changes to yellow.  Proceed to Step 7.5.

      7.4    If a yellow or  orange color  forms  immediately  on  addition of the
mixed indicator, add NaOH solution (Step 5.5) dropwise until  the color changes
to  blue-violet;  then add  HN03  solution  (Step  5.4)  dropwise until  the  color
changes to yellow.

      7.5    Add 1 ml excess  HN03 solution  (Step 5.4).

      7.6    Titrate with  0.025  N  mercuric  nitrate titrant  (Step  5.9) until  a
blue-violet color  persists throughout the solution. If volume  of titrant exceeds
10  ml  or is less  than  1  mL, use the  0.141 N  or 0.0141  N mercuric nitrate
solutions, respectively.  If necessary,  take a small sample aliquot.  Alphazurine
indicator solution (Step 5.12) may be  added with the indicator to sharpen the end
point.  This will  change color shades.   Practice runs should be made.

Note:        The use of indicator modifications  and the presence of heavy metal
             ions can change  solution colors without affecting the accuracy of
             the determination.  For example, solutions containing alphazurine
             may be bright blue when neutral, grayish purple when basic,  blue-
             green  when acidic, and  blue-violet  at  the chloride end  point.
             Solutions  containing  about  100 mg/L  nickel ion and  normal  mixed
             indicator  are purple when neutral, green when acidic, and gray at
             the chloride end point.  When  applying this method to samples that
             contain  colored ions or that  require modified indicator,  it is
             recommended  that the  operator become  familiar  with  the specific
             color changes involved by  experimenting with solutions prepared as
             standards  for comparison of color effects.

             7.6.1    If chromate  is  present  at  <100  mg/L  and  iron is  not
      present,  add 5-10 drops of alphazurine indicator solution (Step 5.12) and
      acidify to a pH of 3  (indicating paper).  End point  will then be an olive-
      purple color.

             7.6.2    If chromate  is  present  at  >100  mg/L  and  iron is  not
      present,  add 2 mL of fresh hydroquinone solution (Step 5.7).

             7.6.3    If ferric ion is  present use a volume containing no more
      than 2.5  mg  of ferric ion or  ferric ion plus chromate  ion.  Add 2 mL fresh
      hydroquinone solution  (Step 5.7).

                                   9252  - 3                        Revision 1
                                                                  November  1990

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             7.6.4    If sulfite ion  is  present,  add 0.5 ml  of H202  solution
      (Step 5.6) to a 50 ml sample and mix for 1 min.

      7.7    Calculation:

                               (A - B)N x 35,450
          mg chloride/liter = 	
                                  ml of sample

             where:

                     A  = mi  titrant  for  sample;

                     B  = ml  titrant  for  blank; and

                     N  = normality  of  mercuric nitrate titrant.

8.0   QUALITY CONTROL

      8.1    Refer to Chapter One for specific quality control procedures.

      8.2    A matrix duplicate and  matrix  spike sample are brought through the
whole sample preparation and analytical process.

9.0   METHOD PERFORMANCE

      9.1    Water samples—A total  of 42 analysts in 18  laboratories analyzed
synthetic water samples containing exact increments of chloride, with the results
shown in Table 1.

      In  a  single  laboratory,  using  surface  water  samples at  an  average
concentration of 34 mg CT/L, the standard  deviation  was  +1.0.

      A synthetic unknown sample containing 241  mg/L chloride, 108 mg/L Ca, 82
mg/L Mg, 3.1 mg/L K,  19.9 mg/L Na, 1.1 mg/L nitrate N, 0.25 mg/L nitrate N, 259
mg/L sulfate and 42.5 mg/L total alkalinity (contributed  by NaHCOJ  in reagent
water was  analyzed  in  10  laboratories  by the mercurimetric method, with  a
relative standard deviation of 3.3% and a relative error  of 2.9%.

      9.2  Oil  combustates--These data  are  based  on 34 data points obtained by
five laboratories who each  analyzed  four  used crankcase oils and three fuel oil
blends with crankcase oil in  duplicate.   The samples were combusted using Method
5050.  A data  point  represents one  duplicate analysis of a sample.   One data
point was judged to be an outlier and was not included in these results.

           9.2.1  Precision and bias.

                  9.2.1.1  Precision.  The precision of the method as determined
           by the statistical examination of interlaboratory test results is as
           follows:
                                   9252  -  4                        Revision 1
                                                                  November 1990

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                  Repeatability -  The  difference between  successive results
           obtained by the same operator with the same apparatus under constant
           operating conditions on  identical test material  would exceed, in the
           long run,  in the normal  and correct operation of the test method, the
           following values  only  in 1 case  in 20  (see Table 2):


                         Repeatability = 7.61 Jx*
           *where x is the average  of two  results in /ng/g.

                  Reproducibilitv  -  The  difference  between  two  single  and
           independent results  obtained  by different  operators  working  in
           different laboratories on identical  test material would exceed, in
           the long run,  the following values only  in 1 case in 20:
                       Reproducibility = 20.02
           *where x is the average  value  of  two results in M9/9-

                  9.2.1.2    Bias.    The  bias  of  this   method   varies  with
           concentration, as shown  in Table  3:


                    Bias =  Amount  found - Amount expected

10.0  REFERENCES

1.    Annual Book of ASTM Standards, Part 31, "Water,"  Standard  D512-67, Method
A, p. 270 (1976).

2.    Standard Methods for  the Examination of Water and Wastewater, 15th ed.,
(1980).

3.    U.S.  Environmental  Protection Agency,  Methods  for  Chemical  Analysis of
Water and Wastes, EPA 600/4-79-020  (1983), Method  325.3.
                                  9252 - 5                       Revision 1
                                                                 November 1990

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          TABLE  1.  ANALYSES OF SYNTHETIC WATER SAMPLES
              FOR CHLORIDE  BY MERCURIC NITRATE METHOD
Increment as         Precision as          Accuracy as
  Chloride        Standard Deviation     Bias      Bias
   (mg/L)               (mg/L)           (%)      (mg/L)
17
18
91
97
382
398
1.54
1.32
2.92
3.16
11.70
11.80
+2.16
+3.50
+0.11
-0.51
-0.61
-1.19
+0.4
+0.6
+0.1
-0.5
-2.3
-4.7
           TABLE 2.  REPEATABILITY AND REPRODUCIBILITY
                FOR CHLORINE  IN USED OILS BY BOMB
             OXIDATION  AND MERCURIC NITRATE  TITRATION
    Average value,        Repeatability,     Reproducibility,
500
1,000
1,500
2,000
2,500
3,000
170
241
295
340
381
417
448
633
775
895
1,001
1,097
                            9252  - 6                        Revision 1
                                                            November 1990

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    TABLE 3.  RECOVERY AND BIAS DATA FOR CHLORINE IN
             USED OILS BY  BOMB OXIDATION  AND
               MERCURIC NITRATE TITRATION
 Amount          Amount
expected,        found,        Bias,         Percent
  M9/9           M9/9          M9/9          bias
   320             460          140           +44
   480             578           98           +20
   920             968           48           +5
 1,498           1,664          166           +11
 1,527           1,515         -  12           -  1
 3,029           2,809         -220           -  7
 3,045           2,710         -325           -11
                        9252  -  7                        Revision 1
                                                       November  1990

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                   METHOD  9252
CHLORIDE  (TITRIMETRIC,  MERCURIC NITRATE)
                 START
            7.1  Place 50 mL
          sample in  titration
           vessel; determine
           concentration of
           mercuric  nitrate
           titrant to use in
          Step 7.6;  determine
          an indicator blank
           7.2  Add indicator
           to sample; shake
             7.3 Is sample
            blue-violet or
                red?
   7.4  Is sample
     yellow or
     orange?
 7.4 Add sodium
 hydroxide  unti1
    sample  is
blue-violet; add
nitric acid until
sample is yellow
          7.3  Add nitric acid
            until sample is
               yellow
7.5  Add 1 mL nitric
      acid
                                   7.6 Titrate with
                                   mercuric nitrate
                                   until  blue-violet
                                    color persists
                                     7.7 Calculate
                                   concentration of
                                  chloride in sampla
                  9252  -  8
      STOP
Revision  1
November 1990

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                                 METHOD 9253

                    CHLORIDE (TITRIMETRIC. SILVER NITRATE)
1.0   SCOPE AND APPLICATION

      1.1    This method  is  intended  primarily  for  oxygen  bomb combustates or
other waters where the chloride content is 5 mg/L or more and where interferences
such as  color  or high concentrations  of  heavy  metal ions render  Method 9252
impracticable.

2.0   SUMMARY OF METHOD

      2.1    Water adjusted to pH 8.3 is titrated with silver nitrate solution
in the presence of potassium chromate  indicator.  The end point is indicated by
persistence of the orange-silver chromate color.

3.0   INTERFERENCES

      3.1    Bromide, iodide, and sulfide are titrated along with the chloride.
Orthophosphate and polyphosphate interfere if present in concentrations greater
than 250 and 25 mg/L, respectively.  Sulfite and objectionable color or turbidity
must be eliminated.  Compounds that precipitate  at pH 8.3 (certain hydroxides)
may cause error by occlusion.

      3.2    Residual sodium carbonate from the bomb combustion may react with
silver nitrate to produce the precipitate, silver carbonate.   This competitive
reaction may interfere with the  visual detection  of the  end  point.   To remove
carbonate from the  test solution, add small quantities of  sulfuric acid followed
by agitation.

4.0   APPARATUS AND MATERIALS

      4.1    Standard laboratory titrimetric equipment,   including 1 mL or 5 mL
microburet with 0.01 mL gradations, and 25 mL buret.

      4.2    Analytical balance:  capable of weighing to 0.0001 g.

      4.3    Class A volumetric  flask:  1 L.

5.0   REAGENTS

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

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

      5.3    Hydrogen peroxide  (30%), H202.

                                   9253 - 1                        Revision 0
                                                                  November 1990

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      5.4     Phenolphthalein  indicator solution  (10 g/L).

      5.5     Potassium chromate indicator solution.  Dissolve 50 g of potassium
chromate (K2CrOJ in 100 ml of reagent water and add silver nitrate  (AgN03) until
a slightly red precipitate is produced.   Allow the  solution to stand, protected
from light, for at least 24 hours after  the  addition  of AgN03.  Then filter the
solution to remove the precipitate and dilute to 1 L with reagent water.

      5.6     Silver nitrate  solution, standard  (0.025N).   Crush approximately
5 g  of silver nitrate  (AgNO,)  crystals  and dry  to  constant weight  at 40°C.
Dissolve 4.2473 ± 0.0002 g of the crushed, dried crystals in reagent water and
dilute  to  1  L  with  reagent  water.   Standardize against  the standard  NaCl
solution, using the procedure given in Section 7.0.

      5.7     Sodium chloride  solution, standard (0.025N).  Dissolve 1.4613 g +
0.0002 g of sodium chloride (dried at 600°C  for  1 hr) in chloride-free water in
a 1 liter Class A volumetric flask and dilute to the mark with reagent water.

      5.8     Sodium hydroxide solution (0.25'N).   Dissolve  approximately  10 g of
NaOH in reagent water and dilute to 1 L with reagent water.

      5.9     Sulfuric acid (1:19), H2S04.   Carefully add 1 volume of concentrated
sulfuric acid to 19 volumes of reagent water, while mixing.

6.0   SAMPLE COLLECTION, PRESERVATION, AND HANDLING

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

      6.2    There are no special requirements for preservation.

7.0   PROCEDURE

      7.1     Pour 50 mL or  less  of the  sample,  containing between 0.25 mg and
20 mg of chloride ion, into a white porcelain container.   Dilute to approximately
50 mL with reagent water, if necessary.  Adjust the pH  to the phenolphthalein end
point (pH 8.3) using H2S04  (Step  5.9) or  NaOH solution  (Step  5.8).

      7.2    Add approximately 1.0 mL of  K2Cr04 indicator solution  and mix.  Add
standard AgN03 solution  dropwise from a 25 mL  buret  until  the  orange color
persists throughout the sample when  illuminated  with  a yellow light or viewed
with yellow goggles.

      7.3    Repeat the procedure described in Steps 7.1 and 7.2 using exactly
one-half as much original  sample, diluted to 50 mL with halide-free water.

      7.4     If  sulfite  ion  is  present, add  0.5 mL  of H202  to the  samples
described in Steps 7.2 and 7.3 and mix for 1 minute. Adjust the pH, then proceed
as described in Steps 7.2 and 7.3.

      7.5    Calculation

             7.5.1    Calculate  the chloride ion concentration in  the original
      sample, in milligrams per liter,  as follows:

                                   9253  - 2                        Revision 0
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             Chloride (mg/L) = [(V, - V2)  x  N  x  71,000] / S

             where:

             V1 =     Milliliters  of  standard  AgNO, solution added in titrating
                      the  sample prepared  in Step 7.1.

             V2 =     Milliliters  of  standard  AgNO, solution added in titrating
                      the  sample prepared  in Step 7.3.

              N =     Normality of standard  AgN03 solution.

              S =     Milliliters  of  original  sample in the 50  ml  test sample
                      prepared  in  Step 7.1.

         71,000 =     2  x  35,500 mg CT/equivalent, since V, -  2V2.

8.0   QUALITY CONTROL

      8.1    Refer to Chapter One  for specific quality control procedures.

      8.2    A matrix duplicate and matrix spike sample are brought through the
whole sample preparation and analytical process.

9.0   METHOD PERFORMANCE

      9.1    These  data  are  based  on  32  data  points  obtained  by  five
laboratories who each  analyzed four used crankcase oils and three  fuel oil blends
with crankcase in duplicate.  The samples were combusted using Method 5050.  A
data point represents  one duplicate analysis  of a sample.  Three data points were
judged to be outliers and were not included  in these results.

             9.1.1    Precision.   The precision  of  the  method  as determined by
      the statistical  examination  of interlaboratory test results  is as follows:

             Repeatability - The difference  between successive results obtained
      by  the  same operator with  the  same apparatus under-  constant operating
      conditions on identical test material  would exceed,  in  the long run, in
      the normal and correct operation of  the  test method, the following values
      only in 1 case in 20 (see Table 1):


                         Repeatability =0.36
      *where x is the average of two results in M9/9-

             Reoroducibilitv - The difference between two single and independent
      results obtained by different  operators working in different laboratories
      on identical test material would exceed,  in  the  long  run,  the following
      values only in 1 case in 20:
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                        Reproducibility =0.71 Jx*
       where x is the average  of two  results  in M9/9-
             9.1.2    Bias.  The bias of this method varies with  concentration,
      as shown in Table 2:
                    Bias = Amount found - Amount expected

10.0  REFERENCES

1.    Rohrbough, W.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.    Gaskill, A.;  Estes, E.  D.;  Hardison, D. L.; and Myers,  L.  E.   "Validation
of Methods for Determining Chlorine in Used Oils and Oil Fuels,"  Prepared  for
U.S. Environmental  Protection Agency,  Office  of Solid Waste.  EPA  Contract  No.
68-01-7075, WA 80.   July 1988.
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                                   TABLE 1.
            REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN USED
              OILS  BY  BOMB OXIDATION  AND SILVER  NITRATE  TITRATION
Average value
  (M9/9)
Repeatability
   (M9/9)
Reproducibility
      (M9/9)
500
1,000
1,500
2,000
2,500
3,000
180
360
540
720
900
1,080
355
710
1,065
1,420
1,775
2,130
                                   TABLE 2.
              RECOVERY AND  BIAS  DATA  FOR  CHLORINE  IN USED OILS  BY
                  BOMB OXIDATION AND  SILVER NITRATE TITRATION
Amount
expected
(M9/9)
320
480
920
1,498
1,527
3,029
3,045
Amount
found
(M9/9)
645
665
855
1,515
1,369
2,570
2,683

Bias,
(M9/9)
325
185
-65
17
-158
-460
-362

Percent
bias
+102
+39
-7
+1
-10
-15
-12
                                   9253 -  5
                                     Revision  0
                                     November 1990

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                                METHOD  9253
              CHLORIDE  (TITRIMETRIC,  SILVER  NITRATE)
                                   START
                              7.1  Place 50 ml
                            sample in porcelain
                                container
     7.4 Add hydrogen
    peroxide; mix for  1
         minute
                        Yea
  7.4  Is
sulfite ion
present in
  sample?
                                     No
                             7.1  Adjust pH to
                                   8.3
                       72 Add  1.0 mL
                     potassium  chromate;
                      stir;  add silver
                        nitrate until
                        orange  color
                          persis ts
 7 . 3  Repeat steps
 7.1  and 7.2 with
1/2 as much sample
 diluted to 50 mL
                        75 Calculate
                      concentration of
                     chloride in sample
                                                            STOP
                                 9253  - 6
                                         Revision  0
                                         November 1990
1} U.a GOVERNMENT PRNTWQ OFFICE: 1981-281-724/28489

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